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Biomimetic and Bioinspired Synthesis of Nanomaterials/

REVIEW
Nanostructures
Guangtao Zan and Qingsheng Wu*

In recent years, due to its unparalleled advantages, the biomimetic and the purpose of synthesizing similar prod-
bioinspired synthesis of nanomaterials/nanostructures has drawn increasing ucts by artificial mechanisms that mimic
natural ones.[9] In recent years, the term
interest and attention. Generally, biomimetic synthesis can be conducted “bioinspired” was put forward, and it has
either by mimicking the functions of natural materials/structures or by gradually become accepted. The main dif-
mimicking the biological processes that organisms employ to produce ference between “biomimetic” and “bioin-
substances or materials. Biomimetic synthesis is therefore divided here into spired” is that the former is generally a
“functional biomimetic synthesis” and “process biomimetic synthesis”. direct mimicry of processes or techniques
employed by nature, while the latter deals
Process biomimetic synthesis is the focus of this review. First, the above two
with direct or indirect mimicry; that is,
terms are defined and their relationship is discussed. Next different levels “bioinspired” has a broader meaning and is
of biological processes that can be used for process biomimetic synthesis more flexible; occasionally, these terms can
are compiled. Then the current progress of process biomimetic synthesis is substitute for one other. In recent decades,
systematically summarized and reviewed from the following five perspectives: taking lessons from nature has motivated
i) elementary biomimetic system via biomass templates, ii) high-level extensive research in many fields, such
as robotics,[10] bioelectronics,[11–19] medi-
biomimetic system via soft/hard-combined films, iii) intelligent biomimetic cine,[20–22] catalysis,[23–26] self-cleaning,[27–31]
systems via liquid membranes, iv) living-organism biomimetic systems, and and energy.[32–36]
v) macromolecular bioinspired systems. Moreover, for these five biomimetic Biomimetic synthesis of materials is
systems, the synthesis procedures, basic principles, and relationships are an important branch of biomimetics;
discussed, and the challenges that are encountered and directions for further among various materials, biomimetic
synthesis of nanomaterials is the fastest
development are considered.
growing and the most promising field.
Herein, we suggest that biomimetic
synthesis should be divided into two cat-
1. Introduction egories: functional biomimetic synthesis (FBS) and process
biomimetic synthesis (PBS). Functional biomimetic synthesis
The idea of learning from nature to solve problems is undoubt- aims at mimicking specific properties of natural materials/
edly as old as humanity itself.[1–8] Although biomimetic behavior structures/systems employing various substances and dif-
can be traced back thousands of years, the term “biomimetics” ferent methods. For example, artificial bones of various mate-
was not suggested until 1960s by Schmitt.[3] The term was rials (bioceramics, polymers, composites, etc.) have been syn-
defined as the investigation of the formation, structure, or func- thesized by different methods, which are expected to possess
tion of biologically produced substances and materials (such high strength, fracture toughness and good biocompatibility
as enzymes or silk) and biological mechanisms and processes at the same time. Process biomimetic synthesis is a kind of
(such as protein synthesis or photosynthesis), especially for synthesis method, that attempts to prepare various valuable
nanomaterials/structures by mimicking the synthesis routes,
processes, or procedures of natural substances and materials/
Dr. G. Zan, Prof. Q. Wu structures. For instance, by mimicking the protein synthesis
Department of Chemistry process, many unique nanosuperstructures (satellite struc-
State Key Laboratory of Pollution Control and tures,[37] dendrimer-like structures,[37] pyramids,[38] cubes,[39]
Resource Reuse
Tongji University 2D nanoparticle arrays,[40] and 3D AuNP tubes,[41] etc.) have
Shanghai 200092, P. R. China been assembled in vitro.
E-mail: qswu@tongji.edu.cn From the above discussions, it can be concluded that FBS
Dr. G. Zan, Prof. Q. Wu and PBS are significantly different. The aim of the former is to
School of Materials Science and Engineering mimic the “properties”, and the aim of the latter is to mimic the
Tongji University
Shanghai 200092, P. R. China
“methods”. Therefore, it is essential to clearly distinguish and
define these terms to make research more targeted. Therefore,
DOI: 10.1002/adma.201503215 researchers may select PBS when they need mild, efficient, and

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green synthesis routes. Alternatively, researchers may think

of FBS when they seek to pursue the properties of materials. Guangtao Zan is currently
However, they also have an internal connection, and this rela- a Ph.D. candidate in the
tionship between FBS and PBS can be perfectly described by School of Materials Science
the Tai Chi symbol of Taoism (Figure 1). The Tai Chi symbol and Engineering of Tongji
consists of two fish-shaped halves, which nestle from head to University under the supervi-
tail against each other to form a circle. Each of the two fish- sion of Prof. Qingsheng Wu.
shaped halves additionally contains one disk (similar to the He received his B.S. degree
eye of the fish) of opposite colors. When the Tai Chi symbol in Chemical Engineering
is employed for describing biomimetic synthesis, the black and Technology from
and the white fish-shaped halves represent PBS and the FBS, Northwestern Polytechnical
respectively. The opposite-colored disks and the boundary of University in 2012. His
the two fish-shaped halves reflect the compatibility relation and research interest is focused
penetrating and cross relation of the PBS and FBS, respectively. on the biomimetic synthesis of nanomaterials and their
The water-drop shaped images represent different paths: FBS electrical properties.
allows for the generation of nanomaterials/structures with
specific properties by different synthesis paths (i.e., different Qingsheng Wu is currently
paths lead to the same destination); PBS allows for the genera- a full professor and academic
tion of various nanomaterials/nanostructures by different bio- leader of Nano-ST in
mimetic paths from the same precursor (i.e., different branches Department of Chemistry of
are derived from the same source). In fact, they can have inter- Tongji University. He received
communication: FBS can employ process biomimetic synthesis his Ph.D. in inorganic
methods; PBS may produce the desired nanomaterials/struc- chemistry in 2001 from
tures for functional biomimetic synthesis. the University of Science
With the generation and development of nanotechnology, and Technology of China.
researchers have begun to further pursue milder, more effi- His scientific interests are
cient, and more ecofriendly synthesis methods for nanomate- focused on biomimetic
rials when conventional physical and chemical methods run synthesis of nanomaterials,
into bottlenecks. Therefore, process-biomimetic- and process- the optical and electrical properties of nanomaterials, and
bioinspired-related methods emerge as required and spring up the biological effects of nanomaterials.
like mushrooms. However, in recent decades, almost all reviews

containing “biomimetic synthesis” or “bioinspired synthesis”

Figure 1. The modified Tai Chi symbol for describing biomimetic syn-
thesis. The white-colored parts represent functional biomimetic synthesis,
and the black-colored parts represent process biomimetic synthesis.
(“…” means “etc.”).
in the titles are about functional biomimetic synthesis.[6,42–46]
Even though a few reviews contain the content of process bio-
mimetic synthesis, they are only elementary or partial process
biomimetic synthesis, and they are entitled “biomineralization”,
“template synthesis”, etc,[47–50] while the nonuse of “biomimetic
synthesis” or “process biomimetic synthesis” may be because
the concepts of FBS and PBS are not explicitly proposed and
differentiated. In fact, PBS has extensive applications and
shows huge potential. It is therefore essential to systematically
and comprehensively summarize and review process biomi-
metic synthesis and this review will focus on this topic.
To better study process biomimetic synthesis, it is essen-
tial to first have a good understanding of the actual biological
processes that can be employed for it. Figure 2 shows dif-
ferent levels of actual biological processes in living organisms.
Thereinto, the meanings of the arrows are as follows: the same-
colored arrows mean a group of constitution relationships;
along the arrows’ direction, several lower biological processes
constitute a certain higher biological process, but the higher
biological process may contain other lower biological processes
that are not shown in the figure; several arrows may come
from the same lower biological process, indicating that a cer-
tain lower biological process can be used by different higher
biological processes. Organisms contain a lot of elementary

2 wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2016,
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biological processes, such as molecular recognition, molecular
assembly, and template regulation (bottom of Figure 2). Organ-
isms often select several elementary biological processes to
form biological unit processes to fulfill specific tasks, such as
biomineralization, which involves the following elementary
biological processes: supramolecular preorganization, molec-
ular recognition, template regulation, and cellular processing.
Another example of a biological unit process is DNA replica-
tion, which involves the following elementary biological pro-
cesses: enzyme catalysis, polymerization, complementary base
pairing, and DNA supercoiling (middle of Figure 2). The coop-
eration of these biological unit processes can achieve higher
life processes (top of Figure 2). It should be noted that the
synthesis of nanomaterials/nanostructures can be conducted
by mimicking one or more different elementary biological pro-
cesses, biological unit processes, or higher life processes in
vitro. All these kinds of synthesis methods belongs to process
Figure 2. Different levels of biological processes in living organisms promising for process biomimetic synthesis.
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biomimetic synthesis. The three levels of biological processes
show increasing complexity and advanced features, and the
difficulty of mimicking these processes increases accordingly.
However, a better performance for process biomimetic syn-
thesis may be obtained if higher levels of biological processes
are successfully mimicked.
It can be concluded from Figure 2 that a lot of biological pro-
cesses can be employed for process biomimetic synthesis. So
far, only some biological processes have been mimicked for the
process biomimetic synthesis of nanomaterials/nanostructures.
This review will summarize and review such related work from
the following perspectives:
1. In the review, for the first time, we divide biomimetic syn-
thesis into FBS and PBS, explicitly define these terms, and
describe in detail the relationship between them using the
modified Tai Chi symbol.
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show degrees of sophistication that surpass current artificial

Figure 3. The relationship of detailed process-biomimetic-synthesis sys-
tems for nanomaterials/nanostructures. The elementary biomimetic sys-
tems, high-level, or intelligent biomimetic systems, and living biomimetic
systems correspond to the elementary biological processes, biological
unit processes, and higher life processes in Figure 2, respectively.
2. We compile many biological processes from life systems,
which are promising for the process biomimetic synthesis of
nanomaterials/nanostructures; we divide them into different
levels and discuss their relationship.
3. We systematically summarize and review
the current state of process biomimetic
systems from the following five per-
spectives (the relationships between the
detailed process biomimetic synthesis sys-
tems are shown in Figure 3):
materials and structures. In recent years, the requirements for
new functional nanomaterials, such as hierarchy and porosity,
have urged researchers to turn to natural biomass templates
for the biomimetic synthesis of nanomaterials. Many biological
processes are mimicked during the biomass template’s biomi-
metic synthesis, such as diffusion, penetration, molecular rec-
ognition, template-inducing, assembly, and space-confinement
processes (Figure 4A). As discussed above, although these pro-
cesses are elementary biological processes, their combination
has shown some characteristics of higher biological processes.
Figure 4B shows the general synthesis process of biomass-
template biomimetic synthesis, which consists of two main
stages: the assembly of the precursor and template removal.
In process biomimetic synthesis, the biomass templates are
immersed into a precursor solution, and the precursor then dif-
fuses and permeates into the biomass templates. Next, the pre-
cursor assembles onto specific sites via a molecular recognition
process, and the precursor further grows through the template-
inducing process. When the precursor reaches a certain thick-
ness, it stops growing due to space confinement. After removal
of the templates, the nanomaterials can replicate the structures
of the biomass templates. Template removal is an artificial pro-
cess, and this artificial process combined with the biomimetic
process can better mimic the full biological synthesis process.
It should be noted that the reaction conditions and the precur-
sors have a great deal of influence on the resultant materials,
and positive, negative, or direct copies can be obtained through
adjusting the reaction parameters. When the precursor infills

i) Elementary biomimetic synthesis via

biomass templates;
ii) High-level biomimetic synthesis via soft/
hard-combined membranes;
iii) Intelligent biomimetic synthesis via
liquid membranes with carriers;
iv) Living-organism biomimetic synthesis
via plants/microorganisms;
v) Bioinspired synthesis via bio-macromole-
cule regulation.

4. We conclude the discussion and offer

perspectives.

2. Elementary Biomimetic Synthesis

via Biomass Templates
Organisms have created abundant biomass
materials with unique and complex struc-
Figure 4. A) The mimicked biological processes of biomass-template biomimetic synthesis.
tures over millions of years of evolution. Par- B) The synthesis process and possible product structures of biomass-template biomimetic
ticularly, at the micrometer and nanometer synthesis: B1) a negative (inverse) replica of the biomass template; B2) a positive (hollow)
scales, natural biomass structures often replica of the biomass template; B3) a full replica of the biomass template.

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eggshell membrane,[81–88] and spider silk[89] for process biomi-

the voids of the template, a negative (inverse) replica can be
obtained (Figure 4B1); when the precursor coats the walls of the
voids of the template, a positive (hollow) replica can be obtained
(Figure 4B2); when the precursor permeates into the template,
a full replica can be obtained (Figure 4B3). Taking advantage of
unique biomass structures, such as wood,[51–55] diatoms,[56–59]
leaves,[60–63] pollen grains,[64–70] insect wings,[71–79] sea urchins,[80]
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metic synthesis has become a shortcut for the designed and con-
trolled preparation of nanomaterials/nanostructures. So far, a
lot of nanomaterials/nanostructures have been prepared via this
process biomimetic method (listed in Table 1).
Wood is a natural cellular composite material composed
of interconnected cells (tracheids) and open spaces (lumens).

Table 1. Nanomaterials/nanostructures obtained using biomass-template biomimetic synthesis.

Material Biotemplate Morphology Size Property Ref

Au sea-urchin skeleton ordered macroporous network 15 µm channels – [80]
Au eggshell membrane nanoparticle <20 nm highly fluorescent [81]
Ag spiral vessels of Photinia fraseri microcoil – DC conductivity and [90]
self-inductance
Ag silk fibroin filament assembled floriated clusters micro–nano scale – [91]
Ti/Ni vessels of vascular plant helical structure diameter of 11.5–12.5 µm – [92]
carbon-rich diatom ordered macroporous–mesoporous – – [56]
material
Au/Cu, CuO diatom freestanding structure – – [57]
Ni-P Cyphochilus spp beetle freestanding structure – – [57]
TiO2 banana leaf hierarchical porous average pore size 13 nm adsorption, photocatalysis [93]
TiO2 Saccharum officinarum linn leaf biomorph structure – photocatalysis [23]
TiO2 china rose petal mesoporous nanosheet 4 nm in thickness; pore size 13 nm photocatalysis [94]
TiO2 rape pollen hollow structure – – [95]
TiO2 dandelion pollen interleaving nanorods – Photocatalysis [64]
TiO2 skins of tomatoes, bulb onions, mesoporous anatase 2–10 nm photocatalysis [96]
grapes, and garlic bulbs
TiO2 butterfly wing quasi-honeycomb – solar cell [74]
TiO2 butterfly wing 3D biomorph structure – – [76]
TiO2 eggshell membrane hierarchical mesoporous 2 nm–4 µm – [82]
TiO2 eggshell membrane interwoven mesoporous 2 nm–8 µm – [83]
TiO2 silk fibroin filament porous filaments 10–100 nm pore size – [97]
TiO2 diatom porous – photocatalysis [59]
ZnO lauan and fir wood hierarchically porous – gas sensing [52]
ZnO butterfly wing porous microtube – / [79]
ZnO butterfly wing hierarchically porous – / [77]
ZnO eggshell membrane hierarchical interwoven structure fibers diameter of 0.2–1.5 µm / [84]
α-Fe2O3 eggshell membrane hierarchically mesoporous – gas sensing [85]
α-Fe2O3 butterfly wings quasi-honeycomb – gas sensing [98]
Fe3O4 butterfly wing biomorph structure – magnetophotonic crystals [71]
Fe3O4 rape pollen porous hollow microspheres – multimodal adhesion [99]
Mn3O4 eggshell membrane hierarchical network – water treatment [86]
Al2O3 rattan stem porous biomorph structure – – [55]
CeO2 maple leaf hierarchical porous – catalysis [61]
CeO2 China rose petal mesoporous nanosheet 7 nm in thicknesss – [100]
2–4 nm in pore size
CeO2 rape pollen porous hollow microspheres 10 µm in diameter photocatalysis [69]
In2O3 cotton fiber biomorphic microtubule 30–60 µm in length, 8–10 µm in gas sensing [101]
width, 300 nm in thickness
SnO2 cotton fiber nanotubular ca. 100 nm in diameter gas sensing [102]
SnO2 eggshell membrane biomorphic film – gas sensing [87]

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Table 1. Continued
Material Biotemplate Morphology Size Property Ref
SnO2 eggshell membrane porous hierarchical meshworks – – [88]
SnO2 pollen grains porous – – [103]
ZrO2 sunflower pollen spinous core–shell microspheres 30–35 µm in diameter hydrogen storage [65]
ZrO2 silk fibroin filament porous 10–100 nm pore size – [97]
ZrO2 butterfly wings hierarchically porous – – [78]
Cu/TiO2 rape pollen hollow microspheres 15–20 µm in diameter; 0.6 µm photocatalysis [66,67]
in wall thickness
NiO/C lotus pollen hierarchically porous microsphere 35 µm in diameter Lithium-ion battery electrodes [104]
composite
ZnAl-MMO legume hierarchically macro/ – photocatalysis [105]
mesoporous
ZnO, NiO, CuO, eggshell membrane interwoven microporous structure – extracting nanoparticles [106]
Co3O4,CeO2
SiO2 rape pollen hollow microsphere microscale – [68,107]
SiO2 rape-, sweet-potato- and camellia hierarchical morphology – – [70]
pollen
SiO2 butterfly wing hierarchical – – [73]
SiO2 spider silk hierarchically ordered hollow meso- 1–2 cm in length; 1–2 µm in – [89]
porous fiber diameter
SiO2 butterfly wing 3D biomorph – optical property [75]
SiO2 butterfly wing biomorph – optical property [108]
SiO2 red blood cells anisotropic mesoporous – [109]
mesoporous particle
SiC pine wood biomorph – – [53]
SiC sea-urchin skeleton hierarchically porous – – [72]
SiC butterfly wing hierarchically porous – – [72]
SiC eggshell membrane hierarchically porous – – [72]
TiC cotton fiber nanorods 80–200 nm in diameter, 1–3 µm – [110]
in length
Fe3C leaf biomorph – water splitting [60]
Zeolite luffa sponge biomorphic hierarchical porous – catalysis [111]
Zeolite Equisetum arvense hierarchically porous – – [62]
Zeolite Equisetum arvense biomorph – – [63]
Si/SiC bamboo biomorph – electrical property [58]
SiSiC/zeolite rattan stem hierarchically porous – catalysis [112]
ZnSnO3 cotton fiber biomorphic hollow fiber 10–15 µm in pore size gas sensing [113]
LaFeO3 cotton fiber biomorphic hollow fiber 4–10 µm in inner diameter gas sensing [114]
FePO4 rape pollen hollow microspheres 7 µm in diameter – [115]
YBa2Cu3O7−δ cuttlebone ordered macroporous – superconducting [116]
Ce0.5Zr0.5O2 spruce wood fibrillar 2–4 nm in diameter – [54]
ESrAl2O4: Eu2+ pine wood biomorph – phosphor [51]

Different types of wood often exhibit different porous microstruc-
tures due to the varied morphology and arrangement of cells in
different species. Hard wood species (e.g., poplar) contain close-
packed tubular cells with sizes of 1–100 µm. In contrast, soft
wood species (e.g., pine) contain close-packed rectangular cells of
approximately the same size, favoring the infiltration of precursor
solutions through uniform cellular structure (Figure 5C,D).
Bamboo,[58] Norway spruce,[54] pine,[51,117] lauan and fir,[52] euca-
lyptus,[118] rattan stem (Figure 5A,B),[55,112] and luffa sponge[111]
have all been utilized for biomimetic and bioinspired synthesis. It
has been demonstrated that pH is a key factor controlling the pos-
itive and negative replicas of the original wood structures. Shin
and Exarhos[53] synthesized hierarchically ordered silica materials
through surfactant-directed in situ mineralization on wood in

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Figure 5. A,B) SEM images of biomorphic rattan-derived Al2O3 ceramic in
axial-cut view (MX: metaxylem, PP: protopholem, and MP: metaphloem).
Reproduced with permission.[55] Copyright 2005, Wiley-VCH. C,D) SEM
images of the axial sections of pine-templated Sr0.97Al2O4:Eu0.03 samples
sintered at 1200 ºC. Reproduced with permission.[51] Copyright 2009,
Wiley-VCH.
solutions of different pH. At low pH, a positive replica of wood
is formed after calcination because the silicic acid only penetrates
the interfaces of the wood’s cellular structure without clogging
the pores. At high pH, a negative replica of the wood is obtained
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because the rapid condensation of hydrolyzed silica fills the open
cells and pits.[53]
Plant leaves are important for photosynthesis and transpira-
tion due to their special structure. In biomimetic synthesis, the
structure of the leaf can be replicated to form porous[62,63] and
3D hierarchical nanomaterials.[23,34] Micro-/mesoporous zeo-
lite that retained all of the morphological features of Equisetum
arvense leaves has been obtained.[63] The large amount of silica
in the epidermal surface of Equisetum arvense provides homo-
geneous and dense silica nuclei to facilitate zeolite nucleation.
Fan’s group prepared leaf-shaped hierarchical N-doped TiO2[23]
and Pt/N-doped TiO2[34] using natural leaves (Figure 6A,B).
The light-harvesting performance and photocatalytic activity of
such systems are higher than those prepared by classic routes.
This ability is due to the hierarchical structures derived from
natural leaves and the effective nitrogen doping during syn-
thesis. Similarly, Schnepp et al. synthesized intact, intricate,
hierarchical microstructures of magnetic iron carbide (Fe3C)
from a leaf skeleton (Figure 6C–G), providing a general pro-
cedure for the biomimetic synthesis of metal carbide mate-
rials using biomass templates.[60] Further study showed that
a homogeneous coating of Fe3C over the whole leaf structure
could be achieved. It is therefore clear that biomimetic and
bioinspired synthesis using plant leaves may represent an
important step toward the design of novel artificial energy and
catalyst systems based on exploring and mimicking the struc-
tural design, such as solar cells, photocatalysts, and photoin-
duced sensors.

Figure 6. A,B) Comparison of natural and artificial leaves from their structures and functions. Reproduced with permission.[34] Copyright 2010,
Wiley-VCH. C) Magnetic replica of a rubber fig (Ficus elastica) leaf attracted by a permanent magnet.[60] D–G) SEM images of the magnetic sacred fig
(Ficus religiosa) leaf replica, showing helical (D), scalariform (E,G), and pitted structures (F) characteristic of xylem vessels. Adapted with permission.[60]
Copyright 2010, Wiley-VCH.

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Some special plant structures, such as spiral vessels, can
be used for the biomimetic synthesis of nanomaterials with
special morphology. It should be noted that it is often diffi-
cult to prepare these special morphologies (e.g., microcoils) by
conventional chemical and physical routes. Kamata et al first
reported the synthesis of left-handed silver microcoils using
spiral vessels in lotus roots (Figure 7A–C).[90] The solenoidal
silver microcoils exhibited self-inductance at picohenry levels,
a property that could be applied for electromagnetic-responsive
materials in high-frequency regions, such as millimeter or tera-
hertz waves.[119] Wang’s group prepared magnetically propelled
helical microswimmers by coating isolated spiral vessels with
a magnetic nickel layer (Figure 7D).[92] Process biomimetic
synthesis leads to biocompatibility, biodegradability, and easy
and large-scale fabrication of the microswimmers. The mag-
netic layer allows for high-speed propulsion and precise direc-
tional control of these plant-derived helical microswimmers
(Figure 7E). In particular, these microswimmers can be pro-
pelled at high speeds in pure human serum, indicating their
great promise for future biomedical applications. Moreover, a
wide variety of spiral vessels from other vascular plants, even
microscopic organisms with desired feature sizes and shapes,
can be utilized for similar microcoil synthesis (Figure 7G–K).
The diameters of these uniform helical spiral microstructures
isolated from various vascular plants vary from approximately
10 µm to over 60 µm, and further tests have shown that the
helical vessels from different leaves can still maintain similar
diameters even when they are stretched to 600% of their initial
pitch length (Figure 7F). In addition, it is estimated that over a
million individual helical swimmers can be generated from a
short single segment of the plant stem due to the high density
of spiral vessels in the leaves. Thus, biomimetic synthesis pro-
vides a simple, cost-effective, and reproducible large-scale route
for fabricating helical microswimmers compared to traditional
physical and chemical methods.
The legume, the fruit of a type of wisteria, also shows a
unique surface structure. The exterior surface of the legume is
covered by unclosed tubal atrichomes with diameters of 10 µm.
Using the legume as a biotemplate, Zhao et al. fabricated a
hierarchical macro-/mesoporous biomorphic ZnAl mixed
metal oxide (ZnAl-MMO) framework.[105] The ZnAl-MMO was
obtained by calcining ZnAl-layered double hydroxides/legume
precursors synthesized via an in situ growth technique. It was
found that the MMO framework catalyst is an effective and
recyclable photocatalyst owing to its high specific surface area
and hierarchical pores (Figure 8A–C). It is anticipated that inex-
pensive and easily available legumes can be employed for the
fabrication of various hierarchical porous nanomaterials, which
are promising in catalysis and adsorption with enhanced effi-
ciency. Moreover, some microorganisms, such as single-celled

Figure 7. A) Photograph of white fibers drawn from cross sections of a rhizome of Nelumbo nucifera (lotus). B) SEM image of one spiral vessel
of Nelumbo nucifera (lotus). C) A silver coating on a spiral vessel of Nelumbo nucifera rhizome. A–C) Adapted with permission.[90] Copyright 2011,
Wiley-VCH. D) SEM image of the helical structure of a single microswimmer from Rhaphiolepis indica. E) Schematic of the microswimmer’s corkscrew
motion. F) Microscopic images of the spiral vessels isolated from the leaves before stretching and at various stretching states. G–K) Photographs
(upper) and microscopy images (lower) of spiral microstructures from xylem of different plants. D–K) Adapted with permission.[92] Copyright 2013,
American Chemical Society.

