Вы находитесь на странице: 1из 19

View Article Online / Journal Homepage / Table of Contents for this issue

Journal of Dynamic Article Links < C


Materials Chemistry
Cite this: J. Mater. Chem., 2012, 22, 12953
www.rsc.org/materials FEATURE ARTICLE
Electrospun composite nanofibers and their multifaceted applications
R. Sahay,ac P. Suresh Kumar,ac R. Sridhar,ab J. Sundaramurthy,ac J. Venugopal,*a S. G. Mhaisalkarc
and S. Ramakrishna*ab
Received 16th February 2012, Accepted 16th April 2012
DOI: 10.1039/c2jm30966a
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

The re-exploration of the nanostructure production technique known as electrospinning was carried
out in the past decade due to its simplicity and uniqueness of producing nanostructures. As
nanotechnology is one of the most promising and growing technologies today, a large amount of work
Downloaded by University of Sussex on 15 December 2012

is being carried out in an extensive area and shows an extremely huge potential for miraculous works in
the fields of medicine and biotechnology. These nanostructures were found to be of great significance
because of their inherent properties such as large surface area to volume ratio and the engineered
properties such as porosity, stability and permeability. The functionality and applicability of these
nanostructures were further improved by incorporating secondary phases either during electrospinning
or in the post-processing resulting in the composite nanostructures. These secondary phases may
include metal oxides, carbon nanotubes, precious metals, gold nanoparticles and hydroxyapatite.
Nanofibrous materials that mimic the native extracellular matrix (ECM) and promote the adhesion of
various cells are being developed as tissue-engineered scaffolds for the skin, bone, vasculature, heart,
cornea, nervous system and other tissues. The article discusses in detail the applicability of these
composite fibers in energy, sensors, filters, biotechnology and details the technological issues, research
challenges and future trends.

1. Introduction nanocomposites contribute to producing light/efficient


batteries,69 fuel cells,1013 fabricating structural components with
During the past few decades, nanomaterials have attracted high strength-to-weight ratio,14,15 lightweight sensors,16 as well as
immense interest in research/industrial applications because of
their unique properties such as large surface area and engineered
properties such as high porosity.15 At the nanoscale, these
nanomaterials provide abundant opportunities to create unique
material combinations by accessing new properties through the
exploitation of the unique synergy between these materials.
Nanocomposites are considered as one of the most highly
researched areas in nanomaterials by the virtue of their improved
mechanical properties, dimensional stability, thermal/chemical
stability, and electrical conductivity. Nanocomposites usually
comprise two or more phases of different chemical constituents
or structures, with at least one of the chemical and/or structural
phases having nanometric dimensions. These nanocomposites,
due to their improved physical/chemical properties, establish
applications ranging from energy, sensors, biotechnology, smart
materials, filtration, and regenerative medicine. These

a
Center for Nanofibers & Nanotechnology, National University of
Singapore, Singapore. E-mail: nnijrv@nus.edu.sg; seeram@nus.edu.sg;
Fax: +65 6773 0339; Tel: +65 6516 4272
b
Department of Mechanical Engineering, National University of Singapore,
Singapore
c
School of Materials Science and Engineering, Nanyang Technological Fig. 1 Fabrication and characterization of electrospun nanocomposites
University, Singapore on the basis of their applications.

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 1295312971 | 12953
View Article Online

magnetic and fluorescent nanocomposites for efficient viewing/


removing of the tumors.17,18
The categorization in Fig. 1 is designed to cover future/
ongoing research/industrial trends pertaining to nanofiber
based nanocomposites. Comprehensive study of properties
in nanoscale dimensions relating to their respective large scale
counterparts were performed to achieve a clear understanding
of the synergistic advantage of nanoscale dimensions. It is
well-known that understanding the change in properties as the
fiber dimensions decrease to the nanoscale is important to
optimize the resultant properties of nanocomposites. As one/
both of the components of the composites are electrospun
nanofibers, emphasis is given to compare/summarize the
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

enhancement or shortcomings of the nanofiber based nano-


composites with respect to the nanoparticle based
nanocomposites.
Nanofibrous scaffolds are ideal for the purpose of tissue
Fig. 2 Schematic of electrospinning and electrospraying set-up with
Downloaded by University of Sussex on 15 December 2012

regeneration because their dimensions are similar to the composite fibers.


components of the extra cellular matrix (ECM) and mimic its
fibrillar structure, providing essential signals for cellular
assembly and proliferation. There are several scaffold fabri- 2. Energy applications
cation techniques namely, electrospinning (random, aligned,
2.1. Catalysis
core shell and vertical nanofibers), self-assembly, phase sepa-
ration, melt-blown and template synthesis. Electrospinning is The degradation of organic pollutants such as dyes and pesticides
one of the most promising techniques for designing natural/ in aqueous solution by photocatalysis, using semiconductor
polymer nanofibrous scaffolds for tissue engineering applica- metal oxides such as titanium oxide, zinc oxide, tin oxide and
tions. ECM is a complex arrangement of proteins and poly- copper oxide (TiO2, ZnO, SnO2, CuO) has been the subject of
saccharides such as collagen, gelatin, chitosan, hyaluronic acid, great research due to their size-tunable physicochemical prop-
proteoglycans, glycosaminoglycans and elastin, fabricated erties, high activities, durability and low cost. However, the fast
nanocomposites are also possess such adhesion factors, recombination rate of photo-generated electron/hole pairs in the
chemical functionalities and mechanical properties. Though bulk semiconductor materials lowers their photo-catalytic effi-
drug molecules have significant potency against the disease for ciency.26 To overcome these drawbacks, composite materials are
their release or the delivery of drugs at the desired site, without being fabricated in order to extend the light absorption spectrum
loss of their activity makes the difference. Thus drug delivery as well as suppressing the recombination of photo-generated
finds its importance and the use of biodegradable polymers for electrons by virtue of the different Fermi levels of the ingredients
this purpose is inevitable. in the composite materials. Due to their very large aspect ratios,
Recently, the synthesis and design of composite materials by photo-catalyst materials with fibrous morphology are superior to
blending nano-sized inorganic and organic materials have particles as far as the recycling and aggregation are concerned.
generated great interests in the fields of material sciences due to Titanium dioxide is widely used as a photo-catalyst due to its
their improved and enhanced properties and applicability. ability to oxidize toxic substances into nontoxic substances such
Simple technique used for the production of these composites, as carbon dioxide and water. TiO2 is one of the photo-catalysts
due to their distinction from the conventional polymer nano-
composites (film or bulky fiber) in the physical size of host
polymer matrix and embedded particles of these inorganic
organic hybrid materials and details of electrospinning/electro-
spraying set-up presented in Fig. 2. The electrospun composite
nanofibers are found to possess both the advantages of organic
polymers such as lightweight, flexibility and moldability, and
special functionality of inorganic species such as high strength
and thermal stability. Through electrospinning, the nano-
composite can be fabricated by any of the methodologies shown
in Fig. 3 and is explained as follows:
 Employing two or more precursor solution for the electro-
spinning to achieve multi-component nanofibers such as
bi-component and core/shell nanofibers.1921
 Electrospinning of polymer solutions with dispersed inor-
ganic nanoparticles such as carbon nanotubes (CNTs).22,23
 Surface treatment of the electrospun nanofibers to achieve
composite nanofibers.24,25 Fig. 3 Mechanism pertaining to composites through electrospinning.

12954 | J. Mater. Chem., 2012, 22, 1295312971 This journal is The Royal Society of Chemistry 2012
View Article Online

widely used for fabricating composites such as TiO2/ZnO found to be considerably higher than ZnS nanopowder under
composite nanofibers having ZnTiO3 in addition to ZnO and UV irradiation. This may be due to the adsorptionmigration
TiO2 crystallites.27 It was observed that nearly 100% Rhodamine- photodegradation of methylene blue in the case of ZnSfluo-
B and 85% phenol was decomposed in the presence of a TiO2/ ropolymer composite nanofibers as compared to pure ZnS
ZnO composite catalyst. The results demonstrated that the nanopowder. Research is in process to fabricate highly efficient/
incorporation of ZnO in the composite nanofibers improved stable nanocomposites employing electrospun nanofibers having
the photocatalytic efficiency with the best result obtained for extended light absorption spectrum with suppressed recombi-
15.76 wt% ZnO. It was inferred that slow charge recombination nation of photo-generated electrons. Electrospun nanofibers are
on the TiO2/ZnO composite catalyst lead to higher degradation one of the ingredients of the composite to avoid coagulation
rates. Kim et al. fabricated TiO2/poly(dimethyl siloxane) usually suffered by nanoparticles, thus improving recyclability of
(PDMS) composite nanofibers and observed that the tensile the nanofibrous composites.
strength and modulus of TiO2/PDMS composite fibers increased
gradually with the increase in PDMS content.28 These composite
2.2. Batteries
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

nanofibers showed an improved photo-degradation activity


against methylene blue, with the strong dependence on the TiO2 Among various energy storage devices available, rechargeable
content. Nakata et al. on the other hand, fabricated Al2O3/TiO2 lithium-ion batteries with their high-energy density, long cycle
composite nanofibers, which displayed appreciable photo- lives, and flexible design, are considered as the effective solution
Downloaded by University of Sussex on 15 December 2012

catalytic decomposition of acetaldehyde under UV irradiation.29 to the ever-increasing demand for high-energy density electro-
Due to the large band-gap of titanium dioxide, research is chemical power sources. This demand has promoted research
being focused on shifting the optical response of titanium dioxide efforts towards the developing high-capacity alternative elec-
from the UV to visible spectral range. Lm et al. took a new trode materials with long life cycle, improved safety, reduced
approach by immobilizing TiO2 particles in/on hydrogel fibers carbon-footprint, and low cost. In this regard, Ji et al. fabricated
for the degradation of dye.30 The dye degradation capacity of the a variety of composite materials through electrospinning and
composite fibers was investigated using both anionic and cationic observed improved performance with regard to their pure
dyes under visible sunlight. The swelling behaviour of the counterparts.37 The composite material included nickel particles
hydrogel confirmed that both anionic and cationic water dispersed in carbon nanofibers, copper/carbon composite and
pollutants/dyes were effectively absorbed on the surface, polyacrylonitrile/polypyrrole composite nanofibers. They
improving their surface area and rapid degradation of the dye by observed that the anode performance improved from the incor-
TiO2. Lm et al. fabricated again uniformly dispersed TiO2 poration of a Li-inactive nickel. Ji et al. also fabricated copper-
particles on the wall of polyacrylonitrile (PAN)-based nano- loaded carbon nanofibers through post annealing of electrospun
fibers.31 The composite nanofibrous mat was employed for the Cu(CH3OO)2/polyacrylonitrile nanofibers able to attain rela-
photo-decomposition of Rhodamine-B dye under UV light. tively high capacity and good cycling performance in comparison
Wang et al. fabricated Y3+ and Nd3+ doped TiO2 nanofibers and to their pure counterparts.38 This improved performance of the
investigated their photo-degradation performance against composite nanofibers may be due to the synergy effect of metallic
Rhodamine-B and phenol.32 They observed that the degradation copper and disordered carbon. Ji et al. fabricated carbon nano-
rate of 1.5 mol% Y/TiO2 nanofibers was higher for Rhodamine- fibers employing the blended mixture of polyacrylonitrile and
B, while the degradation rate of 1.0 mol% Nd/TiO2 nanofibers polypyrrole.39 This particular anode material achieved high
was higher for phenol. reversible capacity, improved cycle performance, and was able to
Pan et al. fabricated Au/TiO2 composite nanofibers by sput- retain its fibrous morphology after 50 cycles. The improved
tering Au particle on TiO2 nanofibers and then observed the electrochemical performance of these composite nanofibers can
morphologies of Au deposited TiO2 nanofibers can be controlled be attributed to their unusual surface properties and unique
by controlling the sputtering time.33 They found that the structural features, which amplify both surface area and exten-
composite fiber achieved better photocatalytic degradation of sive intermingling between electrode and electrolyte phases over
acetaldehyde under UV irradiation in comparison to pure TiO2. small length scales, thereby leading to fast kinetics and short
Teng et al. fabricated an Au/CNF composite with high pathways for both Li ions and electrons.
conductivity and facile electron transfer kinetics.34 This Au/CNF Composite electrolytes based on porous polymer membranes
composite exhibited highly electrocatalytic activity for the have been widely used in lithium ion batteries due to its good
oxidation of dopamine, ascorbic acid and uric acid compared to compatibility, no leakage, low self-discharge, etc. Though
pure CNT. Others widely used semiconductor oxide for photo- composite electrolytes are being fabricated through a variety of
catalysis as ZnO. Ye et al. fabricated ZnO nanocrystallites techniques such as solvent-casting, phase inversion, and additive
embedded in cellulose nanofibers and tested its photo-catalytic extraction. Nevertheless, these electrolytes show low-rate capa-
properties toward Rhodamine-B under the irradiation of bilities at high discharge rates because of low order pore size, low
visible light.35 They observed that as compared to pure ZnO porosity, and poor channel in ionic conduction. Recently, elec-
nanoparticles, the composite nanofibers were highly elastic, trospinning was applied for preparing the ultrafine fibers for
dimensionally stable, and durable as well as easily recyclable. He polymer electrolyte membranes from polyvinylidene fluoride
et al. dispersed ZnS particles on the surface of poly(vinylidene (PVdF), polyvinylidenefluoride-co-hexafluoropropylene, and
difluoride) (PVDF) mixing methacrylic acid (MAA)-tri- polyacrylonitrile. However, electrospun fibers prepared from
fluoroethyl acrylate (TFA) copolymer nanofibers.36 The degra- pure polymers have limited capability in stabilizing the battery at
dation of methylene blue by ZnSfluoropolymer composite was high discharge rate due to polymer degradation and the leakage

