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1. Contact angle and adsorption energies of nanoparticles at the air-liquid interface determined by neutron reflectivity and
molecular dynamics
By Reguera, Javier; Ponomarev, Evgeniy; Geue, Thomas; Stellacci, Francesco; Bresme, Fernando; Moglianetti, Mauro
From Nanoscale (2015), 7(13), 5665-5673. Language: English, Database: CAPLUS, DOI:10.1039/C5NR00620A
Understanding how nanomaterials interact with interfaces is essential to control their self-assembly as well as their
optical, electronic, and catalytic properties. We present here an exptl. approach based on neutron reflectivity (NR) that
allows the in situ measurement of the contact angles of nanoparticles adsorbed at fluid interfaces. Because our method
provides a route to quantify the adsorption and interfacial energies of the nanoparticles in situ, it circumvents problems
assocd. with existing indirect methods, which rely on the transport of the monolayers to substrates for further anal. We
illustrate the method by measuring the contact angle of hydrophilic and hydrophobic gold nanoparticles, coated with
perdeuterated octanethiol (d-OT) and with a mixt. of d-OT and mercaptohexanol (MHol), resp. The contact angles were
also calcd. via atomistic mol. dynamics (MD) computations, showing excellent agreement with the exptl. data. Our
method opens the route to quantify the adsorption of complex nanoparticle structures adsorbed at fluid interfaces
featuring different chem. compns.
~0 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

2. Comparative STM studies of mixed ligand monolayers on gold nanoparticles in air and in 1-phenyloctane
By Ong, Quy Khac; Zhao, Shun; Reguera, Javier; Biscarini, Fabio; Stellacci, Francesco
From Chemical Communications (Cambridge, United Kingdom) (2014), 50(72), 10456-10459. Language: English,
Database: CAPLUS, DOI:10.1039/C4CC04114C
Scanning tunnelling microscopy (STM) studies have found stripe-like domains on gold nanoparticles (NPs) coated with
certain binary mixts. of ligand mols. The majority of these NPs' properties have been investigated for particles in
solvents. Yet, most STM studies are for NPs in a dry state. Images of the same particles in air and liq. have not been
obtained yet. In this work, a judicious choice of ligand mols. led to NPs with close-to-ideal STM imaging conditions in air
and in 1-phenyloctane (PO). Large datasets under both conditions were acquired and rapidly evaluated through power
spectral d. (PSD) anal. The result is a quant. comparison of stripe-like domains in air and PO on the same NPs. PSD
anal. dets. a characteristic length-scale for these domains of 1.0 nm in air and in PO showing persistence of striped
domains in these two media. A length scale of 0.7 nm for homo-ligand NPs was found.
~1 Citing
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

3. Change of Luminescence Properties of Europium Ions Captured by Mixed-Ligand Silver Nanoparticles


By Cho, Eun Seon; Yokoyama, Takahiro; Ertem, Elif; Stellacci, Francesco
From Israel Journal of Chemistry (2014), 54(5-6), 708-711. Language: English, Database: CAPLUS,
DOI:10.1002/ijch.201400069
We present herein silver nanoparticles about 4 nm in diam. coated with a binary mixt. of 1-octanethiol and 2-(2-{2-[(6mercaptohexyl)oxy]ethoxy}ethoxy)ethanol. These particles show an affinity towards optically active Eu3+ ions. The effect
of the nanoparticle on the characteristic emission peaks of Eu3+ is investigated. We use the variation in emission spectra
of the ion to establish its binding to the nanoparticles.
~0 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

4. A general mechanism for intracellular toxicity of metal-containing nanoparticles


By Sabella, Stefania; Carney, Randy P.; Brunetti, Virgilio; Malvindi, Maria Ada; Al-Juffali, Noura; Vecchio, Giuseppe;
Janes, Sam M.; Bakr, Osman M.; Cingolani, Roberto; Stellacci, Francesco; et al
From Nanoscale (2014), 6(12), 7052-7061. Language: English, Database: CAPLUS, DOI:10.1039/c4nr01234h