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Figure 8. A) Optical photograph of a legume. B) SEM images of the tubular trichome on the surface of the legume. C) SEM images of the ZnAl-MMO
framework obtained by calcination of an LDH/legume precursor for the surface view. A–C) Adapted with permission.[105] Copyright 2009, American
Chemical Society. D) SEM image of a starting Aulacoseira sp. diatom frustule. E) SEM image of Cu coated Aulacoseira sp. frustule. D,E) Adapted with
permission.[57] Copyright 2012, Royal Society of Chemstry.

diatoms, can be employed for the biomimetic synthesis of
nanomaterials with special morphologies. Fang et al. prepared
freestanding transition-metal assemblies that retained the
microscale biogenic shapes and nanoscale features of complete,
hierarchically structured diatoms.[57] Particularly, the authors
proposed that dendritic amplification of surface-bound amines
on siliceous diatom frustules enables a high degree of metal
deposition, leading to exact replication (Figure 8D,E).
Pollen grains are ubiquitous, inexpensive, and environmen-
tally friendly, and are therefore ideal for bioinspired synthesis
of hollow nanomaterials with hierarchical pore structures. Par-
ticularly, pollen grains from the same species often show similar
sizes, thus promising the development of uniformly sized and
large-scale synthesis of nanomaterials. Figure 9A shows the
general biomimetic synthesis process for pollen grains. First,
the grains are immersed in a precursor solution, and the pre-
cursor can then nucleate and grow on the surface or core of the
pollen grains via interactions between the functional groups on
the surface of the pollen and the precursors. Then, the pollen
biotemplates are removed via calcination. In this way, hollow
structures with corresponding hierarchically porous surface
morphologies, such as spheres with troughs, ellipsoids with
meshes and spheres with spines, can be obtained (Figure 9B–E).
The biocompatible pollen grain is an ideal biotemplate for the
biomimetic synthesis of biomaterials, which may extend their
applications. For instance, Hall et al. synthesized silica, cal-
cium phosphate, and calcium carbonate facsimiles using dif-
ferent pollen grains, and these replicas showed potential for
the controlled release of drugs due to their unique porous
structure.[120] These authors also developed a non-aqueous
sol–gel synthesis technique for the replication of dandelion
pollen grains in the form of morphologically complex porous
titania (Figure 9E), an important step in the high-fidelity replica-
tion of biotemplates.[121] Goodwin et al. reported the first syn-
thesis of 3D nanocrystalline all-oxide sunflower pollen micro-
particle replicas that were tailored for multimodal adhesion; this
method may be used for other pollen-derived microparticles that
are highly tailorable for multimodal adhesion (Figure 9C).[99]
Moreover, other functional nanomaterials, primarily transition-
metal oxides, can also be produced. These unique structures and
morphologies of resultant nanomaterials may lead to a better per-
formance for photocatalysis, gas sensing, lithium-ion batteries,
and hydrogen storage due to their high specific surface area
and appropriate pore size distribution (Figure 9D).[99,104,121,122]
Porous pollen can also act as both the carbon source and the
template to form hierarchical porous composites. Lotus-pollen-
derived NiO/C composites exhibit remarkable performance for
lithium-ion batteries due to their high specific surface area and
wide pore-size distribution (Figure 9B).[104]
Animal structures, such as butterfly wings,[71–79,98,108,123,124]
sea-urchin skeletons,[72,80] cuttlebone,[116] beetles,[57] silk-fibroin
filaments,[91,97] spider silk,[89] and eggshell membranes,[81–88] are
more uniform and periodic compared with plant structures.
For this reason, unique properties can be obtained utilizing
animal structures for biomimetic synthesis (Figure 10).
Butterfly wings display diverse colors and patterns due to their
periodic surface scales and are widely exploited for biomimetic
synthesis. Notably, Zhang’s group prepared ZnO[77] and ZrO2[78]

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calcite was formed by growing CaCO3 in this

membrane.[125] The resultant product showed
a morphology that perfectly replicated the
membrane structure, demonstrating the
regulation of the space-confinement effect on
the crystal morphology.
Eggshell membrane (ESM) has a macropo-
rous framework composed of interwoven and
coalescing fibers ranging from 0.5 to 1.5 µm
in diameter. Numerous nanomaterials repli-
cating the biomorph have been synthesized,
such as gold,[81] Mn3O4,[86] α-Fe2O3,[85] SiC,[72]
TiO2,[82,83] ZnO,[84] SnO2,[87,88] NiO, CuO,
Co3O4, and CeO2.[106] After calcination in air,
these materials often display hollow, hier-
archically ordered macroporous networks,
showing remarkable performance for photo-
catalysis and gas sensing. Natural cellulose
fibers (e.g., cotton), showing similar inter-
woven structure to ESM, can also be consid-
ered as a support or as a reaction substrate.
These fibers can provide amphoteric surface
hydroxyl groups for the deposition or grafting
of versatile inorganic species.[101,102,110,113,114]
Cells can also be used for the biomimetic
synthesis of nanomaterials. Meyer et al.
found that red blood cells (RBCs) show bio-
logical responses to chemical agents, and
four distinct morphologies, stomatocytes,
echinocytes, spherocytes, discocytes, can
be obtained.[109] These asymmetric RBC
shapes can be translated into anisotropic
composites and inorganic particles using a
Figure 9. A) The biomimetic synthesis mechanism using pollen grains. B) SEM images of process of silica bioreplication. As a result,
NiO/lotus-pollen precursor; Inset) TEM images of hierarchically porous NiO/C microspheres. due to the adjustable shapes of RBCs, the
Adapted with permission.[104] Copyright 2012, Royal Society of Chemistry. C) SEM images of internal structure/porosity of the obtained
Fe3O4 replica synthesized using sunflower (Helianthus annuus) pollen grains. Reproduced with mesoporous material can be tuned. To pro-
permission.[99] Copyright 2013, American Chemical Society. D) SEM images of SnO2 synthe- duce anisotropic particles, purified RBCs are
sized using Brassica capestris pollen grains. Adapted with permission.[122] Copyright 2012, Amer-
fixed before silicification. The silicification is
ican Chemical Society. E) SEM images of single TiO2 particles showing porous architecture, and
replicated lophate ridges and echinate spines synthesized using native dandelion (Taraxacum) conducted in a saline solution at 40 °C con-
pollen grains. Reproduced with permission.[121] Copyright 2006, American Chemical Society. taining 0.1 M silicic acid (pH 3) for 12–18 h.
The silica nucleates and grows on both
photonic crystals and Fe3O4[71] magnetophotonic crystals with internal and external cellular surfaces to form Si-RBC com-
a 3D network using butterfly wings. Mille et al. produced 3D, posites. Particularly, Si-RBCs provide opportunities for shape-
chiral silica replicas with a bicontinuous gyroid structure using preserving transformations into metallic, semiconductive,
the chiral structures of the wing scales of Callophrys rubi as and ferromagnetic particles and assemblies. Furthermore, the
templates.[75] Moreover, other hierarchical functional materials, facile and versatile silicification approach can not only be used
such as ZnO microtubes with adjustable arrayed nanopores in the preservation and analysis of biological structures,[126]
on the walls (Figure 10F),[79] quasi-honeycomb like structures but also offers an unprecedented pathway for the design and
(Figure 10D), shallow concave structures (Figure 10E), and synthesis of various functional materials via other similar cell
cross-ribbing structures for photoanodes[74] have also been syn- templates.
thesized using butterfly wings as biotemplates. These resulting Nature is replete with elaborate biomaterials with complexi-
nanomaterials retained the unique structure of the template ties beyond those currently achievable in the laboratory. These
and have potential for applications, not only in photonics, but materials have been extensively applied for the biomimetic syn-
also in various energy-conversion and energy-storage areas. thesis of various nanomaterials with unique morphologies and
Furthermore, these animal structures may also be utilized for porous structures. In particular, abundant available biomass
the mimicking of biomineralization to probe certain effects. For and facile synthetic routes make biomass-template biomimetic
example, the sea-urchin skeletal plate is used as a biotemplate synthesis a promising method for the large-scale preparation of
to perform polymer membrane replication. A single crystal of nanomaterials. However, biomass templates also show some

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Figure 10. Exploiting animal structures for bioinspired synthesis. A–C) SEM images of butterfly wings at low (A, B) and high (C) magnifications.
A,B) Reproduced with permission.[72] Copyright 2009, Elsevier. C) Reproduced with permission.[75] Copyright 2011, Royal Society of Chemisry.
D) Quasi-beehive structures of TiO2, E) Shallow concavity structures of TiO2. D,E) Reproduced with permission.[74] Copyright 2009, American Chemical
Society. F) Calcined ZnO replica microtubes synthesized using butterfly wings. Reproduced with permission.[79] Copyright 2006, IOP Publishing.
G) SEM image of a fracture section of a free-standing (chitin free) structure generated by pyrolysis of the chitin using Cyphochilus spp beetle. Reproduced
with permission.[57] Copyright 2012, Royal Society of Chemisry. H) SEM images of Ag-doped Y123 cuttlebone replicas. Reproduced with permission.[116]
Copyright 2008, Royal Society of Chemisry. I) SEM image of gold-coated echinoid skeletal shell after in situ dissolution of the calcium carbonate shell.
Reproduced with permission.[80] Copyright 2000, Royal Society of Chemisry.

degree of inflexibility. Therefore, how to improve the smart fea-
tures of biomass for biomimetic synthesis remains a challenge.
In this respect, the physical-processing transformation of mul-
tiple biomass templates may provide additional potential for
biomimetic synthesis. Furthermore, many biomass templates
with unique structures remain to be found and used.
3. High-Level Biomimetic Synthesis via
Soft/Hard-Combined Membranes
Soft templates (e.g., reverse micelles, microemulsions, and
liquid crystals) and hard templates (e.g., anodic aluminum
oxide, and carbon nanotubes) offer powerful tools for the syn-
thesis of nanomaterials through their template-inducing effect
and confinement ability, respectively. Generally, the structures
of nanomaterials that are synthesized using hard templates are
uniform and predictable; however, this method is inflexible,
and it is difficult to produce complicated structures. For soft-
template synthesis, various unique and special nanostructures
may be produced, but it is difficult to control the uniformity and
size of resultant nanomaterials. In controlled and designed syn-
thesis, both flexibility and control are often needed. The question
therefore arises as to whether a template exists that simulta-
neously exhibits the abilities of both hard and soft templates.
Wu’s group found that celloidin membranes, egg-shell
membranes, and some commercial polymer films can do just
that. All of these combined templates show a porous struc-
ture with functional groups on the pore wall. These mem-
branes exhibit rigid structures and space-confinement ability,
which are similar to hard templates; on the other hand, these
membranes show modifiability and template-inducing effects
through the functional groups on the pore walls, which are soft-
template characteristics. Therefore, the authors termed these
templates “soft/hard-combined membranes (films)” (herein-
after referred to as “combined membranes”). These combined
membranes can be divided into two types: artificial membranes
and natural membrane. The two types show different features.
The pore size and thickness of artificial membranes can be
adjusted, and natural membranes possess complicated pore
structures that cannot be obtained through artificial methods.
An additional advantage is that the surface structures of both
types of combined membranes can be modified.
The mechanism of soft/hard-combined membranes
biomimetic synthesis is shown in Figure 11. On the whole,
soft/hard-combined membranes biomimetic synthesis mimics
some of the elementary biological processes and one biological
unit process (i.e., biomineralization) (Figure 11A). These com-
bined membranes are employed for the process biomimetic
synthesis of nanomaterials/nanostructures by separating the

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Figure 11. A) The mimicked biological processes of soft/hard-combined membrane biomimetic synthesis. B) A schematic of the soft/hard-combined
membrane biomimetic system. C) The mechanism of soft/hard-combined membrane biomimetic synthesis.
two reactants (Figure 11B). Then, the two reactants diffuse
into the pores of the combined membrane. During this pro-
cess, the cations are trapped by the surface oxygen groups on
the combined membrane and the anions will meet and react
with these cations. With continued reaction time, crystal nuclei
form, grow, and assemble into a specific morphology under
the inducing effect of the combined membrane (Figure 11C).
Crystal modifiers can also be added into this biomimetic system
and cooperate with the combined membrane to alter the crystal
growth and assembly processes, thereby modulating the mor-
phologies and structures of the obtained nanomaterials.
During the biomimetic synthesis, the combined membranes
can control the diffusion of ions by mimicking the function of
a cell membrane. In addition, modification of the pore struc-
ture and functional groups on the pore walls of combined
membranes can control the nucleation sites, and influence
the oriented growth and assembly of nanomaterials, mim-
icking biomineralization. It is worth noting that the size and
morphology of nanomaterials can both be controlled by tuning
the reaction conditions in soft/hard-combined membrane
biomimetic systems. Studies have shown that the combined
membrane biomimetic system is particularly suitable for the
synthesis of nanotubes,[127–129] ultrathin metal films,[130,131]
and various nano-superstructures.[132–139] Moreover, combined
membrane biomimetic synthesis does not require the
removal of the template, given that most synthesized products
will fall to one side due to gravity and thermal motion.
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However, removal of the template is essential for hard- or
soft-template synthesis and may require acid or alkali etching,
calcining, or demulsification.
3.1. Artificial-Active-Membrane Biomimetic Synthesis
Collodion membranes consist of 3D nitrocellulose networks
and represent a type of combined membrane.[140,141] Studies
have shown that large active nitro groups distribute on the
pore walls of collodion membranes. These membranes can be
prepared artificially by coating collodion on a silicon substrate
using a spin coater. The most significant advantage of col-
lodion membranes is that the pore size and surface structure
can be adjusted. Thus, the size and morphology of the derived
nanomaterials can be simultaneously adjusted.[142] Wu’s group
was the first to exploit collodion membranes for biomimetic
synthesis, preparing several structures, including CdS nano-
tubes;[128] HgS[142] and HgSe[143] nanoparticles;ZnS,[144] PbCrO4,
and BaCrO4 nanorods;[145] CdS nanospheres;[146] ZnSe and
CdSe quantum dots;[143] and other structures.[147] Moreover,
Wen’s group synthesized ultrathin Ni films,[130] Ni–Co alloy
films[130] and Ni–Cu alloy films,[131] utilizing this facile method.
We next consider the synthesis of ultrathin Ni films as an
example to describe biomimetic synthesis in a collodion mem-
brane system (Figure 12A).[130] Collodion membrane biomi-
metic synthesis is conducted by utilizing the membrane to
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Figure 12. A) Schematic illustration of the ion transport and reaction process in the collodion-membrane biomimetic system without (a) and with
(b) crystal modifier. B) The superthin Ni film formed within a collodion membrane biomimetic systems using microemulsion. C) The superthin Ni
film formed within a collodion-membrane biomimetic system using a crystal modifier. Reproduced with permission.[130] Copyright 2009, American
Chemical Society.
separate the two reaction components. Due to concentration
differences, both components tend to diffuse to the other side
through the pores of the collodion membrane, which helps the
ions meet and react. When diffusing through the pores, metal
cations (Ni2+) are captured by the nitro groups on the pore
walls to form metal complexes (Figure 12A(a)). When anions
(H−) spread into the pores, they react with cations anchored on
the pore walls. With increasing numbers of anions spreading
into the pores, crystal nuclei form and grow into a specific mor-
phology under the inducing effects of the pores. Due to the
effects of gravity and thermal motion, the crystals fall from the
pores when they reach a certain size. When the surface struc-
tures of the combined membranes are adjusted using additive
reagents, the type, content, and polarity of the functional groups
on the pore walls are different, influencing the morphology and
structure of the obtained nanomaterials.
When crystal modifiers are added into the collodion mem-
brane biomimetic synthesis system, the reaction is performed
according to case b in Figure 12A.[130] Crystal modifiers are often
chelating agents and are added into the side containing metal
cations. Crystal modifiers first coordinate with metal cations and
form complexes, and when the complexes spread into the collo-
dion membrane pores, nitro groups compete with crystal modi-
fiers to capture the cations. Then, the oriented growth of the
crystal is changed under the synergistic inducing effects of the
collodion membrane and crystal modifiers; thus, the morphology
and size of the nanomaterials can be tuned. For instance, ZnS
quasi-nanorods were formed utilizing ethanediamine, while ZnS
nanospheres were synthesized without additives.[148] When citric
acid, ascorbic acid, and sulfosalicylic acid were added, CaCO3
sphere-assembled structures, shuttle-like structures, and flake-
assembled structures were obtained, respectively.[147]
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The discovery of graphene has triggered enormous enthusiasm
for the preparation of other 2D materials, especially 2D metal
with a thickness of one or a few atomic layers. However, the
excess of surface dangling bonds makes the formation of free-
standing 2D metals unstable, and hence difficult to achieve.
Recently, free-standing single-atom-thickness Rh and Fe mem-
branes were prepared,[149,150] but these reactions were primarily
carried out under harsh conditions. Wen’s group showed
that ultrathin 2D handkerchief-like Co, Co–Ni and Co–Cu
amorphous alloys can be prepared using facile collodion
membrane biomimetic synthesis at room temperature
(Figure 12C).[130,131] These authors also found that reverse
microemulsion can cooperate with the collodion membrane to
prepare 2D nanomaterials, and reverse microemulsion can con-
trol the nanomaterial size, leading to fine-structured materials.
In this process, a solution containing a reductant and a reverse
microemulsion containing metal ions are separated by the col-
lodion membrane. Both components of the reaction diffuse to
the surface of the collodion membrane. The reverse microemul-
sions diffuse to the orifices, to which they adhere. Then, the
reductant transfers by osmosis into the reverse microemulsions
and reacts with the metal ions to form a large number of crystal
nuclei. Then, the neighboring reverse microemulsions fuse,
and the adjacent crystal nuclei can grow into ultrathin films. In
summary, the reverse microemulsion can control the thickness
of the resultant film, and the structure of the collodion mem-
brane can control the size of the film. The authors also found
that additives influence the morphology of the resultant nano-
materials in this biomimetic system. When ethylenediamine
was added to the biomimetic system, the complexing of eth-
ylenediamine with metal ions inhibits the structure-inducing
action. In this way, an actinomorphic-like nanosphere structure
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of assembled nanoparticles was obtained (Figure 12B). The collo-
dion membrane biomimetic system may be a promising method
for the synthesis of other graphene-like 2D metal nanostructures
or ultrathin metal films under mild conditions.
3.2. Eggshell-Membrane (ESM) Biomimetic Synthesis
Semi-permeable eggshell membrane, a natural combined mem-
brane, exhibits an interwoven protein fiber network structure.
Massive collagens, glycoproteins, and proteoglycans are distrib-
uted on the ESM and contain large numbers of amido, carboxyl,
and hydroxy groups. Thus, the ESM is a suitable combined mem-
brane for biomimetic synthesis. Similar to collodion membranes,
the ESM pores offer unique environments for the control of ion
transport and the induction of crystal growth and assembly.
Using ESM as soft/hard-combined membranes for biomimetic
synthesis is different from its use as biomass templates. Bio-
mimetic synthesis using combined ESM is a one-step reaction
that involves the separation of two reaction solutions, while the
use of ESM as a biomass template often involves a sol–gel pro-
cess or a two-step impregnation process. The combined ESM
membrane can reduce the reaction rate by controlling ion
transport, thus allowing the control of crystal growth and
assembly into various morphologies. ESM biomimetic syn-
thesis provides a novel method for the synthesis of various
biominerals, sulfides, and oxysalts with special structures and
good biocompatibility under mild conditions. The obtainable
structures include nanotubes[129] and nanorods,[133] as well as
branch-like,[133,134,139] feather-like,[139] flower-like,[134–136] sphere-
like,[135,137,151,152] fasciculus-like,[135] spiral-like,[134] and elliptical
structures (Figure 13).[137]
ESM can also be used in combination with template-
assisting agents to form different supramolecular templates
through hydrogen bonds or electrostatic effects, inducing the
growth of nanomaterials with different morphologies. The addi-
tive reagent structure (e.g., the polarity and number of groups
and the length and structure of the carbon chains) has impor-
tant effects on the tropistic growth of the crystal. Liu et al.[135]
studied the tropistic inducing effects of different additive rea-
gents on BaWO4 crystals in an ESM biomimetic system. By
adding n-dodecanethiol, β-cyclodextrin, ethylenediamine,
L-ascorbic acid, and polyformaldehyde into the system, flower-
like, double-tapered, anchor-like, quasi-spherical, and fascicular

Figure 13. Various different nanoassembled structures synthesized in ESM biomimetic systems. A) BaSO4 nanotubes. Adapted with permission.[129]
Copyright 2004, Cambridge University Press. B-E) BaWO4 with double-taper-like morphology (B); anchor-like morphology (C); polyhedron morphology
(D) and flower-like morphology (E). Reproduced with permission.[135] Copyright 2005, American Chemical Society. F) bouquet-like SrCrO4. Reproduced
with permission.[133] Copyright 2007, Wiley-VCH. G,H) flower-like CaC2O4. Reproduced with permission.[136] Copyright 2007, World Scientific Publishing
Co Pte Ltd. I) feather-like BaCrO4. Reproduced with permission.[139] Copyright 2004, KISTI.

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product morphologies were obtained, respectively.[135] It is

speculated that the adsorption ability of additive reagents to the
crystal surface can increase with the polarity or content of the
functional groups, which may strengthen the tropistic inducing
effects of these reagents on the crystal morphology. Moreover, it
was observed that the length and structure of the carbon chains
in each additive reagent also affect tropistic crystal growth.
Chainlike additive reagents often easily generate products with
higher length-to-width ratios, whereas cyclic additive reagents
often easily generate spherical or quasi-spherical products. This
result may be due to the template effect of the additive reagent.
Since the discovery of carbon nanotubes, much effort has been
made to synthesize non-carbon nanotubes due to their unique
properties. Although conventional methods are very useful and
are of widespread importance in nanotube preparation, they
often require harsh conditions, expensive instrumentation, or
tedious steps. Studies on inorganic nanotubes primarily focus
on unitary and binary element nanotubes, but little research
has been undertaken regarding multinary element nanotubes.
Liu synthesized uniform tubular BaSO4 nanostructures with
closed ends in an ESM biomimetic system in combination
with n-dodecanethiol.[129] The length of the BaSO4 nanotubes
REVIEW
was 1.5–2.5 µm, and the external and inner diameters were
90–140 nm and 73–122 nm, respectively. This biomimetic
method provides a novel route for the synthesis of oxysalt nano-
tubes, and it could potentially be used to generate other non-
cabon nanotubes.
Some biominerals with special structures can be obtained
in ESM biomimetic systems under ambient conditions. These
materials have good biocompatibility and show great potential
in medical science. For instance, hydroxyapatite with an exqui-
site porous spherulitic superstructure was synthesized in an
ESM biomimetic system using ethylenediamine as a template-
assisting reagent. The results indicated that the large and com-
pact spherulites were assembled by interlaced nanoribbons
around cores formed by shorter nanoribbons (Figure 14A–C).
These nanoribbons had a single-crystal structure and a thick-
ness of 8 nm. During this biomimetic synthesis, ethylen-
ediamine can adsorb on the ESM surface through hydrogen
bonding to alter the template-inducing effect on crystal growth.
Therefore, unique superstructures are produced via mul-
tiple controlled processes, including ion-transport control of
the semi-permeable ESM, as well as the nucleation, growth,
and assembly of ethylenediamine-modified ESM. These

Figure 14. A–C) TEM and EAD of porous hydroxyapatite spherulites. Reproduced with permission.[138] Copyright 2005, Wiley-VCH. D–G) SEM images of
Ag3PO4 crystals synthesized under different conditions: D) no reagent; E) 1 g L-1 of Triton X-100; F) 1 g L-1 of polyglycol-2000; G) 1 g L-1 of sodium poly-
acrylate. H) The formation mechanism of the Ag3PO4 porous structure. D–H) Adapted with permission.[132] Copyright 2012, Royal Society of Chemisry.

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superstructures have a large surface area that contains a large
number of hydroxy groups, which can easily combine with
organic fluorescent compounds containing carboxyl or hydroxy
groups. A fluorescent probe material showing strong lumines-
cence has been successfully prepared utilizing hydroxyapatite
nanoribbons spherulites as substrates.[138]
Moreover, many oxysalts with nano-superstructures have also
been synthesized, such as BaCrO4,[139] SrCrO4,[133] BaSO4,[134]
CaWO4,[137] and PbWO4.[153] Recently, symmetrical Ag3PO4
crystals with porous structures were synthesized in a com-
bined ESM biomimetic system, and the crystals showed distinc-
tive morphologies when different additive reagents were used
(Figure 14D–H).[132] Interestingly, different faces of these crystals
had high physical–chemical–biological activity and large surface
areas, acting as high-activity microreactors (HAMs). The results
showed that the HAMs can effectively improve the photocata-
lytic activity and bacteriostatic activity of the Ag3PO4 crystals.
Using the easily obtained nano-superstructures in ESM bio-
mimetic systems as templates offers more potential for the
synthesis of regular nanomaterials’ nano-superstructures. The
generation of such materials is difficult using conventional
physical and chemical methods. For example, a flower-like
CaC2O4 assembly structure was used to synthesize core/shell
CaC2O4/CaWO4 nanocomposites via a facile “shell conversion
reaction”. The converted product retained the basic structure of
the original CaC2O4 and possessed some new optical properties
that were not possessed by the parent product. The “shell con-
version reaction” provided a facile method for the conversion of
CaC2O4 from one type of nano-/microstructure to a core/shell
assembly nano-superstructure; this method can be utilized for
the synthesis of other nano-superstructures.[136] Moreover, these
nano-superstructures are ideal scaffolds for the deposition and
growth of other nanomaterials to form nanocomposites.
3.3. Commercial-Polymer-Film Biomimetic Synthesis
Commercial polymer films, such as filter membranes and
polymeric separate membranes, comprise another type of com-
bined membrane. These commercial films are abundant and
easily available, and have a uniform pore size.
CdS nanotubes with closed ends were produced under the
inducing effect of a polytetrafluoroethylene (PTFE) porous
membrane.[127] The internal diameter of the CdS nanotubes
was 100–130 nm, the wall thickness was 15–18 nm, and the
length was approximately 1.4 µm. It was observed that the
obtained products were initially dashed-wall tubes for 12 h, and
if the reaction time was prolonged, the nanotubes eventually
grew into nanorods. It was therefore proposed that CdS crystal
nuclei directionally aggregated and took adjacent positions
along the pore walls under the inducing effect of the surface
groups, forming tubes gradually. This route is also applicable
for the fabrication of other nanotubes or nanostructures after
appropriate modifications. However, using collodion mem-
branes, CdS quasi-nanospheres with an average size of 170 nm
were produced. The difference in the results of these two
studies may be due to the different inducing capabilities of the
different functional groups on the pore walls of the PTFE and
collodion membranes.[146]
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In summary, soft/hard-combined membranes biomimetic
synthesis is simple, convenient, cost-effective, and ecofriendly.
Particularly, when both types of templating effect are combined,
the sizes, morphologies, and even the structures of nanomate-
rials can be simultaneously controlled. The advantages of soft/
hard-combined membranes biomimetic synthesis are as follows:
i) the pore size and thickness of artificial membranes can be
adjusted, allowing for modulation of the size and morphologies
of the resultant nanomaterials; ii) the complicated natural mem-
brane structures result in the synthesis of complex hierarchical
nanomaterials/nanostructures; and iii) surface modification of
combined membranes can modulate the morphologies of nano-
materials. However, the efficiency of biomimetic synthesis needs
improving given that the reaction process through the pores is
very slow. In addition, the combination of space-confinement
and template-inducing effects in combined membrane biomi-
metic synthesis is still to be systematically studied. The combi-
nation of different-structured artificial active membranes and
natural membranes to modulate the synthesis of various nano-
materials/nanostructures may be promising.
4. Intelligent Biomimetic Synthesis via Liquid
Membranes with Carriers
In the past forty years, liquid membranes have been extensively
studied as an effective separation and enrichment technique.
The most widely used liquid membranes are emulsion liquid
membranes and supported liquid membranes. Particularly, the
use of mobile carriers greatly facilitates the transport of ions.
In recent years, Wu’s group successfully introduced the emul-
sion liquid membrane (ELM) and supported liquid membrane
(SLM) systems for the intelligent biomimetic synthesis of nano-
materials. Compared with the biomass biomimetic system and
combined membrane biomimetic system, the emulsion liquid
membrane system perfectly mimics biomembranes and shows
more flexibility, exhibiting a dynamically balanced double-layer
membrane structure. Both liquid membrane systems allow for
the control of ion transport via adjustment of the content and
type of mobile carriers; this ability is a key factor in influencing
supersaturation and crystal nucleation. The detailed mecha-
nisms underlying this process will be introduced in the fol-
lowing section. Moreover, reverse micelle and microemulsion
biomimetic synthesis will be introduced due to their softness
and flexibility, similar to ELM.
4.1. ELM Biomimetic Synthesis
The ELM, which was first invented by Li in 1968,[154] was
initially applied for the separation and enrichment of con-
taminants.[155] Recently, Zheng and Wu’s group successfully
introduced the ELM system for the biomimetic synthesis of
nanomaterials.[148,156–161] Notably, these authors proposed a
transport-template-induced biomimetic synthesis model for
nanomaterials in ELM based on the study results. Moreover,
Hirai’s group from Osaka University also performed excel-
lent work on the synthesis of various rare-earth phosphors
using ELM systems.[162–170] ELM biomimetic synthesis has
proven to be a facile and general method for the preparation
of various nanomaterials/nanostructures (listed in Table 2).
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Table 2. Nanomaterials/nanostructures synthesized via ELM biomimetic synthesis.