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 1295312971 | 12955
View Article Online

of organic liquid electrolyte since these polymer nanofiber SEBS (E-PSS) fibers resulted in higher electrochemical capacity
membranes only exhibit macro-porous structures. In order to due to the increased doping level, high electrical conductivity,
overcome this shortcoming, Jung et al. fabricated silica (SiO2)/ low interfacial resistance, and high reversibility by easy interca-
polyacrylonitrile (PAN) three-dimensional composite electrolyte lation of Li ion compared to composites (C-PS) prepared by
membranes.40 The processing parameters were optimized to casting. Due to the ever-increasing growth of integrated circuit
obtain nanofiber membrane having very small fiber diameter, and micro-electromechanical systems (MEMS), demand of
highest porosity, and large specific surface area. Composite compact batteries has increased exponentially. In order to
electrolyte membranes were prepared by soaking these porous enlarge the contact area between cathode and anode for the
nanofiber membranes in 1 M lithium hexafluorophosphate capacity enhancement of the compact batteries, 3D structure
(LiPF6) in ethylene carbonate (EC)/dimethyl carbonate (DMC) electrodes with high specific surface area have been fabricated.
(1 : 1 vol%). It was noted that composite membrane delivered the Lu et al. fabricated 3D network structures of NiO-SWNTs fibers
discharge capacity 139 mA h g1 as 98% of the theoretical value, with diameter smaller than 50 nm having relatively high revers-
and retained a high value 127 mA h g1 as 89% at 150th cycle, ible capacity compared to NiO at the charge and discharge
current density of 2 C.6
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

which was significantly higher than pure PAN nanofiber-based


electrolyte membranes. Jung et al. fabricated Si/carbon fibers
by employing 25 wt% poly(amide imide) (PAI) nanofibers con-
2.3. Fuel cells
taining various silicon content ratios.41 They observed that the
Downloaded by University of Sussex on 15 December 2012

electrochemical activity of Si/CFs gradually improved due to The fuel cells work on the same principle as batteries for con-
buffering effect of large Si volume expansion and shrinkage. In verting chemical energy into electricity with the difference that
addition, the nanofibers exhibited large accessible surface area, the batteries are standalone devices whereas chemicals are
high reversible capacity, and relatively good cycling performance constantly supplied into the fuel cell. The majority of fuel cells
at high current densities compared to pure carbon nanofibers. used hydrogen and oxygen as the main fuel source for producing
Jeong et al. fabricated poly(vinylidene fluoride) (PVDF)/ electricity. Fuel cells are usually classified based on the operating
organo-modified clay (OC)/tripropylene-glycol-diacrylate temperature or the type of electrolyte used. On the basis of
(TPGDA) composite nanofibers as the electrolyte membranes.42 operating temperatures, the fuel cells can be classified as polymer
Compared with pure PVDF film-based electrolyte membranes, exchange membrane fuel cell (low temperature 60 to 80  C i.e.
the composite electrolyte membranes exhibited improved low warm-up time), solid oxide fuel cell (high temperature 700 to
mechanical and electrochemical performance. This improved 1000  C, low reliability with high stability in continuous use) and
performance may be due to the ultraviolet photo-polymerization molten-carbonate fuel cell (600  C). The proton exchange
of electrospun PVDF/OC/TPGDA nanofibers generated chemi- membrane fuel cell converts chemical energy into electrical
cally cross-linked TPGDA-grafted PVDF/OC nanofibers energy with high efficiency and low pollutants and thus making it
exhibiting robust mechanical and electrochemical properties. For one of the most promising power sources for portable and
grafting and cross-linking between electrospun nanofibers, automotive applications. The focus is on developing membranes
a membrane was immersed in a solution of methyl-ethyl-ketone that are able to achieve appreciably high proton conductivity,
containing 1 wt% photo-initiator (2-benzyl-2-(dimethylamino)- low gas permeability into the fuel and oxidant, high thermal
4-morpholinobutylrophenone), and irradiated with ultraviolet stability, and durability. The perfluorosulfonated membranes
light (360 nm) for 12 h as shown in Fig. 4.42 DSC analysis such as Nafion have been widely used because of their excellent
showed that the percentage of the amorphous region in the oxidative and chemical stability as well as high-proton conduc-
semi-crystalline PVDF gradually increased by 10% by the tivity. For instance, Molla et al. synthesized ultrathin Nafion/
incorporation of OC and TPGDA. It was also noted that PVA composite ion-exchange membranes for fuel cells.44 It was
compared with pure PVDF film-based electrolyte, composite found that PVA increased the mechanical strength of membranes
electrolyte membranes exhibited superior ionic conductivity, but reduced the conductivity of composite membranes as
cyclability as well as improved mechanical stability. compared to pure Nafion nanofibers. It was noted that the high
Ju et al. compared composite polypyrrole (PPy)/sulfonated- performance was exhibited by 19 mm thick composite membranes
poly(styrene-ethylene-butylenes-styrene) (S-SEBS) nanofibers carried out in a single cell fed with H2/air owing to its low ionic
with PPy/poly(styrene-ethylene-butylenes-styrene) (SEBS) resistance. Lee et al., on the other hand, fabricated SiO2 nano-
nanofibers prepared by casting method.43 The electrospun PPy/S- particle-coated polyimide (PI) nonwoven substrate having a low
thickness, high porosity, and strong affinity for Nafion.45 SiO2
nanoparticles were introduced for the purpose of improving
mechanical strength and hydrophilicity of the electrospun poly-
imide nonwoven mat. It was observed that with the increase in
dimensional stability, the composite membrane is effective in
retarding the steep decline of proton conductivity at low
humidity owing to the presence of SiO2/PEI-coated PI nonwoven
substrate.
The perfluorosulfonated membranes have limitations such as
low thermal stability and high gas permeability resulting in the
development of sulfonated aromatic hydrocarbon based polymer
Fig. 4 Schematic diagram of grafting of TPGDA on PVDF fibers.42 electrolyte membranes. However, due to the presence of a large

12956 | J. Mater. Chem., 2012, 22, 1295312971 This journal is The Royal Society of Chemistry 2012
View Article Online

number of sulfonic acid groups results in swelling of membranes methanol. Lin et al. prepared cross-linked poly(vinyl alcohol)
and reduction in their mechanical properties. Tamura et al. (PVA) nanofiber with glutaraldehyde vapours, then impreg-
synthesized composite membranes from sulfonated polyimide nated with Nafion solution to prepare Nafion/PVA composite
nanofibers to improve the proton transportation.46 They found membranes.48 The incorporation of cross-linked PVA nano-
that during electrospinning, the hydrophobic and hydrophilic fibers in the Nafion membrane allowed reducing the thickness
domains in the polymer were separated to the outside at the air of composite membrane to 50 mm without causing a large
surface and inside of the polymer solution, respectively resulting increment of methanol cross-over across the membrane
in phase separation shown in Fig. 5 leading to the rapid proton resulting in better DMFC performance. Choi et al. fabricated
transport.46 It was clear that the polyimides within the aligned three-dimensional composite nanofibrous membranes by
nanofibers were significantly oriented resulting in highly stable impregnating Nafion into the pores of electrospun PVDF.49
composite membranes. It was also noted that the composite Although the composite membranes exhibit lower proton
membrane was able to achieve high proton conductivity, low gas conductivity than Nafion 115, the composite membrane
permeability into the fuel and good chemical and thermal exhibits better performance than pure Nafion 115 in direct
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

stabilities. However, the measurement of proton conductivity for methanol fuel cells (DMFCs) due to the smaller thickness and
the composite membrane was conducted only in the axial suppressed methanol cross-over from the anode to cathode
direction; research is on-going to perform precise measurements through the membrane.
in the radial direction as it is needed for the actual use of Glucose fuel cells are of increasing interest due to the
Downloaded by University of Sussex on 15 December 2012

electrolyte membranes in fuel cells. advantages of employing glucose as a fuel, as it is nontoxic,


Direct methanol fuel cells (DMFCs) have recently attracted non-explosive and non-volatile, and has relatively high energy
much attention as they can provide green power for electric content. However, glucose results in partial oxidation involving
vehicles and electronic portable devices by direct conversion of only 2 electrons per molecule, requiring metal catalyst such as
methanol fuel. The methanol conversion is carried out in the platinum to improve the oxidation of glucose.50 Prilutsky et al.
membrane electrode assembly, which consists of a polymer synthesized carbonized polyacrylonitryle (cPAN) nanofibers,
electrolyte membrane and two catalyst-loaded porous elec- with(out) embedded MWCNTs as anodes for glucose fuel
trodes for methanol oxidation at the anode and oxygen cells.51 The anodes showed improved activity with the incor-
reduction at the cathode. To improve the efficiency, Lin et al. poration of MWCNTs. The orientation of graphitic layers
fabricated composite nanofibers by depositing PtRu nano- along the carbon fiber axis and the coherence of layer packing
particles onto electrospun carbon nanofibers using a polyol were shown to be important for enhanced electrode activity.
processing technique.47 The morphology and size of PtRu The maximum values of open circuit voltage and peak power
nanoparticles were controlled by 1-aminopyrene functionaliza- density for composite anodes were found to be 0.4 V and 30 mW
tion of carbon nanofibers. The PtRu/carbon composite cm2. They found silver metallization of the composite elec-
nanofibers with 1-aminopyrene functionalization were found to trodes leads to the improvement of open circuit voltage and
have uniform distribution of smaller nanoparticles compared peak power density to 0.9 V and 400 mW cm2, respectively. Zhi
with those pre-treated with conventional acids found to show et al. fabricated solid oxide fuel cell cathode using the yttria-
improved performance towards the electrocatalytic oxidation of stabilized zirconia (YSZ) nanofiber scaffold with the infiltrated
La(1x)SrxMnO3 (LSM) showing an enhanced catalytic activity
towards oxygen reduction.52 The cathode was found to show
a continuous path for charge transport and an increased
number of triple-phase boundary sites. Jeong et al. fabricated
FeCoCNF composite electrocatalysts for the oxygen reduction
reaction in alkaline fuel cells via electrospinning and the
subsequent pyrolysis of a mixture of a nitrogen-containing
polymer and organo-metallic compounds.53 The electrochemical
analysis showed that the resultant FeCoCNFs catalysts was
comparable to commercial carbon-supported platinum (Pt/C)
with better ethanol tolerance than Pt/C in an alkaline electro-
lyte. It was also noted that the metal inclusion resulted in the
increment in oxygen-related active site and enhancement of
electrical conductivity.

2.4. Solar cells


Gratzel was the first person to fabricate dye-sensitized solar cells
(DSCs) in 1991.54 Within the past decade, DSCs have gained
Fig. 5 (a) Chemical structure of NTDA-BDSA-r-APPF, (b) schematic considerable attention as a potential technique for harnessing
representation of sulfonated copolyimide nanofiber, (c) TEM image of sunlight, a largely abundant renewable-energy source. In DSCs,
cross-sectional aligned nanofiber in radial direction, (d) TEM image of a sensitizer is anchored to the surface of a wide-band semi-
cross-sectional aligned nanofiber in axial direction, (d) SEM image of conductor oxide to absorb the sunlight. Charge separation takes
aligned nanofiber electrospun on specially designed collector.46 place at the interface via photo-induced electron injection from

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 1295312971 | 12957
View Article Online

the sensitizer to the conduction band of the semiconductor oxide. NUS-Center for Nanofibers & Nanotechnology to further
Later, these electrons are collected at the charge collector. The improve the efficiency of the solar cells.
use of broad absorption band sensitizers in conjunction with
nanocrystalline semiconductor oxides are employed to harvest 3. Filters
a large fraction of sunlight. Benefits of these DSCs include simple
non-vacuum fabrication resulting in potential large-scale Air filtration technologies have traditionally found numerous
production.55 The wide-band semiconductor oxides usually applications such as in semiconductor and the health-care
employed are TiO2, SnO2 and ZnO, etc. TiO2 nanostructures are industry. One of the key elements for effective air filtration is the
extensively used as photoelectrodes for DSCs by virtue of their filter media, usually made of nonwoven fabrics, such as glass
low production cost and chemically stable nature. Overall energy fibers, electrospun fibers, etc. The usual criteria for high perfor-
conversion efficiencies (conversion of solar to electrical energy) mance air filters are high filtration efficiency with low pressure
over 10% have been achieved. Nevertheless, novel steps are being drop. Kim et al. fabricated poly(acrylonitrile) nano-web on
employed to improve the overall energy conversion efficiency of a commercial melt-blown poly(propylene) (PP) filter medium to
generate composite filter media as shown in Fig. 6.63 Structural
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