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The assessment of the risks exerted by nanoparticles is a key challenge for academic, industrial, and regulatory
communities worldwide. Exptl. evidence points towards significant toxicity for a range of nanoparticles both in vitro and
in vivo. Worldwide efforts aim at uncovering the underlying mechanisms for this toxicity. Here, we show that the
intracellular ion release elicited by the acidic conditions of the lysosomal cellular compartment - where particles are
abundantly internalized - is responsible for the cascading events assocd. with nanoparticles-induced intracellular toxicity.
We call this mechanism a "lysosome-enhanced Trojan horse effect" since, in the case of nanoparticles, the protective
cellular machinery designed to degrade foreign objects is actually responsible for their toxicity. To test our hypothesis,
we compare the toxicity of similar gold particles whose main difference is in the internalization pathways. We show that
particles known to pass directly through cell membranes become more toxic when modified so as to be mostly
internalized by endocytosis. Furthermore, using expts. with chelating and lysosomotropic agents, we found that the
toxicity mechanism for different metal contg. NPs (such as metallic, metal oxide, and semiconductor NPs) is mainly
assocd. with the release of the corresponding toxic ions. Finally, we show that particles unable to release toxic ions
(such as stably coated NPs, or diamond and silica NPs) are not harmful to intracellular environments.
~14 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

5. Scanning tunneling microscopy and small angle neutron scattering study of mixed monolayer protected gold
nanoparticles in organic solvents
By Moglianetti, Mauro; Ong, Quy Khac; Reguera, Javier; Harkness, Kellen M.; Mameli, Marta; Radulescu, Aurel;
Kohlbrecher, Joachim; Jud, Corinne; Svergun, Dmitri I.; Stellacci, Francesco
From Chemical Science (2014), 5(3), 1232-1240. Language: English, Database: CAPLUS, DOI:10.1039/c3sc52595c
When a binary mixt. of ligand mols. is used to coat gold nanoparticles, stripe-like domains can occur. These
nanodomains confer nanoparticles unique structure-dependent properties. The domain structure has been characterized
primarily using scanning tunneling microscopy (STM) in air and in vacuum. Here we show the first STM images of
striped nanoparticles in a solvent, 1-phenyloctane. We achieve stable imaging conditions on dodecanethiol-hexanethiol
(C12 : C6) 2 : 1 protected gold nanoparticles. These features are persistent across many images and retain their
direction and overall morphol. when recorded at different scan angles. We also perform small angle neutron scattering
(SANS) on two hybrid C6 : C12 nanoparticle samples dissolved in chloroform. The hybrid nanoparticles have the same
compn. and size distribution as samples imaged with STM, but one of the two ligands (either C6 or C12) is deuterated.
Low resoln. models reconstructed ab initio by simultaneous fitting of the SANS data reveal striped patterns of C6 and
C12 on the gold surface. We use image anal. to quant. compare STM and SANS data, achieving remarkable agreement.
This is the first paper to compare evidence of the existence of stripe-like domains for particles in soln. using two
independent techniques, and we believe that a combination of STM and SANS could become a major approach to
characterize mixed ligand nanomaterials in soln.
~6 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

6. Nanoscale Topography and Chemistry Affect Embryonic Stem Cell Self-Renewal and Early Differentiation
By LaPointe, Vanessa L. S.; Fernandes, Ana Tiago; Bell, Nia C.; Stellacci, Francesco; Stevens, Molly M.
From Advanced Healthcare Materials (2013), 2(12), 1644-1650. Language: English, Database: CAPLUS,
DOI:10.1002/adhm.201200382
Adherent cells respond to a wide range of substrate cues, including chem., topog., hydrophobicity, and surface energy.
The cell-substrate interface is therefore an important design parameter in regenerative medicine and tissue engineering
applications, where substrate cues are used to influence cell behavior. Thin films comprising 4.5 nm (av. diam.) gold
nanoparticles coated with a mixt. of two alkanethiols can confer hemispherical topog. and specific chem. to bulk
substrates. The behavior of murine embryonic stem cells (ESCs) on the thin films can then be compared with their
behavior on self-assembled monolayers of the same alkanethiols on vapor-deposited gold, which lack the topog.
features. Cells cultured both with and without differentiation inhibitors are characterized by immunofluorescence for Oct4
and qPCR for Fgf5, Foxa2, Nanog, Pou5f1, and Sox2. Nanoscale chem. and topog. are found to influence stem cell
differentiation, particularly the early differentiation markers, Fgf5 and Foxa2. Nanoscale topog. also affects Oct4
localization, whereas the chem. compn. of the substrate does not have an effect. It is demonstrated for the first time that
ESCs can sense topog. features established by 4.5 nm particles, and these findings suggest that nanoscale chem. and
topog. can act synergistically to influence stem cell differentiation. This study furthers the understanding of the effects of
these substrate properties, improving our ability to design materials to control stem cell fate.
~5 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