Material Oil phase Surfactant Carrier Morphology Dimension Ref

CaCO3 Kerosene Span20 n-hexylacetoacetone calcite rhombs 1 µm [171]
CaCO3 Kerosene Span83 D2EHPA particles 50–1300 nm [172]
CdS CHCl3 Span80 o-phenanthroline nanoparticles 4.5 nm [156]
HgSe Kerosene Span80 N7301 quantum dots 2–3 nm [158]
CdSe Kerosene L152 N7301 quantum dots 3–4 nm [157]
ZnSe Kerosene Span80 N7301 orthohexagonal slices 1.5–3.5 µm [161]
PbCrO4 Kerosene Span80 N7301 nanoparticles 5–15 nm [159]
Ag2CrO4 Kerosene Span80 N7301 nanorods; nanowires diameter: 180–300 nm, length: [160]
<2300 nm; diameter: 15–25 nm,
length: <1000 nm
BaCrO4 Kerosene Span80 N7301 thin flakes/crystalline micrometer size [148]
rods
oxalate of Y, Pr Kerosene Span83 VA-IO spherical particles 20–60 nm [163]
oxalate of Ce, Pr, Nd, Sm, Gd Kerosene Span83 EHPNA spherical particles sub-micrometer size [162]
oxalate of Pr, Sm, Eu, Gd, Dy, Y, Yb Kerosene Span83 DTMBPA spherical particles <0.5 µm [164]
Sr-Pb oxalate Kerosene Span83 D2EHPA spherical particles sub-micrometer sized [165]
Y-Eu oxalate Kerosene Span83 DTMBPA particles 60–400 nm [173]
VA-10 particles ca. 200 nm
TNOA particles 60–200 nm
Y-Yb-Er oxalate Kerosene Span83 VA-10 ultrafine particles 20–60 nm [167]
DTMBPA spherical particles 60–400 nm
Cyanex272 spherical particles 200 nm
CeO2 Kerosene Span80 TBP sponge-like rods diameters of 170–810 nm and [174]
lengths of 5–10 µm
CeO2 n-hexane PE4LE / particles 5.8 ± 0.2 nm [175]
Y2O3 Kerosene Span83 VA-10 nanoparticulate thin <20 nm (nanoparticle) [176]
films
Sr2CeO4; Sr2CeO4: Kerosene Span83 D2EHPA fine particles sub-micrometer size [177]
Ln3+(Ln = Eu,Ho,Tm,Er)
Sr2CeO4; Sr2CeO4:Eu3+,Dy3+ Kerosene Span83 VA-10 particles thin films sub-micrometer size [178]
3+ 3+
Y2SiO5:Eu (Tb ,Sm ); 3+ Kerosene Span83 VA-10 fine particles sub-micrometer size [179]
Gd9.33(SiO4)6O2:Eu3+(Tb3+)
Gd2O3:Eu3+; Gd2O2S:Eu3+ Kerosene Span83 DTMBPA spherical particles sub-micrometer size [168]
Gd2O3:Yb,Er; Gd2O2S:Yb,Er Kerosene Span83 VA-10 fine particles sub-micrometer size [170]
Y2O2S:Yb,Er Kerosene Span83 VA-10 nanoparticles nanosize (ca. 50 nm) [169]
Y2O2S:Yb,Ho
Y2O2S:Yb,Tm
calcium phosphate Kerosene Span83 VA-10 spherical particles 0.5–20 µm [180]
calcium phosphate and alumina Kerosene Span83 VA-10 spherical particles micrometer size [181]
LaPO4 :Ce3+,Tb3+ Kerosene Span83 EHPNA spherical particles 0.28–0.65 µm [166]
CoFe2O4NiFe2O4 Kerosene Span83 D2EHBA acicular particles length: <1.5 µm [182]
Hydroxyapatite iso-octane Span20/Tween80 caproic acid spherical particles <70 nm [183]

Particularly, it is feasible to prepare various nanomaterials and
nanostructures by rational design and artificial control. In addi-
tion, ELM biomimetic synthesis also provides a new idea for
the coupling treatment of industrial waste water with different
anion and cation pollutants.[159]
A typical ELM biomimetic system is constructed as follows.
The system often contains three phases: the internal aqueous
phase, the intermediate oil phase, and the external aqueous phase
(Figure 15C). The internal and external aqueous phases can con-
tain different reactants according the reaction requirements. The

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Figure 15. A) Schematic illustration of the selective transport of Na+ and K+ by Na,K-ATPase in cell membrane. B) The typical biomineralization pro-
cesses in living organism. C) Schematic illustration of the ELM structure. D) The mechanism of intelligent ELM biomimetic synthesis.

oil phase (a liquid membrane) often consists of an organic sol-
vent, a surfactant, and mobile carriers. The surfactant favors the
stability of the oil phase. The mobile carriers facilitate ion trans-
port by combining and releasing ions at the external and internal
oil–water interfaces, respectively. The detailed preparation steps of
the water-in-oil-in-water ELM system are as follows. Initially, the
surfactant and mobile carriers are dissolved in the organic solvent
to form the oil phase, and the oil phase is subsequently mixed
with an internal aqueous solution to prepare a stable emulsion
by agitation (8000–10 000 rpm). The obtained emulsion is then
added to the external aqueous solution and stirred (300–500 rpm).
Generally, the external aqueous solution is a continuous phase.
The internal aqueous phase droplets show micrometer sizes and
the size can be adjusted according to the reaction requirements
and conditions. The effective thickness of the liquid membrane
can also be adjusted by reaction conditions, and it is often
1–10 µm.
The mechanism of ELM biomimetic synthesis is illustrated
in Figure 15. Figure 15A shows the selective transport process
of Na+ and K+ through a Na+/K+ pump in a cell membrane.
Studies have revealed that the “Na,K-pump” is a Na,K-ATPase
that has E1 and E2 conformations, and the surface of each con-
formation has binding sites for Na+ and K+. E1 has high affinity
with Na+ but low affinity with K+, with the opposite being true
for E2.[184] This transport process via the “Na,K-pump” consists
of six steps. Figure 15B shows the typical biomineralization pro-
cess in a living organism, which often consists of four stages.
Figure 15C,D shows the basic principle for the synthesis
of nanomaterials/nanostructures in an intelligent ELM
biomimetic system. Figure 15C shows the ELM structure,

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which consists of a bilayer membrane and can provide a
confined environment for the synthesis of nanomaterials/
nanostructures. ELM biomimetic synthesis often consists of
several elementary biomimetic processes (i.e., diffusion, trans-
membrane transport, controlled nucleation, template regula-
tion, space confinement, crystal growth, assembly, etc.). These
elementary processes belong to two high-level biomimetic pro-
cesses: transmembrane transport against a concentration gra-
dient and biomineralization (Figure 15D). The general design
idea is that ions in an external aqueous phase are transported
by mobile carriers through the liquid membrane to react
with ions in an internal aqueous solution. Crystal nucleation,
growth and assembly then occur under the control of the ELM
biomimetic system. The transmembrane transport process in
the ELM system often contains four stages: i) the metal ions
from the external aqueous phase bind with mobile carriers to
form complexes at the external oil–water interface; ii) the com-
plexes are transported inward through the liquid membrane to
the internal oil–water interface; iii) the metal ions are captured
by corresponding anions from the internal aqueous phase;
iv) the mobile carriers return to the external oil–water interface
through the liquid membrane and carry out the next transport
process (Figure 15D (left)). It should be mentioned that, com-
pared with mobile carriers, the anions in the internal aqueous
solution often have a stronger binding affinity for metal ions,
allowing the anions to capture metal ions from the mobile car-
riers and release them. At the internal oil–water interface, func-
tional groups on surfactants, such as C = O, –O–, and –OH,
can bind with ions in the internal water phase through electro-
static accumulation or structural correspondence. When more
metal ions are transported inward and react with the anions
in the internal aqueous phase, the degree of supersaturation
increases. Crystal nuclei will then form on the interface of the
liquid membrane and the internal aqueous solution, and the
crystals can further grow and assemble into nanomaterials with
specific structure and morphology under the control of mem-
brane regulation and space confinement effects (Figure 15D
(right)). In fact, this ELM biomimetic system can also be used
for the molecular assembly and even the synthesis of organic
nanomaterials/nanostructures by rational design.
The sizes and morphologies of nanomaterials can be influ-
enced by many factors, and it is possible to control the syn-
thesis of nanomaterials/nanostructures by adjusting the com-
ponents of the ELM biomimetic system. For example, the
types and ratios of mobile carriers can be adjusted to regulate
the transport rate of ions, thereby influencing the supersatu-
ration and the rate of crystal nucleation and growth. There-
fore, the selection of these mobile carriers is crucial, and an
appropriate mobile carrier should generally fulfill the fol-
lowing requirements: i) it should complex with specific ions;
ii) the carrier itself and the formed complex must be soluble
in the membrane phase but not in the aqueous phase; iii) it
should be selective and efficient in transporting specific ions;
iv) it should have a weaker affinity for specific ions from the
external aqueous phase than for anions from the internal
aqueous phase. It should be mentioned that the content of the
carriers in organic phase should be appropriately chosen given
that excess carriers in membrane phase can decrease emulsion
stability. The morphology of the products can be controlled by
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adjusting the ratio of the mobile carriers. For instance, Ag2CrO4
nanowires and nanorods can be obtained by including and
excluding mobile carriers in ELM biomimetic systems, respec-
tively.[160] With an increasing content of mobile carriers, crystal
wafers, crystal rods, and special flower-like BaCrO4 superstruc-
tures can be obtained in an ELM system (Figure 16C).[148] The
surfactant is another crucial factor for the synthesis of nano-
materials/nanostructures in that it influences crystal nucleation
and growth. Wu and co-workers demonstrated that the ELM
system is able to synthesize quantum dots, such as CdS,[156]
CdSe,[156] HgSe,[158] and ZnSe,[161] which show optical proper-
ties that are different from the bulk materials due to quantum
confinement. It is proposed that the efficient control of the size
of nanomaterials is greatly attributed to the surfactants. The
large biomimetic membrane structure provides many sites for
crystal nucleation, and the interaction between the resultant
particles and surfactant molecules can stabilize the particles. In
addition, the surfactant may also play a crucial role in the self-
assembly. An interesting assembly of ZnSe quantum dots into
2D orthohexagonal ZnSe single-crystal slices (Figure 16A,B)
was observed in an ELM biomimetic system, and a control
experiment indicated that orthohexagonl slices could not form
without surfactant. During synthesis, surfactant molecules self-
organize into hexagonal liquid-crystalline templates by inter-
acting with ZnSe nanoparticles, and at the same time, ZnSe
nanoparticles self-assemble into orthohexagonal slices through
the effects of the surfactant liquid-crystalline template.[161]
The ELM biomimetic system shows a unique advantage in the
synthesis of rare-earth luminescent materials with homogeneous
size and adjustable components. Hirai and co-workers prepared
various single-component rare-earth oxalate particles[162–164] and
Figure 16. Some unique nanostructures formed in the ELM biomimetic
system. A) TEM image of one orthohexagonal ZnSe slice. B) SAD of
orthohexagonal ZnSe slice. Reproduced with permission.[161] Copyright
2005, Elsevier. C) TEM images of a BaCrO4 superstructure. Reproduced
with permission.[148] Copyright 2006, Wiley-VCH. D) SEM image of a com-
posite Co–Fe oxalate. Reproduced with permission.[182] Copyright 1999,
American Chemical Society.
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REVIEW
composite oxalate particles containing two or more different rare
earth metals.[165–170,173,177–179,182] After calcination of these oxalate
particles, rare-earth luminescent materials were obtained. Inter-
estingly, the authors found that a LaPO4: Ce3+, Tb3+ phosphate
material obtained in the ELM system emitted photoluminescence
without calcination. This characteristic is advantageous over
the use of a calcining oxalate precursor.[166] Recently, the upcon-
verting phosphor compounds, which emit visible or ultraviolet
radiation when excited by infrared light, are drawing increasing
attention. Such materials are typically composed of trivalent
rare-earth absorbing (e.g., Yb, Er, and Sm) and emitting (e.g., Er,
Ho, Pr, and Tm) ions. Rare-earth oxide composite phosphors,
including upconverting phosphors, such as Y2O3:Yb, Er,[167]
Y2O2S:Yb, Ho, Y2O2S:Yb, Tm, Y2O3:Yb, Er,[169] Gd2O3:Yb, Er,
and Gd2O2S:Yb, Er[170] can be obtained by calcining composite
oxalate precursors obtained in an ELM system.
ELM biomimetic synthesis is also a facile route for designing
composite structures and components via the control of the
transport rate and charge ratios.[182] Composite structure vari-
ation was observed when preparing acicular ferrite CoFe2O4 in
an ELM biomimetic system (Figure 16D). Co2+ and Fe2+ were
transported from the external water phase into the internal
water phase and reacted with oxalate to form composite oxalate
particles. The particles obtained in the ELM system have a struc-
ture in which Co atoms are located near the surface of the par-
ticles than in the core. In contrast, in a homogeneous aqueous
solution, more Fe atoms are located near the surface of the
particles. This variation is caused by the difference of the rela-
tive transport rate and the precipitation rate for each metal ion.
Moreover, the molar composition of the particles, or (Co/Fe)p,
prepared in the ELM system, was nearly proportional to that
of the feed external solution, or (Co/Fe)f. ELM biomimetic syn-
thesis may also be extended to the synthesis of other multicom-
ponent nanomaterials/nanostructures.
In addition, vesicles and lipidosomes also show bilayer mem-
brane structures, and have been used for the biomimetic syn-
thesis of organic nanomaterials/nanostructures. In this process,
surfactants and hydrophobic monomers spontaneously assemble
into vesicles containing monomers within the bilayer. It should
be noted that the synergistic action of monomers and surfactants
is essential in the self-assembly process.[185] The polymerization
of monomers in the bilayer forms various organic nanoma-
terials/nanostructures, such as nanocapsules, nanodiscs, and
nanorods.[186–193] In addition, hybrid nanomaterials/nanostruc-
tures, such as nanorattles, can be synthesized. In this process,
the hydrophobic bilayer interior is used for the templating of
organic nanomaterials/nanostructures, and the aqueous core is
used for the templating of inorganic nanomaterials/nanostruc-
tures. For instance, in one step, Shmakov and Pinkhassik syn-
thesized hollow polymer nanocapsules with entrapped silver
nanoparticles using lipid vesicles.[194] It can be concluded that the
ELM biomimetic system may also be promising for the synthesis
of various organic and hybrid nanomaterials/nanostructures.
4.2. SLM Biomimetic Synthesis
SLM, a type of monodispersive liquid membrane, was initially
applied for separating and enriching noble-metal ions from
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waste water.[195] Recently, Wu and co-workers introduced this
system into nanomaterial synthesis for the first time,[196] and
further studies indicated that this system is versatile for the
synthesis of nanomaterials/nanostructures. ZnS chain-like
nanospheres,[197] CdS hollow/solid nanospheres,[198] bunched
PbMoO4 nanobelts,[199] and Cd(OH)2 nanowires[200] were syn-
thesized via this SLM biomimetic system.
SLM consists of a solid support and membrane phase, with
the latter containing a membrane solvent and mobile carriers.
The SLM is prepared by soaking the support with the membrane
phase, and the membrane phase is thereby immobilized in the
pores of the solid support through surface-tension and capillary
forces. In this way, surfactants are often not needed to stabilize
the liquid membrane in the SLM biomimetic system. The pri-
marily used supports for SLM are various polymers, especially
some hydrophobic and microporous polymers because they can
increase the stability of the supported liquid membrane.
Compared with ELM biomimetic system, the SLM biomi-
metic system is more stable given that many factors can desta-
bilize ELM system, such as swelling, loss of the oil phase, and
the fusion of emulsion droplets; in contrast, the instability of
SLM systems is generally caused only by loss of the oil phase.
The product collection in SLM systems is convenient in that
the resultant products are on the support’s surface. However,
a demulsification process is necessary to collect the products
in the ELM biomimetic system, which may be a dangerous or
energy-consuming process. Moreover, the surfactants make
the separating and washing processes difficult. In addition, the
effective membrane areas in ELM and SLM systems are dif-
ferent, with the reaction efficiency of the ELM systems being
much higher than that of SLM. In the context of biomimetic
synthesis, the two types of liquid membranes both have the
advantage of recyclability without wastewater discharge.
SLM biomimetic synthesis is conducted by separating two
types of reaction solutions using a supported liquid membrane.
Similar to ELM, the SLM system: i) can mimic the transmem-
brane transport process of biomembrane via mobile carriers
in a liquid membrane and ii) offers an inorganic–organic
interface for crystal nucleation and growth. Based on experi-
mental results, a transport-induce-assemble synthesis process
was proposed for SLM biomimetic synthesis (Figure 17 (left)).
The SLM system affects crystal nucleation by controlling ion
transport and template regulation. Initially, ions from one
side combine with the mobile carriers, and the complexes are
then transported to the other side of the SLM system. Subse-
quently, transported ions are captured by ions from the other
side, resulting in supersaturation of the solution as the reaction
time increases. The crystal nuclei form in the supersaturated
solution and continue to grow and self-assemble into specific
morphologies under the SLM’s inducing effect. In this process,
the types and contents of the mobile carriers are the key fac-
tors affecting SLM biomimetic synthesis as they can determine
the degree of supersaturation via selective ion transport.[197,201]
It should be noted that the formed crystal nuclei adhere to the
membrane surface spontaneously to decrease their surface
energy; in this way, the membrane’s surface strength encour-
ages oriented crystal growth.[197,202,203]
It has been suggested that soluble macromolecules can change
the crystal habit and morphology in biomineralization processes by
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Figure 17. Schematic illustration of the mechanism via SLM biomimetic synthesis (left) and obtained products in an SLM biomimetic system through
cooperation with different crystal modifiers (right). A) Shuttle-like BaMoO4. B) Peanut-like SrWO4. C) Cd(OH)2 nanowire. B,C) Reproduced with
permission.[200] Copyright 2011, the Institution of Engineering and Techonology. D) PbMoO4 nanobelt. Reproduced with permission.[199] Copyright
2008, Springer. E) Rod-like BaWO4. Reproduced with permission.[204] Copyright 2009, Elsevier. F) Bud-like SrWO4. G) BaMoO4 sphere. H) Feather-like
SrWO4. A,F–H) Adapted with permission.[205] Copyright 2008, Springer. I) BaCO3 hollow sphere. J) MnCO3 hollow sphere. K) SrCO3 sphere. L) CaCO3
nanosheet. M) Twin-ball-like MnCO3. J,M) Reproduced with permission.[206] Copyright 2008, Springer. N) Shuttle-like SrCO3. O)Shttle-like SrCO3.
I,K,L,N,O) Reproduced with permission.[202] Copyright 2006, Wiley-VCH. (EDA: ethylenediamine; CA: citric acid; EDTA: ethylene diamine tetraacetic
acid; NTA: nitrilotriacetic acid).

absorbing onto a specific crystal surface. The crystal modifiers are
often used to cooperate with the SLM to modulate crystal growth.
In the SLM system, crystal modifiers exhibit functions that are sim-
ilar to soluble macromolecules in the biomineralization process.
The crystal surface energy can be modulated by different crystal
modifiers that adsorb onto the surfaces of growing crystallites.
Thus, crystal modifiers can affect crystal anisotropic growth and
aggregated orientation. Therefore, morphology-tunable synthesis
of CaCO3,[201,203] SrWO4,[205] BaWO4,[204] SrCO3,[202] MnCO3[206] can
be realized under the synergetic inducing effect of SLM and dif-
ferent crystal modifiers. (Figure 17 (right)).
The functional-group patterns and functional degree, as
well as the type of functional groups of crystal modifiers, will
influence the structures and morphologies of the final prod-
ucts.[202,205–206] For example, linear ethylenediamine (EDA)
often results in the crystals growing in line- or rod-like mor-
phologies, and these crystals can further self-assemble into
nanobelt,[199] nanorod,[204] bud-like[205] or short-branch[206]
morphologies. Citric acid (CA) is also linear, but it has three
–COOH functional groups. These –COOH groups make CA
strongly adsorb onto specific crystal faces and affect their ten-
dency to grow as flakes, which then assemble into feather-like
flakes.[205]
In addition, semipermeable ESM has been studied as a sup-
port for SLM. The fabricated ESM SLM biomimetic system is
different from the conventional SLM because the special sur-
face structure of the ESM support, and some special nanostruc-
tures can be obtained. Unique CdS solid/hollow nanospheres
and chains thereof were synthesized in this ESM SLM system
with CHCl3 used as the organic solvent and o-phenanthroline
as the mobile carrier. The average diameters of the CdS solid/
hollow spheres were approximately 10 and 40 nm, respectively;
the wall thickness of the hollow spheres was approximately
5 nm. It is speculated that a curving interface may form due to
the nonwettability between the inner wall of the ESM channels
and the CHCl3, which is key to forming the chain structure.
According to interface nucleation principle, CdS crystals form
around the orifice at first, then spread along the liquid–liquid
interface of the CHCl3 and Na2S solution until they form a
close cavum under the inducing effect of macromolecules on
the ESM. The functional groups of additive reagents are cru-
cial for controlling crystal morphologies. The results also show
that additive reagents containing –COOH groups (e.g., citric
acid, ethylene diamine tetraacetic acid, and nitriloriacetic acid)
enhances the template-inducing effect on the formation of
CdS hollow spheres. In contrast, additive reagents containing

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–NH2 groups (e.g., ethylenediamine) can weaken this type of
effect and favor the formation of CdS nanoparticles.[198] ZnS
chain-like nanospheres were also synthesized in this biomi-
metic system.[197] These chain-like structures show potential
applications in nanodevices, such as closed-circuit, quantum
chain transmission. This facile ESM SLM biomimetic system
is promising for the synthesis of other inorganic hollow nano-
spheres and nanochain structures.
In addition, SLM biomimetic synthesis may provide a new
route for metastable crystal synthesis. Wu et al.[203] reported
an abnormal structure conversion of CaCO3 from calcite to
vaterite in an SLM system for the first time (Figure 6); this is
an abnormal conversion and against Ostwald’s law.[203] Under
normal conditions, the thermodynamically stable form of
CaCO3 is calcite. However, in an SLM biomimetic system,
although calcite formed initially (Figure 18A), it gradu-
ally transformed into vaterite with prolonged reaction time
(Figure 18B,C). Eventually, all of the calcite transformed into
vaterite (Figure 18D). It appears that vaterite is more stable
than calcite in the SLM system. The results also show that the
sub-micrometer-sphere vaterite prepared by the SLM system
is a nano-self-assembled structure. It is speculated that the
abnormal polymorph conversion is controlled by the coopera-
tion of SLM system components. At first, as Ca2+ ions are trans-
ported to the other side of the SLM by carriers and captured
by CO32− ions, calcite rapidly nucleates due to thermodynamic
mechanisms. As the microenvironment of crystal growth is the
oil/water interface, it may be unfavorable for calcite stabiliza-
tion. Calcite then dissolves gradually, and the solution becomes
supersaturated with CaCO3, benefiting the growth of vaterite.
In addition, oxygen-containing groups on the esterified fibrin
micropore film as well as the film itself can influence the
crystal growth.
Furthermore, SLM biomimetic synthesis is promising for
the coupling treatment of inorganic and organic wastewater.
Figure 18. SEM images of abnormal polymorph conversion of CaCO3 in
SLM system for 5 min (A), 30 min (B), 4 h (C), 60 h (D). Adapted with
permission.[203] Copyright 2004, American Chemical Society.
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www.MaterialsViews.com
Specifically, the SLM system can be used to synthesize semi-
conductor photocatalytic nanomaterials for the degradation of
organics in waste water.[200] This method is feasible for waste
water containing heavy-metal ions (e.g., Hg2+, Cd2+, Pb2+,
Zn2+, Fe2+, Ni2+, and Ag+) and their corresponding anions
(e.g., CrO42−, MoO42−, S2−, OH−), which are essential ions for
photocatalyst synthesis. The resultant photocatalyst then can
be utilized to degrade organics in wastewater. This integrated
design provides a new idea for industrial wastewater treatment
with reduced processing steps and cost.[196] However, a more
reasonable SLM system design is still needed to improve the
efficiency of industrial waste-water treatment.
4.3. Reverse-Micelle or Microemulsion Biomimetic Synthesis
Reverse micelles[207,208] or microemulsions[209,210] can also
be applied for biomimetic synthesis due to their confined
space and template effects. Microemulsions, a term coined
by Schulman in 1959,[211] are transparent thermodynamically
stable dispersions of two immiscible liquids containing appro-
priate amounts of surfactant; micelles (or reverse micelles)
exist at certain compositional ranges of oil-in-water (or water-
in-oil) microemulsions. For reverse micelle or microemulsion,
the surfactant molecules form a monolayer at the oil/water
interface, with the hydrophobic tails of the surfactant mol-
ecules dissolved in the external oil phase and the hydrophilic
head groups in the internal aqueous phase. The ELM structure
is different in that the oil phase of ELM forms two interfaces
with the internal aqueous phase and external aqueous phase.
Thus, the surfactant molecules form two monolayers at the
external oil/water interface and the internal oil/water inter-
face (Figure 15C). Generally, the size of micelles (or reversed
micelles) is less than 10 nm and that of microemulsions is
10–100 nm In contrast, emulsion droplets are 0.5–5 mm, with
an effective liquid membrane thickness of 1–10 µm, and ELM
internal aqueous phase droplets are 1–100 µm in size.
Vesicles, which are double-layer membrane structures, are
common in organisms and play an important role in the trans-
port of substances, such as proteins and neurotransmitters.
Recent studies show that vesicles also participate in the biomin-
eralization process in vivo. During synthesis, the vesicles form
a relatively stable and unique environment for the growth and
assembly of materials. Reverse micelle or microemulsion bio-
mimetic systems mimic the morphological structure, mass-
transfer abilities and partial biomineralization capacity of vesi-
cles (Figure 19A). Generally, process biomimietic synthesis in
reverse micelles or microemulsions is conducted as shown in
Figure 19B,C. The ion-transport process in reverse micelle or
microemulsion biomimetic systems can occur through: i) colli-
sion between microdroplets that carry different reactants within
their aqueous cores (i.e., the multiple microemulsion approach)
(Figure 19B) or ii) by osmosis of the hydrophilic precipitating
reactant to the microemulsion droplets containing the to-be-
precipitated reactant (i.e., the single microemulsion approach)
(Figure 19C). Then, crystal nuclei are formed on the inner sur-
face of the reverse micelle or microemulsion upon local super-
saturation. Subsequently, crystal nuclei grow and assemble into
a specific morphology under the inducing and spatial confine-
ment effects of the reverse micelles or microemulsion.
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Figure 19. A) The mimicked biological processes of reverse-micelle or microemulsion biomimetic synthesis. B,C) The mechanisms of reverse-micelle
or microemulsion biomimetic synthesis.
Due to the confined space and unique inducing capacity,
reverse micelles and microemulsions are ideal systems for
mimicking the formation of various biominerals, and a series
of CaCO3,[212–214] silica[215–217] and phosphate[218–221] materials
have been synthesized. The influence of the synthesis condi-
tions on crystal size, morphology, and structure have been
studied in detail. In general, the synthesis of biominerals in
biomimetic reverse micelle or microemulsion systems has pro-
vided an important reference for the understanding of certain
stages of biomineralization.
By mimicking the mass-transfer process and some of the
biomineralization process, reverse micelle or microemulsion
biomimetic synthesis are capable of synthesizing various metal
nanoparticles,[222–229] semiconductors,[227,230–236] and compos-
ites.[237–244] In addition, this system shows good performance
for controlling the size and shape of inorganic nanocrystals.
Due to the adjustable shape and unique inducing effect of the
reverse micelles, nanomaterials with various morphologies have
been prepared, such as nanowires,[208,245–247] nanorods,[208,245,248]
nanotubes,[207,208,249–251] nanobelts,[252] nanoshuttles,[207,253] nano-
spheres,[253–255] and hexabranched structures.[256] Wu’s group
found that the shape and size of a micelle depends on the sur-
factant molecule’s structure and the solution conditions, which
can be manipulated to induce the formation of nanomaterials
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with different morphologies and sizes (Figure 20A).[207] Yu’s
group,[257] and Qi’s group[258–260] found that adding directing
agents (primarily block copolymers) into the reverse micelle
systems easily induces the formation of various nano-super-
structures, such as flower-like BaCrO4 plates, penniform BaWO4
nanostructures, and bare-tree-like BaCrO4 superstructures
(Figure 20B–H). It is proposed that the presence of these poly-
mers can induce the formation of superaggregates consisting of
primary micelles and polymer molecules, which provide suitable
sites for the nucleation and growth of the nano-superstructures.
In addition, a stepwise-assembly-growth process of
CaSO4·2H2O nanoparticles, nanotubes, nanorods, and nanow-
ires in reverse micelle systems was observed (Figure 20I).[208] At
the beginning of this process, the different reactants in the two
types of reverse micelles meet due to osmosis or fusion, and the
reaction begins. Then, crystal nuclei form on the surface of the
micelles upon local supersaturation, and the crystals can con-
tinue to grow to form nanoparticles. These incompact nanopar-
ticles can assemble and grow into nanotubes under the interac-
tion of coated surfactant molecules. When excess micelles fuse
with the tube micelles, more ions enter the nanotubes through
the interstices between nanoparticles on the nanotube wall.
Thus, hollow tubes will continue to assemble and grow, and
nanorods are obtained after sufficient growth time. These short
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Figure 20. A) Schematic illustration of different structures formed by the self-assembly of reverse micelles. Adapted with permission.[207] Copyright
2005, Elsevier. B–H) Different structures of nanomaterials synthesized via reverse micelles: B–E) BaWO4; F) GeO2; G) Eu2(CO3)3; H) BaWO4.
B–E) Reproduced with permission.[260] Copyright 2006, American Chemical Society. F) Reproduced with permission.[256] Copyright 2009, American
Chemical Society. G) Reproduced with permission.[261] Copyright 2007, American Chemical Society. H) Reproduced with permission.[259] Copyright 2003,
American Chemical Society. I) Schematic illustration of the transformation process of nanoparticles, nanotubes, nanorods, and nanowires in reverse
micelles and corresponding products separated at different times. I) Adapted with permission.[208] Copyright 2007, Wiley-VCH.

rods coated with surfactant can also assemble and grow into
long nanowires with extended aging time. Further studies have
shown that this growth process is somewhat universal in the
synthesis of inorganic salts with 0D/1D and solid/hollow struc-
tures in reverse micelle systems.
Generally, organic nanomaterials with controlled shapes and
sizes are particularly difficult to prepare. Micelle biomimetic
synthesis may provide an attractive synthesis method for well-
controlled organic nanomaterials/nanostructures. Yang et al.
synthesized quasi-decahedra and well-defined nanosheets of
triptycene in P123 and CTAB micelle systems, respectively.[262]
Becerra et al. prepared small and rigid polystyrene nanorods in
worm-like micelles. These studies show the feasibility and great
potential of biomimetic synthesis for organic nanomaterials/
nanostructures.[263]
The liquid membrane biomimetic system perfectly mimics
the processes of osmosis, diffusion, transmembrane transport,
controlled nucleation, template regulation, space confinement,
crystal growth, and (composite) assembly processes in organ-
isms. These mimicked processes can primarily be summarized
as two high-level processes: substance transmembrane trans-
port and biomineralization. All of these synthesis processes
are controllable and ecofriendly, showing great potential for
industrial-scale production of nanomaterials. However, more