DSCs. They include incorporation of hole/electron blocking


layers, nanosized scattering layer, avoiding leakage of the elec- characterization performed on the composite filter showed that
trolyte and fabrication of composite nanomaterial as photo- a thin layer of electrospun nano-web can improve the overall
electrode, etc. For instance, Feng et al. fabricated a composite performance by increasing filtration efficiency without signifi-
Downloaded by University of Sussex on 15 December 2012

photoelectrode by depositing TiO2 nanofibers onto the TiO2 cantly increasing the pressure drop of the composite membrane.
nanoparticles as a light scattering layer.56 It was argued that the
efficiency of the cells with nanofibrous scattering layer improved 3.1. Gaseous filters
in comparison to nanoparticles due to improved scattering effect
Patanaik et al. fabricated composite air filters by sandwiching
observed in case of nanofibers as compared to nanoparticles. On
polyethylene oxide (PEO) nanofibrous membranes between
the other hand, Lee et al. prepared poly(vinylidenefluoride-co-
another nonwoven mat.64 The increase in diameter of poly-
hexafluoropropylene) (PVDF-HFP) nanofibers containing
ethylene oxide nanofibers with the increased concentration was
nanosized inorganic BaTiO3 to suppress the leakage of the
found to improve the filtration efficiency and decrease the pres-
electrolyte in DSCs.57 They also showed that PVDF-HFP
sure drop. They observed that the cyclic compression employed
nanofibers containing inorganic filler have better ionic conduc-
during the working cycle plays an important role in defining the
tivity resulting in better efficiency than those of without filler.
longevity of the filter media. A composite filter media was found
Whereas, Joshi et al. fabricated composite from electrospun TiO2
to be more stable against cyclic compression as compared to
nanofibers and TiO2 nanoparticles, which was found to improve
membranes deposited over nonwoven mats. Improved filter
the harvesting of light.58
efficiency and longevity was observed for composite filter media
A variety of TiO2 based composite materials are being
as compared to membranes deposited over nonwoven mats. This
designed as photoelectrodes for DSCs, such as TiO2MWCNT
may be due to relatively no increase in pore sizes after cyclic
and TiO2graphene.59,60 Functionalized CNTs or graphene was
compression due to relatively less pressure drop in the case of
introduced into the precursor solution usually employed for the
composite filter media. Sundarrajan et al. combined electro-
production of rice-grain TiO2 nanostructures.61 Later, these
spinning and electrospraying for the deposition of inorganic
precursor solutions was electrospun and subsequently heat-
nanoparticles over polymeric nanofibers resulting in filter media
treated to fabricate single crystalline nanostructures applicable
for protective clothing.65 They observed by the precisely
as photoelectrode for DSCs. In case of TiO2MWCNT nano-
controlling process parameters, it was possible to achieve well
structures, the rice grain morphology was retained at low
dispersed nanoparticle in polymer matrix. It was claimed that
MWCNT loadings of the order of 0.10.3 wt% of TiO2. The
these composite media will be able to detoxify chemical warfare
optimum MWCNT loading for best performance was found to
agents and will have the potential to replace the existing charcoal
be 0.2 wt%, which showed 32% enhancement in the energy
based protection suits wherein the warfare agents are not
conversion efficiency due to the improved charge transfer and
detoxified rather adsorbed. Uyar et al. fabricated beta-cyclo-
collection by the incorporation of CNTs into the rice grain-
dextrin (beta-CD) doped polystyrene (PS) fibers as a filter
shaped TiO2 network. Similarly, 0.250.75 wt% loading of gra-
phene with respect to TiO2 was employed to fabricate composite
nanostructures to evaluate their effect on the performance of
DSCs. For, TiO2graphene nanostructures, 0.5 wt% loading
were found to be the optimum concentration enhancing the
overall energy conversion efficiency by 33%. The other approach
employed is replacing liquid sanitizer (Ru-based dyes) by a solid
sanitizer to enhance the stability of the solar cells. Shengyuan
et al. synthesized MSA-capped CdS, chemically conjugated to
the surfaces of TiO2 photoelectrode. These composite was
assembled into a Quantum dot solar cell (QDSC) by sandwiching
against a Pt counter electrode in presence of parafilm spacer and
polysulfide electrolyte.62 The best energy conversion efficiency Fig. 6 A structural diagram of the filter media used by Kim et al. A
for QDSC was 0.07%. Extensive work is in process at nano-web of PAN was electrospun on top of the melt-blown web.63

12958 | J. Mater. Chem., 2012, 22, 1295312971 This journal is The Royal Society of Chemistry 2012
View Article Online

medium against organic compounds such as phenolphthalein, of combination for all these mechanisms. For most particle sizes,
etc.66 The filter media was based on the principle that the beta- the filtering contribution of the gravitational force is appeared to
CD molecules from inclusion complexes with organic be minimal. Brownian diffusion, which is the dominant filtration
compounds, resulting in their separation from the fluid. mechanism for fine particles, is of negligible importance when
dealing with coarse particles. In case of sub-micron particulates,
Brownian diffusion, interception and inertial impaction as well
3.2. Liquid filters
as the electrostatic capture gets significance. Electrostatic
One of the generally used materials for water filtration is Nylon-6 attraction is widely used in many different types of aerosol
nanofibers. Park et al. fabricated Nylon-6 nanofibers containing filtration devices against sub-micron particulates. Yeom et al.
well dispersed silver nanoparticles.67 They observed that the fabricated composite nano-fibrous mat consisting of Nylon-6
composite nanofibers showed better antibacterial activity in nanofibers with boehmite nanoparticles, these nanoparticles act
comparison to its single phase Nylon-6, thus making them as an electrostatic charging agent.72 These composite fibers
a potential material for water filtration. The other approach showed significant improvement in the submicron aerosol
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

employed is the fabrication of nanofibrous support material for capture efficiency without appreciable change in the air flow
nanocomposites. Pant et al. synthesized composite electrospun resistance. This improved performance of the filter was found to
Nylon-6 mats incorporating TiO2 nanoparticles.68 The presence be due to the improved surface potential of the fibrous mat
of a small amount of TiO2 nanoparticles in Nylon-6 solution was fabricated through electrospinning as well as the incorporation
Downloaded by University of Sussex on 15 December 2012

found to improve the hydrophilicity, mechanical strength, anti- of boehmite nanoparticles. Work is also in the process to employ
microbial and UV protecting ability of electrospun mats. The a variety of composite fibers electrospinning as aerosol filters.73
resultant Nylon-6/TiO2 antimicrobial spider-net like composite
mat with antifouling effect can be considered as a potential
4. Smart materials
candidate for future water filter applications. One of the possible
nano-fibrous support materials can be silicon carbide (SiC) due In the recent times, the research pertaining to the fabrication of
to its unique properties such as high mechanical robustness, reinforced polymer nano-composites has increased drastically
chemical inertness, and thermal stability. Liu et al. fabricated due to their potential application in defence and industrial
beta-SiC through the technique of concentric electrospinning sectors. These materials can be employed not only for reinforcing
with the diameter ranging from 1 to 2 nm.69 The other support applications but also in multifunctional applications where the
material employed was poly(ethylene terephthalate) (PET) non- properties of the nanoparticles can be combined with mechanical
woven mat to impart high mechanical strength to poly- reinforcement to offer significant advances in material design and
ethersulfone (PES) electrospun nanofibers.70 It was noted that function. There are reasons for this approach as the conventional
the heat treatment of PES/PET mat enhanced the interfacial laminates suffer from drawbacks such as (a) aggregation of
stability, thus preserving the structure of nanofibrous layer and particles in the polymer matrices, (b) reduction of mechanical
its effective porosity. It was also noted that the filtration strength due to the addition of particles, (c) negative effect of
performance was directly proportional to the size distribution of surface modification of carbon fibers on the mechanical strength.
the suspended particles. A possible remedy to the above mentioned drawbacks is the
Wang et al. fabricated high flux thin film nanofibrous addition of non-woven nanofibrous sheets in the inter-laminar
composite membrane containing a hydrophilic barrier layer and interface of two adjacent laminates resulting in improved struc-
a nanofibrous substrate.71 PVA/PAN nanofibrous composite tural and functional properties of laminates. The benefits are (a)
membranes were prepared having a very thin micrometre PVA high surface area/volume ratio resulting in increased bonding
nanofibrous layer on the electrospun PAN nanofibrous area between the nanofibers and the base material, (b) mixing of
substrate, followed by re-melting of PVA nanofibrous layer to nanoparticles with a polymer solution prior to electrospinning to
form a barrier PVA film by water vapor treatment and chemical achieve its uniform distribution in the nanofibrous membrane,
cross-linking in glutaraldehyde water/acetone solution. The (c) porous, thin and lightweight membrane resulting in no
depositing time during PVA electrospinning and the water appreciable increase in the weight of the laminate. Sihn et al.
content of the cross-linking solution were utilized to control investigated improvement of the damage resistance in laminated
the thickness and swelling degree of the PVA barrier layer. The composites with the incorporation of nanofibers as the interleave
highest permeate flux of 210 l m2 h1 was achieved with material.74 A composite nanofibrous web was fabricated from
the rejection of 99.5% for the composite membrane under the polycarbonate, poly(phenylene oxide) and polystyrene with(out)
operating pressure of 0.3 MPa. CNTs. Uniaxial tensile tests were carried out with a delamina-
tion-prone layup [30/30/90/90/30/30] by placing the nanofibril
mats at the interface between each ply. The stress levels at the
3.3. Aerosol filters
first micro-cracking damage, delamination damage and ultimate
The most common method of filtration is via fibrous membrane load-drop increased by 8.4%, 8.1% and 9.8%, respectively, with
filters consisting of a single or multi-components are predomi- the addition of nano-interlayers as compared with pristine
nately employed due to their high collection efficiency and specimens. The number of micro-cracks decreased significantly
durability. Five mechanisms for the deposition of aerosol parti- with the addition of nano-interlayers.
cles on a fiber in a fibrous filter are interception, inertial impac- Yoon et al. fabricated layered fabric systems having varying
tion, diffusion, gravitational force and electrostatic attraction. levels of electrospun nanofibers web density, different substrates as
The cumulative particle removal efficiency of a filter is the result well as different layered structures for the breathability and

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 1295312971 | 12959
View Article Online

waterproofing applications.75 The electrospun waterproof breath- higher sensitivity and improved stability.78,79 Many strategies
able materials provided different levels of breathability and have been developed to fabricate composite sensors with high
waterproof to meet diverse end uses and consumer needs. It was sensitivity and excellent reproducibility. Enhancement of sensor
noted that composite structure design influences the breathability performance can be achieve through (i) an accurate control of the
and waterproof devising a way to achieve a combination of high morphology in the nanometre range of composition and of
barrier and comfort performance, thus enhancing thermal comfort the surface state of the sensing materials, (ii) the integration of
for adequate protection. The comparison with traditional water- the sensor components (iii) the optimization of the working
proof breathable materials revealed that the layered structures temperature of sensitive layer, the operating mode, and the signal
based on nanofiber webs provide better resistance to water pene- processing, and (iv) the use of filters exhibiting selective gas
tration than densely woven fabrics and better moisture vapor and retention or conversion properties. All these rely on new, highly
air permeability than micro-porous membrane laminates and sensitive materials and good fabrication technology.
coated fabrics. On the similar lines, Lee et al. fabricated an poly- Many researchers expect to obtain composite nanofiber
urethane nanofibrous layered fabric system as protective textile sensors with high sensitivity, rapid response, reversibility at room
material protecting against liquid pollutants.76 Air permeability
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

temperature and convenient operation. Conducting polymers


and water vapor transmission of fabrics were evaluated against such as polyaniline, polypyrrole, and polythiophene have been
a pesticide mixture evaluating its thermal comfort performance. widely investigated as effective materials for chemical sensors.80
Protection performance and air/moisture vapor transport proper- Among the family of conducting polymers, polyaniline (PANI)
Downloaded by University of Sussex on 15 December 2012

ties were compared against the existing commercial materials, the has been one of the most extensively studied because of its
fabric achieved barrier performance between micro-porous mate- stability and reversible acidbase doping/dedoping chemistry.81
rials and nonwovens used for protective clothing. Akangah et al. These composite conducting polymer/metal oxides for gas-
tested the impact resistance of electrospun Nylon-6 interleaved sensing application have attracted particular interest because the
laminate against the base material and observed an improvement in hybridization and synergic effect of the pure organic and inor-
the threshold impact as well as the reduction in the impact damage ganic materials could enhance the sensing performance. In recent
growth rate with impact height and impact force.77 Interleaved years a large number of nanomaterials synthesis and fabrication
panels consist of one layer of polymer nanofabric in-between two methods have been proposed and demonstrated by using both
consecutive AS4/3501-6 are shown in Fig. 7. Sixteen-ply of these physical and chemical methods such as the solgel method82
quasi-isotropic composite laminates impacts were tested. The sputtering83 layer by layer (LbL) adsorption84 and plasma-
impact velocity, force, and energy were varied from 2.0 to 4 m s1, enhanced chemical vapor deposition (PEVCD).85 Among these
900 to 2100 N and 0.46 to 1.8 J, respectively. The author concluded methods, electrospinning is one of the simplest and most cost-
that the incorporation of nanofibrous layer marginally increased effective techniques to produce organic/inorganic nanofibers.
the laminate thickness with the increase in threshold impact force Various composite nanofibers have been prepared by the heat
by about 60% compared to the pure laminate. Polymer nanofabric treatment of electrospun composite nanofibers comprising
also reduced the impact damage growth rate to one-half with height a matrix polymer and target-material precursors. Electro-
impact. The damage growth rate was also found to reduce from spinning, nanofibers with a variety of morphologies, including
0.115 to 0.105 mm2 N1 with the impact force. dense, hollow, porous, and core-sheath structures for specific
applications, have been achieved by varying the process param-
eters.8689 Among different nanostructures, composite nanofibers
5. Sensors
have attracted more attention recently due to their inherent large
In recent years, the development of composite based gas sensor specific surface area and highly porous structure, which facilitate
technology has received considerable attention in many areas the adsorption/desorption process and minimize the diffusion
such as agriculture, medicine, meteorology, aerospace applica- resistance of molecules to the surface of materials.
tion on board space vehicles and other industrial facilities. Li et al. have synthesized polyaniline/titanium dioxide (PANI/
Polymer and metal oxide composites have been extensively TiO2) composite nanofibers via polymerization of aniline with
investigated as sensitive materials, which exhibited better sensing electrospun Mn3O4/TiO2 nanofibers.90 The PANI/TiO2
properties, such as shorter response time, smaller hysteresis, composite nanofibers with ammonia concentration ranging from