7. Gold nanoparticles protected by fluorinated ligands for 19F MRI

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By Boccalon, Mariangela; Franchi, Paola; Lucarini, Marco; Delgado, Juan Jose; Sousa, Fernanda; Stellacci,
Francesco; Zucca, Ileana; Scotti, Alessandro; Spreafico, Roberto; Pengo, Paolo; et al
From Chemical Communications (Cambridge, United Kingdom) (2013), 49(78), 8794-8796. Language: English,
Database: CAPLUS, DOI:10.1039/c3cc44572k
Gold nanoparticles coated with fluorinated ligands (F-MPCs) present features suitable for 19F MRI as obsd. from
phantom expts. Cellular uptake, by HeLa cells, and toxicity of fluorescent dye-decorated F-MPCs are presented together
with their ability to bind hydrophobic mols. allowing for a potential combination of targeting, delivery and imaging features.
~6 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

8. Colloidal Stability of Self-Assembled Monolayer-Coated Gold Nanoparticles: The Effects of Surface Compositional and
Structural Heterogeneity
By Huang, Rixiang; Carney, Randy P.; Stellacci, Francesco; Lau, Boris L. T.
From Langmuir (2013), 29(37), 11560-11566. Language: English, Database: CAPLUS, DOI:10.1021/la4020674
Surface heterogeneity plays an important role in controlling
colloidal phenomena. This study studied the self-aggregation
and bacterial adsorption of self-assembled monolayer coated
gold nanoparticles (AuNPs) with different surface compositional
and structural heterogeneity. Evaluation was performed on
AuNPs coated with (1) one ligand with charged terminals
(MUS), (2) two homogeneously distributed ligands with resp.
charged and nonpolar terminals (brOT) and (3) two ligands with
resp. charged and nonpolar terminals with stripe-like
distribution (OT). The brOT particles have less neg.
electrophoretic mobility (EPM) values, smaller crit. coagulation
concn. (CCC) and larger adsorption rate on Escherichia coli
than that of AuNPs with homogeneously charged groups, in
good agreement with DLVO predictions. Although the ligand
compn. on the surface of AuNPs is the same, OT particles
have less neg. EPM values and faster rate of bacterial
adsorption, but much larger CCC compared to brOT. The
deviation of OT particles from brOT and MUS in their selfaggregation behavior reflects the effects of surface
heterogeneity on elec. double layer structures at the interface.
Results from the present study demonstrated that, besides
chem. compn., organization of ligands on particle surface is
important in detg. their colloidal stability.
~5 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

9. Protein-nanoparticle interactions: the effects of surface compositional and structural heterogeneity are scale
dependent
By Huang, Rixiang; Carney, Randy P.; Stellacci, Francesco; Lau, Boris L. T.
From Nanoscale (2013), 5(15), 6928-6935. Language: English, Database: CAPLUS, DOI:10.1039/c3nr02117c
Nanoparticles (NPs) in the biol. environment are exposed to a large variety and concn. of proteins. Proteins are known
to adsorb in a corona' like structure on the surface of NPs. In this study, we focus on the effects of surface compositional
and structural heterogeneity on protein adsorption by examg. the interaction of self-assembled monolayer coated gold
NPs (AuNPs) with two types of proteins: ubiquitin and fibrinogen. This work was designed to systematically investigate
the role of surface heterogeneity in nanoparticle-protein interaction. We have chosen the particles as well as the proteins
to provide different types (in distribution and length-scale) of heterogeneity. The goal was to unveil the role of
heterogeneity and of its length-scale in the particle-protein interaction. Dynamic light scattering and CD spectroscopy
were used to reveal different interactions at pH above and below the isoelec. points of the proteins, which is related to
the charge heterogeneity on the protein surface. At pH 7.4, there was only a monolayer of proteins adsorbed onto the
NPs and the secondary structure of proteins remained intact. At pH 4.0, large aggregates of nanoparticle-protein
complexes were formed and the secondary structures of the proteins were significantly disrupted. In terms of interaction
thermodn., results from isothermal titrn. calorimetry showed that ubiquitin adsorbed differently onto (1) AuNPs with
charged and nonpolar terminals organized into nano-scale structure (66-34 OT), (2) AuNPs with randomly distributed
terminals (66-34 brOT), and (3) AuNPs with homogeneously charged terminals (MUS). This difference in adsorption
behavior was not obsd. when AuNPs interacted with fibrinogen. The results suggested that the interaction between the
proteins and AuNPs was influenced by the surface heterogeneity on the AuNPs, and this influence depends on the scale
of surface heterogeneity and the size of the proteins.