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in-depth studies on liquid membrane biomimetic synthesis
need to be performed. Particularly, the stability of the liquid
membrane and demulsification are contradictory, and the bal-
ance between them is still a challenge. Further studies are yet
to to be performed in the following aspects: i) the controlled
synthesis via liquid membrane biomimetic synthesis should be
further enhanced; ii) the application range should be expanded
from inorganic nanomaterials/nanostructures to organic and
hybrid nanomaterials/nanostructures; 3) new carriers and sur-
factants need to be studied to solve the problem of stability and
demulsification of the liquid membrane.
5. Living-organism Biomimetic Synthesis via
Plants/Microorganisms
Plants and microorganisms show unique capacities for the con-
trolled synthesis of materials in vivo, such as the SiO2 cell walls
of diatoms and the magnetic nanoassemblies of protists.[264]
Particularly, due to the distinct tolerance of plants and micro-
organisms to heavy metals, these organisms are able to survive
even when they take up unnecessary elements from the envi-
ronment. These properties of living plants and microorganisms
have inspired researchers to combine the unique synthesis
capacity of intact biosystems with artificial control for biomi-
metic synthesis of nanomaterials/nanostructures. Generally,
living-organism biomimetic synthesis mimics several higher
life processes, including substance uptake, substance transport,
stimulus and response, and biomineralization (Figure 21A). A
series of nanomaterials with sophisticated structures and excel-
lent properties have been synthesized via this mild and control-
lable biomimetic route (listed in Table 3).
Wu’s group reported the synthesis of CdS nanocrystals
using living mung bean sprouts (MBS) for the first time,[318]
revealing the feasibility of exploiting living plants for nano-
materials synthesis. Subsequently, these authors synthesized
a series of nanomaterials with special morphologies or struc-
tures using different living plants. For instance, mung bean
sprouts are used for the biomimetic synthesis of BaCrO4 with
a dendritic nano-superstructure, CaCO3 nanorods along with
dendritic and flowerlike nano-superstructures, CdSe nano-
tubes and nanorods, ZnSe nanorods and nanoslats, and PbSe
nanotubes and nanorods.[265–267,325] In addition, the squama
inner layer of the onion has been employed for the synthesis
of Ni(OH)2 microspheres and SrCrO4 nanospheres, nanorods,
and dumbbell-shaped nano-superstructures;[314,268] garlic root is
used for the synthesis of multiarmed Se nanorods and Se nano-
chains;[281] and rush plants are employed for the synthesis of
multiarmed Se nanorods and Se nanobars (Figure 21C–H).[282]
In general, honeycomb-structured mung bean sprouts, layer-
assembled structural squama inner coats of onions and capil-
lary channel structural garlic root can be used for the biomi-
metic synthesis of various nanomaterials/nanostructures using
the procedure shown in Figure 21B.
The basic principle of living-organism biomimetic synthesis
is shown in Figure 21B. First, the plant is immersed in a solu-
tion containing specific ions (usually anions), and the plant
absorbs these ions into its cells. Then, the plant is rinsed, and
the ions on the outer membrane surface are removed. Then, the
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plant is immersed in a solution containing other specific ions,
at which point the plants discharge the ions they previously
absorbed and uptake the new ions via a similar transport mech-
anism. The two types of ions then meet and react at specific
sites of the biomembrane. Thus, crystal nuclei form upon local
supersaturation, grow, and assemble into a specific morphology
on the surface under the inducing effects of the biomembrane.
It can be concluded that living-organism biomimetic synthesis
is a combined processes of living-organism control and artifi-
cial control. In fact, the exact crystal growth and assembly pro-
cess of living biomimetic synthesis is very complicated because,
in living plants, it involves biochemical responses (e.g., enzyme
production), complexation with bio-macromolecules, and other
unknown biological processes that may influence the formation
and growth of crystals.[327]
Figure 21B(a,b) show the inner and outer surface structures
of the mung bean sprout (MBS). The inner surface of the MBS
is composed of uniform canaliculi with apertures of approxi-
mately 100 µm. The outer surface of MBS has well-distributed
grooves, with widths of 80–120 µm and diameters of 10–20 µm.
Wu’s group found that the different surface structures can be
used to synthesis nanomaterials with different morphologies.
Based on the results, they proposed the concept of “living
biomembrane bi-templates simultaneous synthesis” for the
first time.[267] This term reflects the simultaneous synthesis
of the same nanomaterial with two different morphologies via
the different structures and inducing abilities of a living plant’s
inner and outer biomembranes. In fact, all living plants with
porous inner structures can be used for the simultaneous
biomimetic synthesis of nanomaterials. For example, living
MBS,[265,267,315,325,326] rush,[282] and garlic root[281] have acted as
ideal bi-templates for the simultaneous synthesis of nanoma-
terials, such as nanorods and the nanospheres of alkaline-earth
tungstate,[315] dendritic hierarchical and bouquet-like calcium
oxalate,[326] dendritic superstructural and fractal crystals of
BaCrO4,[265] PbSe nanorods and nanotubes,[267] CdSe (nano-
tubes, nanorods) and ZnSe (nanorods, nanoslats),[325] multi-
armed nanorods and nanobars of selenium,[174] and selenium
nanorods and nanochains.[281]
Other artificial control processes can also be involved for the
designed synthesis of nanomaterials/nanostructures, such as
adding crystal modifiers in the solutions. For instance, CaCO3
with elaborate pine-like dendritic superstructures, flower-like
nano-superstructures, and nanorods were prepared in living
MBS using CA, NTA, and EDTA, respectively, as cooperative
modifiers under ambient conditions (Figure 21C–E).[266] When
the crystal modifiers are added to the living-organism biomi-
metic system, the crystal-formation process is under the cooper-
ative control of the modifiers and the living plant, and this pro-
cess is very complex. It is supposed that in the process of nucle-
ation, the plant’s biomembrane is dominant in determining
the nucleation positions through transporting and adsorbing
the ions onto specific sites of biomembrane. Over time, func-
tional groups on the internal surface of the biomembrane com-
bine with the modifiers to form a cooperating space template.
This template preferentially adsorbs onto some crystal faces
and inhibits their further growth. Meanwhile, organic groups
have the special function of inducing the nanocrystals to grow
and assemble in an oriented manner, generating units with
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Figure 21. The biomimeitc processes, the mechanism of living-organism biomimetic synthesis, and the obtained nanomaterials/nanostructures from
living plants. A) The biomimetic processes of living-organism biomimetic synthesis. B) The synthesis process and mechanism of livng-organism bio-
mimetic synthesis from living plants; the inner surface (a) and outer surface (b) structure of a mung bean sprout. Reproduced with permission.[265]
Copyright 2006, American Chemical Society. C–E) Superstructures produced in mung-bean-sprout biomimetic systems utilizing different additives.
Reproduced with permission.[266] Copyright 2011, Taylor & Francis Group. F,G) A simultaneously synthesized PbSe nanorod and nanotube on the inner
and outer biomembranes of mung-bean-sprout biomimetic systems. Reproduced with permission.[267] Copyright 2004, IOP Publishing. H) Ni(OH)2
obtained in mung-bean-sprout biomimetic systems. Adapted with permission.[268] Copyright 2010, Springer.

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Table 3. Nanomaterials obtained using living-organism biomimetic synthesis.

Nanomaterial Biotemplate Morphology Size Property Ref

Au live alfalfa plant nanoparticles <20 nm – [269]
Au S. drummondii seedling nanoparticles – catalytic [270]
Au geranium leaf nanoparticles 8–40 nm – [271]
Au tobacco mosaic virus nanoparticle rings 22 nm optoelectronic properties [272]
Au tobacco mosaic virus nanoparticle assembled nanowire 30 nm diameter and optical property [273]
150–400 nm length
Au chilo iridescent virus nanoparticles 2–5 nm – [274]
Au M13 Phage nanoparticle arrays, hetero-nanoparticle nanoscale electrical property [275]
architectures, nanowire
Au M13 virus nanowires 10–50 nm electrocatalysis [276]
Au bacterial cell nanoparticles – catalysis [277]
Ag squama inner coat of onion nanoparticles 5–8 nm optical property [278]
Ag live alfalfa plant nanoparticles <10 nm – [279]
Ag tomato bushy stunt virus 2D assembled Ag nanoparticles – – [280
Se garlic root nanorods and nanochains diameter < 150 nm – [281]
Se rush nanorods and nanobars nanoscale – [282]
Pd-TMV complex tobacco mosaic virus nanowire – catalysts [283]
Pd-TMV complex tobacco mosaic virus nanowire – – [284]
Pd-TMV complex tobacco mosaic virus nanowire – catalysts [285]
Au, Ag, Pd tobacco mosaic virus clusters nanoscale – [286]
Au–Ag–Cu alloy seeds of B. juncea nanoparticles 5–50 nm – [287]
Ni, Co tobacco mosaic virus nanowire diameter of 3 nm – [288]
Co-Pt tomato mosaic virus aligned nanoparticle 3 nm magnetic property [289]
Pt-TMV complex tobacco mosaic virus nanowire Pt nanoparticle size: 3 nm – [290]
CoPt and FePt M13 Phage nanowires nanoscale – [291]
Au/Pd Alloy tobacco mosaic virus nanoparticle <20 nm – [292]
CoPt and FePt3 tobacco mosaic virus nanowire 3 nm in diameter – [293]
Co–Ni–P bacillus rod-shaped shell 200 nm in thickness microwave absorption [294]
TiO2 yeast cell ordered mesoporous 5 nm; 11 nm photocatalysis [295]
TiO2 yeast cell ordered hierarchical mesoporous 5 nm; 11 nm Electrocatalysis [296]
TiO2 cocci and bacillus hollow sphere and hollow tube micro–nano scale photocatalytic hydrogen [297]
evolution
TiO2 M13 Phage nanowires 20–40 nm solar cells [298]
TiO2 M13 Phage network – solar cells [299]
TiO2 M13 Phage nanowires 150 nm in diameter and solar cells [300]
2–3 µm in length
TiO2 M13 Phage nanocrystal – photovoltaic device [301]
Fe2O3 yeast cell mesoporous 5–60 nm in pore size photocatalysis [302]
Co3O4 yeast cell hollow microsphere 3.7 µm in length; 2 µm – [303]
in width
Co3O4 M13 virus assembled nanowire – lithium-ion battery [304]
electrodes
Co3O4 M13 virus assembled nanowire ca. 50 nm in diameter and lithium–oxygen battery [305]
ca. 1 um in length
V2O5 tobacco mosaic virus nanowire 900 nm in length; 100 nm lithium-ion battery [306]
in diameter electrodes
Ni-Rh@CeO2 M13 Phage nanowire – catalysis [307]

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Table 3. Continued
Nanomaterial Biotemplate Morphology Size Property Ref
FePO4 yeast cell flake shapes length of 500–600 nm, – [308]
width of 200–300 nm
FePO4 yeast cell mesoporous 14 nm pore size – [309]
FePO4 M13 Phage nanowires diameters of 10 to 20 nm lithium-ion battery [310]
FePO4 M13 Phage nanoparticles 10–30 nm Sodium-ion battery [311]
Ca3(PO4)2 yeast cell hollow microsphere 5–10 µm in diameter – [312]
Zr3(PO4)4 yeast cell mesoporous 2.7 nm pore size electrocatalysis [313]
SrTiO3 M13 virus nanowire – Solar-energy conversion [35]
BiFeO3 M13 virus nanowire – Solar-energy conversion [35]
SrCrO4 squama coat of onion nanospheres, nanorods and dumbbell- micro–nano scale optical property [314]
shaped superstructure
BaCrO4 mung bean sprouts dendritic superstructure and fractal micro–nano scale optical properties [265]
CaWO4,SrWO4,BaWO4 mung bean sprouts sphere and rod nanoscale optical property [315]
CaCO3 mung bean sprouts nano-superstructure nanoscale – [266]
ZnS, CdS M13 Phage single-crystal nanowire 20 nm in diameter; 600–650 – [291]
nm in length for ZnS and
475 to 500 nm for cds
ZnS M13 Phage quantum dot – – [316]
PbS and ZnS Cocci, bacillus biomorphic porous hollow nanostructure – photocatalysis [317]
CdS mung bean sprouts nanoparticles 5 nm – [318]
Ag2S,CdS,PbS squama inner coat of onion hollow/solid nanoparticles <100 nm Fluorescent [319]
virus nanotube array tobacco mosaic virus 2D array – – [320]
polyaniline/TMV composite tobacco mosaic virus nanofibers and macroscopic bundle – – [321]
copper-deposited TMV tobacco mosaic virus nanoparticle – – [322]
IrO2-porphyrin M13 virus nanowire – photocatalytic [26]
water-splitting
Hydroxylapatite M13 virus nanocrystal – – [323]
quantum dot M13 Phage oriented nanowires – – [324]
PbSe mung bean sprouts nanorods and nanotubes diameter 50 nm optical properties [267]
CdSe, ZnSe mung bean sprouts nanotubes, nanorods, nanoslats diameter < 150 nm luminescence [325]
Ni(OH)2 squama coat of onion nanoribbons assembled microsphere nanoscale – [268]
calcium oxalate mung bean sprouts dendritic hierarchical, bouquet-like shape microscale – [326]

different substructures. Ultimately, induced by the cooperating
space template, these substructure units assemble into specific
structures and form elaborate morphologies. Another focus of
nanomaterial synthesis using living plants is metal nanoparti-
cles (primarily Au and Ag nanoparticles). Gardea-Torresdey first
reported the formation and growth of Au[269] and Ag nanoparti-
cles[279] inside live alfalfa plants. Importantly, plants can actively
bioreduce metal ions without additional reductants. Studies
have indicated that biomolecules in plants, such as proteins,
amino acids, vitamins, polysaccharides, polyphenols, terpe-
noids, and organic acids, play an important role in this syn-
thesis process. These biomolecules can not only reduce the ions
to the nanosize, but also stabilize the nanoparticles by capping
the nanoparticles.[271]Sesbania drummondii (leguminous shrub)
seedlings can take up high levels of gold(III) ions, resulting
in the intracellular formation of monodisperse spherical gold
nanoparticles (6–20 nm) inside plant cells and tissues. Interest-
ingly, a gold-nanoparticle-bearing biomatrix can directly reduce
the toxic pollutant 4- nitrophenol.[270] In another study, after
nine weeks of growth in gold, silver, and copper-enriched soil,
Brassica juncea seeds grow into plants containing Au–Ag–Cu
alloy nanoparticles.[287] The synthesis of metal nanoparticles
using plants is ecofriendly and cost effective and is therefore a
potential and valuable alternative for the large-scale production
of metal nanoparticles.
In addition to living plants, microorganisms also exhibit
many ideal characteristics for living-organism biomimetic
synthesis, such as prescribed composition, monodispersity,
site-specific heterogeneous surface chemistry, accessible inte-
rior, and extensive chemical tailorability.[274] Microorganisms
can produce various minerals, including metals, sulfides, and
oxides, which generally exist as nanosized materials in the
inter-, intra-, or extracellular spaces of organisms, depending
on the synthesis mechanism and interactions at the organic/
inorganic interface. Microorganism biomimetic synthesis can
produce biomorphic hollow structures (e.g., hollow spheres,

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hollow nanotubes, hollow nanohelices, and hollow chain
spheres),[274,294–297,303,312,317] as well as nanoparticles,[289,292,328]
solid nanowires,[288,290,291,324] quantum dots,[316] and various
assembled structures.[272,275,280,304,329] The most studied micro-
organisms for biomimetic synthesis are yeast cells, the tobacco
mosaic virus, and the M13 bacteriophage.
Biomimetic synthesis using microorganisms is conducted
in the following manner. First, cultivation and purification is
needed to obtain sufficient micro-organisms. Then, the micro-
organisms are mixed with a solution containing specific cations
for some time, during which ions (usually metals) can adsorb
onto the micro-organism’s surface via electrostatic interac-
tions. Subsequently, the micro-organisms are centrifuged and
mixed with other solutions containing a reductant or precipi-
tating agent. Thus, metal nanoparticles or corresponding nano-
materials can be obtained on the micro-organism surface after
REVIEW
sufficient time. Lastly, the micro-organisms are removed by cal-
cination or other methods to obtain biomorphic nanomaterials.
The micro-organisms are alive during this process and show
unique inducing effects on the synthesis of nanomaterials.
Yeast cells are a type of ubiquitous unicellular eukary-
otic micro-organism and often exhibit an oval shape
(Figure 22B).[303] The yeast cell wall consists of phospho-
mannan, mannan, glucan, and dextran; however, yeast cells
cannot induce spontaneous mineralization on their surface
due to a relatively low charge density. During the cultivation of
yeast cells, a bioemulsifier with acidic matrix macromolecule
metabolites, including extracellular proteins and polysaccha-
rides, is produced on the cell surface. These biosurface-active
macromolecules contain hydrophilic anion groups, including
–COO− and –OPO32−, which can improve the mineralization
ability of the yeast cells by providing oriented nucleation sites

Figure 22. Living biomimetic synthesis using bacteria. A) Schematic illustration of the general controlled synthesis of shape-controllable biomorphic
porous metal chalcogenide hollow nanostructures using bacteria. B) SEM image of original yeast cell. Reproduced with permission.[303] Copyright 2010,
Elsevier. C,D) Calcium phosphate microspheres obtained using yeast cells at different magnifications. Reproduced with permission.[312] Copyright 2012,
Royal Society of Chemistry. E) SEM image of biomorphic PbS hollow nanotubes by using L. bulgaricus. F) SEM image of a broken ZnS hollow sphere
using Str. thermophilus; inset) TEM image of hollow spheres.[215] G) TEM image of biomorphic porous ZnS hollow nanotubes using L. acidophilus;
inset) SAED pattern of porous ZnS hollow nanotubes.[215] A,E) Reproduced with permission.[317] Copyright 2009, IOP Publishing. F,G) Reproduced with
permission.[215] Copyright 2009, IOP Publishing.

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for target cations. For example, in the mineralization of TiO2 on
yeast,[295,296] when titanium cations are added into the bioemul-
sion, positively charged titanium cations combine with nega-
tively charged –COO− and –OPO32− groups and self-assemble
on the yeast cell surface via electrostatic interactions. This self-
assembly process induces the formation of a titania layer on the
surface of the yeast cell wall. Subsequently, when an ammonia
hydroxide solution is added to the system, yeast/Ti(OH)4 core–
shell spheres form due to in situ hydrolysis and polyconden-
sation of titanium cations. Lastly, the yeast/Ti(OH)4 core–shell
spheres are converted to yeast–TiO2 through calcination. The
surface of the sphere is covered by numerous TiO2 nanopar-
ticles that are approximately 10 nm in diameter. Using yeast-
cell biomimetic synthesis, Co3O4,[303] Fe2O3,[302] Ca3(PO4)2,[312]
Zr3(PO4)4,[313] and FePO4[308,309] hollow or mesoporous struc-
tures can be obtained (Figure 22C,D). Bacteria, such as Strepto-
coccus thermophiles and Lactobacillus bulgaricus, can also be used
for the synthesis of TiO2,[297] PbS, and ZnS hollow spheres and
hollow tubes (Figure 22A,E–G).[317]
Studies have also shown that the growth characteristic
of living bacterial cells may provide a new route for the syn-
thesis of asymmetrical catalysts. Kaehr and Brinker deposited
positively charged Au nanoparticles on the rod-like Escherichia
coli cell envelope via electrostatic interactions with negatively
charged functional groups.[277] Notably, the E. coli cells were
alive following the deposition of the Au nanoparticles. Then,
the E. coli cells continued to grow under appropriate conditions.
During growth, the cells double in size prior to dividing at their
midpoint, and a new cell membrane forms primarily along the
central surface of the cell rod, with the polar caps remaining
metabolically inert. In this way, after division, the deposited
Au nanoparticles are primarily distributed on the polar caps of
the E. coli cells. This form of biomimetic synthesis using living
bacterial cells may also extend to other cell types and cell-cycle-
dependent behaviors (e.g., sporulation, pili/flagella expression)
and lead to the development of more complex materials and
architectures. Such asymmetric materials are promising for the
fields of energy storage, self-assembly, and nanopropulsion.
The tobacco mosaic virus (TMV) is stable against changes
in pH, relatively high temperatures, and mild to relatively
strong reductants, making it widely used for biomimetic syn-
thesis. The TMV has a 300 nm-long tubular structure with
outer and inner diameters of 18 nm and 4 nm, respectively
(Figure 23B,C). Studies have shown that the outer surface pre-
sents primarily hydroxyl groups and the carboxylate terminus
of the proteins. The protein loops in the channel are flexible
and can expose various functional groups, such as hydroxyl,
primary amide, carboxylate, and amine groups (Figure 23D).
These well-defined chemical groups at specific locations on the
TMV can serve as versatile platforms for the in situ nucleation
and growth of a range of inorganic materials. Significantly, site-
directed mutagenesis of TMV through genetic modification
can change or increase functional groups on expressed protein,
thus improving its ability for biomimetic synthesis.[286,288] For
instance, Lee et al.[286] used the polymerase-chain-reaction-
based mutagenesis technique to insert two cysteine residues
at positions 2 and 3 within the open reading frame of TMV
coat protein. The results demonstrated that the insertion of
cysteine into the TMV coat protein does not significantly affect
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the assembly or stability of the virus. Moreover, gold, silver,
and palladium clusters coat cysteine-modified viruses more
densely and stably than similar coatings on unmodified, wild-
type viruses. This effect occurs because the increased number
of functional groups on cysteine mutant TMVs improves the
uptake and mineralization capacity for metal precursors.[286]
The typical biomimetic synthesis process using the outer and
inner surfaces of TMVs involves ion adsorption, in situ nuclea-
tion and growth, and assembly. To date, aggregates of nanopar-
ticles of gold,[273,286] silver,[286] palladium,[283,284,286] copper,[322]
and 2D metallic arrays[280] have been produced on the external
surface of TMV tubes (Figure 23E). In addition, 3 nm silver
NPs and nanowires of nickel,[288] cobalt,[288] CoPt,[289,293] and
FePt3[293] have been synthesized within the confined environ-
ment of the central channel (Figure 23F). Figure 23A illustrates
biomimetic synthesis in the inner channel, a process that dif-
fers from biomimetic synthesis on the outer surface. In the
inner channel, it is essential that the TMV is first activated by
the selective binding of Pd(II) or Pt(II) ions with amine groups
on the inner surface. The finely dispersed activation centers
(Pd or Pt clusters) can then support the synchronous growth
of each center. Coalescence of the growing nuclei inside the
channel ultimately results in a wire shape without gaps in
the metal structure (Figure 23A).[288,293] Therefore, increasing
the positive charge at a specific site in the central channel can
result in the fine growth of nanowires inside the virus.[289] Knez
et al. also found that TMVs can aggregate in a linear head-to-tail
manner, allowing the preparation of a nanowire of up to 600 nm
in length.[288] Generally, the confined space of the TMV cen-
tral channel can better control the size of the obtained metallic
nanowires and provide more possibilities for further modifica-
tion of the outer surface to generate functional materials.
Special assembled structures can also be obtained by bio-
mimetic synthesis using TMV. Zahr and Blum successfully
fabricated a 22-nm-gold-nanoparticle-rings metamaterial with
and without a central nanoparticle assembled on TMV coat
protein disks by manipulating the solution pH (Figure 23G).
This nanoparticle-rings metamaterial is predicted to have a
number of interesting spectroscopic properties applicable to
next-generation optical and electronic devices.[272] McCarthy
et al. fabricated biomimetic hierarchical superhydrophobic
surfaces using TMV assembled onto an array of micropillars
(Figure 23H–K).[27] Other viruses, such as the Tomato Bushy
Stunt Virus, can also control the 2D organization of metallic
nanoparticles (Figure 23L).[280]
Similar to TMV, the filamentous M13 bacteriophage can also
induce the nucleation and growth of a variety of inorganic mate-
rials on the surface proteins. The M13 bacteriophage is approxi-
mately 880 nm in length and 6.6 nm in diameter, showing a
fiber structure coated by helically arranged proteins. Notably,
the incorporation of specific peptides into the generic scaffold
of the M13 coat structure using phage display techniques led to
the improvement of preferential binding and control over nano-
particle nucleation.[291] Up to now, this technique has been used
to prepare Au nanowires,[275] CoPt, FePt nanowires,[291] Co3O4
nanowires,[304] IrO2–porphyrin nanowires,[26] Ni@CeO2 nanow-
ires,[307] SrTiO3 nanowires,[35] BiFeO3 nanoparticles,[35] ZnS,
CdS nanowires,[324] and single-crystal ZnS, CdS nanowires, and
ZnS quantum dots[316] (Figure 23O).
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Figure 23. A) The formation process of a metal nanowire in the TMV inner channel. B–D) Schematic illustration of the TMV structure. Adapted with
permission.[289] Copyright 2010, American Chemical Society. E) SEM image of a TMV-templated Ni/V2O5 core–shell cathode. Reproduced with permis-
sion.[306] Copyright 2012, Elsevier. F) TEM images of TMV/Au nanowires. Reproduced with permission.[273] Copyright 2008, Royal Society of Chemisry.
G) Schematic illustration of ring assembly process with and without a central nanoparticle using TMV. Reproduced with permission.[272] Copyright
2012, American Chemical Society. H–K) SEM images of the biomimetic hierarchical structures synthesized using the TMV assembled onto an array of
micropillars at various scales. Adapted with permission.[27] Copyright 2012, AIP Publishing LLC. L) Hexagona 2D superlattices by Tomato Bushy Stunt
Virus. Reproduced with permission.[280] Copyright 2011, American Chemical Society. M) Schematic diagram of oriented nucleation and growth of HAP
nanocrystals within aligned phage nanofibers. Reproduced with permission.[323] Copyright 2010, American Chemical Society. N) Schematic diagram
of the virus-enabled synthesis and assembly of nanowires as negative electrode materials for Li-ion batteries. Adapted with permission.[304] Copyright
2006, the American Association for the Advancement of Science. O) SEM image of preannealed ZnS viral nanowires. Reproduced with permission.[291]
Copyright 2004, the American Association for the Advancement of Science.

Moreover, M13 bacteriophages show directed self-assembly
capacity, thus greatly expanding their applications by forming
various 2D and 3D nanomaterials/nanostructures. Wang et al.
designed the oriented nucleation and growth of hydroxylapatite
nanocrystals within aligned phage nanofibers, and the obtained
composites resembled some of the features of the lowest level of
the hierarchical structure of bone (Figure 23M).[323] Nam et al.
reported the self-assembly of M13-bacteriophage-loaded Co3O4
nanowires for flexible lithium-ion-battery electrodes, and the
obtained materials exhibited improved performance in proper-
ties such as specific capacity and rate capability (Figure 23N).[304]
Moreover, Belcher’s group synthesized a series of nanomate-
rials with network structures using TMV, such as Au–Pt,[276]
Co3O4,[305] TiO2,[298–301,330] and FePO4,[310,311] and these nanoma-
terials showed high performance in the area of energy conver-
sion and storage. These studies show that, compared with tradi-
tional nanoparticle-based photoanodes, biomimetic networked
nanomaterials that are synthesized via TMV have much longer
electron diffusion lengths while maintaining a comparable
light-harvesting capacity, leading to improved power conversion
efficiencies. Similarly, these network structures can enhance
the electronic conductivity of the active material of rechargeable
batteries, showing high performance in terms of rate capability
and cycling stability. Other viruses, such as the tomato mosaic
virus[196] and the chilo iridescent virus,[223] can also be used for
biomimetic synthesis.