Fig. 7 Fabrication of interleaved test panel (upper half of the panel).77

12960 | J. Mater. Chem., 2012, 22, 1295312971 This journal is The Royal Society of Chemistry 2012
View Article Online

25 ppb to 200 ppb showed better sensing performance, depending of 2% RH and short response time (t90%: 7 s and 19 s for
on the constituent content, than that of pure PANI sensor. When adsorption and desorption between 33 and 97% RH,
the ratio of PANI/TiO2 is below the optimal value (TiO2 of respectively).
around 40.74 wt%), the sensitivity increases with TiO2 content in Solid-state gas sensors are particularly attractive because of
the composite, when the ratio is above the optimal value, the their low expenditure and wide range of applications used to
sensitivity decreases with the TiO2 content in the composites. control air pollution and to detect volatile, combustible and toxic
Sadek et al. developed a polyaniline/In2O3 nanofiber composite gases in air and in the field of domestic, laboratories and
sensor for H2, CO and NO2 gas sensing application.91 The poly- industrial applications. Because of their wide direct band gap and
aniline/WO3 nanofiber composite was deposited onto a layered high surface to volume ratio, many 1D metal oxides such as SnO2
ZnO/64 YXLiNbO3 based surface acoustic wave (SAW) gas and ZnO demonstrate to be excellent candidates for ultrasensi-
sensor has been investigated towards hydrogen (H2). The average tive gas sensors.96 In particular, the coupled oxide nano-
thickness of the polyaniline/WO3 nanofiber layer on the substrate composites such as SnO2/TiO2 or ZnO/SnO2 have received great
measured by profile-meter is 0.4 mm with average diameter of the attention and investigations to improve the gas-sensitive prop-
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

fibers around 90 nm. With hydrogen exposure, the conductivity erties of the sensors. Khorami et al. have demonstrated electro-
of polyaniline/WO3 nanofiber composite layer increases resulting spun SnO2/ZnO composite nanofibers which attributed to
in a decrease in the acoustic wave velocity, thereby decreasing the various diffraction plans of SnO2 with tetragonal rutile structure
resonant frequency. These changes in frequency were related to and ZnO with hexagonal wurtzite structure.97 Surface analysis of
Downloaded by University of Sussex on 15 December 2012

the concentration of H2 present in the environment. The SnO2/ZnO composite nanofibers shows good distribution of
measured sensor response was approximately 7 kHz towards 1% uniform nanofibers with an average diameter size of about
of H2 in synthetic air. The 90% response time of 40 s and recovery 75 nm. The ethanol sensor based on these composite nanofibers
time of 100 s with good repeatability were observed at room showed a good and desirable sensing behavior such as high
temperature.92 Wang et al. successfully fabricated Pd(IV)-doped sensitivity, quick response and recovery times at optimum
CuO oxide composite nanofibers (PCNFs) via electrospinning temperature of 360  C. Ji et al. synthesized polyacrylonitrile
and then employed to construct an amperometric non-enzymatic (PAN)/zinc(II) chloride (ZnCl2) composite nanofibers and
glucose sensor.93 The PCNFs based glucose sensors display the response of these nanofibers to hydrogen sulfide (H2S).98 The
distinctly enhanced electro-catalytic activity towards the oxida- authors observed that increasing ZnCl2 concentration in the
tion of glucose, shows significantly lower overvoltage (0.32 V) spinning solution reduces the fiber diameter, most likely due to
and ultrafast (1 s) and ultrasensitive current (1061.4 mA mM1 the increased solution conductivity. Exposing PAN/ZnCl2 fibers
cm2) response with a lower detection limit of 1.9  108 M to H2S leads to the formation of PAN/zinc sulfide (ZnS)
(S/N 3). When the sensor is stored in air at 4  C, it retains 94% composite nanofibers that contain ZnS crystals on the surface.
of its initial response current after 50 days which shows good These results indicate that PAN/ZnCl2 composite nanofibers
reproducibility and stability. could find applications in H2S sensing.
Li et al. fabricated PANI/Ag composite nanotubes using Wang et al. demonstrated the preparation and improved
a suitable fiber as template in the presence of H4SiW12O40 hydrogen monitoring properties based on p-NiO/n-SnO2 hetero-
(SiW12) and silver nitrate (AgNO3) as a dopant and an oxidant.94 junction composite nanofibers via electrospinning technique.99
They observed the nanotubes with average outer and inner The pure SnO2 nanofibers and as-prepared p-NiO/n-SnO2
diameters are 200 and 170 nm, respectively and length of the composite nanofibers (NSNFs) with different molar ratio
nanotubes is several thousand nanometres. The resistance of contents of NiO, shows an average diameter of nanofibers
PANI/Ag composite nanotubes increases gradually with the ranging from 100 to 200 nm and with many interconnected grains
increase in the concentration of NH3. These composite films have of around 20 nm in size. The geometry and dimension of the
a small increase in resistance when exposed to 5 ppm of NH3, sensor device structure and the corresponding TEM image of
which indicates PANI/Ag composite nanotubes synthesized by 4.11 mol% NSNFs are shown in Fig. 8(a). In contrast to the pure
this method have superior gas sensing performance even to very SnO2 nanofibers, the introduction of NiO has enhanced the
low concentration of NH3 gas, comparison with conventional sensitivity to 100 ppm H2 at 320  C dramatically. When the
PANI. Li et al. synthesized composite nanofibers of Si containing intermingled quantity of NiO is 4.11 mol%, its response is more
polyelectrolyte, polyethylene oxide and polyaniline (PANI) by than three times that of pure SnO2 nanofibers are shown in
electrospinning.95 The nanofibers showed a smooth fiber surface Fig. 8(b). The responserecovery behaviors of 4.11 mol% NSNFs
with the diameters of the fibers ranged from 250 to 500 nm. sensor, the sensor were sequentially exposed to 5, 50, 100, 500,
Heating of the composite nanofibers lead to joining of the and 1000 ppm H2 at 320  C. Author has observed extremely fast
intersected fibers, but the nanofibers in general maintained responserecovery behavior (3 s) has been obtained at the
a three-dimensional configuration. Therefore, the electrospun operable temperature of 320  C, with the detection limit of
non-woven nanofiber mat of the composite exhibited much approximate 5 ppm H2 concentration (Fig. 8(c)). The role of the
higher surface to volume ratio and larger porosity compared with addition of NiO into SnO2 nanofibers is to form pn hetero-
the composite film. Polymer composite nanofibers showed junction in which the electrons associated with these charged
impedance change from 6.3  106 to 2.5  104 U with the species are drawn from the conduction band of the bulk material,
increment of relative humidity (RH) from 22 to 97% at room leading to an increase in resistance. H2 increases the number of
temperature, exhibiting high sensitivity and good linearity on electrons in SnO2 and decreases the concentration of holes in
a semi-logarithmic scale. In addition, they exhibited fast and NiO; therefore, the thinner depletion layer thickness leads to
highly reversible response characterized by very small hysteresis lower resistance. The addition of p-type NiO enhanced the

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 1295312971 | 12961
View Article Online
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A
Downloaded by University of Sussex on 15 December 2012

Fig. 8 SEM images of (a) 4.11 mol% NiOSnO2 composite nanofibers, (b) responses of the sensors to 100 ppm H2 at 320  C, (c) response and recovery
characteristic curves of the sensor based on 4.11 mol% NSNFs to H2 in the range of 51000 ppm at 320  C.99

hydrogen adsorption kinetics thereby increasing the sensitivity of a nanostructured complex, polyethyleneimine (PEI) functional-
the hetero-contact sensor. ized polyamide 6 (PA 6) (PEI-PA 6) nanofiber/nets (NFN), as
Hwang et al. reported on LaOClNiO based composite a novel sensor coating on quartz crystal microbalance (QCM) for
nanofiber mats for p-type gas sensors which were prepared via highly sensitive formaldehyde detection.101 The PA 6 composite
electrospinning of LaNiO3 precursor/poly(vinyl acetate) NFN membranes formed with different voltages, indicating that
composite fibers are shown in Fig. 9(a).100 The crystallite sizes the resultant nanofibers were randomly oriented as 3D porous
within the nanofibers were found to be 150 and 200 nm by membranes with a diameter of several hundred nanometres
increasing the calcinations temperatures and more porous between 180 and 500 nm with BET measurements are found to be
microstructures were developed in specimens calcined at the around 19 to 34 surface area/m2 g1. When exposed to 100 ppm
higher temperature (950  C) are shown in Fig. 9(b). The LaOCl of formaldehyde, the maximum frequency shifts of QCM sensors
NiO composite fiber mats calcined at 550  C and 650  C exhibit coated with PEI flat film, PEI-PA 6 NFN (20 kV) and PEI-PA 6
unique p-type semiconducting gas sensing properties increasing NFN (30 kV) were 19.0, 25.6, and 52.8 Hz, respectively. The
the resistance in the presence of reducing gases (CO, H2, NH3, PEI-PA 6 NFN nanostructure based sensor showed excellent
and C2H5OH) and decreasing in the presence of an oxidizing gas sensing performance towards formaldehyde in terms of higher
(NO2) are shown in Fig. 9(c). The enhanced gas sensing char- response, fast response, good selectivity and reproducibility.
acteristics of LaOClNiO composite fiber mats are attributed to Liao et al. have synthesized single-walled carbon nanotube/poly-
their highly porous fibrillar structure with a high surface area aniline composite nanofibers for use as high-performance che-
that facilitates fast gas transport and effective surface reaction. mosensors.102 Interestingly, composites loaded with single-walled
Composite fiber mats calcined at #650  C showed p-type gas carbon nanotubes (SWCNTs) up to 5 wt% possess widely
sensing behavior, in which the exact carrier type for composite tunable conductivities of about 104 to 102 S cm1. Chemosensors
fibers through hole measurement was difficult due to the very fabricated from the composite nanofibers synthesized with
porous and rough surface. The LaOClNiO composite fiber mats a 1.0 wt% SWCNT loading respond much more rapidly to low
calcined at 550  C shows the detection limit of C2H5OH was <20 concentrations (100 ppb) of HCl and NH3 vapors compared to
ppm which is far below the general requirements (200 ppm, polyaniline nanofibers alone (120 s vs. 1000 s). Gas chemosensors
0.5 g C2H5OH per litre of blood). Ding et al. developed made from SWCNT/PANi composite nanofibers demonstrate

12962 | J. Mater. Chem., 2012, 22, 1295312971 This journal is The Royal Society of Chemistry 2012
View Article Online