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~12 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

10. Determination of monolayer-protected gold nanoparticle ligand-shell morphology using NMR


By Liu, Xiang; Yu, Miao; Kim, Hyewon; Mameli, Marta; Stellacci, Francesco
From Nature Communications (2012), 3(Nov.), 2155/1-2155/9. Language: English, Database: CAPLUS,
DOI:10.1038/ncomms2155
It is accepted that the ligand shell morphol. of nanoparticles coated with a monolayer of mols. can be partly responsible
for important properties such as cell membrane penetration and wetting. When binary mixts. of mols. coat a
nanoparticle, they can arrange randomly or sep. into domains, for example, forming Janus, patchy or striped particles.
To date, there is no straightforward method for the detn. of such structures. Here we show that a combination of onedimensional and two-dimensional NMR can be used to det. the ligand shell structure of a series of particles covered with
aliph. and arom. ligands of varying compn. This approach is a powerful way to det. the ligand shell structure of patchy
particles; it has the limitation of needing a whole series of compns. and ligands' combinations with NMR peaks well sepd.
and whose shifts due to the surrounding environment can be large enough.
~3 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

11. Electrical Method to Quantify Nanoparticle Interaction with Lipid Bilayers


By Carney, Randy P.; Astier, Yann; Carney, Tamara M.; Voitchovsky, Kislon; Jacob Silva, Paulo H.; Stellacci,
Francesco
From ACS Nano (2013), 7(2), 932-942. Language: English, Database: CAPLUS, DOI:10.1021/nn3036304
Understanding as well as rapidly screening the interaction of
nanoparticles with cell membranes is of central importance for
biol. applications such as drug and gene delivery. Recently, we
have shown that "striped" mixed-monolayer-coated gold
nanoparticles spontaneously penetrate a variety of cell
membranes through a passive pathway. Here, we report an
elec. approach to screen and readily quantify the interaction
between nanoparticles and bilayer lipid membranes.
Membrane adsorption is monitored through the capacitive
increase of suspended planar lipid membranes upon fusion
with nanoparticles. We adopt a Langmuir isotherm model to
characterize the adsorption of nanoparticles by bilayer lipid
membranes and ext. the partition coeff., K, and the std. free
energy gain by this spontaneous process, for a variety of sizes
of cell-membrane-penetrating nanoparticles. We believe that
the method presented here will be a useful qual. and quant.
tool to det. nanoparticle interaction with lipid bilayers and
consequently with cell membranes.
~14 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

12. Dynamic cellular uptake of mixed-monolayer protected nanoparticles


By Carney, Randy P.; Carney, Tamara M.; Mueller, Marie; Stellacci, Francesco
From Biointerphases (2012), 7(1-4), 17. Language: English, Database: CAPLUS, DOI:10.1007/s13758-011-0017-3
Nanoparticles (NPs) are gaining increasing attention for potential application in medicine; consequently, studying their
interaction with cells is of central importance. Both ligand arrangement and compn. on gold nanoparticles play a crucial
role in their cellular internalization. Previosly shown that 66-34OT nanoparticles coated with stripe-like domains of
hydrophobic (octanethiol, OT, 34%) and hydrophilic (11-mercaptoundecane sulfonate, MUS, 66%) ligands permeated
through the cellular lipid bilayer via passive diffusion, in addn. to endo-/pino-cytosis. NP internalization by DC2.4, 3T3,
and HeLa cells were analyzed at two temps. and multiple time points. Four NPs that differ in their surface structures and
ligand compns. and report on their cellular internalization by intracellular fluorescence quantification. Using confocal
laser scanning microscopy we have found that all three cell types internalize the 66-34OT NPs more than particles
coated only with MUS, or particles coated with a very similar coating but lacking any detectable ligand shell structure, or
'striped' particles but with a different compn. (34-66OT) at multiple data points.

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~13 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