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Living-organism biomimetic synthesis via plants/micro-
organisms provides an effective way for the controlled syn-
thesis of nanomaterials/nanostructures. This form of synthesis
maintains the smart features of the intact natural biosynthesis
process and simultaneously overcomes certain shortcomings of
biosynthesis through the application of artificial control. How-
ever, the exact synthesis mechanism is far from clear because
of the complexity of the organisms. Moreover, it is still chal-
lenging to reconcile the smart features of biosynthesis pro-
cesses in living organisms with artificial synthesis desires. It
should be noted that some special nanomaterials that are dif-
ficult to obtain through artificial methods can be prepared via
biomimetic synthesis using living organisms. These materials
include smart nanomaterials with good biocompatibility and
functional properties, superstructured nanomaterials, and met-
astable phase nanomaterials.
6. Bioinspired Synthesis via Bio-Macromolecule
Regulation
One important characteristic of biomineralization is the prepa-
ration of highly controlled hierarchical and complex structures
utilizing preassembled supramolecular templates or organic
aggregates. This principle inspires researchers to exploit (bio-)
macromolecules for the mineralization of biominerals in vitro
on the initial biomimetic study. Many specialized macromol-
ecules extracted from mineralized biological systems have
been directly exploited to study the biomineralizaiton process
in vitro. For instance, macromolecules extracted from mol-
lusk shells and sponge spicules show inducing and control
capacity for the formation of CaCO3 in vitro.[331–333] In addi-
tion, silaffins and long-chain polyamides from diatoms, as well
as silicateins from sponge spicules, can induce the deposition
of silica in vitro at room temperature.[334–336] These proteins
show controlled and inducing capacity for crystal growth when
used as additives and provide valuable mechanistic insights
into the control of mineral formation. Moreover, much effort
has been made to exploit various synthetic macromolecules for
simulating biomineralization and biomimetic synthesis, such
as poly(aspartic acid), poly(acrylic acid), and polystyrene sul-
fonate.[337–339] Particularly, double hydrophilic block copolymers
are typical synthetic macromolecules used as crystal-growth
modifiers. These polymers consist of a hydrophilic polyelectro-
lyte domain and a non-interacting hydrophilic block, and have
shown remarkable performance in the morphosynthesis of
superstructured CaCO3.[340–344] With an in-depth understanding
of the biomineralization process, these biomimetic and bioin-
spired synthesis strategies can be extended to the synthesis of
other inorganic nanomaterials/nanostructures, even organic
and organic/inorganic hybrid nanomaterials/nanostructures.
Bio-macromolecules often display well-defined chain
lengths, monomer sequences, and stereochemistry. Particularly,
bio-macromolecules show excellent biocompatibility and bio-
degradability, which are promising characteristics for the syn-
thesis of biomedically applicable nanomaterials. Due to their
sophisticated nanostructures and highly precise molecular rec-
ognition capabilities, bio-macromolecules can be used to exert
rational control over inorganic nanomaterial nucleation, phase
32 wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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stabilization, assembly, and pattern formation at the molecular
scale. Specifically, the integration of these unique capabilities of
biomolecules with rational molecular design through genetics
or chemical modification is expected to offer more opportuni-
ties for the hierarchical assembly of complex architectures.[275]
Generally, the bioinspired synthesis of nanomaterials/nano-
structures via bio-macromolecules is conducted by mimicking
the processes with which organisms use the molecules; these
processes can be summarized in the following four categories
(Figure 24): i) insoluble bio-macromolecules or their assembled
structures can act as scaffolds for crystal nucleation and growth;
in this process, some elementary biological processes are mim-
icked (i.e., diffusion, molecular preorganization, molecular
recognition, nucleation, template-inducing, and the assembly
processes) (Figure 24A); ii) soluble bio-macromolecules
can be adsorbed onto the surface of crystals or specific crystal
faces, thus controlling the size of the obtained nanomaterials
or inducing the oriented growth of nanomaterials; in this
process, some elementary biological processes are mimicked
(i.e., diffusion, molecular recognition, and template-inducing)
(Figure 24B); iii) some bio-macromolecules such as apoferritin
and helices formed by polysaccharides, can be used as reactors
for the synthesis of nanomaterials/nanostructures; in this pro-
cess, these reactors not only provide the sites for crystal nuclea-
tion and growth but also confine the size of the resultant nano-
materials (Figure 24C). Some biological unit processes (i.e.,
substance transport, stimulus and response, and biomineraliza-
tion) can be mimicked in these systems; iv) some bio-macro-
molecules, such as single-stranded DNA, can link onto the pre-
formed NPs and assemble them into specific structures or onto
preassembled single-stranded DNA templates (Figure 24D).
This process somewhat mimics peptide synthesis, in which
the pre-assembled template in analogous to mRNA, the DNA
linked onto the preformed NP is analogous to tRNA, and the
preformed nanoparticle is analogous to the amino acid. This
process may involve some biological unit processes (e.g., tran-
scription and translation).
6.1. Protein-Template Biomimetic Synthesis
It has been demonstrated that both soluble and insoluble pro-
teins can influence the crystal morphology during biominerali-
zation. Insoluble proteins can serve as scaffolds or nanoreactors
for crystal nucleation and growth, and soluble proteins can
adsorb preferentially to specific facets and influence the ori-
ented growth of crystals. In vitro, these effects can be mimicked
to either probe the mechanism of biomineralization or to syn-
thesize complex nanostructures and functional inorganic nano-
materials. In addition, proteins can be genetically modified to
further improve their synthesis capacity for nanomaterials/
nanostructures.[345] Some typical protein nanoreactors (e.g.,
apoferritin), scaffolds (e.g., S-layer proteins and microtubulin,)
and modifiers (e.g., peptides) can be introduced for the biomi-
metic synthesis of biominerals and other functional nanomate-
rials; these processes will be discussed in this section.
Apoferritin is ubiquitous in living organisms and serves
as an iron-storage protein that maintains iron homeostasis in
cells. Apoferritin consists of 24 polypeptide subunits, exhibiting
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Figure 24. The role of bio-macromolecules in bioinspired synthesis. A) The bio-macromolecules assemble into a specific scaffold for the growth
of nanomaterials/nanostructures; B) the bio-macromolecules are adsorded onto the surface or specific crystal faces to stabilize or induce oriented
growth of nanomaterials/nanostructures; C) cavity of natural or assembled bio-macromolecules can act as reactor for the synthesis of nanomaterials/
nanostructures; D) some bio-macromolecules can link onto the preformed nanoparticles, and then assemble the nanoparticles into specific structures
or onto a preassembled template.

a spherical structure with a diameter of 12 nm and an internal
cavity of 7 nm. Within the three-fold symmetry axis of the protein
shell, there are eight channels consisting of negatively charged
amino acids (glutamic and aspartic acids). Studies have shown
that the biomineralization reaction in apoferritin is a multi-
step process involving the uptake of Fe II, oxidation to Fe III,
hydrolysis, nucleation, and crystal growth.[346] The detailed
process is as follows: i) first, Fe2+ ions are attracted by the
negative charges on the outer surface surrounding the chan-
nels, through which the ions pass; ii) once in the cavity, Fe2+
ions are condensed and oxidized to form nuclei at negatively
charged amino acid areas on the inner surface; iii) as more ions
are transported into the cavity, the nuclei grow into iron oxide
nanoparticles.
The understanding of this biomineralization process allows
researchers to use the apoferritin cavity as a spatially restricted
reactor for control of the size and shape of various NPs in
vitro. Reaction outside apoferritin may prevent ions from pene-
trating into the cavity, so it is crucial to suppress chemical reac-
tions outside the cavity. Yamashita’s group precisely designed
a slow chemical reaction system (SCRY) to overcome this
problem.[347–350] Considering the synthesis of ZnO in SCRY
as an example (Figure 25A), Zn2+ ions first form complexes
with NH3. It was suggested that [Zn(NH3)4]2+ decoupled four
ammonia molecules near the apoferritin three-fold channels to
allow Zn2+ to enter the cavity. The OH− ions also diffused into
the cavity even though the inner wall surface of the channel is
negatively charged. It was demonstrated that the introduction
of Zn2+ ions into the cavity prior to OH− ion entry is essential
for the synthesis. This requirement is because Zn2+ ions should
first be condensed at nucleation sites to promote nucleation,
which occurs subsequent to anion introduction. Meanwhile,
the suppression of chemical reactions outside the apoferritin
remained essentially effective. Thus, Zn(OH)2 was selectively
synthesized in the cavity by hydroxylation, and Zn(OH)2 was
subsequently converted to ZnO via the dehydration reaction.
Moreover, polymers can be used to depress the reaction out-
side the cavity.[351] Various metal, metallic oxide, and metal-salt
NPs have been obtained by process biomimetic synthesis, such
as Au,[352] Ag,[353,354] AuPd,[355] Gd2O3,[356] ZnO,[347] CeO2,[357]
Co3O4,[358] In2O3,[359] CdS,[360] FeS,[361] CdSe,[348,362] ZnSe,[349]
Ni(OH)3,[363] and Cr(OH)3.[363] Studies have also revealed that
other cage-shaped proteins, such as small heat shock pro-
tein,[364] stable proteins,[365] and DNA-binding proteins,[350,362]
have a similar capacity as apoferritin, in that they can be used
as nanoreactors for the biomimetic synthesis of nanomaterials.
In addition to the synthesis of the above functional rnanoma-
terials, apoferritin can be used for the study of biomimetic min-
eralization study in vitro. Mann and co-workers showed that
Fe3O4 (or γ-Fe2O3) NPs could be artificially synthesized within
apoferritin cages under elevated temperature and pH.[366]
Fukano et al. synthesized uniform and dispersive calcium car-
bonate nanoparticles with average diameters of 5.8 ± 1.2 nm
in the apoferritin cavity.[367] These authors also concluded that
electrostatic potential control is important for the movement of
ions into the apoferritin cavity. It should be mentioned that this
biomimetic synthesis is a combination of process biomimetic
synthesis and functional biomimetic synthesis, showing great
potential for the design of new biological functional materials.
Other bio-macromolecules should also be studied for similar
biomimetic mineralization effects to further extend their bio-
functional applications, such as in medicine.

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Figure 25. Exploiting apoferritin for biomimetic synthesis. A) Schematic for the modified SCRY for the synthesis of ZnO NP inside apoferritin
(represented in green). Reproduced with permission.[347] Copyright 2012, American Chemical Society. B) HRTEM images of individual CdS@ferritin
containing two, three, and four single crystals, and one single crystal. Adapted with permission.[360] Copyright 2010, Wiley-VCH. C) The synthesis of CeO2
nanoparticles in apoferritins and assembly into 2D and 3D array structures. Adapted with permission.[357] Copyright 2011, American Chemical Society.

The structures and components of nanomaterials can also
be controlled within apoferritin. Chiral configurations of the
chelating amino acids in horse spleen ferritin cores were trans-
ferred to CdS quantum-dot crystal lattices during anisotropic
crystal growth, resulting in left-handed circularly polarized
luminescence (CPL) (Figure 25B). Notably, CdS@ferritin con-
sists of single and multiple crystals, resulting in CPL double
emissions from the direct transition and surface-trapping
sites.[360] CoNi bimetallic nanoparticles of different compo-
sitions were synthesized by varying the ratio of Co and Ni in
the reactants.[368] Moreover, two types of Au–Pd structures (i.e.,
Au–Pd alloy NPs and core–shell NPs) were synthesized within
apoferritin through a co-reduction and sequential-reduction
method. Further design of the internal space of apoferritin by
site-directed mutagenesis for fine-tuned multi-metal nanopar-
ticles is feasible and promising for various applications.[355]
The obtained nanomaterials within apoferritin can further
assemble into complex, well-defined 2D and 3D structures that
show potential for applications in optics and photocatalysis. It
was reported that 2D crystals can be formed through crystal-
lizing ferritin molecules on a water–air interface using a dena-
tured protein film via cadmium salt bridging.[359,369] Ce salt
bridges between the products can also induce the formation of
hexagonal-close-packed (hcp) 2D crystal arrays and octahedral,
prismatic 3D crystals (Figure 25C).[357] In addition, considering
apoferritin with nanomaterials in the core, the modification
or further growth of other materials on the shell may extend
their applications. Some unique 2D-array structures of protein
assemblies, such as S-layer proteins,[370,371] protein strepta-
vidin,[372] and stable proteins,[365] can act as scaffolds for the
biomimetic synthesis of metallic/semiconducting nanostruc-
tures and arrays in vitro. Particularly, the use of native and engi-
neered proteins offers the prospect of producing lattice arrays,
which may be difficult by other self-assembly approaches.
S-layer proteins are extensively studied 2D crystalline arrays
found on the outermost surfaces of many bacteria. Depending
on the bacteria species, S-layer proteins exhibit oblique,
square, or hexagonal lattice symmetries with unit-cell dimen-
sions in the range of 3 to 30 nm and thicknesses of 5–10 nm
(Figure 26A,B).[373] Functional groups on the surface are aligned
in well-defined positions and orientations, acting as binding
sites for the fixation of various nanomaterials (Figure 26C).
Numerous regular 2D nanoparticle arrays have been prepared
through the template-directed synthesis of S-layer proteins,

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Au,[401,402] Ag,[388,389] Pd,[403] Ni,[404] FePt,[388]

Figure 26. A) Schematic illustration of the morphological structure and hexagonal (p6) sym- architecture can serve as a template for the
metry of the HPI S-layer. B) TEM image of the extracellular face of a native HPI S-layer protein synthesis of Au nanoflake films with remark-
fragment. Reproduced with permission.[373] Copyright 2007, Elsevier. C) Schematic illustration able surface-enhanced Raman spectroscopy
of the fixation of Au nanoparticles on the S-layer. Reproduced with permission.[386] Copyright properties (Figure 28C).[413] Based upon the
2008, American Chemical Society. D) SEM images of Ge nanowires grown from biotemplated Pd/peptide ratio, different Pd morphologies
10 nm Au nanoparticles on Ge (111) substrates. Reproduced with permission.[387] Copyright
2010, American Chemical Society.
such as Au NPs,[371,373–378] FePt NPs,[379–381] Pt,[382,383] Pd,[384]
CdSe/ZnS core/shell quantum dots,[371] and silica.[370] More-
over, gold NPs of different diameters and small size (5–20 nm)
on S-layer proteins can serve as catalysts to produce orientation-
controlled growth of Ge nanowires (Figure 26D).[239,385] It has
been revealed that the match between NP geometry and the
regularly patterned surface morphology of S-layer proteins is
important for achieving a high degree of nanoparticle ordering.
Deposited NPs are preferentially located at the hollows of
appropriate size on the S-layer surface, allowing the particle to
reduce its surface free energy by maximizing its contact area
with the exposed S-layer surface.[378,379]
Moreover, widespread filamentous proteins and their assem-
blies in organisms have also been exploited as scaffolds for the
controlled synthesis of various 1D nanomaterials (Figure 27).
Microtubules,[388,389] bacterial flagella,[390–393] α-synuclein,[390]
insulin fibrils,[379,394,395] glucagon fibrils,[396] lysozyme fibrils,[397]
skin collagen fibers, [ 398,399 ] and γ-prefoldin filamentous pro-
teins[400] have been used to control the assembly of metal or
semiconductor NPs into nanowires or linear arrays. Specifi-
cally, microtubules, or ordered linear tubulin assemblies, are
cylindrical protein filaments with outer diameters of approxi-
mately 25 nm and lengths up to tens of micrometers. Micro-
tubules exhibit chemically functional surfaces with defined
patterns of amino-acid side chains, providing active sites
for the nucleation and organization of various NPs, such as
REVIEW
CdSe,[405] CdS,[406] and FeOOH.[407] Microtu-
bules can also be used to synthesize various
2D and 3D nanomaterials, such as ring-like
Ag nanostructures (Figure 27A),[408] helical
Pd nanoparticle arrays (Figure 27B),[409] and
microtubule asters (Figure 27C).[410,411] Bacte-
rial flagella are another example of natural,
self-assembled protein nanotubes (diameter:
12–25 nm, length: 10–15 µm). Flagella can
be used as universal biotemplates for the
green synthesis of nanotubes with tunable
wall thicknesses and morphology by varying
certain reaction parameters, including ionic
strength, pH, temperature, reaction time,
and subunit sequences (Figure 27D,E).[391,392]
Peptides, the secondary structures of pro-
teins, have also been explored as scaffolds
for crystal nucleation and growth, and they
can be designed to self-assemble into a large
variety of structures (Figure 28A–C). For
example, self-assembled peptide frameworks
can generate linear, networked Pd materials
(Figure 28A).[412] A self-assembled, well-
ordered, flower-like hierarchical dipeptide
can be prepared, such as nanoparticles, linear
nanoribbons, and complex nanoparticle
networks (NPNs); enhanced reactivity was
observed for the Pd nanoparticles and NPNs over nanoribbons.
Such results are important for the design and development of
selective nanocatalytic systems, where the composite structures
work in conjunction to mediate the overall activity.[414,415]
Peptides have also been demonstrated to direct the forma-
tion of particular nanocrystal shapes through selective adsorp-
tion on a specific crystal face.[418] Molecular dynamics simula-
tions of the selective binding of several short peptides to Au
and Pd surfaces showed a clear preference for adsorption to the
{111} surface over the {100} surface. This effect may be due
to the available face-centered-cubic (fcc) lattice sites above the
metal substrate.[419] Sarikaya’s group also reported the forma-
tion of an ordered supramolecular self-assembly of a geneti-
cally engineered gold-binding peptide on Au{111}.[420] The
adsorption process is dynamic and involves multiple stages of
structure evolution over time with accompanying surface dif-
fusivities.[421] It is anticipated that generating predictable and
programmable materials may be possible by: i) understanding
how the peptides bind and arrange on the surface, ii) designing
rational peptides sequences; and iii) tuning the reaction condi-
tions (Figure 28D).[416]
Further studies showed that the molecular conformation
and amino-acid sequence of peptides may be the key deter-
minants facilitating the selective binding of peptides on solid
materials, thereby influencing the growth and assembly of
nanocrystals.[422,423] Huang’s group reported the predictable

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Figure 27. A,B) Deposition of Ag particles on microtubules (A), and tubulin spirals (B), and based on microtubule protein. A) Reproduced with
permission.[389] Copyright 2004, American Chemical Society. B) Reproduced with permission.[408] Copyright 2006, Wiley-VCH. C) Fluorescence micros-
copy images of fluorescent nanocrystals grown on microtubule asters. Reproduced with permission.[410] Copyright 2013, American Chemical Society.
D) Schematic representation of the procedure for the fabrication of double-layered titania/silica nanotubes. Reproduced with permission.[391] Copyright
2012, Wiley-VCH. E) Nucleation of silica on a flagella surface: the morphology of the flagella can be controlled under different pH values and then the
resulting products exhibit the morphology of the flagella. Reproduced with permission.[392] Copyright 2012, Royal Society of Chemistry.

Figure 28. Exploiting peptides for biomimetic synthesis. A) Schematic diagram for networked Pd nanostructures formation using the peptide tem-
plates. Reproduced with permission.[412] Copyright 2012, American Chemical Society. B) SEM image of palladium oxide NP chains using glucagon fibril
as template. Reproduced with permission.[396] Copyright 2012, Royal Society of Chemistry. C) Higher-magnificatopm SEM image of the hierarchical
flower-like morphology of peptide mesocrystals. Reproduced with permission.[413] Copyright 2011, Wiley-VCH. D) The route to rational and predictable
nanostructure modulations. Reproduced with permission.[416] Copyright 2013, American Chemical Society. E) Facet-specific peptides are used to direct
the synthesis of platinum nanocrystal cubes and tetrahedrons, respectively. Adapted with permission.[417] Copyright 2011, Nature Publishing Group.

36 wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2016,
DOI: 10.1002/adma.201503215

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control of Pt nanocrystal structures using facet-specific pep-
tide sequences.[416,417,424] Peptide sequences that can recog-
nize Pt-{100} and Pt-{111} planes have been rationally iden-
tified and used to direct the preparation of Pt nanocrystals
(Figure 28E). The shape transformation of nanocrystals from
cubes to tetrahedrons is achieved by simply switching the
binding peptide sequence in aqueous solution at room tem-
perature, suggesting the possibility of post-growth dynamic
control over material structures using biomolecules.[417] An
artificial bifunctional peptide was designed to synthesize inor-
ganic nanocomposites (i.e., TiO2–Ag, TiO2–Au, and SiO2–Ag).
In this process, the positively charged moiety accelerated the
polycondensation of the negatively charged Ti or Si precursors,
and the phenolic hydroxyl moiety reduced Ag+ or Au3+ ions.[417]
Moreover, biomimetic synthesis can be substantially affected
by the reaction conditions, such as pH and the concentration
of the salt precursors and peptides. Single peptides can pro-
duce sub-2-nm seed crystals, monodisperse 4 nm platinum
polyhedra, and 7–8 nm platinum cubes simply by changing the
metal reduction rates.[425] The synergistic effects of the primary
peptide structure and the reaction conditions can well tune the
products, and gold nanostructures of diverse shapes (nanopar-
ticles, nanowires, nanoribbons, kite and tail structures, and
nanometer-thick platelets) and sizes (from a few nanometers
to nearly 100 µm) can be synthesized.[426] A similar influence
is observed for silica biomineralization using polycationic pep-
tides or polyamino acids derived from proteins. By changing
the shear forces for the reaction, silica particles with various
morphologies can be obtained, such as nanospheres, hexag-
onal plates, organized fibrillar structures, and 3D structures
with periodic voids.[427,428]
Figure 29. The strategies utilizing DNA for biomimetic and bioinspired synthesis. A) Electrostatic-interaction-induced electroless deposition.
B) Molecular-recognition-driven assembly of decorated NPs through DNA base pairing. Adapted with permission.[429] Copyright 2000, American Chem-
ical Society. C) Molecular-recognition-driven placement of decorated NPs on DNA origami. Adapted with permission.[430] Copyright 2010, American
Chemical Society.
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6.2. Nucleic-Acid-Template Biomimetic and
Bioinspired Synthesis
6.2.1. DNA-Template Biomimetic and Bioinspired Synthesis
DNA consists of two helical strands that are selectively assem-
bled through precise base pairing, and the DNA strand back-
bones display a negative charge due to the phosphate groups.
Thus, the shape, length, and sequences can be designed to have
a highly specific and precise molecular recognition capability
using rational genetic engineering or chemical modification.
For these reasons, the custom synthesis of nanomaterials is fea-
sible by tuning the DNA template. Two main strategies have
been proposed for DNA-template biomimetic and bioinspired
nanomaterial synthesis: i) electrostatic-interaction-induced elec-
troless deposition of NPs on the DNA template (Figure 29A);
and ii) molecular-recognition-driven assembly or placement of
decorated NPs through DNA base-pairing (Figure 29B,C). DNA
has been demonstrated to be an ideal template for directing
self-assembly of building blocks into a wide range of nanoarchi-
tectures, such as 1D linear arrangements, 2D nanoarrays, 3D
discrete nanoassemblies, and 3D crystalline superlattices.
In the first strategy, the negatively charged phosphate back-
bones serve as nucleation sites and induce crystal growth along
the DNA strands (Figure 30A). Coffer’s group pioneered the
synthesis of CdS nanowires using DNA, proving the possibility
of NP synthesis via electrostatic-interaction-induced assembly.
Later, various semiconductor nanowires (e.g., CdS[431–434] and
Fe3O4[435]) and metal nanoparticles/nanowires (e.g., gold, [436–439]
silver,[440–443] palladium,[444–447] platinum,[448,449] cobalt,[450]
nickel,[451] and copper[452]) have been prepared via this method.
wileyonlinelibrary.com 37
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Figure 30. A) Electrostatic interaction between the phosphate backbone and surface Cd2+ ions. Reproduced with permission.[455] Copyright 2012,
American Chemical Society. B) High-magnification image of a meshlike 2D array of Pd nanowires formed by the metallization of a 2D-aligned DNA
sample. Reproduced with permission.[446] Copyright 2003, American Chemical Society. C) Schematic depiction of selective metal deposition by control-
ling the location of boranephosphonate DNA (orange tiles). Reproduced with permission.[454] Copyright 2013, American Chemical Society. D,E) SEM
images of BaSO4 crystals formed on calf-thymus DNA at different supersaturations. Reproduced with permission.[456] Copyright 2002, American Chem-
ical Society. F) TEM image of DNA-mediated functional gold nanoflowers. Reproduced with permission.[457] Copyright 2010, American Chemical Society.
G) SEM image of the enantiomeric impeller-like helical DNA–silica complexes (left- and right-handed impellers are denoted by + and , respectively).
H) Illustration of the macroscopic enantiomeric helical morphologies and corresponding opposite DNA chiral packing of the impeller-like helical
DNA–silica complexes. Reproduced with permission.[458] Copyright 2012, Wiley-VCH.

The common process for nanowire synthesis in solution is as
follows: cations first absorb onto the DNA backbone to form
complexes due to electrostatic interactions. When the anions
or reductants are added, the metal ions react with anions or
are slowly reduced due to the controlled release of ion–DNA
complexes. This process effectively inhibits metal ions from
growing into large clusters. Therefore, NPs are synthesized and
assembled on the DNA in a single step. DNA templates can
also be designed and assembled to specific shapes before the
reaction, such as bundles and rings,[436] 1D parallel/2D crossed
metallic nanowire arrays (Figure 30B,C),[443,446] and three-
branched nanostructures.[453] It is also possible to program the
metallization process to occur only on selected DNA strands
by specifically labeling the DNA with aldehyde groups[442] or
boranephosphonate internucleotide linkages (Figure 30C).[454]
Some studies have also explored the influence of DNA on
the shape or morphology of NPs. Rautaray et al. synthesized
BaSO4 crystals using calf-thymus DNA at different supersatu-
ration ratios, and star-shape and flowerlike morphologies were
obtained at supersaturation ratios of 400 and 50, respectively
(Figure 30D,E).[456] Wang et al. investigated the influences
of different DNA molecules of the same length on the mor-
phology of gold nanoparticles, obtaining spherical gold nano-
particles (AuNS) and flower-like gold nanoparticles (AuNF)
(Figure 30F).[457] Detailed mechanistic studies have indicated
that the difference in DNA affinity to the gold nanoparticles
plays a major role in morphology control. The formation of
the AuNF can result from either the selective deposition of the
reduced gold on the AuNS template by surface-bound DNA
or uneven growth of the AuNS due to the binding of DNA
to the surface. The authors also showed that DNA-function-
alized nanoflowers can be readily taken up by cells, showing
promise for biosensing and biomedicine. Moreover, Che’s
group successfully synthesized enantiomeric impeller-like hel-
ical chiral DNA–silica complexes by regulating the interaction
between the DNA, and inorganic and alkaline-earth-metal ions
(Figure 30G,H).[458] It was found that chiral, 2D square-struc-
tured DNA packing gives rise to impeller-like helical DNA–
silica complexes. It was also shown to be possible to prepare 2D
DNA–silica platelets with 2D square p4mm and 2D hexagonal
p6mm symmetries through the self-assembly of DNA and silica
mineralization.[459,460]

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hexagons,[464] pyramids,[38] cubes,[39] and more-complicated

It should be mentioned that electrostatic-interaction-induced
deposition is often disordered and non-uniform, which is unfa-
vorable for nanoelectronics and nanophotonics. Molecular-
recognition-driven assembly or placement of decorated NPs
through DNA base-pairing may overcome this problem. Single-
stranded DNA can act as linkers to functionalize preformed
NPs. Then the specific, complementary hydrogen bonding of
the base pairs allows the functionalized NPs to be assembled by
the hybridization of single-stranded DNA into a double helix.
Careful sequence design and induced assembly of functional-
ized NPs have been used to obtain dimeric nanostructures,[461]
various liner structures,[462] cat-paw structures,[37] satellite struc-
tures,[37] dendrimer-like structures,[37] triangles,[463] squares,[463]
REVIEW
polyhedral, even 2D nanoparticles arrays,[40] 3D AuNP tubes,[41]
and other assemblies[465] (Figure 31A–C). In all cases, to
create well-defined programmable crystalline structures using
DNA-linked NPs, it is essential to control the strength of the
attractive forces between the DNA and highly monodisperse
particles. Moreover, hollow nanoparticles[466] and anisotropic
nanoparticles with inherent shape-directed crystallization[467]
have also been reported in the programmable assembly of well-
defined 3D crystalline superlattices (Figure 31D).
However, linked DNA templates are not sufficiently rigid, and
the assembly of AuNPs suffers from deformation. Occasion-
ally, the lack of control in the orientation of the DNA strand on

Figure 31. A) Representative schematic diagrams and TEM images of DNA-programmed quantum-dot complexes. Adapted with permission.[462] Copy-
right 2011, Nature Publishing Group. B,C) 3D and 2D nanostructures assembled by DNA-decorated NPs. Reproduced with permission.[38] Copyright
2009, American Chemical Society. Reproduced with permission.[40] Copyright 2006, American Chemical Society. D) Crystalline superlattice assembled
from DNA polyvalent nanoconjugates as building block. Reproduced with permission.[467] Copyright 2010, Nature Publishing Group. E) DNA-origami-
directed self-assembly of discrete silver-nanoparticle architectures. Adapted with permission.[468] Copyright 2010, Wiley-VCH. F) Self-assembly of gold
prototype nanoelectronic components into closely packed rows with precisely defined inter-row spacings by in situ hybridization of DNA-functionalized
components to a preassembled 2D DNA scaffolding. Adapted with permission.[469] Copyright 2004, American Chemical Society. G) Schematic diagram
and TEM images of 3D AuNP helices formed by the tubular DNA origami dressed with AuNPs. Reproduced with permission.[470] Copyright 2011,
American Chemical Society.

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into conductive metal nanowires.[473,477,478] Moreover, aniso-

REVIEW

AuNPs generates undesired assemblies. DNA origami scaffolds

are more robust and stiff platforms for bioinspired synthesis
of nanomaterials, particularly 2D and 3D well-ordered nano-
structures. DNA origami contains known sequences at known
locations that can be used to position DNA-binding inorganic
NPs. This bioinspired synthesis process is performed as follows.
First origami scaffolds and motifs are designed into the desired
shape or structure using staple strands. Then inorganic NPs are
decorated with single-stranded DNA of the designed sequences.
The designed sequences are composed of two segments: one is
used to provide high affinity for the surface of the NPs, and the
other is for localization of the NPs. Subsequently, the decorated
NPs are assembled at desired positions in the final geometry
through the base-pairing between DNA segments on the sur-
face of AgNPs and the origami scaffolds/motifs, resulting in the
formation of different dimensional arrangements. The design
of origami scaffolds/motifs and the decoration of NPs are both
crucial for the synthesis process. A variety of origami scaffolds
or motifs have been designed for the controlled attached of NPs,
such as triangles,[430,471,472] rings,[473] regular arrays,[474–476] and
helical geometry.[470] These geometries have potential applica-
tions in molecular electronics, optoelectronic devices, and plas-
monic and molecular sensors (Figure 31E–G). These preformed
NPs can also serve as seeds for further metallization to grow
tropic NPs, such as Au nanorods,[472] can also be positioned on
scaffolds with various angles.
6.2.2. RNA-Template Biomimetic and Bioinspired Synthesis
RNA, a single-stranded structure, has a very similar structure
to single-stranded DNA except that it has a C2′-OH group on
the ribose sugar, and thymine is replaced by uracil. In the bio-
mimetic synthesis process, RNA provides the necessary micro-
environment for triggering crystal nucleation and growth under
thermodynamic control.[479–481] Because the electrostatic bar-
rier for bringing clusters into close proximity is too large to be
overcome, RNA may also act as a stabilizing electrostatic shell
and prevent further aggregation upon reaching a critical size
(Figure 32A).[482,483]
RNA has been demonstrated to be an outstanding biotem-
plate for controlled synthesis of metal and semiconductor nano-
materials, such as Pd,[485–487] Ag,[482] CdS,[479,483] PbS,[481,484,488]
and PbSe (Figure 32C–F).[480,489,490] Particularly, RNA’s sequence
flexibility, composition, and structure hold enormous poten-
tial for the designed synthesis of nanomaterials. Hexagonal Pd
platelets, Pd cubes, and Pd nanoparticles have been synthesized

Figure 32. A) Proposed roles of phosphate and base functionalities on GTP in nanoparticle nucleation, growth, termination, stabilization, and passiva-
tion. Adapted with permission.[484] Copyright 2006, American Chemical Society. B) Schematic illustration of the folding of RNA to form a porous building
block and a honeycomb-like supernanostructure in the process of self-assembly. C) SEM images of honeycomb-like PbSe nanostructures. Adapted with
permission.[480] Copyright 2013, American Chemical Society. D) TEM images of PbS nanostructures. Reproduced with permission.[481] Copyright 2009,
American Chemical Society. E,F) SEM images of CdS having a Cd/S molar ratio of 2: aged for two months (E), and F) a magnified image of the circled
portion in (E), synthesized using RNA. Reproduced with permission.[479] Copyright 2008, American Chemical Society.