Fig. 9 (a) SEM images of as-electrospun LaNiO3 precursor/PVAc composite nanofibers, (b) nanofibers calcined at 950  C (Inset: magnified image) (c)
bar graphs represent the gas sensitivities to 100 ppm CO, H2, NH3, NO2, and C2H5OH operated at 400  C. (Insets in display the dynamic gas sensing
responses of LaOClNiO nanofiber mats calcined at 550  C.)100
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

large improvements in sensitivity (120 s vs. 1000 s) compared to Drug delivery is viable with nanofibrous systems incorporating
devices fabricated from only pristine PANi nanofibers. Thus the drug within the nanofibrous matrices and release them slowly
Downloaded by University of Sussex on 15 December 2012

combinations of these new classes of composite nanofiber according to the need of organs. Herein, we classify (Fig. 10) the
materials can lead to exciting opportunities in advance sensors nanofiber composites according to their specific biomedical
applications. applications, namely; (i) tissue engineering or regenerative
medicine and (ii) drug delivery. Electrospinning has been
recognized as an efficient and well established technique capable
of producing nanofibers by electrically charging a suspended
6. Electrospun composite nanofibrous scaffolds for droplet of polymer melt or solution.105110 Various polymers
biomedical applications including synthetic ones such as poly(3-caprolactone) (PCL),
The principle of tissue engineering and regenerative medicine is poly(lactic acid) (PLA), poly(glycolic acid) (PGA), poly(lactic-
the application of biomaterial scaffolds to produce living struc- co-glycolic acid) (PLGA), polystyrene, polyurethane (PU),
tures with sufficient size and function to improve human lives. polyethyelene terephthalate (PET), poly(L-lactic acid)-co-poly(3-
Multiple technologies and strategies have evolved and it was only caprolactone) (PLACL) and biological materials such as
with the application of nanotechnology that the field improved collagen, gelatin, chitosan have been successfully electrospun to
tremendously. Tissue engineering, the multidisciplinary area of obtain fibers with diameters ranging from 3 nm to 5 mm.111113
research aims to repair, replace or regenerate cells, tissues or Co-axial electrospinning is a modification or extension of tradi-
organs to restore impaired function owing to defects and ageing. tional electrospinning technique with a major difference being
Nanotechnology for tissue engineering application focuses on a compound spinneret used. Using the spinneret, two compo-
the role of extracellular matrix (ECM) with a biomimetic nents are fed through different co-axial capillary channels and
migration, proliferation and differentiation.103 Tissue growth or are integrated into coreshell structured composite fibers to fulfil
regeneration is achieved with a stimulation assisted by cells or different application purposes.114 For example; bioactive
drug or growth factor loaded matrix at the damage tissue sites. composite scaffolds are fabricated using collagen (imparting
The requirement for such a matrix to induce tissue regeneration bioactivity) as the shell and PCL (synthetic polymer) as the core.
is that it has to be physically stable within implanted injury site, Coreshell structured nanofibers (360400 nm) prepared by co-
to direct and control tissue growth, biodegradable in vivo after axial electrospinning, have the advantages of being able to
the process and should not produce toxic metabolic byproducts. control the shell thickness and manipulate overall mechanical
These biomimetic tissue regeneration scaffolds are made by strength and degradation properties of resulting composite
natural and synthetic polymers with certain optimal mechanical nanofibers, without changing its biocompatibility. Alternatively,
strength and form that include sponge type or fibrous matrix or
hydrogel types. To engineer such a complex and multifunctional
scaffolds numerous nanotechnology techniques were evolved
that can fabricate porous, nanometre sized nanofiber scaffolds
with surface properties that influence cell fate determination,
allow regulation of specific protein expression patterns and
encourage cell-specific scaffold remodeling. These nano-
techniques can modulate surface topography down to submi-
cron/nanometre range and include nanoscale surface pattern
fabrication, electrospinning and self-assembly fabrication.104
Incorporating biological signals in the form of growth factors,
angiogenic factors, cell surface receptors, drug entities, reactive
oxygen species and spatial cues can further influence cellular
proliferation, migration, differentiation and 3D organization of Fig. 10 Schematic representation nanofiber composites for biomedical
tissues. applications.

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 1295312971 | 12963
View Article Online

coreshell structured composite nanofibers are functionalized for minerals have their long crystallographic c-axis oriented in
potential use in drug or growth factor encapsulation and release, parallel to each other and as well aligned with collagen tropo-
and development of highly sensitive sensors and tissue engi- collagen molecules.120 Collagen is easily biodegradable and
neering applications. resorbed by the body and facilitates excellent attachment to
cells. However, its mechanical properties are relatively low
(E z 100 MPa) especially with respect to bone (E z 25 GPa)121
6.1. Applications of composite nanofibrous scaffolds in tissue
and it is therefore highly cross-linked or found in composites,
engineering
such as collagenglycosaminoglycans for skin regeneration122 or
Tissue engineering is the application of knowledge and expertise Col/HAp for bone remodeling.123 The advantage of collagen and
from a multidisciplinary field, to develop and manufacture HAp devices in comparison with the synthetic PLGA124 devices is
therapeutic products that utilize the combination of matrix that the biocomposite significantly inhibited the growth of
scaffolds with viable human cell systems or cell responsive bacterial pathogens, which is often associated with prosthesis.
biomolecules derived from such cells, for the repair, restoration Electrostatic co-spinning nanoHAp and collagen improved the
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

or regeneration of cells or tissue damaged by injury, disease or mechanical properties of scaffold to mimic the complex nano-
congenital defects. Tissue engineering (TE) involve scaffolds or structured architecture. When collagen supports cell adhesion,
matrices to provide support for cells in order to express new proliferation and HAp acts as a seed for biomineralization of
ECM. The biocompatibility of scaffold materials actively osteoblasts in bone tissue regeneration.125 The bio-composites of
Downloaded by University of Sussex on 15 December 2012

participates in the signaling process for the requirement of safe collagen and nanoHAp is bioactive, osteoconductive, osteoin-
degradation and also provides a substratum for cell migration ductive and is a natural choice for bone grafting as it mimics the
into the defect sites of the tissue. TE is one of the most promising bone components.126,127 Bone like orientation of c-axes of HAp
techniques for the regeneration of tissues by autologous, allo- nanocrystals with regular alignment along collagen fibrils was
geneic cells and tissue transplantation. However, autografts are fabricated and demonstrated.128 The HAp/Col composite,
associated with limitations such as donor site morbidity and designed to simulate bone tissue, is produced using atelocollagen
limited availability. An alternative to autografts is allografts, to reduce antigenicity by condensing Ca(OH)2/H3PO4 suspen-
which have potential to cause an immune response and also carry sion.129 It was noted that the biomineralisation on Coll/HAp
the risk of disease transfer. Potential applications of electrospun composite nanofibrous scaffolds cultured with human foetal
composite nanofibers for TE are envisioned mainly in the hard osteoblasts was significantly higher than on collagen nanofibrous
tissue engineering, especially bone. scaffolds during 10 days of culture period. It was found that
mineral deposition was significantly lower up to 56% in collagen
6.1.1. ECM proteins (collagen and gelatin). Collagen is nanofibrous scaffolds without inorganic HAp. Thus it was
a fibrous protein found in animals, especially in the flesh and demonstrated that Col/HAp composite nanofibrous scaffold
connective tissues of mammals. It is the most abundant protein in provided a space for cell adhesion, growth, and also stimulated
mammals, containing up to 35% of the whole-body protein mineralization, the functional activity of osteoblasts for bone
content commonly created by fibroblast cells. Collagen is mostly tissue engineering.129
found as elongated fibrils in fibrous tissues such as tendon,
ligament and skin, and is also abundant in cornea, cartilage, 6.1.2. Gelatin. As the main practical problem associated with
bone, blood vessels, gut, and intervertebral disc. Collagen is collagen is its cost, and poor definition of commercial sources the
a major ECM component possesses fibrous structure with fibrils alternative gelatin is used for designing tissue engineering scaf-
of varying diameters (50500 nm). This fibrils influence cell folds. Gelatin (Gel), is a protein obtained from partial hydrolysis
behavior by allowing cell attachment to the nano-featured of collagen extracted from skin, bone, cartilage, ligaments etc.
collagen matrix. Cells seeded on this nanofibrous matrix tend to The composite of gelatin with other biodegradable synthetic
maintain their normal phenotype and guided growth along the polymers, known as bioartificial polymeric materials, has been
fiber orientation. The motif behind the biomimetic nano-strate- well adopted by researchers. This approach of blending gelatin
gies is to dictate, control and fabricate the morphology and with synthetic polymers reduces cytotoxicity by means of cross-
composition of developed biomaterials, in which the nano-crys- linking agents. Furthermore, this new biomaterial with excellent
tallites of inorganic hydroxyapatite (HAp) are being dispersed biocompatibility and improved mechanical and physical/chem-
with preferential orientation to enhance bone tissue regeneration. ical properties overcomes the obstacle associated with the use of
Because of potential biomedical application, many studies report single natural polymer.130 Interaction between cells and the
fabrication of bone-mimicking bio-composites of HAp and scaffold material depends on various physical-chemical proper-
bioactive organic components such as collagen, gelatin, chon- ties of the material and particle size, and surface properties which
droitin sulfate, chitosan and amphiphilic peptide by direct include topography, roughness, surface energy and wettability.
precipitation methods,115,116 poly(lactic acid) through a solvent- Chandrasekaran et al. demonstrated better fibroblast cell density
cast technique,117 and polyamide by solution method.118 HAp has and morphology in PLACL/gelatin scaffold after plasma treat-
inorganic crystalline nature that of natural bone and is ment compared to nanofibrous PLACL scaffolds.131 Further-
biocompatible, bioactive and osteoconductive in nature. High more, they observed the secretion of collagen on fibroblasts
levels of type I collagen and several non-collagenous proteins grown on PLACL and PLACLgelatin nanofibrous scaffolds.
(such as osteopontin, bone sialoprotein and osteocalcin) consti- But the plasma treated PLACLgelatin nanofibrous scaffolds
tute bone tissue. The dimension of bone mineral is around 50 nm have sufficient porous structures, hydrophilicity, mechanical
of length, 25 nm of width, and 25 nm of thickness.119 These bio- stability and the loose peripheral regions favorable for cell

12964 | J. Mater. Chem., 2012, 22, 1295312971 This journal is The Royal Society of Chemistry 2012
View Article Online

infiltration. It also provided enough space for fibroblast in- a modified two-step approach via the in situ co-precipitation
growth and thus resulted in the development of dermal substitute synthesis route was designed to overcome (Fig. 11) the usual
in skin tissue regeneration. Liu et al. fabricated 3D nanofiber- problem of nanoparticles agglomeration.144 The electrospinning
gelatin/apatite composite scaffolds that mimic both nanoscale process was adopted for preparation of HAp/CTS nano-
architecture and chemical composition of natural bone ECM.132 composite nanofibers with a higher (30 wt%) loading of HAp
With a new thermally induced phase separation and porogen nanoparticles. It was confirmed with electron diffraction and
leaching technique these 3D nanofibrous gelatin scaffolds with X-ray diffraction analysis that the acetic acid used for chitosan
well-defined macrospores were designed. The inorganic HAp was dissolution had minor or no influence on the crystallinity of HAp
deposited all along the 3D porous structure is ideal for control- nanoparticle incorporated within the nanocomposite nano-
ling surface topography and chemistry within complex nano- fibrous structure. Bone regeneration ability of the scaffold was
structures. And it was shown that these scaffolds have excellent assessed on these HAp/chitosan nanocomposite nanofibrous
biocompatibility and mechanical properties with enhanced scaffolds by conducting MTS and ARS assays of human fetal
osteoblast adhesion, proliferation and differentiation suitable for osteoblasts cultured for up to 15 days. The results confirmed that
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

bone tissue engineering. the HAp/chitosan nanocomposite scaffolds significantly


enhanced bone formation compared to the electrospun chitosan
6.1.3. Silk proteinsilk fibroin. Silk fibroin is considered as alone scaffold.
the most promising natural fibrous protein replacement for
Downloaded by University of Sussex on 15 December 2012

collagen in bone tissue engineering due to their biocompatibility, 6.1.5. Synthetic polymer nanofibers for tissue engineering.
slow biodegradation, and excellent mechanical properties. In the Synthetic polymers used for tissue engineering scaffolds facili-
past few years, two natural silk sources (e.g., silkworm silk tate a higher mechanical stability compared to natural scaffolds.
Bombyx mori and spider dragline silk Nephila clavipes) have been Furthermore, they avoid use of available cross-linking agents
processed for making nanofibers via electrospinning. In order to for slow degradation of the scaffold. And they constitute a new
improve electrospinnability of silk protein solutions and to avoid generation biomaterials to mimic the structure and character-
potential influences of polar hazardous organic solvents such as istic of native ECM, such as fibrillar structure, viscoelasticity,
hexafluoroisopropanol,133 hexafluoroacetone,134 and formic cell addition domains, growth factor binding and proteolytic
acid135 on scaffolds biocompatibility, Jin et al. used an all- sensitivity. HAp nanoparticles were electrosprayed on PLACL/
aqueous electrospinning by blending silk fibroin with a fiber gelatin nanofibers and thus produced scaffolds with controlled
forming agent PEO at a ratio from to 2/3 .136 Methanol treat- morphology which were found to be suitable for bone tissue
ment of the electrospun scaffold renders water insolubility of the engineering. Gupta et al. used a simultaneous electrospraying
scaffold because of the structural conformational change into and electrospinning concept and fabricated PLACL/Gel/HAp
native b-sheet structure. Silk-based biocomposite nanofibers of nanofibers and compared their mechanical and cellular prop-
HAp and bone morphogenetic protein-2 (BMP-2) as growth erties (Fig. 12) with blend electrospun PLACL/Gel/HAp
factor were fabricated by Li et al. to realize enhanced bone
formation outcomes by culturing with human bone marrow-
derived mesenchymal stem cells (hMSCs).137 It was observed that
the inclusion of BMP-2 and HAp with electrospun silk fibroin
nanofibers resulted in the highest calcium deposition and up
regulation of BMP-2 transcript levels compared to other elec-
trospun silk-based scaffolds.