40 wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2016,
DOI: 10.1002/adma.201503215

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by changing the RNA Pdase sequences.[486,487] Moreover, certain
reaction parameters, such as the types and amounts of metal
ions, may significantly influence RNA folding and self-assembly
for biomimetic synthesis. For instance, different levels of Zn2+
ions induced the folding of RNA to produce a honeycomb-like
porous PbSe super-nanostructure[480] and PbS nanowires[481]
(Figure 32B–D), whereas Pb2+ ions induced the production of
PbSe nanotubes.[489]
6.3. Polysaccharide Templates for Biomimetic and Synthesis
Polysaccharide, such as cellulose, starch, agarose, dextran, chi-
tosan, alginate, and carrageenan, can also participate in the bio-
mimetic synthesis process in vitro. Compared with proteins and
nucleic acids, polysaccharides are easily available, abundant and
low-cost. Similar to proteins and nucleinic acids, polysaccha-
rides can also form various templates with different conforma-
tions and molecular weights through intrachain or interchain
hydrogen bonding of monosaccharide residues. Up to now,
metal nanoparticles (e.g., Au,[491,492] Ag,[493] Au–Pd[494]), metal
oxides (e.g., ZnO,[495] TiO2,[496,497] SnO2,[496] Al2O3,[496] ZrO2,[496]
Fe3O4[498]), CdS,[499] Ca3(PO4)2,[500] silica,[501–503] YBa2Cu3O7δ,[504])
have been synthesized, exploiting various polysaccharides.
In the biomimetic synthesis process, the insoluble poly-
saccharides can act as scaffolds for crystal nucleation and
growth.[496,505] The numerous functional groups (such as
hydroxyl groups, epoxy groups, acetyl groups) on the polysac-
charides can adsorb with ions, thus controlling the nuclea-
tion sites. For example, oligopropylamino-functionalized
celluloses have been used to induce the growth of hollow
silica nanotubes.[502] The numerous functional groups of the
polysaccharide also play a crucial role in influencing crystal
growth: they can adsorb to specific crystal faces to change
the crystalline growth direction, or they can adsorb to crystal
surface to stabilize nanoparticles by steric and electrostatic
interaction.[492,493,499]
Many polysaccharides can form helices in water, and these
helices often have hydrophobic cores. These special helices can
be used for biomimetic synthesis of long-range-ordered nano-
materials or anisotropic nanostructures. Particularly, the size of
helical cores is flexible, depending on the interaction between
the polysaccharides and the molecular precursors. Up to now,
aligned gold, gold nanotapes, and silica nanofibers have been
synthesized in helices formed by polysaccharides.[491,506,507]
Moreover, the chirality of the helices can also be retained in the
resultant nanomaterials. For instance, left-handed amylose or
right-handed schizophyllan were used to induce the formation
of chiral oligosilane.[508] It can be concluded that this biomi-
metic system may be applicable to the design of other nanow-
ires, nanocircuits, and organic/inorganic hybrid nanomaterials,
even some devices.
Polysaccharides can also form a gel that traps water in the
networks. Then, the precursors are stabilized in the gel and the
diffusion rate of ions in the gel is greatly reduced through com-
plexing or forming hydrogen bonding to the polysaccharides.
Thus the polysaccharide gel can control the nucleation and
growth of nanoparticles. Nanoparticles with small and uniform
sizes, even some quantum dots, can be synthesized in the gel
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DOI: 10.1002/adma.201503215
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of polysaccharides.[498–500,509–511] Furthermore, some gels are
REVIEW
responsive to changes of temperature, pH value, or metal pre-
cursors. The appropriate control over the responsiveness of gels
may control the sizes and morphologies for the biomimetic
synthesis of nanomaterials/nanostructures.
In addition, polysaccharides also can be used for the syn-
thesis of organic nanomaterials.[512] Yu et al. synthesized large
quantities of polyaniline–sodium alginate nanofibers with
controlled diameters by adjusting the concentration of aniline
and sodium alginate.[513] The results showed sodium alginate–
aniline complexes are important and they play a template-like
role in the formation of nanofibers. Numata and co-workers
used the hydrophilic cavity formed by schizophyllan to syn-
thesize polyaniline nanofibers and supramolecular dye assem-
blies.[514,515] This schizophyllan system may bring new creation
methods for other supramolecular nanofibers.
Bio-macromolecules bioinspired synthesis shows control-
lability and selectivity for the synthesis of nanomaterials/
nanostructures based on precise molecular recognition and
assembly. The diversity and flexibility of bio-macromolecules
provide tremendous possibilities for tuning the structure, size,
and morphology of nanomaterials. Particularly, chiral nanoma-
terials can be obtained through replicating the chiral structures
of assembled bio-macromolecules. In recent years, the develop-
ment of nanoscience and nanotechnology has greatly advanced
bio-macromolecule bioinspired synthesis. However, it is still a
challenge to determine the assembly rules of bio-macromole-
cules for effective regulation and control over nanomaterials/
nanostructures due to the diverse types, complex structures,
multiple combinations, and numerous binding sites involved.
7. Conclusion and Perspective
Process biomimetic synthesis is systematically summarized
and reviewed from five perspectives; it has proven to be a kind
of versatile and effective synthesis method for various nano-
materials/nanostructures, which possess the advantages of
mild reaction conditions (i.e., ambient temperature and pres-
sure, and neutral or near-neutral pH), high selectivity, control-
lability, atom economy, and environmental friendliness, etc. It
should be noted that biomimetic synthesis is not the mechan-
ical copying of biological processes. Researchers can appropri-
ately add some non-biological processes, which may be harsh,)
in process biomimetic synthesis. The combination of those
non-biological processes and biological processes for PBS may
bring more convenience and better performance. In this paper,
the five aspects of PBS are discussed according to the differ-
ence of the mimicked biological processes. Biomass-template
biomimetic systems mimic some combined elementary bio-
logical processes, making them facile and effective for the syn-
thesis of sophisticated structures; however, their adjustability
is poor and the products are often relatively onefold. The soft/
hard-combined membrane biomimetic system and liquid
membrane biomimetic system are high-level/intelligent due
to their mimicking of one or more biological unit processes;
thus, they can regulate and control the size, morphology, and
structure of the resultant nanomaterials/nanostructures. This
kind of method is not only mild and controllable but also able
wileyonlinelibrary.com 41
 www.advmat.de
REVIEW
to solve certain issues by conventional methods. For instance, 91122025, 51072134), the State Major Research Plan (973) of China (No.
nano-superstructures are easily obtained, and graphene-like 2011CB932404), and the Nano-Foundation of Shanghai Science and
ultrathin metal films can be prepared under mild conditions. Technology Committee in China (Nos. 0852nm01200, 11 nm0501300).
Moreover, abnormal structure conversion from stable to meta-
stable crystal forms can be realized. However, the synthetic effi-
ciency requires improvement. Living organisms are so far the
smartest PBS systems because they contain multiple higher life
processes. In this system, nano-superstructures and biocom-
patible nanomaterials can be easily obtained, but the detailed
synthesis mechanisms are still unclear. Bio-macromolecule [1]
bioinspired synthesis can dynamically mimic biological pro- [2]
cesses through the interaction between bio-macromolecules [3]
and precursors. Thus, it can mimic different levels of biological [4]
processes to synthesize different levels of nanomaterials/nano- [5]
structures. However, experience and skills are essential for pre-
cise regulation in this biomimetic system. On the whole, the
[6]
reviewed five aspects of PBS show gradually increasing com- [7]
plexity and intelligence, and studies of PBS have undergone a [8]
shift from elementary to smart mimicry.
Though current studies of PBS have involved the mimicking [9]
of all the three levels of biological processes shown in Figure 2,
such research is still far from perfection of real biological sys- [10]
tems and the content of definition and in-depth studies are [11]
necessary to promote the development of PBS. At present, [12]
for process biomimetic synthesis, the mimicking of elemen-
[13]
tary biological processes is much more than that of higher
life processes; it is therefore essential to enhance the mimicry [14]
of various high-level and complex biological processes. From [15]
the perspective of products, the biomimetic synthesis of inor- [16]
ganic nanomaterials/nanostructures is much more than that [17]
of organic nanomaterials/nanostructures. For this reason, the
biomimetic synthesis of various organic nanomaterials/nano- [18]
structures, particularly organic/inorganic hybrid nanomate- [19]
rials/nanostructures, should be further studied. Moreover, bio-
mimetic synthesis mechanisms and artificial regulation should [20]
[21]
be enhanced, and the combination of FBS and PBS should be
explored. [22]
From the above discussions, it can be seen that, compared [23]
with physical methods and chemical methods, process biomi-
metic synthesis shows many unique advantages, and in many [24]
cases, it cannot be substituted or explained by physical and
chemical methods. We therefore suggest that biomimetic (or [25]
biological) methods be classified as the third kind of synthesis [26]
method for nanomaterials/nanostructures in addition to phys-
ical methods and chemical methods.
[27]
To better study process biomimetic synthesis, it is essential to
obtain a good understanding of the essence of biological processes [28]
in organisms. Meanwhile, process biomimetic synthesis may in
turn promote the understanding of biological process mecha-
nisms in organisms. It can be expected that in the near future, [29]
process biomimetic synthesis will eventually be a high-level,
smart, mild, and green method combined with artificial control. [30]
[31]
[32]
Acknowledgements [33]
The authors are grateful to Prof. Yadong Li of Tsinghua University for his
kind help. The authors appreciate the financial support of the National [34]
Natural Science Foundation of China (Nos. 21471114, 20471042,
42 wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.MaterialsViews.com
Received: July 3, 2015
Revised: September 9, 2015
Published online:
C. Sanchez, H. Arribart, M. Guille, Nat. Mater. 2005, 4, 277.
B. Bhushan, Philos. Trans. R. Soc. Ldn., Ser. A 2009, 367, 1445.
Y. Bar-Cohen, Bioinspiration Biomimetics 2006, 1, 1.
T. Douglas, Science 2003, 299, 1192.
A. H. Heuer, D. J. Fink, V. J. Laraia, J. L. Arias, P. D. Calvert,
K. Kendall, G. L. Messing, J. Blackwell, P. C. Rieke,
D. H. Thompson, Science 1992, 255,1098.
K. S. Liu, L. Jiang, Nano Today 2011, 6, 155.
P. Fratzl, F. G. Barth, Nature 2009, 462, 442.
J. F. Vincent, O. A. Bogatyreva, N. R. Bogatyrev, A. Bowyer, A. Pahl,
J. R. Soc. Interfaces 2006, 3, 471.
O. H. Schmitt, presented at Proc. 3rd Int. Biophysics Congress.,
Boston, MA, USA, August 1969.
R. Pfeifer, M. Lungarella, F. Iida, Science 2007, 318, 1088.
M. Ma, L. Guo, D. G. Anderson, R. Langer, Science 2013, 339, 186.
G. Schwartz, B. C. Tee, J. Mei, A. L. Appleton, H. Wang, Z. Bao,
Nat. Commun. 2013, 4, 1859.
C. Wang, D. Hwang, Z. Yu, K. Takei, J. Park, T. Chen, B. Ma,
A. Javey, Nat. Mater. 2013, 12, 899.
S. Bauer, Nat. Mater. 2013.
W. Wu, X. Wen, Z. L. Wang, Science 2013, 340, 952.
A. Chortos, Z. N. Bao, Mater. Today 2014, 17, 321.
M. L. Hammock, A. Chortos, B. Tee, J. Tok, Z. A. Bao, Adv. Mater.
2013, 25, 5997.
M. Ramuz, B. Tee, J. Tok, Z. N. Bao, Adv. Mater. 2012, 24, 3223.
D. J. Lipomi, M. Vosgueritchian, B. Tee, S. L. Hellstrom, J. A. Lee,
C. H. Fox, Z. N. Bao, Nat. Nanotechnol. 2011, 6, 788.
P. X. Ma, Adv. Drug Delivery Rev. 2008, 60, 184.
Z. Tang, Y. Wang, P. Podsiadlo, N. A. Kotov, Adv. Mater. 2006, 18,
3203.
R. Esfand, D. A. Tomalia, Drug Discovery Today 2001, 6, 427.
X. F. Li, T. X. Fan, H. Zhou, S. K. Chow, W. Zhang, D. Zhang,
Q. X. Guo, H. Ogawa, Adv. Funct. Mater. 2009, 19, 45.
J. M. Slocik, A. O. Govorov, R. R. Naik, Angew. Chem. Int. Ed. 2008,
47, 5335.
L. Que, W. B. Tolman, Nature 2008, 455, 333.
Y. S. Nam, A. P. Magyar, D. Lee, J. W. Kim, D. S. Yun, H. Park,
T. S. Pollom, D. A. Weitz, A. M. Belcher, Nat. Nanotechnol. 2010,
5, 340.
M. McCarthy, K. Gerasopoulos, R. Enright, J. N. Culver,
R. Ghodssi, E. N. Wang, Appl. Phys. Lett. 2012, 100.
X. Jin, B. R. Shi, L. C. Zheng, X. H. Pei, X. Y. Zhang, Z. Q. Sun,
Y. Du, J. H. Kim, X. L. Wang, S. X. Dou, K. S. Liu, L. Jiang, Adv.
Funct. Mater. 2014, 24, 2721.
S. Yang, J. Ju, Y. C. Qiu, Y. X. He, X. L. Wang, S. X. Dou, K. S. Liu,
L. Jiang, Small 2014, 10, 294.
Y. Cai, L. Lin, Z. X. Xue, M. J. Liu, S. T. Wang, L. Jiang, Adv. Funct.
Mater. 2014, 24, 809.
P. Guo, Y. M. Zheng, C. C. Liu, J. Ju, L. Jiang, Soft Matter 2012, 8,
1770.
D. Gust, T. A. Moore, A. L. Moore, Acc. Chem. Res. 2001, 34, 40.
K. Kalyanasundaram, M. Graetzel, Curr. Opin. Biotechnol. 2010,
21, 298.
H. Zhou, X. F. Li, T. X. Fan, F. E. Osterloh, J. Ding, E. M. Sabio,
D. Zhang, Q. X. Guo, Adv. Mater. 2010, 22, 951.
Adv. Mater. 2016,
DOI: 10.1002/adma.201503215

www.MaterialsViews.com
[35] N. Nuraje, X. N. Dang, J. F. Qi, M. A. Allen, Y. Lei, A. M. Belcher,
Adv. Mater. 2012, 24, 2885.
[36] C. Zhang, C. Chen, H. Dong, J. Shen, H. Dau, J. Zhao, Science
2015, 348, 690.
[37] X. Xu, N. L. Rosi, Y. Wang, F. Huo, C. A. Mirkin, J. Am. Chem. Soc.
2006, 128, 9286.
[38] A. J. Mastroianni, S. A. Claridge, A. P. Alivisatos, J. Am. Chem. Soc.
2009, 131, 8455.
[39] S. Y. Park, A. K. Lytton-Jean, B. Lee, S. Weigand, G. C. Schatz,
C. A. Mirkin, Nature 2008, 451, 553.
[40] J. Zheng, P. E. Constantinou, C. Micheel, A. P. Alivisatos,
R. A. Kiehl, N. C. Seeman, Nano Lett. 2006, 6, 1502.
[41] J. Sharma, R. Chhabra, A. Cheng, J. Brownell, Y. Liu, H. Yan, Sci-
ence 2009, 323, 112.
[42] E. Munch, M. E. Launey, D. H. Alsem, E. Saiz, A. P. Tomsia,
R. O. Ritchie, Science 2008, 322, 1516.
[43] A. R. Studart, Adv. Mater. 2012, 24, 5024.
[44] T. L. Sun, G. Y. Qing, B. L. Su, L. Jiang, Chem. Soc. Rev. 2011,
40, 2909.
[45] M. K. Kwak, C. Pang, H. Jeong, H. Kim, H. Yoon, H. Jung, K. Suh,
Adv. Funct. Mater. 2011, 21, 3606.
[46] C. Pang, M. K. Kwak, C. Lee, H. E. Jeong, W. G. Bae, K. Y. Suh,
Nano Today 2012, 7, 496.
[47] B. Liu, Y. Cao, Z. Huang, Y. Duan, S. Che, Adv. Mater. 2015, 27,
479.
[48] A. Xu, Y. Ma, H. Cölfen, J. Mater. Chem. 2007, 17, 415.
[49] A. Dey, G. de With, N. Sommerdijk, Chem. Soc. Rev. 2010, 39, 397.
[50] Y. Liu, J. Goebl, Y. Yin, Chem. Soc. Rev. 2013, 42, 2610.
[51] M. H. Kostova, C. Zollfrank, M. Batentschuk, F. Goetz-Neunhoeffer,
A. Winnacker, P. Greil, Adv. Funct. Mater. 2009, 19, 599.
[52] Z. T. Liu, T. X. Fan, D. Zhang, X. L. Gong, J. Q. Xu, Sens. Actuators,
B 2009, 136, 499.
[53] Y. Shin, G. J. Exarhos, Cellulose 2007, 14, 269.
[54] A. S. Deshpande, I. Burgert, O. Paris, Small 2006, 2, 994.
[55] C. R. Rambo, H. Sieber, Adv. Mater. 2005, 17, 1088.
[56] M. Perez-Cabero, V. Puchol, D. Beltran, P. Amoros, Carbon 2008,
46, 297.
[57] Y. N. Fang, J. D. Berrigan, Y. Cai, S. R. Marder, K. H. Sandhage,
J. Mater. Chem. 2012, 22, 1305.
[58] D. Mallick, O. Chakrabarti, D. Bhattacharya, M. Mukherjee,
H. S. Maiti, R. Majumdar, J. Appl. Phys. 2007, 101.
[59] E. Van Eynde, T. Tytgat, M. Smits, S. W. Verbruggen,
B. Hauchecorne, S. Lenaerts, Photochem. Photobiol. Sci. 2013, 12,
690.
[60] Z. Schnepp, W. Yang, M. Antonietti, C. Giordano, Angew. Chem.
Int. Ed. 2010, 49, 6564.
[61] F. Chen, Z. G. Chen, J. C. Qian, C. B. Liu, W. Wang, J. Inorg. Mater.
2012, 27, 69.
[62] V. P. Valtchev, M. Smaihi, A. C. Faust, L. Vidal, Chem. Mater. 2004,
16, 1350.
[63] V. Valtchev, M. Smaihi, A. C. Faust, L. Vidal, Angew. Chem. Int. Ed.
2003, 42, 2782.
[64] S. J. Bao, C. Lei, M. W. Xu, C. J. Cai, D. Z. Jia, Nanotechnology
2012, 23.
[65] X. H. Yang, X. Q. Song, Y. Wei, W. Wei, L. X. Hou, X. J. Fan, Scr.
Mater. 2011, 64, 1075.
[66] D. Bu, H. S. Zhuang, Appl. Surf. Sci. 2013, 265, 677.
[67] D. Bu, H. S. Zhuang, Catal. Commun. 2012, 29, 24.
[68] F. Cao, D. X. Li, Biomed. Mater. 2009, 4.
[69] F. Chen, W. Wang, Z. G. Chen, T. B. Wang, J. Rare Earth. 2012, 30,
350.
[70] Z. S. Guan, Y. Zhang, C. H. Lu, Z. Z. Xu, Chin. J. Chem. 2008, 26,
467.
[71] W. H. Peng, S. M. Zhu, W. L. Wang, W. Zhang, J. J. Gu, X. B. Hu,
D. Zhang, Z. X. Chen, Adv. Funct. Mater. 2012, 22, 2072.
Adv. Mater. 2016, © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/adma.201503215
www.advmat.de
REVIEW
[72] A. R. Maddocks, A. T. Harris, Mater. Lett. 2009, 63, 748.
[73] G. Cook, P. L. Timms, C. Göltner Spickermann, Angew. Chem. Int.
Ed. 2003, 42, 557.
[74] W. Zhang, D. Zhang, T. X. Fan, J. J. Gu, R. Ding, H. Wang,
Q. X. Guo, H. Ogawa, Chem. Mater. 2009, 21, 33.
[75] C. Mille, E. C. Tyrode, R. W. Corkery, Chem. Commun. 2011, 47,
9873.
[76] M. R. Weatherspoon, Y. Cai, M. Crne, M. Srinivasarao, K. H. Sandhage,
Angew. Chem. Int. Ed. 2008, 47, 7921.
[77] Y. Chen, X. Zang, J. Gu, S. Zhu, H. Su, D. Zhang, X. Hu, Q. Liu,
W. Zhang, D. Liu, J. Mater. Chem. 2011, 21, 6140.
[78] Y. Chen, J. Gu, S. Zhu, T. Fan, D. Zhang, Q. Guo, Appl. Phys. Lett.
2009, 94, 53901.
[79] W. Zhang, D. Zhang, T. X. Fan, J. Ding, Q. X. Gu, H. Ogawa, Nano-
technology 2006, 17, 840.
[80] F. C. Meldrum, R. Seshadri, Chem. Commun. 2000, 29.
[81] P. S. Devi, S. Banerjee, S. R. Chowdhury, G. S. Kumar, RSC Adv.
2012, 2, 11578.
[82] Q. Dong, H. L. Su, W. Cao, D. Zhang, Q. X. Guo, Y. J. Lai, J. Solid
State Chem. 2007, 180, 949.
[83] Q. Dong, H. L. Su, D. Zhang, Z. T. Liu, Y. J. Lai, Microporous
Mesoporous Mater. 2007, 98, 344.
[84] Q. Dong, H. L. Su, J. Q. Xu, D. Zhang, R. B. Wang, Mater. Lett.
2007, 61, 2714.
[85] N. N. Song, H. X. Jiang, T. L. Cui, L. L. Chang, X. J. Wang, Micro
Nano Lett. 2012, 7, 943.
[86] R. Mallampati, S. Valiyaveettil, J. Nanosci. Nanotechnol. 2012, 12,
618.
[87] Q. Dong, H. L. Su, D. Zhang, F. Y. Zhang, Nanotechnology 2006,
17, 3968.
[88] Q. Dong, H. L. Su, D. Zhang, N. Zhu, X. Q. Guo, Scr. Mater. 2006,
55, 799.
[89] L. Huang, H. Wang, C. Y. Hayashi, B. Tian, D. Zhao, Y. Yan,
J. Mater. Chem. 2003, 13, 666.
[90] K. Kamata, S. Suzuki, M. Ohtsuka, M. Nakagawa, T. Iyoda,
A. Yamada, Adv. Mater. 2011, 23, 5509.
[91] Q. Dong, H. L. Su, W. Cao, J. Han, D. Zhang, Q. X. Guo, Mater.
Chem. Phys. 2008, 110, 160.
[92] W. Gao, X. Feng, A. Pei, C. R. Kane, R. Tam, C. Hennessy, J. Wang,
Nano Lett. 2013, 14, 305.
[93] H. Hu, W. W. Liu, S. W. Zhu, Y. S. Fan, B. J. Cheng, Acta Chim. Sin.
2012, 70, 2353.
[94] X. B. Zhao, F. Wang, J. C. Qian, Chem. J. Chin. Univ. 2012, 33, 442.
[95] Y. Wang, Z. M. Liu, B. X. Han, Z. Y. Sun, J. M. Du, J. L. Zhang,
T. Jiang, W. Z. Wu, Z. J. Miao, Chem. Commun. 2005, 2948.
[96] Y. C. Miao, Z. B. Zhai, J. A. He, B. Li, J. J. Li, J. Q. Wang, Sci. Eng. C:
Mater. Biol. Appl. 2010, 30, 839.
[97] J. H. He, T. Kunitake, Chem. Mater. 2004, 16, 2656.
[98] W. H. Peng, C. L. Zhu, S. M. Zhu, F. Yao, Y. Li, D. Zhang, J. Mater.
Sci. 2013, 48, 4336.
[99] W. B. Goodwin, I. J. Gomez, Y. N. Fang, J. C. Meredith,
K. H. Sandhage, Chem. Mater. 2013, 25, 4529.
[100] J. C. Qian, F. Chen, X. B. Zhao, Z. G. Chen, J. Nanopart. Res. 2011,
13, 7149.
[101] P. Song, Q. Wang, Z. X. Yang, Sens. Actuators, B 2012, 168, 421.
[102] S. M. Zhu, D. Zhang, J. J. Gu, J. Q. Xu, J. P. Dong, J. L. Li, J. Nano-
part. Res. 2010, 12, 1389.
[103] A. A. Fazil, J. U. Bhanu, A. Amutha, S. Joicy, N. Ponpandian,
S. Amirthapandian, B. K. Panigrahi, P. Thangadurai, Microporous
Mesoporous. Mater. 2015, 212, 91.
[104] Y. Xia, W. K. Zhang, Z. Xiao, H. Huang, H. J. Zeng, X. R. Chen,
F. Chen, Y. P. Gan, X. Y. Tao, J. Mater. Chem. 2012, 22, 9209.
[105] Y. F. Zhao, M. Wei, J. Lu, Z. L. Wang, X. Duan, ACS Nano 2009, 3,
4009.
[106] R. Mallampati, S. Valiyaveettil, Nanoscale 2013, 5, 3395.
wileyonlinelibrary.com 43
 www.advmat.de
REVIEW
[107] F. Cao, D. X. Li, Z. S. Guan, J. Inorg. Mater. 2009, 24, 501.
[108] Z. W. Han, S. C. Niu, W. Li, L. Q. Ren, Appl. Phys. Lett. 2013, 102.
[109] K. C. Meyer, E. N. Coker, D. S. Bolintineanu, B. Kaehr, J. Am. Chem.
Soc. 2014, 136, 13138.
[110] X. Y. Tao, J. Du, Y. C. Yang, Y. P. Li, Y. Xia, Y. P. Gan, H. Huang,
W. K. Zhang, X. D. Li, Cryst. Growth Des. 2011, 11, 4422.
[111] A. Zampieri, G. T. P. Mabande, T. Selvam, W. Schwieger,
A. Rudolph, R. Hermann, H. Sieber, P. Greil, Mater. Sci. Eng. C
2006, 26, 130.
[112] A. Zampieri, S. Kullmann, T. Selvam, J. Bauer, W. Schwieger,
H. Sieber, T. Fey, P. Greil, Microporous Mesoporous. Mater. 2006,
90, 162.
[113] P. Song, Q. Wang, Z. X. Yang, Sens. Actuators, B 2011, 156, 983.
[114] P. Song, Q. Wang, Z. Zhang, Z. X. Yang, Sens. Actuators, B 2010,
147, 248.
[115] F. Cao, D. X. Li, Bioinspiration Biomimetics 2010, 5.
[116] E. Culverwell, S. C. Wimbush, S. R. Hall, Chem. Commun. 2008,
1055.
[117] L. Carreno-Fuentes, J. A. Ascencio, A. Medina, S. Aguila,
L. A. Palomares, O. T. Ramirez, Nanotechnology 2013, 24.
[118] Z. Q. Zhu, Y. N. Zhu, H. Qin, Y. H. Li, Y. P. Liang, H. Deng,
H. L. Liu, Mater. Manuf. Process. 2015, 30, 285.
[119] Y. Xia, W. Zhang, H. Huang, Y. Gan, Z. Xiao, L. Qian, X. Tao,
J. Mater. Chem. 2011, 21, 6498.
[120] S. R. Hall, H. Bolger, S. Mann, Chem. Commun. 2003, 2784.
[121] S. R. Hall, V. M. Swinerd, F. N. Newby, A. M. Collins, S. Mann,
Chem. Mater. 2006, 18, 598.
[122] F. Song, H. L. Su, J. Han, W. M. Lau, W. J. Moon, D. Zhang,
J. Phys. Chem. C 2012, 116, 10274.
[123] R. J. Martin-Palma, C. G. Pantano, A. Lakhtakia, Appl. Phys. Lett.
2008, 93.
[124] C. Yin, S. M. Zhu, Z. X. Chen, W. Zhang, J. J. Gu, D. Zhang,
J. Mater. Chem. A 2013, 1, 8367.
[125] R. J. Park, F. C. Meldrum, Adv. Mater. 2002, 14, 1167.
[126] J. L. Townson, Y. Lin, S. S. Chou, Y. H. Awad, E. N. Coker,
C. J. Brinker, B. Kaehr, Nat. Commun. 2014, 5.
[127] Z. L. Zhang, Q. S. Wu, Y. P. Ding, Inorg. Chem. Commun. 2003, 6,
1393.
[128] M. W. Shao, Z. C. Wu, F. Gao, Y. Ye, X. W. Wei, J. Cryst. Growth
2004, 260, 63.
[129] J. K. Liu, Q. S. Wu, Y. P. Ding, S. Y. Wang, J. Mater. Res. 2004, 19,
2803.
[130] M. Wen, Y. F. Wang, F. Zhang, Q. S. Wu, J. Phys. Chem. C 2009,
113, 5960.
[131] M. Wen, Y. F. Wang, Q. S. Wu, Y. Jin, M. Z. Cheng, J. Colloid Inter-
face Sci. 2010, 342, 229.
[132] J. K. Liu, C. X. Luo, J. D. Wang, X. H. Yang, X. H. Zhong, CrystEng-
Comm 2012, 14, 8714.
[133] X. H. Yang, Q. S. Wu, J. K. Lju, Cryst. Res. Technol. 2007, 42, 211.
[134] J. K. Liu, Q. S. Wu, Y. P. Ding, Chem. Res. Chinese U. 2005, 21, 243.
[135] J. K. Liu, Q. S. Wu, Y. P. Ding, Cryst. Growth Des. 2005, 5, 445.
[136] J. K. Liu, Z. Z. Xu, Q. S. Wu, Nano 2007, 2, 97.
[137] J. K. Liu, Q. S. Wu, Y. P. Ding, J. Cryst. Growth 2005, 279, 410.
[138] J. K. Liu, Q. S. Wu, Y. P. Ding, Eur. J. Inorg. Chem. 2005, 4145.
[139] J. K. Liu, Q. S. Wu, Y. P. Ding, Y. Yi, B. Kor. Chem. Soc. 2004, 25,
1775.
[140] A. Yamauchi, Y. Shin, M. Shinozaki, M. Kawabe, J. Membrane Sci.
2000, 170, 1.
[141] B. Q. Yan, Z. D. Nan, Y. Liu, Chin. J. Chem. 2008, 26, 2302.
[142] J. K. Liu, Q. S. Wu, Y. P. Ding, B. Wang, Chem. J. Chin. Univ. 2003,
24, 2147.
[143] Y. Wang, Q. S. Wu, Y. P. Ding, J. Nanopart. Res. 2004, 6, 253.
[144] J. K. Liu, Q. S. Wu, Y. P. Ding, Chinese J. Inorg. Chem. 2003, 19,
1322.
44 wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.MaterialsViews.com
[145] J. K. Liu, Q. S. Wu, Y. P. Ding, Acta Phys.-Chim. Sin. 2004, 20, 221.
[146] Q. S. Wu, J. K. Liu, Y. P. Ding, Q. Liu, Acta Chim. Sin. 2003, 61,
1824.
[147] X. H. Yang, X. D. Chen, J. K. Liu, Y. Lu, Q. S. Wu, Rare Met. Mater.
Eng. 2009, 38, 532.
[148] L. Liu, Q. S. Wu, Y. P. Ding, H. J. Liu, Cryst. Res. Technol. 2006, 41,
27.
[149] H. Duan, N. Yan, R. Yu, C. Chang, G. Zhou, H. Hu, H. Rong,
Z. Niu, J. Mao, H. Asakura, Nat. Commun. 2014, 5, 3093.
[150] J. Zhao, Q. Deng, A. Bachmatiuk, G. Sandeep, A. Popov, J. Eckert,
M. H. Rümmeli, Science 2014, 343, 1228.
[151] X. H. Yang, J. Guang, Q. S. Wu, Mater. Technol. 2008, 23, 100.
[152] M. M. Li, Q. S. Wu, J. L. Shi, Mater. Technol. 2009, 24, 108.
[153] M. M. Li, Q. S. Wu, J. L. Shi, Mater. Technol. 2009, 24, 108.
[154] N. N. Li, US 3410794, 1968.
[155] R. A. Bartsch, J. D. Way, presented at ACS Symp. Ser., Washington
DC, USA, May 1996.
[156] Q. Wu, N. Zheng, Y. Li, Y. Ding, J. Membrane Sci. 2000, 172, 199.
[157] L. Liu, Q. S. Wu, Y. P. Ding, H. J. Liu, B. Q. Zhang, Chin. J. Chem.
2004, 22, 441.
[158] L. Liu, Q. S. Wu, Y. P. Ding, H. J. Liu, B. Q. Zhang, Colloids Surf., A
2004, 240, 135.
[159] H. J. Liu, Q. S. Wu, Y. P. Ding, L. Liu, Acta Chim. Sin. 2004, 62, 946.
[160] L. Liu, Q. S. Wu, Y. P. Ding, H. J. Liu, J. Y. Qi, Q. A. Liu, Aust. J.
Chem. 2004, 57, 219.
[161] L. Liu, Q. S. Wu, Y. P. Ding, H. J. Liu, Chin. Chem. Lett. 2005, 16,
375.
[162] T. Hirai, N. Okamoto, I. Komasawa, AIChE J. 1998, 44, 197.
[163] T. Hirai, N. Okamoto, I. Komasawa, J. Chem. Eng. Jpn 1998, 31,
474.
[164] T. Hirai, N. Okamoto, I. Komasawa, Langmuir 1998, 14, 6648.
[165] T. Hirai, J. Kobayashi, I. Komasawa, J. Chem. Eng. Jpn 1998, 31,
787.
[166] S. Nishihama, T. Hirai, I. Komasawa, J. Mater. Chem. 2002, 12,
1053.
[167] T. Hirai, T. Orikoshi, I. Komasawa, Chem. Mater. 2002, 14, 3576.
[168] T. Hirai, T. Hirano, I. Komasawa, J. Colloid Interface Sci. 2002, 253,
62.
[169] T. Hirai, T. Orikoshi, J. Colloid Interface Sci. 2004, 273, 470.
[170] T. Hirai, T. Orikoshi, J. Colloid Interface Sci. 2004, 269, 103.
[171] R. J. Davey, T. Hirai, J. Cryst. Growth 1997, 171, 318.
[172] Q. H. Sun, Y. L. Deng, J. Colloid Interface Sci. 2004, 278, 376.
[173] T. Hirai, T. Hirano, I. Komasawa, J. Mater. Chem. 2000, 10, 2306.
[174] M. Ge, C. S. Guo, L. Li, B. Q. Zhang, Y. C. Feng, Y. Q. Wang, Mater.
Lett. 2009, 63, 1269.
[175] S. Supakanapitak, V. Boonamnuayvitaya, S. Jarudilokkul, Mater.
Charact. 2012, 67, 83.
[176] T. Hirai, Y. Kawamura, I. Komasawa, J. Colloid Interface Sci. 2004,
275, 508.
[177] T. Hirai, Y. Kawamura, J. Phys. Chem. B 2004, 108, 12763.
[178] T. Hirai, Y. Kawamura, J. Phys. Chem. B 2005, 109, 5569.
[179] T. Hirai, Y. Kondo, J. Phys. Chem. C 2007, 111, 168.
[180] T. Hirai, M. Hodono, I. Komasawa, Langmuir 2000, 16, 955.
[181] T. Hirai, M. Hodono, I. Komasawa, Langmuir 2000, 16, 8213.
[182] T. Hirai, J. Kobayashi, I. Komasawa, Langmuir 1999, 15, 6291.
[183] S. Jarudilokkul, W. Tanthapanichakoon, V. Boonamnuayvittaya,
Colloids Surf., A 2007, 296, 149.
[184] J. F. Collawn, Z. Bebök, Curr. Top. Membr. 2008, 61, 1.
[185] S. A. Dergunov, A. G. Richter, M. D. Kim, S. V. Pingali, V. S. Urban,
E. Pinkhassik, Chem. Commun. 2013, 49, 11026.
[186] C. A. McKelvey, E. W. Kaler, J. Colloid Interface Sci. 2002, 245, 68.
[187] D. C. Danila, L. T. Banner, E. J. Karimova, L. Tsurkan, X. Wang,
E. Pinkhassik, Angew. Chem. Int. Ed. 2008, 47, 7036.
[188] S. Tekobo, E. Pinkhassik, Chem. Commun. 2009, 1112.
Adv. Mater. 2016,
DOI: 10.1002/adma.201503215