6.1.4. Amino polysaccharide chitosan composites (calcium


carbohydrate composites). Chitosan, an amino polysaccharide,
derived from the structural biopolymer chitin, exists abundantly
in crustacean shells (e.g., crabs) and plays a key role as that of
collagen in higher vertebrates. Chitosan retains a number of
salient features such as structural similarity to glucosaminogly-
can found in bone, osteoconductivity, excellent biocompatibility,
tailorable biodegradability, low immunogenicity, and better
mechanical properties, as an alternative to collagen from a tissue
engineering perspective138140 but at cheaper cost. Chitosan is
poorly electrospinnable, forms aggregates with non-electro-
spinnable HAp nanoparticles and formulating a robust chitosan
solution is a prerequisite to generate nanofibrous HAp/chitosan
biocomposite scaffolds. Because of these limitations in chitosan
electrospinning.141,142 There are only a few reports on nano-
fibrous HA/chitosan composites for bone tissue engineering. Fig. 11 FESEM images of electrospun HAp/CTS nanocomposite
With ultrahigh molecular weight poly(ethylene oxide) nanofibers: doped with 20 wt% conventional PEO with a moderate
(UHMWPEO) as support polymer, Zhang et al. demonstrated molecular weight (A), doped with 10 wt% UHMWPEO at low magnifi-
that chitosan nanofibers could be prepared.143,144 After this cation (B), at higher magnification (C), and after alkali treatment (D).144

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 1295312971 | 12965
View Article Online

scaffolds.145 Electrospun PLACL/Gel/HAp (blend) nanofibers infiltration of endogenous cells when scaffolds were placed
had the drawback of trapping HAp embedded inside the within calvarial organ cultures. Thus the sacrificial PEO
nanofibers (diameter 198  107 nm), while the HAp nano- nanofiber enhances cell infiltration and hence overcomes one of
particles were found to be uniformly sprayed, forming a layer of the major limitations of bone-mimetic promising matrix in
HA on the surface of the other PLACL/Gel/HAp scaffold bone tissue regeneration.
(diameter 406  155 nm). The tensile stress for HAp electro-
sprayed scaffold was higher than PLACL/Gel/HA (blend) 6.1.7. Poly(lactic acid) (PLLA). PLLA is a thermoplastic
scaffold and this was due to the fact that the electrospraying of aliphatic polyester derived from renewable resources, and can be
HAp nanoparticles resulted in superficial dispersion of HAp synthesized from cyclic D,L-lactide via ring opening polymeriza-
nanoparticles. A significant increase in hFOB proliferation was tion. Upon seeding human Fetal Osteoblasts (hFOBs) on PLLA/
observed on the HAp electrosprayed scaffold than on the HAp and PLLA/Coll/HAp,117,149 the biocomposite PLLA/Coll/
PLACL/Gel/HAp (blend) nanofibers after 15 days of cell HAp nanofibrous scaffold was found superior than PLLA/HAp
seeding. Further the electrosprayed scaffolds showed 50% for effective bone regeneration and mineralization. In addition,
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

higher biomineralization than the PLACL/Gel/HAp (blend), the tensile strength of biocomposite scaffold was higher than the
thus proving the versatility of the electrospraying method collagen fibrous matrix (1.68 MPa) and even PCL/HAp scaf-
compared to blend technique with respect to scaffold design for folds. The ALP activity was 25% higher on biocomposite
bone tissue engineering.145 nanofibrous scaffolds compared to PLLA/HAp scaffolds after 20
Downloaded by University of Sussex on 15 December 2012

days of cell culture. The bone nodule formation of hFOB


6.1.6. Polycaprolactone (PCL). Electrospun PCL nano- cultured on different electrospun nanofibers were characterized
fibrous scaffolds were fabricated by Yoshimoto et al. and by ARS staining, and the mineralization was found to be 57%
MSCs from bone marrow of neonatal rats were seeded with higher on biocomposite scaffolds compared to PLLA/HAp
osteogenic supplements.146 Cell penetration into the fibrous scaffolds. Elemental analysis by EDX measurement primarily
matrix was observed along with abundant ECM deposits in the consisted of calcium and phosphorus deposition, showing that
cellpolymer constructs, thus favoring PCL as potential scaf- osteoblasts seeded on PLLA/Coll/HAp nanofibers formed bio-
folds for bone tissue engineering. PCL/HAp,147 PCL/Coll/ mineralized tissue. Scaffolds with HAp containing composites
HAp,148 PCL/Gel/HAp,130 were fabricated and tried for the enhanced the formation of new bone tissue with increased oste-
suitability of the scaffold for bone tissue engineering. Electro- oblast adhesion, osteointegration and calcium mineral deposi-
spun PCL/HAp nanofibrous scaffold after plasma treatment tion on its surface.150 Recently, Rajeswari et al. fabricated
found to enhance the wettability and thus accelerated the nanohydroxyapatite decorated PLLA/PBLG/Col nanofibers for
biodegradation rate of nanofibrous scaffolds. It was observed the differentiation of adipose derived stem cells to osteogenic
that PCL/HAp plasma treated scaffold showing the mineral lineage (Fig. 13).151 Furthermore, they claim that bioactive
formation on the surface of osteoblast cell layers within 6 days PBLG/n-HA drives and directs the specific biological functions
of culture. With increase in pore size from 424 to 1826.11 mm2 like adhesion, proliferation and differentiation of ADSC into
of PCL/HAp/Coll148 scaffolds created with sacrificial fibers of bone tissue and thus providing promising scaffolds for bone
PEO it was shown to facilitate MSC infiltration in vitro and also tissue engineering.

Fig. 12 SEM micrographs showing morphology and mineralization of hFOB cells on nanofibrous substrates after day 15 of culture. (a) PLACL (b)
PLACL/Gel (c) PLACL/Gel/HA (blend) (d) PLACL/Gel/HA (spray) nanofibers (e) TCP.145

12966 | J. Mater. Chem., 2012, 22, 1295312971 This journal is The Royal Society of Chemistry 2012
View Article Online

6.2. Drug loaded nanofibers (composites) for cancer peptide amphiphile (PA) comprising a cell-adhesive matrix
chemotherapy metalloproteinase-2 (MMP-2)-sensitive GTAGLIGQRGDS and
a fatty acid.153 The incorporation of the drug inside the self-
Drug loaded nanofibers ensure persistent degradation of nano-
assembled CDDPPA nanofibers was confirmed with trans-
fibers with the utilization of suitable polymer and there by
mission electron microscopy (TEM). Bioresponsive controlled
continuous release of the encapsulated or entrapped drug in
delivery of the drug from biomimetic gel was demonstrated by in
a controlled manner. Furthermore, the coreshell electro-
vitro MMP-2-triggered CDDP release. Chen et al. fabricated
spinning entraps the drug inside the shell polymer which slowly
PLA nanofibers incorporated with cisplatin and tested the effi-
degrades and releases the drug or growth factor. Also, in blend
cacy of drug loaded nanofibers against human tumor spc-a-1
electrospinning, the release of drugs can be controlled by drug
cells.154 They have demonstrated that cisplatin incorporated
polymer interaction which can help in the slow release of drug
fibers could continuously release the drug in an active form and
from the nanofiber matrix. The drug delivery through composite
foreseen the potential application of the system as an implantable
nanofibrous formulations are summarized in Table 1.152159
drug for lung tumor in the future.
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

6.2.1. Titanium as titanocene. A titanium nanofiber


6.2.3. Drug loaded nanofibers (composites) for wound healing/
composite in the form of titanocene drug loaded nanofiber has
dressing silver nanoparticles. Silver (Ag) nanoparticles fight
been applied as a drug delivery system for cancer chemotherapy.
infection from bacteria, virus and fungi basically by blocking
Chen et al. have shown titanocene dichloridePLLA nanofibers
Downloaded by University of Sussex on 15 December 2012

oxygen uptake to the microorganisms. Furthermore, Ag nano-


as a sustained delivery system and the drug continuously be
particles are long known for their usefulness in wound healing.
released in an active form from the system.152 Furthermore, it
Yuan et al. have made antimicrobial nanofibers of PCL by
was suggested that this method can control the release of anti-
electrospinning of a PCL solution with small amounts of silver-
cancer drug not only to improve safety, but also to enhance the
loaded zirconium phosphate nanoparticles (AgZ) for potential
efficacy of cancer chemotherapy.
use in wound dressing applications.155 Strong biocidal activity of
Ag+ in nanoAgZ was observed from the antimicrobial tests
6.2.2. Platinum as cisplatin. Bioresponsive cisplatin, a plat-
against bacterial strains. Furthermore, the study with primary
inum drug (cis-dichlorodiamine platinum (II) (CDDP)) as
human dermal fibroblasts culturing on the nanofibrous mats has
a nanofiber composite was first designed with a self-assembling
shown good cell attachment and proliferation as continuous
layers on the nanoAgZ-containing nanofibers with healthier
morphology of human dermal fibroblasts. Thus the nanoAgZ-
containing PCL nanofibers envisaged as potential materials for
wound dressing applications, based on their bacteriostatic
activity and biocompatibility. The well-known wound dressing
material polyurethane was electrospun with silver nanoparticles
(Fig. 14) by Lakshman et al. and observed that the material
exhibited good antibacterial and cytocompatibility, which are
very essential criteria for wound dressing applications.156 Nguyen
et al. fabricated Silver nanoparticles incorporated nanofiber in
two different methods and tested their antibacterial activity
against Escherichia coli.157 Furthermore, it was observed that
there exists a synergistic effect between silver and chitosan by
chelation mechanism, which added to the antibacterial property
of the electrospun webs.

7. Future perspectives
The global demand for energy and health care are growing even
faster than the population, and the escalating demand from
developing countries will further exacerbate this situation. Owing
to its simplicity and adoptability of the electrospinning process
yielded nanostructures of various composite metal-oxides with
tunable morphologies, increased surface area and hollow/core
shell structures, effective electron transfer and interaction along
the structures. The composite electrospun nanostructures such as
TiO2, ZnO, Fe2O3, CuO, SnO2, MnO2 have wide variety of
Fig. 13 Confocal microscopy images to confirm the osteogenic differ- potential applications in dye-sensitized solar cells, batteries,
entiation of ADSCs using ADSC specific marker proteins, characteristic magnetic materials, catalysis, fuel cells, water-splitting, thermo-
of ADSC cells which have undergone osteogenic differentiation (c, f, I, electric, anti-reflective and photonic materials. These nano-
l, o) on TCP (ac), PLLA (df), PLLA/PBLG (gi), PLLA/PBLG/Col composites have good potential for scale-up and cost
(jl) and PLLA/PBLG/Col/n-HA (mo) at 60 magnification.151 effectiveness in nano-electronic domain is yet to be explored.

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 1295312971 | 12967
View Article Online

Table 1 Composite nanofibrous scaffolds that find applications in drug delivery and skin regeneration

Electrospinning or fabrication
Polymer conditions Material incorporated Cells

PLLA Titanium/PLLA nanofiber Titanium in the form of Sustained release of anticancer


composite in the form of titanocene dichloride drug152
titanocene drug
Self-assembling peptide Self-assembling peptide amphiphile Platinum drug Bioresponsive anticancer drug
with cisplatin (cis-dichlorodiammine release from the biomimetic gel153
platinum(II))
PLA Electrospun PLA nanofibers Platinum drug Continuous release of anticancer
incorporated with cisplatin (cis-dichlorodiammine drug154
platinum(II))
PCL Electrospinning of a PCL solution Silver-loaded zirconium Yuan et al.,155 primary human
with small amounts of silver-loaded phosphate nanoparticles dermal fibroblasts
zirconium phosphate nanoparticles
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

PU Electrospinning of polyurethane Silver nanoparticles Antibacterial and


with silver nanoparticles for wound cytocompatibility156
dressing material
Chitosan Electrospinning chitosan and Silver nanoparticles Synergistic effect between silver
Ag nanoparticles and chitosan by chelation
Downloaded by University of Sussex on 15 December 2012

mechanism157
Poly(N-isopropylacrylamide)- Blend with functionalized gold Gold nanoparticles Synergistic enhancement effects of
co-polystyrene nanoparticles to form the new the gold nanocomposites on the
nanofiber nanocomposites daunorubicin drug uptake158
PU/MWNT Polyurethane/multiwalled carbon Multiwalled carbon Growth and anticoagulant function
nanotube composite nanofiber nanotubes of human umbilical vein
endothelial cells159

8. Conclusions
A comprehensive study of the functionality and applicability of
composite nanostructures with potential for fabricating novel
nanocomposite scaffolds for energy, sensors, filters and
biomedical applications has been carried out. It was noted that
the functionalities of these composites can be improved either by
incorporating secondary phases during electrospinning or in the
post-processing for fabricating the scaffolds. This article
discusses in detail the applicability of these nanocomposites in
energy, sensors, filters and bio-technology, critically analyzing
their performance with respect to their respective parent mate-
rials. As a better understanding of the electrospinning and co-
axial electrospinning process is achieved through theoretical
Fig. 14 SEM images of PU fiber and silver nanoparticles incorporated modeling and practically fabricating nanocomposites, it is
PU fibers (a) PU fiber, (b) PU fiber with (0.005% Ag), (c) PU fiber (with expected that all these technical problems will be solved in the
0.01% Ag), and (d) PU fiber (with 0.015% Ag).156 near future to generate 4th generation bio-composite materials.
The article also provides a first-hand detailed discussion
In bone tissue engineering, synthetic hydroxyapatite has been regarding the technological issues, research challenges, and
extensively used as an implant material for bone substitute owing future trends in the fast-developing field of nanocomposites.
to its excellent osteoinductive properties. Materials that can
induce specific biological activity to repair the damaged organs
are called bioactive materials. Calcium phosphate ceramics have
Acknowledgements
been tested for several years and are most commonly used for This study was supported by the Singapore NRF-CRP grant (R-
clinical applications. Especially HAp and b-tricalcium phosphate 398-000-071-592), NRF-Technion (R-398-001-065-592),
resemble the mineral phase of bone and are characterized as Ministry of Education (R-265-000-318-112) and NUSNNI,
biocompatible, bioactive, osteoconductive and osteoinductive. National University of Singapore, Singapore.
These composites are used in dental and orthopedic surgery as
fillers for bone defects and as coatings on metallic implants to
improve the integration of implants in host bone. Further studies References
on assessing the long-term in vivo performance employing the
1 L. J. Zhang and T. J. Webster, Nano Today, 2009, 4, 6680.
current technologies are indispensable for attaining clinical 2 L. J. Zhang, J. Rodriguez, J. Raez, A. J. Myles, H. Fenniri and
success. T. J. Webster, Nanotechnology, 2009, 20, 175101.