www.MaterialsViews.com
[189] S. A. Dergunov, E. Pinkhassik, Angew. Chem. Int. Ed. 2008, 47,
8264.
[190] S. A. Dergunov, B. Miksa, B. Ganus, E. Lindner, E. Pinkhassik,
Chem. Commun. 2010, 46, 1485.
[191] J. F. P. Da Silva Gomes, A. F. Sonnen, A. Kronenberger, J. Fritz,
M. A. Neto Coelho, D. Fournier, C. Fournier-Noel, M. Mauzac,
M. Winterhalter, Langmuir 2006, 22, 7755.
[192] S. Tekobo, A. G. Richter, S. A. Dergunov, S. V. Pingali, V. S. Urban,
B. Yan, E. Pinkhassik, J. Nanopart. Res. 2011, 13, 6427.
[193] S. A. Dergunov, K. Kesterson, W. Li, Z. Wang, E. Pinkhassik, Mac-
romolecules 2010, 43, 7785.
[194] S. N. Shmakov, E. Pinkhassik, Chem. Commun. 2010, 46, 7346.
[195] N. M. Kocherginsky, Q. Yang, L. Seelam, Sep. Purif. Technol. 2007,
53, 171.
[196] D. M. Sun, Q. S. Wu, Y. P. Ding, J. Inorg. Mater. 2004, 19, 487.
[197] D. M. Sun, Q. S. Wu, Y. Zhu, Y. P. Ding, Acta Chim. Sin. 2005, 63,
1479.
[198] S. M. Duan, Q. S. Wu, R. P. Jia, X. B. Liu, J. Nanopart. Res. 2008,
10, 525.
[199] F. Q. Dong, Q. S. Wu, Appl. Phys. A: Mater. Sci. Process. 2008, 91,
161.
[200] Q. C. Chen, Q. S. Wu, Micro Nano Lett. 2011, 6, 150.
[201] D. M. Sun, Q. S. Wu, Chin. J. Chem. 2004, 22, 1067.
[202] D. M. Sun, Q. S. Wu, Y. P. Ding, J. Appl. Crystallogr. 2006, 39, 544.
[203] Q. S. Wu, D. M. Sun, H. J. Liu, Y. P. Ding, Cryst. Growth Des. 2004,
4, 717.
[204] F. Q. Dong, Q. S. Wu, Y. P. Ding, J. Alloys Compd. 2009, 476, 571.
[205] F. Q. Dong, Q. S. Wu, D. M. Sun, Y. P. Ding, J. Mater. Sci. 2008,
43, 2970.
[206] D. M. Sun, D. Z. Zhu, Q. S. Wu, J. Chem. Crystallogr. 2008, 38, 949.
[207] X. H. Yang, Q. S. Wu, L. Li, Y. P. Ding, G. X. Zhang, Colloids Surf.,
A 2005, 264, 172.
[208] Y. Chen, Q. S. Wu, Y. Dingibi, Eur. J. Inorg. Chem. 2007, 4906.
[209] S. Vaucher, J. Fielden, M. Li, E. Dujardin, S. Mann, Nano Lett.
2002, 2, 225.
[210] Q. Gong, X. Qian, X. Ma, Z. Zhu, Cryst. Growth Des. 2006, 6, 1821.
[211] J. H. Schulman, W. Stoeckenius, L. M. Prince, J. Phys. Chem. 1959
, 63, 1677.
[212] S. H. Kang, I. Hirasawa, W. S. Kim, C. K. Choi, J. Colloid Interface
Sci. 2005, 288, 496.
[213] A. K. Sugih, D. Shukla, H. J. Heeres, A. Mehra, Nanotechnology
2007, 18.
[214] N. Wang, X. Q. Wang, L. J. Yang, H. S. Chen, Micro Nano Lett.
2013, 8, 94.
[215] M. Harada, S. Itakura, A. Shioi, M. Adachi, Langmuir 2001, 17,
4189.
[216] L. L. Wang, G. W. Jia, Y. S. Xu, Chin. J. Inorg. Chem. 2005, 21,
1505.
[217] L. Yao, G. Y. Xu, W. L. Dou, Y. Bai, Colloids Surf., A 2008, 316, 8.
[218] C. Lai, S. Q. Tang, Y. J. Wang, K. Wei, Mater. Lett. 2005, 59, 210.
[219] C. Lai, S. Q. Tang, Y. J. Wang, K. Wei, S. Y. Zhang, Synth. React.
Inorg. Met.-Org. Nano-Met. Chem. 2005, 35, 717.
[220] S. Sadasivan, D. Khushalani, S. Mann, Chem. Mater. 2005, 17,
2765.
[221] C. Lai, Y. J. Wang, K. Wei, Colloids Surf., A 2008, 315, 268.
[222] D. Singha, N. Barman, K. Sahu, J. Colloid Interface Sci. 2014, 413,
37.
[223] A. E. Hart, D. B. Akers, S. Gorosh, C. L. Kitchens, J. Supercrit.
Fluids 2013, 79, 236.
[224] A. A. Revina, M. A. Kuznetsov, S. A. Busev, O. A. Boeva,
K. N. Zhavoronkova, Prot. Met. Phys. Chem. Surf. 2013, 49, 471.
[225] T. Yu, T. Koh, B. Lim, J. Nanosci. Nanotechnol. 2013, 13, 3250.
[226] W. G. Menezes, V. Zielasek, K. Thiel, A. Hartwig, M. Baumer,
J. Catal. 2013, 299, 222.
Adv. Mater. 2016, © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/adma.201503215
www.advmat.de
REVIEW
[227] J. Z. Jiang, Y. N. He, L. P. Wan, Z. Cui, Z. G. Cui, P. G. Jessop,
Chem. Commun. 2013, 49, 1912.
[228] F. Heshmatpour, R. Abazari, S. Balalaie, Tetrahedron 2012, 68,
3001.
[229] S. Y. Zhang, Y. Zhao, Langmuir 2012, 28, 3606.
[230] R. Whiffen, D. J. Jovanovic, Z. Antic, B. Bartova, D. Milivojevic,
M. D. Dramicanin, M. G. Brik, J. Lumin. 2014, 146, 133.
[231] N. Zhang, J. W. Shi, S. S. Mao, L. J. Guo, Chem. Commun. 2014,
50, 2002.
[232] O. D. Bekasova, A. A. Revina, A. L. Rusanov, E. S. Kornienko,
B. I. Kurganov, Radiat. Phys. Chem. 2013, 92, 87.
[233] H. R. Shakur, Physica E 2011, 44, 641.
[234] H. G. Manyar, P. Iliade, L. Bertinetti, S. Coluccia, G. Berlier, J. Col-
loid Interface Sci. 2011, 354, 511.
[235] J. Mao, X. L. Li, W. J. Qin, K. Y. Niu, J. Yang, T. Ling, X. W. Du,
Langmuir 2010, 26, 13755.
[236] Q. Qiu, Z. K. Luo, Rare Met. Mater. Eng. 2010, 392, 157.
[237] T. V. Gavrilovic, D. J. Jovanovic, V. Lojpur, M. D. Dramicanin, Sci.
Rep. 2014, 4.
[238] L. Matejova, V. Vales, R. Fajgar, Z. Matej, V. Holy, O. Solcova,
J. Solid State Chem. 2013, 198, 485.
[239] T. Ahmad, I. Rhee, S. Hong, Y. Chang, J. Lee, J. Korean Phys. Soc.
2010, 57, 1545.
[240] J. Chandradass, D. S. Bae, K. H. Kim, J. Non-Cryst. Solids 2009,
355, 2429.
[241] M. Bellusci, A. La Barbera, L. Seralessandri, F. Padella, A. Piozzi,
F. Varsano, Polym. Int. 2009, 58, 1142.
[242] J. Chandradass, K. H. Kim, J. Cryst. Growth 2009, 311, 3631.
[243] M. Yuasa, T. Masaki, T. Kida, K. Shimanoe, N. Yamazoe, Sens.
Actuators, B 2009, 136, 99.
[244] G. Bahmanrokh, M. Hashim, N. Soltani, I. Ismail, P. Vaziri,
M. Navaseri, M. Erfani, S. Kanagesan, Mater. Res. Bull. 2013, 48,
4039.
[245] N. W. Zheng, Q. S. Wu, Y. P. Ding, Y. D. Li, Chem. Lett. 2000, 638.
[246] Q. S. Wu, N. W. Zheng, Y. P. Ding, Chem. J. Chin. Univ. 2001, 22,
898.
[247] Q. S. Wu, N. W. Zheng, Y. P. Ding, Y. D. Li, Inorg. Chem. Commun.
2002, 5, 671.
[248] Y. Chen, Q. S. Wu, Y. P. Ding, Nano 2007, 2, 195.
[249] X. H. Yang, Q. S. Wu, Y. P. Ding, G. X. Zhang, Rare Met. Mater.
Eng. 2006, 35, 959.
[250] Y. Chen, Q. S. Wu, R. H. Yin, Y. P. Ding, J. Nanopart. Res. 2007, 9,
283.
[251] Y. Chen, Q. S. Wu, Colloids Surf., A 2008, 325, 33.
[252] X. H. Yang, Q. S. Wu, Y. P. Ding, J. K. Liu, B. Kor. Chem. Soc. 2006,
27, 377.
[253] L. Y. Cheng, Y. Chen, Q. S. Wu, Acta Chim. Sin. 2007, 65, 1851.
[254] L. Li, Q. S. Wu, Y. P. Ding, P. M. Wang, Mater. Lett. 2005, 59, 1623.
[255] Q. S. Wu, G. X. Zhang, Y. P. Ding, J. Nanopart. Res. 2006, 8, 737.
[256] Y. Chiu, M. H. Huang, J. Phys. Chem. C 2009, 113, 6056.
[257] S. H. Yu, H. Cölfen, M. Antonietti, Chem. Eur. J. 2002, 8, 2937.
[258] H. Shi, L. Qi, J. Ma, H. Cheng, B. Zhu, Adv. Mater. 2003, 15, 1647.
[259] H. Shi, L. Qi, J. Ma, H. Cheng, J. Am. Chem. Soc. 2003, 125, 3450.
[260] H. Shi, X. Wang, N. Zhao, L. Qi, J. Ma, J. Phys. Chem. B 2006, 110,
748.
[261] F. Gu, Z. Wang, D. Han, G. Guo, H. Guo, Cryst. Growth Des. 2007,
7, 1452.
[262] S. Yang, Z. Lin, N. Shi, L. Jin, M. Yu, L. Xie, M. Yi, W. Huang, Cryst-
EngComm 2015, 17, 1448.
[263] F. Becerra, J. Soltero, J. E. Puig, P. C. Schulz, J. Esquena, C. Solans,
Colloid Polym. Sci. 2003, 282, 103.
[264] D. Schüler, R. B. Frankel, Appl. Microbiol. Biotechnol. 1999, 52, 464.
[265] Y. Yan, Q. S. Wu, L. Li, Y. P. Ding, Cryst. Growth Des. 2006, 6, 769.
[266] D. Z. Zhu, D. M. Sun, Q. S. Wu, J. Exp. Nanosci. 2011, 6, 622.
wileyonlinelibrary.com 45
 www.advmat.de
REVIEW
[267] L. Li, Q. S. Wu, Y. P. Ding, Nanotechnology 2004, 15, 1877.
[268] P. Chen, Q. S. Wu, X. H. Yang, J. Nanopart. Res. 2010, 12, 1561.
[269] J. L. Gardea-Torresdey, J. G. Parsons, E. Gomez, J. Peralta-Videa,
H. E. Troiani, P. Santiago, M. J. Yacaman, Nano Lett. 2002, 2, 397.
[270] N. C. Sharma, S. V. Sahi, S. Nath, J. G. Parsons, J. L. Gardea-Torresde,
T. Pal, Environ. Sci. Technol. 2007, 41, 5137.
[271] S. S. Shankar, A. Ahmad, R. Pasricha, M. Sastry, J. Mater. Chem.
2003, 13, 1822.
[272] O. K. Zahr, A. S. Blum, Nano Lett. 2012, 12, 629.
[273] K. M. Bromley, A. J. Patil, A. W. Perriman, G. Stubbs, S. Mann,
J. Mater. Chem. 2008, 18, 4796.
[274] C. Radloff, R. A. Vaia, J. Brunton, G. T. Bouwer, V. K. Ward, Nano
Lett. 2005, 5, 1187.
[275] Y. Huang, C. Chiang, S. K. Lee, Y. Gao, E. L. Hu, J. D. Yoreo,
A. M. Belcher, Nano Lett. 2005, 5, 1429.
[276] Y. Lee, J. Kim, D. S. Yun, Y. S. Nam, Y. Shao-Horn, A. M. Belcher,
Energy Environ. Sci. 2012, 5, 8328.
[277] B. Kaehr, C. J. Brinker, Chem. Commun. 2010, 46, 5268.
[278] P. Chen, Q. S. Wu, Y. P. Ding, J. Nanopart. Res. 2008, 10, 207.
[279] J. L. Gardea-Torresdey, E. Gomez, J. R. Peralta-Videa, J. G. Parsons,
H. Troiani, M. Jose-Yacaman, Langmuir 2003, 19, 1357.
[280] D. Alloyeau, B. Stephanidis, X. Zhao, E. Larquet, N. Boisset,
C. Ricolleau, J. Phys. Chem. C 2011, 115, 20926.
[281] X. H. Yang, Q. S. Wu, P. Chen, J. Exp. Nanosci. 2008, 3, 215.
[282] L. Li, Q. S. Wu, Y. P. Ding, P. Li, Sci. China Ser. B 2004, 47, 507.
[283] C. X. Yang, A. K. Manocchi, B. Lee, H. M. Yi, J. Mater. Chem. 2011,
21, 187.
[284] J. S. Lim, S. M. Kim, S. Y. Lee, E. A. Stach, J. N. Culver, M. T. Harris,
Nano Lett. 2010, 10, 3863.
[285] C. X. Yang, H. M. Yi, Biochem. Eng. J. 2010, 52, 160.
[286] S. Y. Lee, E. Royston, J. N. Culver, M. T. Harris, Nanotechnology
2005, 16, S435.
[287] R. G. Haverkamp, A. T. Marshall, D. van Agterveld, J. Nanopart.
Res 2007, 9, 697.
[288] M. Knez, A. M. Bittner, F. Boes, C. Wege, H. Jeske, E. Maiss,
K. Kern, Nano Lett. 2003, 3, 1079.
[289] M. Kobayashi, M. Seki, H. Tabata, Y. Watanabe, I. Yamashita, Nano
Lett. 2010, 10, 773.
[290] M. Kobayashi, K. Onodera, Y. Watanabe, I. Yamashita, Chem. Lett.
2010, 39, 616.
[291] C. Mao, D. J. Solis, B. D. Reiss, S. T. Kottmann, R. Y. Sweeney,
A. Hayhurst, G. Georgiou, B. Iverson, A. M. Belcher, Science 2004,
303, 213.
[292] J. S. Lim, S. M. Kim, S. Y. Lee, E. A. Stach, J. N. Culver, M. T. Harris,
J. Nanomater. 2010.
[293] R. Tsukamoto, M. Muraoka, M. Seki, H. Tabata, I. Yamashita,
Chem. Mater. 2007, 19, 2389.
[294] J. H. Liu, X. L. Zhang, S. M. Li, M. Yu, Appl. Surf. Sci. 2011, 257, 2383.
[295] W. He, J. J. Cui, Y. Z. Yue, X. D. Zhang, X. Xia, H. Liu, S. W. Lui,
J. Colloid Interface Sci. 2011, 354, 109.
[296] J. J. Cui, W. He, H. T. Liu, S. J. Liao, Y. Z. Yue, Colloids Surf.,
B. 2009, 74, 274.
[297] H. Zhou, T. X. Fan, J. Ding, D. Zhang, Q. X. Guo, Opt. Express
2012, 20, A340.
[298] P. Y. Chen, X. N. Dang, M. T. Klug, N. Courchesne, J. F. Qi,
M. N. Hyder, A. M. Belcher, P. T. Hammond, Chem. Mater. 2015,
27, 1531.
[299] P. Y. Chen, R. Ladewski, R. Miller, X. N. Dang, J. F. Qi, F. Liau,
A. M. Belcher, P. T. Hammond, J. Mater. Chem. A 2013, 1, 2217.
[300] P. Y. Chen, X. N. Dang, M. T. Klug, J. F. Qi, N. Courchesne,
F. J. Burpo, N. Fang, P. T. Hammond, A. M. Belcher, ACS Nano
2013, 7, 6563.
[301] X. N. Dang, H. J. Yi, M. H. Ham, J. F. Qi, D. S. Yun, R. Ladewski,
M. S. Strano, P. T. Hammond, A. M. Belcher, Nat. Nanotechnol.
2011, 6, 377.
46 wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.MaterialsViews.com
[302] W. J. Zhou, W. He, J. Y. Ma, M. T. Wang, X. D. Zhang, S. P. Yan,
X. Y. Tian, X. A. Sun, X. X. Han, Mater. Sci. Eng. C: Mater. Biol.
Appl. 2009, 29, 1893.
[303] L. Yang, W. S. Guan, B. Bai, Q. Xu, Y. Xiang, J. Alloys Compd. 2010,
504, L10.
[304] K. T. Nam, D. Kim, P. J. Yoo, C. Chiang, N. Meethong,
P. T. Hammond, Y. Chiang, A. M. Belcher, Science 2006, 312, 885.
[305] D. Oh, J. F. Qi, B. H. Han, G. R. Zhang, T. J. Carney, J. Ohmura,
Y. Zhang, Y. Shao-Horn, A. M. Belcher, Nano Lett. 2014, 14, 4837.
[306] E. Pomerantseva, K. Gerasopoulos, X. Y. Chen, G. Rubloff,
R. Ghodssi, J. Power Sources 2012, 206, 282.
[307] B. Neltner, B. Peddie, A. Xu, W. Doenlen, K. Durand, D. S. Yun,
S. Speakman, A. Peterson, A. Belcher, ACS Nano 2010, 4, 3227.
[308] W. J. Zhou, W. He, X. D. Zhang, S. P. Yan, X. A. Sun, X. Y. Tian,
X. X. Han, Powder Technol. 2009, 194, 106.
[309] W. J. Zhou, W. He, X. D. Zhang, H. S. Zhao, Z. M. Li, S. P. Yan,
X. Y. Tian, X. N. Sun, X. X. Han, Mater. Chem. Phys. 2009, 116, 319.
[310] Y. J. Lee, A. M. Belcher, J. Mater. Chem. 2011, 21, 1033.
[311] M. Moradi, Z. Li, J. F. Qi, W. T. Xing, K. Xiang, Y. M. Chiang,
A. M. Belcher, Nano Lett. 2015, 15, 2917.
[312] M. J. Huang, Y. J. Wang, J. Mater. Chem. 2012, 22, 626.
[313] X. Y. Tian, W. He, J. J. Cui, X. D. Zhang, W. J. Zhou, S. P. Yan,
X. N. Sun, X. X. Han, S. S. Han, Y. Z. Yue, J. Colloid Interface Sci.
2010, 343, 344.
[314] P. Chen, Q. S. Wu, Y. P. Ding, P. S. Yuan, Bull. Mat. Sci. 2008, 31,
603.
[315] D. M. Sun, D. Z. Zhu, Q. S. Wu, J. Mater. Res. 2009, 24, 347.
[316] S. Lee, C. Mao, C. E. Flynn, A. M. Belcher, Science 2002, 296, 892.
[317] H. Zhou, T. X. Fan, T. Han, X. F. Li, J. Ding, D. Zhang, Q. X. Guo,
H. Ogawa, Nanotechnology 2009, 20.
[318] Q. S. Wu, N. W. Zheng, Y. P. Ding, Y. D. Li, Chem. J. Chin. Univ.
2000, 21, 1471.
[319] P. Chen, Q. S. Wu, Y. P. Ding, Mater. Lett. 2008, 62, 3254.
[320] A. Mueller, F. J. Eber, C. Azucena, A. Petershans, A. M. Bittner,
H. Gliemann, H. Jeske, C. Wege, ACS Nano 2011, 5, 4512.
[321] Z. W. Niu, M. A. Bruckman, S. Q. Li, L. A. Lee, B. Lee, S. V. Pingali,
P. Thiyagarajan, Q. Wang, Langmuir 2007, 23, 6719.
[322] S. Y. Lee, J. N. Culver, M. T. Harris, J. Colloid Interface Sci. 2006,
297, 554.
[323] F. K. Wang, B. R. Cao, C. B. Mao, Chem. Mater. 2010, 22, 3630.
[324] C. Mao, C. E. Flynn, A. Hayhurst, R. Sweeney, J. Qi, G. Georgiou,
B. Iverson, A. M. Belcher, Proc. Natl. Acad. Sci. USA 2003, 100,
6946.
[325] L. Li, Q. S. Wu, Y. P. Ding, Can. J. Chem. 2006, 84, 782.
[326] S. Li, D. M. Sun, Q. S. Wu, Y. P. Ding, Cryst. Res. Technol. 2008, 43,
740.
[327] B. Bekesiova, S. Hraska, J. Libantova, J. Moravcikova,
I. Matusikova, Mol. Biol. Rep. 2008, 35, 579.
[328] T. J. Zhang, W. Wang, D. Y. Zhang, X. X. Zhang, Y. R. Ma,
Y. L. Zhou, L. M. Qi, Adv. Funct. Mater. 2010, 20, 1152.
[329] D. Y. Zhang, L. M. Qi, Chem. Commun. 2005, 2735.
[330] N. Courchesne, M. T. Klug, P. Y. Chen, S. E. Kooi, D. S. Yun,
N. Hong, N. X. Fang, A. M. Belcher, P. T. Hammond, Adv. Mater.
2014, 26, 3398.
[331] G. Falini, S. Albeck, S. Weiner, L. Addadi, Science 1996, 271, 67.
[332] A. M. Belcher, X. H. Wu, R. J. Christensen, P. K. Hansma,
G. D. Stucky, D. E. Morse, Nature 1996, 381, 56.
[333] J. Aizenberg, G. Lambert, L. Addadi, S. Weiner, Adv. Mater. 1996, 8,
222.
[334] N. Kroger, S. Lorenz, E. Brunner, M. Sumper, Science 2002, 298,
584.
[335] N. Kroger, R. Deutzmann, M. Sumper, Science 1999, 286, 1129.
[336] N. Kroger, R. Deutzmann, C. Bergsdorf, M. Sumper, Proc. Natl
Acad. Sci. USA 2000, 97, 14133.
[337] N. Sommerdijk, G. de With, Chem. Rev. 2008, 108, 4499.
Adv. Mater. 2016,
DOI: 10.1002/adma.201503215

www.MaterialsViews.com
[338] F. C. Meldrum, H. Colfen, Chem. Rev. 2008, 108, 4332.
[339] L. B. Gower, Chem. Rev. 2008, 108, 4551.
[340] Y. X. Gao, S. H. Yu, H. P. Cong, J. Jiang, A. W. Xu, W. F. Dong,
H. Colfen, J. Phys. Chem. B 2006, 110, 6432.
[341] M. Lei, W. H. Tang, J. G. Yu, Mater. Res. Bull. 2005, 40, 656.
[342] L. M. Qi, J. Li, J. M. Ma, Chem. J. Chin. Univ. 2002, 23, 1595.
[343] L. M. Qi, J. Li, J. M. Ma, Adv. Mater. 2002, 14, 300.
[344] H. Colfen, L. M. Qi, Chem. Eur. J. 2001, 7, 106.
[345] D. Moll, C. Huber, B. Schlegel, D. Pum, U. B. Sleytr, M. Sára, Proc.
Natl. Acad. Sci. USA 2002, 99, 14646.
[346] N. D. Chasteen, P. M. Harrison, J. Struct. Biol. 1999, 126, 182.
[347] Y. Suzumoto, M. Okuda, I. Yamashita, Cryst. Growth Des. 2012, 12,
4130.
[348] I. Yamashita, J. Hayashi, M. Hara, Chem. Lett. 2004, 33, 1158.
[349] K. Iwahori, K. Yoshizawa, M. Muraoka, I. Yamashita, Inorg. Chem.
2005, 44, 6393.
[350] K. Iwahori, T. Enomoto, H. Furusho, A. Miura, K. Nishio,
Y. Mishima, I. Yamashita, Chem. Mater. 2007, 19, 3105.
[351] M. Li, C. Viravaidya, S. Mann, Small 2007, 3, 1477.
[352] R. Fan, S. W. Chew, V. V. Cheong, B. P. Orner, Small 2010, 6, 1483.
[353] O. Kasyutich, A. Ilari, A. Fiorillo, D. Tatchev, A. Hoell, P. Ceci,
J. Am. Chem. Soc. 2010, 132, 3621.
[354] R. M. Kramer, C. Li, D. C. Carter, M. O. Stone, R. R. Naik, J. Am.
Chem. Soc. 2004, 126, 13282.
[355] M. Suzuki, M. Abe, T. Ueno, S. Abe, T. Goto, Y. Toda, T. Akita,
Y. Yamada, Y. Watanabe, Chem. Commun. 2009, 4871.
[356] P. Sánchez, E. Valero, N. Gálvez, J. M. Domínguez-Vera,
M. Marinone, G. Poletti, M. Corti, A. Lascialfari, Dalton Trans.
2009, 800.
[357] M. Okuda, Y. Suzumoto, I. Yamashita, Cryst. Growth Des. 2011, 11,
2540.
[358] R. Tsukamoto, K. Iwahori, M. Muraoka, I. Yamashita, Bull. Chem.
Soc. Jpn. 2005, 78, 2075.
[359] M. Okuda, Y. Kobayashi, K. Suzuki, K. Sonoda, T. Kondoh,
A. Wagawa, A. Kondo, H. Yoshimura, Nano Lett. 2005, 5, 991.
[360] M. Naito, K. Iwahori, A. Miura, M. Yamane, I. Yamashita, Angew.
Chem. Int. Ed. 2010, 49, 7006.
[361] T. Douglas, D. P. Dickson, S. Betteridge, J. Charnock, C. D. Garner,
S. Mann, Science 1995, 269, 54.
[362] M. Okuda, Y. Suzumoto, K. Iwahori, S. Kang, M. Uchida,
T. Douglas, I. Yamashita, Chem. Commun. 2010, 46, 8797.
[363] M. Okuda, K. Iwahori, I. Yamashita, H. Yoshimura, Biotechnol.
Bioeng. 2003, 84, 187.
[364] M. L. Flenniken, D. A. Willits, S. Brumfield, M. J. Young,
T. Douglas, Nano Lett. 2003, 3, 1573.
[365] I. Medalsy, O. Dgany, M. Sowwan, H. Cohen, A. Yukashevska,
S. G. Wolf, A. Wolf, A. Koster, O. Almog, I. Marton, Nano Lett.
2008, 8, 473.
[366] K. Wong, T. Douglas, S. Gider, D. D. Awschalom, S. Mann, Chem.
Mater. 1998, 10, 279.
[367] H. Fukano, T. Takahashi, M. Aizawa, H. Yoshimura, Inorg. Chem.
2011, 50, 6526.
[368] N. Gálvez, E. Valero, M. Ceolin, S. Trasobares, M. López-Haro,
J. J. Calvino, J. M. Domínguez-Vera, Inorg. Chem. 2010, 49, 1705.
[369] H. Yoshimura, T. Scheybani, W. Baumeister, K. Nagayama, Lang-
muir 1994, 10, 3290.
[370] C. Gobel, B. Schuster, D. Baurecht, U. B. Sleytr, D. Pum, Colloids
Surf., B 2010, 75, 565.
[371] S. S. Mark, M. Bergkvist, X. Yang, L. M. Teixeira, P. Bhatnagar,
E. R. Angert, C. A. Batt, Langmuir 2006, 22, 3763.
[372] M. M. Shindel, D. R. Mumm, S. Wang, Langmuir 2010, 26, 11103.
[373] S. S. Mark, M. Bergkvist, P. Bhatnagar, C. Welch, A. L. Goodyear,
X. Yang, E. R. Angert, C. A. Batt, Colloids Surf., B 2007, 57, 161.
[374] M. Bergkvist, S. S. Mark, X. Yang, E. R. Angert, C. A. Batt, J. Phys.
Chem. B 2004, 108, 8241.
Adv. Mater. 2016, © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/adma.201503215
www.advmat.de
REVIEW
[375] H. Badelt-Lichtblau, B. Kainz, C. Vollenkle, E. M. Egelseer,
U. B. Sleytr, D. Pum, N. Ilk, Bioconjugate Chem. 2009, 20, 895.
[376] J. Tang, H. Badelt-Lichtblau, A. Ebner, J. Preiner, B. Kraxberger,
H. J. Gruber, U. B. Sleytr, N. Ilk, P. Hinterdorfer, ChemPhysChem
2008, 9, 2317.
[377] S. Howorka, J. Mater. Chem. 2007, 17, 2049.
[378] S. S. Puranik, H. M. Joshi, S. B. Ogale, K. M. Paknikar, J. Nanosci.
Nanotechnol. 2008, 8, 3565.
[379] U. Queitsch, C. Hamann, F. Schaffel, B. Rellinghaus, L. Schultz,
A. Bluher, M. Mertig, J. Phys. Chem. C 2009, 113, 10471.
[380] U. Queitsch, D. Pohl, A. Blüher, M. Mertig, L. Schultz,
B. Rellinghaus, J. Phys. D: Appl. Phys. 2008, 41, 134019.
[381] U. Queitsch, E. Mohn, F. Schäffel, L. Schultz, B. Rellinghaus,
A. Blüher, M. Mertig, Appl. Phys. Lett. 2007, 90, 113114.
[382] R. Huttl, F. Ullrich, G. Wolf, A. Kirchner, P. Lothman,
B. Katzschner, W. Pompe, M. Mertig, Catal. Lett. 2009, 132, 383.
[383] S. S. Mark, M. Bergkvist, X. Yang, E. R. Angert, C. A. Batt, Biomac-
romolecules 2006, 7, 1884.
[384] B. Aichmayer, M. Mertig, A. Kirchner, O. Paris, P. Fratzl, Adv.
Mater. 2006, 18, 915.
[385] Y. Sierra-Sastre, S. Choi, S. T. Picraux, C. A. Batt, J. Am. Chem. Soc.
2008, 130, 10488.
[386] S. Sotiropoulou, Y. Sierra-Sastre, S. S. Mark, C. A. Batt, Chem.
Mater. 2008, 20, 821.
[387] Y. Sierra-Sastre, S. A. Dayeh, S. T. Picraux, C. A. Batt, ACS Nano
2010, 4, 1209.
[388] S. Behrens, W. Habicht, J. Wu, E. Unger, Surf. Interface Anal. 2006,
38, 1014.
[389] S. Behrens, J. Wu, W. Habicht, E. Unger, Chem. Mater. 2004, 16, 3085.
[390] S. Padalkar, K. Schroeder, Y. H. Won, H. S. Jang, L. Stanciu,
J. Nanosci. Nanotechnol. 2012, 12, 227.
[391] D. Li, B. Mathew, C. B. Mao, Small 2012, 8, 3691.
[392] D. Li, X. W. Qu, S. M. C. Newton, P. E. Klebba, C. B. Mao, J. Mater.
Chem. 2012, 22, 15702.
[393] P. Gopinathan, A. M. Ashok, R. Selvakumar, Appl. Surf. Sci. 2013,
276, 717.
[394] C. W. Hsieh, P. Y. Lin, S. C. Hsieh, J. Nanophotonics 2012, 6.
[395] L. G. Zhang, F. M. Gao, J. Nanopart. Res. 2012, 14.
[396] X. F. Zhou, L. F. Zheng, R. Li, B. Li, S. Pillai, P. Xu, Y. Zhang,
J. Mater. Chem. 2012, 22, 8862.
[397] J. Juarez, A. Cambon, A. Topete, P. Taboada, V. Mosquera, Chem.
Eur. J. 2011, 17, 7366.
[398] J. L. Guo, X. L. Wang, X. P. Liao, W. H. Zhanga, B. Shi, J. Phys.
Chem. C 2012, 116, 8188.
[399] G. Xiao, X. Huang, X. P. Liao, B. Shi, J. Phys. Chem. C 2013, 117,
9739.
[400] J. M. Slocik, S. N. Kim, T. A. Whitehead, D. S. Clark, R. R. Naik,
Small 2009, 5, 2038.
[401] J. C. Zhou, X. H. Wang, M. Xue, Z. Xu, T. Hamasaki, Y. Yang,
K. Wang, B. Dunn, Mater. Sci. Eng. 2010, 30, 20.
[402] J. C. Zhou, Y. Gao, A. A. Martinez-Molares, X. Y. Jing, D. Yan,
J. Lau, T. Hamasaki, C. S. Ozkan, M. Ozkan, E. Hu, B. Dunn, Small
2008, 4, 1507.
[403] Y. Yang, B. H. Constance, P. A. Deymier, J. Hoying, S. Raghavan,
B. Zelinski, J. Mater. Sci. 2004, 39, 1927.
[404] R. Kirsch, M. Mertig, W. Pompe, R. Wahl, G. Sadowski, K. J. Bohm,
E. Unger, Thin Solid Films 1997, 305, 248.
[405] M. Achermann, S. Jeong, L. Balet, G. A. Montano,
J. A. Hollingsworth, ACS Nano 2011, 5, 1761.
[406] E. D. Spoerke, B. A. Connor, D. V. Gough, B. B. McKenzie,
G. D. Bachand, Part. Part. Syst. Char. 2014, 31, 863.
[407] A. K. Boal, T. J. Headley, R. G. Tissot, B. C. Bunker, Adv. Funct.
Mater. 2004, 14, 19.
[408] S. Behrens, W. Habicht, K. Wagner, E. Unger, Adv. Mater. 2006, 18,
284.
wileyonlinelibrary.com 47
 www.advmat.de
REVIEW
[409] S. Behrens, K. Rahn, W. Habicht, K. J. Bohm, H. Rosner, E. Dinjus,
E. Unger, Adv. Mater. 2002, 14, 1621.
[410] E. D. Spoerke, A. K. Boal, G. D. Bachand, B. C. Bunker, ACS Nano
2013, 7, 2012.
[411] V. Verma, J. M. Catchmark, N. R. Brown, W. O. Hancock, J. Biol.
Eng. 2012, 6.
[412] R. Bhandari, M. R. Knecht, Langmuir 2012, 28, 8110.
[413] Y. Su, Q. He, X. H. Yan, J. B. Fei, Y. E. Cui, J. B. Li, Chem. Eur. J.
2011, 17, 3370.
[414] R. Bhandari, M. R. Knecht, ACS Catal. 2011, 1, 89.
[415] A. Jakhmola, R. Bhandari, D. B. Pacardo, M. R. Knecht, J. Mater.
Chem. 2010, 20, 1522.
[416] L. Ruan, H. Ramezani-Dakhel, C. Chiu, E. Zhu, Y. Li, H. Heinz,
Y. Huang, Nano Lett. 2013, 13, 840.
[417] C. Chiu, Y. Li, L. Ruan, X. Ye, C. B. Murray, Y. Huang, Nat. Chem.
2011, 3, 393.
[418] S. K. Ramakrishnan, M. Martin, T. Cloitre, L. Firlej, F. J. Cuisinier,
C. Gergely, J. Chem. Inf. Model. 2013, 53, 3273.
[419] H. Heinz, B. L. Farmer, R. B. Pandey, J. M. Slocik, S. S. Patnaik,
R. Pachter, R. R. Naik, J. Am. Chem. Soc. 2009, 131, 9704.
[420] C. R. So, J. L. KulpIII, E. E. Oren, H. Zareie, C. Tamerler, J. S. Evans,
M. Sarikaya, ACS Nano 2009, 3, 1525.
[421] C. R. So, C. Tamerler, M. Sarikaya, Angew. Chem. Int. Ed. 2009, 48,
5174.
[422] M. Hnilova, E. E. Oren, U. O. Seker, B. R. Wilson, S. Collino,
J. S. Evans, C. Tamerler, M. Sarikaya, Langmuir 2008, 24, 12440.
[423] Y. Li, G. P. Whyburn, Y. Huang, J. Am. Chem. Soc. 2009, 131,
15998.
[424] Y. Li, Y. Huang, Adv. Mater. 2010, 22, 1921.
[425] L. M. Forbes, A. P. Goodwin, J. N. Cha, Chem. Mater. 2010, 22,
6524.
[426] J. Kim, Y. Rheem, B. Yoo, Y. Chong, K. N. Bozhilov, D. Kim,
M. J. Sadowsky, H. Hur, N. V. Myung, Acta Biomater. 2010, 6,
2681.
[427] R. R. Naik, P. W. Whitlock, F. Rodriguez, L. L. Brott, D. D. Glawe,
S. J. Clarson, M. O. Stone, Chem. Commun. 2003, 238.
[428] S. V. Patwardhan, N. Mukherjee, M. Steinitz-Kannan, S. J. Clarson,
Chem. Commun. 2003, 1122.
[429] C. A. Mirkin, Inorg. Chem. 2000, 39, 2258.
[430] B. Ding, Z. Deng, H. Yan, S. Cabrini, R. N. Zuckermann, J. Bokor,
J. Am. Chem. Soc. 2010, 132, 3248.
[431] H. Liang, T. E. Angelini, P. V. Braun, G. C. Wong, J. Am. Chem. Soc.
2004, 126, 14157.
[432] J. L. Coffer, S. R. Bigham, X. Li, R. F. Pinizzotto, Y. G. Rho,
R. M. Pirtle, I. L. Pirtle, Appl. Phys. Lett. 1996, 69, 3851.
[433] Y. Yao, Y. Song, L. Wang, Nanotechnology 2008, 19, 405601.
[434] T. Torimoto, M. Yamashita, S. Kuwabata, T. Sakata, H. Mori,
H. Yoneyama, J. Phys. Chem. B 1999, 103, 8799.
[435] D. Nyamjav, A. Ivanisevic, Biomaterials 2005, 26, 2749.
[436] R. Schreiber, S. Kempter, S. Holler, V. Schüller, D. Schiffels,
S. S. Simmel, P. C. Nickels, T. Liedl, Small 2011, 7, 1795.
[437] O. Harnack, W. E. Ford, A. Yasuda, J. M. Wessels, Nano Lett. 2002,
2, 919.
[438] S. Kundu, V. Maheshwari, R. F. Saraf, Langmuir 2008, 24, 551.
[439] A. Wu, W. Cheng, Z. Li, J. Jiang, E. Wang, Talanta 2006, 68, 693.
[440] E. Braun, Y. Eichen, U. Sivan, G. Ben-Yoseph, Nature 1998, 391,
775.
[441] K. Keren, M. Krueger, R. Gilad, G. Ben-Yoseph, U. Sivan, E. Braun,
Science 2002, 297, 72.
[442] G. A. Burley, J. Gierlich, M. R. Mofid, H. Nir, S. Tal, Y. Eichen,
T. Carell, J. Am. Chem. Soc. 2006, 128, 1398.
[443] Z. Deng, C. Mao, Angew. Chem. Int. Ed. 2004, 43, 4068.
[444] J. Richter, R. Seidel, R. Kirsch, M. Mertig, W. Pompe, J. Plaschke,
H. K. Schackert, Adv. Mater. 2000, 12, 507.
48 wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.MaterialsViews.com
[445] J. Richter, M. Mertig, W. Pompe, I. Mönch, H. K. Schackert, Appl.
Phys. Lett. 2001, 78, 536.
[446] Z. Deng, C. Mao, Nano Lett. 2003, 3, 1545.
[447] C. Fang, Y. Fan, J. M. Kong, G. J. Zhang, L. Linn, S. Rafeah, Sens.
Actuators, B 2007, 126, 684.
[448] W. E. Ford, O. Harnack, A. Yasuda, J. M. Wessels, Adv. Mater.
2001, 13, 1793.
[449] M. Mertig, L. Colombi Ciacchi, R. Seidel, W. Pompe, A. De Vita,
Nano Lett. 2002, 2, 841.
[450] Q. Gu, D. T. Haynie, Mater. Lett. 2008, 62, 3047.
[451] H. A. Becerril, P. Ludtke, B. M. Willardson, A. T. Woolley, Langmuir
2006, 22, 10140.
[452] C. F. Monson, A. T. Woolley, Nano Lett. 2003, 3, 359.
[453] H. A. Becerril, R. M. Stoltenberg, D. R. Wheeler, R. C. Davis,
J. N. Harb, A. T. Woolley, J. Am. Chem. Soc. 2005, 127, 2828.
[454] S. Roy, M. Olesiak, S. Shang, M. H. Caruthers, J. Am. Chem. Soc.
2013, 135, 6234.
[455] L. Gao, N. Ma, ACS Nano 2012, 6, 689.
[456] D. Rautaray, A. Kumar, S. Reddy, S. R. Sainkar, M. Sastry, Cryst.
Growth Des. 2002, 2, 197.
[457] Z. Wang, J. Zhang, J. M. Ekman, P. J. Kenis, Y. Lu, Nano Lett. 2010,
10, 1886.
[458] B. Liu, L. Han, S. Che, Angew. Chem. Int. Ed. 2012, 51, 923.
[459] C. Jin, L. Han, S. Che, Angew. Chem. Int. Ed. 2009, 48, 9268.
[460] L. Han, C. Y. Jin, B. Liu, S. N. Che, Chem. Mater. 2012, 24, 504.
[461] M. P. Busson, B. Rolly, B. Stout, N. Bonod, E. Larquet, A. Polman,
S. Bidault, Nano Lett. 2011, 11, 5060.
[462] G. Tikhomirov, S. Hoogland, P. E. Lee, A. Fischer, E. H. Sargent,
S. O. Kelley, Nat. Nanotechnol. 2011, 6, 485.
[463] F. A. Aldaye, H. F. Sleiman, J. Am. Chem. Soc. 2007, 129, 4130.
[464] F. A. Aldaye, H. F. Sleiman, Angew. Chem. Int. Ed. 2006, 45,
2204.
[465] D. Nykypanchuk, M. M. Maye, D. van der Lelie, O. Gang, Nature
2008, 451, 549.
[466] E. Auyeung, J. I. Cutler, R. J. Macfarlane, M. R. Jones, J. Wu, G. Liu,
K. Zhang, K. D. Osberg, C. A. Mirkin, Nat. Nanotechnol. 2012, 7, 24.
[467] M. R. Jones, R. J. Macfarlane, B. Lee, J. Zhang, K. L. Young,
A. J. Senesi, C. A. Mirkin, Nat. Mater. 2010, 9, 913.
[468] S. Pal, Z. T. Deng, B. Q. Ding, H. Yan, Y. Liu, Angew. Chem. Int. Ed.
2010, 49, 2700.
[469] J. D. Le, Y. Pinto, N. C. Seeman, K. Musier-Forsyth, T. A. Taton,
R. A. Kiehl, Nano Lett. 2004, 4, 2343.
[470] X. Shen, C. Song, J. Wang, D. Shi, Z. Wang, N. Liu, B. Ding, J. Am.
Chem. Soc. 2011, 134, 146.
[471] Z. Deng, A. Samanta, J. Nangreave, H. Yan, Y. Liu, J. Am. Chem.
Soc. 2012, 134, 17424.
[472] S. Pal, Z. Deng, H. Wang, S. Zou, Y. Liu, H. Yan, J. Am. Chem. Soc.
2011, 133, 17606.
[473] M. Pilo-Pais, S. Goldberg, E. Samano, T. H. LaBean, G. Finkelstein,
Nano Lett. 2011, 11, 3489.
[474] C. H. Lalander, Y. Zheng, S. Dhuey, S. Cabrini, U. Bach, ACS Nano
2010, 4, 6153.
[475] J. Sharma, R. Chhabra, C. S. Andersen, K. V. Gothelf, H. Yan,
Y. Liu, J. Am. Chem. Soc. 2008, 130, 7820.
[476] J. Zhang, Y. Liu, Y. Ke, H. Yan, Nano Lett. 2006, 6, 248.
[477] A. C. Pearson, J. Liu, E. Pound, B. Uprety, A. T. Woolley,
R. C. Davis, J. N. Harb, J. Phys. Chem. B 2012, 116, 10551.
[478] S. Park, T. A. Taton, C. A. Mirkin, Science 2002, 295, 1503.
[479] A. Kumar, V. Kumar, J. Phys. Chem. C 2008, 112, 3633.
[480] A. Kumar, B. Singh, J. Phys. Chem. C 2013, 117, 5386.
[481] A. Kumar, A. Jakhmola, J. Phys. Chem. C 2009, 113, 9553.
[482] V. Chaudhary, A. K. Bhowmick, J. Nanopart. Res. 2013, 15.
[483] N. Ma, C. J. Dooley, S. O. Kelley, J. Am. Chem. Soc. 2006, 128,
12598.
Adv. Mater. 2016,
DOI: 10.1002/adma.201503215

www.MaterialsViews.com
[484] S. Hinds, B. J. Taft, L. Levina, V. Sukhovatkin, C. J. Dooley,
M. D. Roy, D. D. MacNeil, E. H. Sargent, S. O. Kelley, J. Am. Chem.
Soc. 2006, 128, 64.
[485] L. A. Gugliotti, D. L. Feldheim, B. E. Eaton, Science 2004, 304, 850.
[486] L. A. Gugliotti, D. L. Feldheim, B. E. Eaton, J. Am. Chem. Soc.
2005, 127, 17814.
[487] D. Liu, L. A. Gugliotti, T. Wu, M. Dolska, A. G. Tkachenko,
M. K. Shipton, B. E. Eaton, D. L. Feldheim, Langmuir 2006, 22, 5862.
[488] A. Kumar, A. Jakhmola, Langmuir 2007, 23, 2915.
[489] A. Kumar, B. Singh, Chem. Commun. 2011, 47, 4144.
[490] A. Kumar, B. Singh, Dalton Trans. 2013, 42, 11455.
[491] K. Sugikawa, K. Kaneko, K. Sada, S. Shinkai, Langmuir 2010, 26,
19100.
[492] T. K. Sarma, A. Chattopadhyay, Langmuir 2004, 20, 3520.
[493] P. Raveendran, J. Fu, S. L. Wallen, J. Am. Chem. Soc. 2003, 125,
13940.
[494] S. R. Hall, A. M. Collins, N. J. Wood, W. Ogasawara, M. Morad,
P. J. Miedziak, M. Sankar, D. W. Knight, G. J. Hutchings, RSC Adv.
2012, 2, 2217.
[495] P. Mishra, R. S. Yadav, A. C. Pandey, Struct. Chem. 2011, 22, 1281.
[496] A. El Kadib, K. Molvinger, T. Cacciaguerra, M. Bousmina,
D. Brunel, Microporous Mesoporous. Mater. 2011, 142, 301.
[497] Y. Shchipunov, I. Postnova, Colloids Surf., B 2009, 74, 172.
[498] M. Nidhin, R. Indumathy, K. J. Sreeram, B. U. Nair, B. Mater. Sci.
2008, 31, 93.
[499] R. J. White, V. L. Budarin, J. H. Clark, Colloids Surf., A 2014, 444, 69.
[500] S. Yamane, A. Sugawara, A. Watanabe, K. Akiyoshi, J. Bioact.
Compat. Polym. 2009, 24, 151.
Adv. Mater. 2016, © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/adma.201503215
www.advmat.de
REVIEW
[501] T. Witoon, M. Chareonpanich, Mater. Lett. 2012, 81, 181.
[502] C. Zollfrank, H. Scheel, P. Greil, Adv. Mater. 2007, 19, 984.
[503] C. Gautier, N. Abdoul-Aribi, C. Roux, P. J. Lopez, J. Livage,
T. Coradin, Colloids Surf., B 2008, 65, 140.
[504] Z. L. Zhang, S. C. Wimbush, A. Kursumovic, H. Y. Wang, J. H. Lee,
H. L. Suo, J. L. MacManus-Driscoll, CrystEngComm 2012, 14, 5765.
[505] V. Singh, S. K. Singh, S. Pandey, R. Sanghi, Int. J. Biol. Macromol.
2011, 49, 233.
[506] A. H. Bae, M. Numata, T. Hasegawa, C. Li, K. Kaneko, K. Sakurai,
S. Shinkai, Angew. Chem. Int. Ed. 2005, 44, 2030.
[507] M. Numata, C. Li, A. H. Bae, K. Kaneko, S. C. Kazuo, S. Shinkai,
Chem. Commun. 2005, 4655.
[508] T. Sanji, N. Kato, M. Kato, M. Tanaka, Angew. Chem. Int. Ed. 2005,
44, 7301.
[509] K. Katagiri, K. Ohta, K. Koumoto, K. Kurosu, Y. Sasaki, K. Akiyoshi,
Colloid Polym. Sci. 2013, 291, 1375.
[510] X. H. Wang, D. Li, Y. Z. Guo, X. Y. Wang, Y. M. Du, R. C. Sun, Opt.
Mater. 2012, 34, 646.
[511] A. Sugawara, S. Yamane, K. Akiyoshi, Macromol. Rapid Comm.
2006, 27, 441.
[512] K. Sugikawa, T. Shiraki, Y. Tsuchiya, S. Haraguchi, K. Sada,
S. Shinkai,Supramol. Chem. 2010, 23, 239.
[513] Y. J. Yu, Z. H. Si, S. J. Chen, C. Q. Bian, W. Chen, G. Xue, Langmuir
2006, 22, 3899.
[514] M. Numata, T. Hasegawa, T. Fujisawa, K. Sakurai, S. Shinkai, Org.
Lett. 2004, 6, 4447.
[515] M. Numata, S. Tamesue, T. Fujisawa, S. Haraguchi, T. Hasegawa,
A. H. Bae, C. Li, K. Sakurai, S. Shinkai, Org. Lett. 2006, 8, 5533.
wileyonlinelibrary.com 49