12968 | J. Mater. Chem., 2012, 22, 1295312971 This journal is The Royal Society of Chemistry 2012
View Article Online

3 H. S. Park, B. G. Choi, S. H. Yang, W. H. Shin, J. K. Kang, D. Jung 39 L. W. Ji, Y. F. Yao, O. Toprakci, Z. Lin, Y. Z. Liang, Q. Shi,
and W. H. Hong, Small, 2009, 5, 17541760. A. J. Medford, C. R. Millns and X. W. Zhang, J. Power Sources,
4 N. L. Nerurkar, B. M. Baker, S. Sen, E. E. Wible, D. M. Elliott and 2010, 195, 20502056.
R. L. Mauck, Nat. Mater., 2009, 8, 986992. 40 H. R. Jung, D. H. Ju, W. J. Lee, X. W. Zhang and R. Kotek,
5 N. Mathews, B. Varghese, C. Sun, V. Thavasi, B. P. Andreasson, Electrochim. Acta, 2009, 54, 36303637.
C. H. Sow, S. Ramakrishna and S. G. Mhaisalkar, Nanoscale, 41 K. H. J. K. H. Jung and S. J. Park, in Multi-Functional Materials and
2010, 2, 19841998. Structures Iii, Pts 1 and 2, Trans Tech Publications Ltd, Stafa-
6 H. W. Lu, D. Li, K. Sun, Y. S. Li and Z. W. Fu, Solid State Sci., Zurich, 2010, pp. 10871090.
2009, 11, 982987. 42 K. U. Jeong, H. D. Chae, C. Il Lim, H. K. Lee, J. H. Ahn and
7 L. F. Cui, Y. Yang, C. M. Hsu and Y. Cui, Nano Lett., 2009, 9, C. Nah, Polym. Int., 2010, 59, 249255.
33703374. 43 Y. W. Ju, J. H. Park, H. R. Jung and W. J. Lee, Electrochim. Acta,
8 L. W. Ji and X. W. Zhang, Carbon, 2009, 47, 32193226. 2007, 52, 48414847.
9 A. Goyal, A. L. M. Reddy and P. M. Ajayan, Small, 2011, 7, 1709 44 S. Molla, V. Compan, E. Gimenez, A. Blazquez and I. Urdanpilleta,
1713. Int. J. Hydrogen Energy, 2011, 36, 98869895.
10 J. J. Lee, E. W. Park and S. H. Hyun, Fuel Cells, 2010, 10, 145155. 45 J. R. Lee, N. Y. Kim, M. S. Lee and S. Y. Lee, J. Membr. Sci., 2011,
11 S. Molla and V. Compa~ n, J. Membr. Sci., 2011, 372, 191200. 367, 265272.
12 Z. Z. Li, X. L. Cui, X. S. Zhang, Q. F. Wang, Y. Y. Shao and 46 T. Tamura and H. Kawakami, Nano Lett., 2010, 10, 13241328.
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

Y. H. Lin, J. Nanosci. Nanotechnol., 2009, 9, 23162323. 47 Z. Lin, L. W. Ji, W. E. Krause and X. W. Zhang, J. Power Sources,
13 B. G. Choi, J. Hong, Y. C. Park, D. H. Jung, W. H. Hong, 2010, 195, 55205526.
P. T. Hammond and H. Park, ACS Nano, 2011, 5, 51675174. 48 H. L. Lin, S. H. Wang, C. K. Chiu, T. L. Yu, L. C. Chen,
14 L. Liu, Z. M. Huang, C. L. He and X. J. Han, Mater. Sci. Eng., A, C. C. Huang, T. H. Cheng and J. M. Lin, J. Membr. Sci., 2010,
2006, 435, 309317. 365, 114122.
Downloaded by University of Sussex on 15 December 2012

15 S. Sihn, R. Y. Kim, W. Huh, K. H. Lee and A. K. Roy, Compos. Sci. 49 S. W. Choi, Y. Z. Fu, Y. R. Ahn, S. M. Jo and A. Manthiram,
Technol., 2008, 68, 673683. J. Power Sources, 2008, 180, 167171.
16 S. M. Dong, X. Chen, L. Gu, L. X. Zhang, X. H. Zhou, Z. H. Liu, 50 S. Kerzenmacher, J. Ducree, R. Zengerle and F. von Stetten,
P. X. Han, H. X. Xu, J. H. Yao, X. Y. Zhang, L. F. Li, C. Q. Shang J. Power Sources, 2008, 182, 117.
and G. L. Cui, Biosens. Bioelectron., 2011, 26, 40884094. 51 S. Prilutsky, P. Schechner, E. Bubis, V. Makarov, E. Zussman and
17 B. Khlebtsov, E. Panfilova, V. Khanadeev, O. Bibikova, Y. Cohen, Electrochim. Acta, 2010, 55, 36943702.
G. Terentyuk, A. Ivanov, V. Rumyantseva, I. Shilov, A. Ryabova, 52 M. Zhi, N. Mariani, R. Gemmen, K. Gerdes and N. Wu, Energy
V. Loshchenov and N. G. Khlebtsov, ACS Nano, 2011, 5, 7077 Environ. Sci., 2011, 4, 417420.
7089. 53 B. Jeong, S. Uhm and J. Lee, Iron-Cobalt Modified Electrospun
18 L. Balogh, S. S. Nigavekar, B. M. Nair, W. Lesniak, C. Zhang, Carbon Nanofibers as Oxygen Reduction Catalysts in Alkaline Fuel
L. Y. Sung, M. S. T. Kariapper, A. El-Jawahri, M. Llanes, Cells, Polymer Electrolyte Fuel Cells 10, 218th ECS Meeting, Las
B. Bolton, F. Mamou, W. Tan, A. Hutson, L. Minc and Vegas, NV, 2010, pp. 17571767.
M. K. Khan, Nanomed.: Nanotechnol., Biol. Med., 2007, 3, 281296. 54 B. ORegan and M. Gratzel, Nature, 1991, 353, 737740.
19 L. M. Bellan and H. G. Craighead, Trans. ASME, Ser. B, 2009, 131, 55 M. Gratzel, J. Photochem. Photobiol., A, 2004, 164, 314.
03400110340014. 56 X. M. Feng, X. W. Huang, H. Huang, P. Shen, B. Zhao and
20 L. Nikkola, K. Vapalahti, R. Huolman, J. Seppala, A. Harlin and S. T. Tan, Acta Chim. Sin., 2010, 68, 11231129.
N. Ashammakhi, J. Biomed. Nanotechnol., 2008, 4, 331338. 57 J. K. Lee, H. J. Choi, S. H. Park, D. H. Won, H. W. Park, J. H. Kim,
21 N. Wang, H. Chen, L. Lin, Y. Zhao, X. Cao, Y. Song and L. Jiang, C. J. Lee, S. H. Jeong and M. R. Kim, Mol. Cryst. Liq. Cryst., 2010,
Macromol. Rapid Commun., 2010, 31, 16221627. 519, 234244.
22 J. Ayutsede, M. Gandhi, S. Sukiraga, H. Ye, C. M. Hsu, Y. Gogotsi 58 P. Joshi, L. Zhang, D. Davoux, Z. Zhu, D. Galipeau, H. Fong and
and F. Ko, Biomacromolecules, 2006, 7, 208214. Q. Qiao, Energy Environ. Sci., 2010, 3, 15071510.
23 S. Aryal, C. K. Kim, K. W. Kim, M. S. Khil and H. Y. Kim, Mater. 59 Z. Peining, A. S. Nair, Y. Shengyuan, P. Shengjie, N. K. Elumalai
Sci. Eng., C, 2008, 28, 7579. and S. Ramakrishna, J. Photochem. Photobiol., A, 2012, 231, 918.
24 O. Ayodeji, E. Graham, D. Kniss, J. Lannutti and D. Tomasko, J. 60 Z. Peining, A. S. Nair, P. Shengjie, Y. Shengyuan and
Supercrit. Fluids, 2007, 41, 173178. S. Ramakrishna, ACS Appl. Mater. Interfaces, 2012, 4, 581585.
25 A. Bianco, G. Iardino, C. Bertarelli, L. Miozzo, A. Papagni and 61 Y. Shengyuan, Z. Peining, A. S. Nair and S. Ramakrishna, J. Mater.
G. Zerbi, Appl. Surf. Sci., 2007, 253, 83608364. Chem., 2011, 21, 65416548.
26 S. T. Martin, H. Herrmann, W. Y. Choi and M. R. Hoffmann, J. 62 Y. Shengyuan, A. S. Nair, R. Jose and S. Ramakrishna, Energy
Chem. Soc., Faraday Trans., 1994, 90, 33153322. Environ. Sci., 2010, 3, 20102014.
27 R. L. Liu, H. Y. Ye, X. P. Xiong and H. Q. Liu, Mater. Chem. Phys., 63 K. Kim, C. Lee, I. W. Kim and J. Kim, Fibers Polym., 2009, 10, 60
2010, 121, 432439. 64.
28 Y. B. Kim, D. Cho and W. H. Park, J. Appl. Polym. Sci., 2010, 116, 64 A. Patanaik, V. Jacobs and R. D. Anandjiwala, J. Membr. Sci., 2010,
449454. 352, 136142.
29 K. Nakata, N. Watanabe, Y. Yuda, D. A. Tryk, T. Ochiai, 65 S. Sundarrajan, D. Pliszka, A. Jaworek, A. Krupa, M. Lackowski
T. Murakami, Y. Koide and A. Fujishima, J. Ceram. Soc. Jpn., and S. Ramakrishna, J. Nanosci. Nanotechnol., 2009, 9, 44424447.
2009, 117, 12031207. 66 T. Uyar, R. Havelund, Y. Nur, J. Hacaloglu, F. Besenbacher and
30 J. S. Lm, B. C. Bai, S. J. In and Y. S. Lee, J. Colloid Interface Sci., P. Kingshott, J. Membr. Sci., 2009, 332, 129137.
2010, 346, 216221. 67 S. W. Park, H. S. Bae, Z. C. Xing, O. H. Kwon, M. W. Huh and
31 J. S. Lm, M. Il Kim and Y. S. Lee, Mater. Lett., 2008, 62, 36523655. I. K. Kang, J. Appl. Polym. Sci., 2009, 112, 23202326.
32 J. X. Wang, Y. Q. Guo, X. T. Dong, Z. G. Li and G. X. Liu, J. Inorg. 68 H. R. Pant, M. P. Bajgai, K. T. Nam, Y. A. Seo, D. R. Pandeya,
Mater., 2010, 25, 379385. S. T. Hong and H. Y. Kim, J. Hazard. Mater., 2011, 185, 124130.
33 C. Pan, Z. Z. Gu and L. Dong, Acta Chim. Sin., 2009, 67, 19811986. 69 H. A. Liu and K. J. Balkus, Mater. Lett., 2009, 63, 23612364.
34 H. Teng, Y. Liu and T. Y. You, Chem. Res. Chin. Univ., 2011, 27, 70 S. S. Homaeigohar, K. Buhr and K. Ebert, J. Membr. Sci., 2010, 365,
496499. 6877.
35 S. H. Ye, D. Zhang, H. Q. Liu and J. P. Zhou, J. Appl. Polym. Sci., 71 X. Wang, K. Zhang, Y. Yang, L. Wang, Z. Zhou, M. Zhu,
2011, 121, 17571764. B. S. Hsiao and B. Chu, J. Membr. Sci., 2010, 356, 110116.
36 T. S. He, H. H. Ma, Z. F. Zhou, W. B. Xu, F. M. Ren, Z. F. Shi and 72 B. Y. Yeom, E. Shim and B. Pourdeyhimi, Macromol. Res., 2010, 18,
J. Wang, Polym. Degrad. Stab., 2009, 94, 22512256. 884890.
37 L. W. Ji, Z. Lin, A. J. Medford and X. W. Zhang, Chem.Eur. J., 73 A. A. Kirsh, A. K. Budyka and V. A. Kirsh, Russ. J. Gen. Chem.,
2009, 15, 1071810722. 2009, 79, 20452050.
38 L. W. Ji, Z. Lin, R. Zhou, Q. Shi, O. Toprakci, A. J. Medford, 74 S. Sihn, R. Y. Kim, W. Huh, K. H. Lee and A. K. Roy, Compos. Sci.
C. R. Millns and X. W. Zhang, Electrochim. Acta, 2010, 55, 1605 Technol., 2008, 68, 673683.
1611. 75 B. Yoon and S. Lee, Fibers Polym., 2011, 12, 5764.

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 1295312971 | 12969
View Article Online

76 S. Lee and S. K. Obendorf, Fibers Polym., 2007, 8, 501506. 113 C. H. Lee, H. J. Shin, I. H. Cho, Y. M. Kang, I. A. Kim, K. D. Park
77 P. Akangah, S. Lingaiah and K. Shivakumar, Compos. Struct., 2010, and J. W. Shin, Biomaterials, 2005, 26, 12611270.
92, 14321439. 114 Y. Z. Zhang, J. Venugopal, Z. M. Huang, C. T. Lim and
78 G. J. Cadena, J. Riu and F. X. Rius, Analyst, 2007, 132, 1083 S. Ramakrishna, Biomacromolecules, 2005, 6, 25832589.
1099. 115 M. Kikuchi, S. Itoh, S. Ichinose, K. Shinomiya and J. Tanaka,
79 A. A. Tomchenko, G. P. Harmer, B. T. Marquis and J. W. Allen, Biomaterials, 2001, 22, 17051711.
Sens. Actuators, B, 2002, 93, 126134. 116 F. Chen, Z. C. Wang and C. Lin, J. Mater. Lett., 2002, 57, 658
80 J. Janata and M. Josowicz, Nat. Mater., 2003, 2, 1924. 662.
81 J. Huang, S. Virji, B. H. Weiller and R. B. Kaner, J. Am. Chem. Soc., 117 S. S. Liao, F. Z. Cui and Q. L. Feng, J. Biomed. Mater. Res. B: Appl.
2003, 125, 314315. Biomater., 2004, 69, 158165.
82 H. Karami, Int. J. Electrochem. Sci., 2010, 5, 720730. 118 J. Wei, Y. B. Li, W. Q. Chen and Y. Zuo, J. Mater. Sci., 2003, 38,
83 H. Kawasaki, T. Ueda, Y. Suda and T. Ohshima, Sens. Actuators, B, 33033306.
2004, 100, 266269. 119 E. Sachlos, D. Gotora and J. T. Czernuszka, Tissue Eng., 2006, 12,
84 M. Ferreira, P. A. Fiorito, O. N. Oliveira Jr and S. I. C. de Torresi, 24792487.
Biosens. Bioelectron., 2004, 19, 16111615. 120 S. Weiner and W. Traub, Connect. Tissue Res., 1989, 21, 589595.
85 H. Huang, C. Y. Ong, J. Guo, T. White, M. S. Tse and O. K. Tan, 121 K. I. Clarke, S. E. Graves, A. T. C. Wong, J. T. Triffit,
Nanoscale, 2010, 2, 12031207. M. J. O. Francis and J. T. Czernuszka, J. Mater. Sci.: Mater.
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A

86 S. Ramakrishna, K. Fujihara, W. E. Teo, T. C. Lim and Med., 1993, 4, 107110.


Z. W. L. Ma, Introduction to Electrospinning and Nanofibers, 122 F. J. OBrien, B. A. Harley, I. V. Yannas and L. Gibson,
World Scientific Publishers, 2005, pp. 1382. Biomaterials, 2004, 25, 10771086.
87 I. S. Chronakis, J. Mater. Process. Technol., 2005, 167, 283 123 J. Venugopal, S. Low, A. T. Choon, T. S. Sampath Kumar and
293. S. Ramakrishna, J. Mater. Sci.: Mater. Med., 2008, 19, 2039
Downloaded by University of Sussex on 15 December 2012

88 Y. Dzenis, Science, 2004, 304, 19171919. 2046.


89 K. Jayaraman, M. Kotaki, Y. Zhang, X. Mo and S. Ramakrishna, 124 G. A. Carlson, J. L. Dragoo, B. Samimi, D. A. Bruckner and
J. Nanosci. Nanotechnol., 2004, 4, 5265. P. Benhaim, Biochem. Biophys. Res. Commun., 2004, 321, 472
90 Y. Li, J. Gong, G. He and Y. Deng, Mater. Chem. Phys., 2011, 129, 478.
477482. 125 W. J. Landis, M. J. Song, A. Leith, L. McEwen and B. F. McEwen,
91 A. Z. Sadek, W. Wlodarski, K. Shin, R. B. Kaner and K. Kalantar- J. Struct. Biol., 1993, 110, 3954.
zadeh, Nanotechnology, 2006, 17, 4488. 126 D. Wahl and J. T. Czernuszka, Eur. Cells Mater., 2006, 11, 4356.
92 A. Z. Sadek, W. Wlodarski, K. Shin, R. B. Kaner and K. Kalantar- 127 D. A. Wahl, E. Sachlos, C. Liu and J. T. Czernuszka, J. Mater. Sci.:
zadeh, Synth. Met., 2008, 158, 2932. Mater. Med., 2007, 18, 201209.
93 W. Wang, Z. Li, W. Zheng, J. Yang, H. Zhang and C. Wang, 128 A. Porter, N. Patel, R. Brooks and W. Bonfield, J. Mater. Sci.:
Electrochem. Commun., 2009, 11, 18111814. Mater. Med., 2005, 16, 899907.
94 X. Li, Y. Gao, J. Gong, L. Zhang and L. Qu, J. Phys. Chem. C, 2009, 129 J. Venugopal, S. Low, A. T. Choon, T. S. Sampath Kumar and
113, 6973. S. Ramakrishna, J. Mater. Sci.: Mater. Med., 2008, 19, 2039
95 P. Li, Y. Li, B. Ying and M. Yang, Sens. Actuators, B, 2009, 141, 2046.
390395. 130 J. Venugopal, S. Low, A. T. Choon, A. Bharath Kumar and
96 H. Gullapalli, V. S. M. Vemuru, A. Kumar, A. B. Mendez, R. Vajtai, S. Ramakrishna, Artif. Organs, 2008, 32, 388397.
M. Terrones, S. Nagarajaiah and P. M. Ajayan, Small, 2010, 15, 131 A. R. Chandrasekaran, J. Venugopal, S. Sundarrajan and
16411646. S. Ramakrishna, Biomed. Mater., 2011, 6, 015001.
97 H. A. Khorami, M. Keyanpour-Rad and M. R. Vaezi, Appl. Surf. 132 X. Liu, L. A. Smith, J. Hu and P. X. Ma, Biomaterials, 2009, 30,
Sci., 2011, 257, 79887992. 22522258.
98 L. Ji, A. J. Medford and X. Zhang, Polymer, 2009, 50, 605 133 S. Zarkoob, R. K. Eby, D. H. Reneker, S. D. Hudson, D. Ertley and
612. W. W. Adams, Polymer, 2004, 45, 39733977.
99 Z. Wang, Z. Li, J. Sun, H. Zhang, W. Wang, W. Zheng and 134 S. H. Kim, Y. S. Nam, T. S. Lee and W. H. Park, Polym. J., 2003, 35,
C. Wang, J. Phys. Chem. C, 2010, 114, 61006105. 185190.
100 D. K. Hwang, S. Kim, J. H. Lee, I. S. Hwang and I. D. Kim, 135 K. Ohgo, C. Zhao, M. Kobayashi and T. Asakura, Polymer, 2003,
J. Mater. Chem., 2011, 21, 19591965. 44, 841846.
101 B. Ding, X. Wang, J. Yu and M. Wang, J. Mater. Chem., 2011, 21, 136 H. J. Jin, S. V. Fridrikh, G. C. Rutledge and D. L. Kaplan,
1278412792. Biomacromolecules, 2002, 3, 12331239.
102 Y. Liao, C. Zhang, Y. Zhang, V. Strong, J. Tang, X. G. Li, 137 C. Li, C. Vepari, H. J. Jin, H. Kim and D. Kaplan, Biomaterials,
K. K. Zadeh, E. M. V. Hoek, K. L. Wang and R. B. Kaner, Nano 2006, 27, 31153124.
Lett., 2011, 11, 954959. 138 I. Yamaguchi, K. Tokuchi, H. Fukuzaki, Y. Koyama, K. Takakuda
103 C. M. Kelleher and J. P. Vacanti, J. R. Soc. Interface, 2010, 7, S717 and H. Monma, J. Biomed. Mater. Res., 2001, 55, 2027.
S729. 139 C. Muzzarelli and R. A. A. Muzzarelli, J. Inorg. Biochem., 2002, 92,
104 C. E. Ayres, B. Jha, S. Sell, G. L. Bowlin and D. G. Simpson, Wiley 8994.
Interdiscip. Rev.: Nanomed. Nanobiotechnol., 2010, 2, 20 140 Q. Hu, B. Li, M. Wang and J. Shen, Biomaterials, 2004, 25, 779785.
34. 141 V. M. Rusu, C. H. Ng, M. Wilke, B. Tiersch, P. Fratzl and
105 D. H. Reneker, A. L. Yarin, H. Fong and S. Koombhangse, J. Appl. M. G. Peter, Biomaterials, 2005, 26, 54145426.
Phys., 2010, 87, 45314547. 142 D. Z. Yang, Y. Jin, G. P. Ma, X. M. Chen, F. M. Lu and J. Nie, J.
106 D. H. Reneker, A. L. Yarin, E. Zussman and H. Xu, Electrospinning Appl. Polym. Sci., 2008, 110, 33283335.
of Nanofibers from Polymer Solutions and Melts, Advances in 143 Y. Z. Zhang, B. Su, S. Ramakrishna and C. T. Lim,
Applied Mechanics, Elsevier, Oxford, 2007, vol. 41, pp. 43 Biomacromolecules, 2008, 9, 136141.
195. 144 Y. Z. Zhang, J. R. Venugopal, A. El-Turki, S. Ramakrishna, B. Su
107 A. Frenot and I. S. Chronakis, Curr. Opin. Colloid Interface Sci., and C. T. Lim, Biomaterials, 2008, 29, 43144322.
2003, 8, 6475. 145 D. Gupta, J. Venugopal, S. Mitra, V. R. Giri Dev and
108 Z. M. Huang, Y. Z. Zhang, M. Kotaki and S. Ramakrishna, S. Ramakrishna, Biomaterials, 2009, 30, 20852094.
Compos. Sci. Technol., 2003, 63, 22232253. 146 H. Yoshimoto, Y. M. Shin, H. Terai and J. P. Vacanti, Biomaterials,
109 Y. Dzenis, Science, 2004, 304, 19171919. 2003, 24, 20772082.
110 G. Aleksander, S. Rahul, T. Velmurugan and S. Ramakrishna, 147 J. Venugopal, S. Low, A. T. Choon, A. B. Kumar and
Polym. Rev., 2011, 51, 265287. S. Ramakrishna, J. Biomed. Mater. Res., 2008, 85A, 408
111 C. Y. Xu, R. Inai, M. Kotaki and S. Ramakrishna, Biomaterials, 417.
2004, 25, 877886. 148 M. C. Phipps, W. C. Clem, J. M. Grunda, G. A. Clines and
112 F. Yang, R. Murugan, S. Wang and S. Ramakrishna, Biomaterials, S. L. Bellis, Biomaterials, 2012, 33, 524534.
2005, 26, 26032610. 149 P. G. Cordeiro, Plast. Reconstr. Surg., 1989, 83, 10131019.

12970 | J. Mater. Chem., 2012, 22, 1295312971 This journal is The Royal Society of Chemistry 2012
View Article Online

150 M. P. Prabhakaran, J. Venugopal and S. Ramakrishna, Acta 155 D. Y. Yuan, J. Jun, W. Shao-hai, Y. Wei, J. Lei and W. Zhong-yi, J.
Biomater., 2009, 5, 28842893. Appl. Polym. Sci., 2007, 106, 12081214.
151 R. Rajeswari, J. R. Venugopal, S. Sundarrajan, M. Shayanti and 156 L. R. Lakshman, K. T. Shalumon, V. N. Sreeja, R. Jayakumar and
S. Ramakrishna, Biomaterials, 2012, 33, 846 S. V. Nair, J. Macromol. Sci., Part A: Pure Appl. Chem., 2010, 47,
855. 10121018.
152 P. Chen, Q. S. Wu, Y. P. Ding, M. Chu, Z. M. Huang and W. Hu, 157 T. T. T. Nguyen, B. Tae and J. S. Park, J. Mater. Sci., 2011, 46,
Eur. J. Pharm. Biopharm., 2010, 76, 413420. 65286537.
153 J. K. Kim, J. Anderson, H. W. Jun, M. A. Repka and S. Jo, Mol. 158 M. Song, X. Wang, C. Wang, C. Pan, D. Fu and Z. Gu, J. Nanosci.
Pharmaceutics, 2009, 6, 978985. Nanotechnol., 2009, 9, 876879.
154 P. Chen, Q. Shengwu, Y. P. Ding and Z. C. Zhu, NANO: Brief 159 J. Meng, Z. Han, H. Kong, X. Qi, C. Wang, S. Xie and H. Xu,
Reports and Reviews, 2011, 6, 325332. J. Biomed. Mater. Res., Part A, 2010, 95, 312320.
Published on 18 April 2012 on http://pubs.rsc.org | doi:10.1039/C2JM30966A
Downloaded by University of Sussex on 15 December 2012

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 1295312971 | 12971

Вам также может понравиться