13. New mixed ligand coated platinum nanoparticles for heterogeneous catalytic applications
By Ghosh, Anirban; Stellacci, Francesco; Kumar, Rajiv
From Catalysis Today (2012), 198(1), 77-84. Language: English, Database: CAPLUS,
DOI:10.1016/j.cattod.2012.03.079
A series of platinum nanoparticles was prepd. for the first time in presence of one hydrophobic ligand and one hydrophilic
ligand contg. terminal sulfonic acid headgroup. This mixed ligand combination causes stripe-like domains circumscribing
the nanoparticles, thereby enhancing the catalytic efficiency compared to single ligand coated Pt nanocatalysts. This
could be achieved by strategically replacing the hydrophilic ligand (3-mercaptopropane-1-sulfonic acid or MPSA) with
hydrophobic ligands (linear alkanethiols like 1-octanethiol or OT) on the surface of the nanoparticles. Apart from the
ligand compn., the metallic core of the nanocomposite also influences the catalytic efficiency of the ligand shell through a
synergistic effect. Herein we report the effects of ligand shell compn. and structure on the efficiency of the
nanocomposites on catalytic acylation reactions. Quite high conversion of benzyl alc. to benzyl acetate (with >99%
selectivity) was obsd. when acetic acid was used as the acetylating reagent and MPSA-OT-Pt as nanocatalyst at 80 C.
The turnover frequency of reaction using MPSA-OT-Pt nanocatalyst was found to be an order of magnitude higher than
that using well known solid acid catalyst zeolite USY under identical reaction conditions. Further, the selectivity toward
benzyl acetate using USY was 80%, the remaining 20% being dibenzylether. It was also found that the MPSA-OT-Pt
nanocatalyst system shows higher activity than gold nanoparticles coated with same set of ligands (such as MPSA-OTAu nanocatalyst). Addnl., the effects of changing the substrate (such as 1-butanol) and the acylating agent (such as
propionic acid) were also studied.
~5 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

14. Molecular dynamics study of the effects of nanoscale surface patterning on the interfacial properties of mixedmonolayer protected nanoparticles
By Jiang, Hao; Stellacci, Francesco; Glotzer, Sharon C.
From Abstracts of Papers, 243rd ACS National Meeting & Exposition, San Diego, CA, United States, March 25-29,
2012 (2012), PHYS-5. Language: English, Database: CAPLUS
Recent expts. have shown that surface structure has significant influence on the interfacial properties of substrates
protected by mixed surfactant monolayers. Interestingly, the total work of adhesion of a monolayer-protected
nanoparticle (NP) varies non-monotonically with the size of the striped surface domains of the hydrophilic and
hydrophobic coating mols. We investigated the mol. mechanisms of this non-monotonic behavior using mol. dynamics
(MD) simulations. Our simulations revealed that the mol. organization of the interfacial water is substantially affected by
the sizes of the hydrophobic and hydrophilic domains on the NP surface. When the size of the hydrophobic domains is
small ( < 1 nm), bridge-like hydrogen-bonded water structures are formed across these domains, stabilizing the water
interface and increasing the water d. in the regions immediately above the domains. At the same time, due to the
entropic effect, water mols. are driven away from the hydrophilic domains as the domain size decreases, decreasing the
interfacial water d. These two competing effects, both of which depend on domain size, combine in a complex way to
result in the non-monotonic dependence of interfacial energy and work of adhesion on the size of surface domains. We
also investigate via MD simulations the application of these nanoparticles to sensors and show how interfacial
mechanisms give rise to sensitive selectivity.
~0 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

15. Oligonucleotide Delivery by Cell-Penetrating "Striped" Nanoparticles


By Jewell, Christopher M.; Jung, Jin-Mi; Atukorale, Prabhani U.; Carney, Randy P.; Stellacci, Francesco; Irvine, Darrell
J.
From Angewandte Chemie, International Edition (2011), 50(51), 12312-12315, S12312/1-S12312/8. Language:
English, Database: CAPLUS, DOI:10.1002/anie.201104514

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When mixed self-assembled monolayers of dislike mols. are used to coat AuNPs, nanoscale domains spontaneously
form in the particles' ligand shell. In particular, "stripe-like" domains form for ca. 1:1 binary mixed ligand compns. The
formation of these domains provides AuNPs with structure-dependent properties. We recently reported the unexpected
finding that highly water-sol. striped NPs coated with sulfonate- and methylterminated ligands are capable of penetrating
the plasma membrane of cells through non-endocytic energy-independent mechanisms, in contrast to AuNPs bearing
similar ligands in random configurations, which are only endocytosed. Given our finding that membrane penetration is
highly sensitive to ligand arrangement, a major question raised by this study was whether the membrane penetration
mechanism would support the transport of AuNP-conjugated drug cargos into cells, esp. large, membrane-impermeable
hydrophilic macromols. that are the most challenging agents for drug delivery. Here we report on the cellular uptake of
striped NPs (and non-striped control NPs) conjugated with thiolterminated DNA oligonucleotides (ODNs), in order to
answer this fundamental question and det. how cell entry of striped particles is influenced by cargo size and structure.
~31 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

16. Determination of nanoparticle size distribution together with density or molecular weight by 2D analytical
ultracentrifugation
By Carney, Randy P.; Kim, Jin Young; Qian, Huifeng; Jin, Rongchao; Mehenni, Hakim; Stellacci, Francesco; Bakr,
Osman M.
From Nature Communications (2011), 2(June), 1338/1-1338/8, S1338/1-S1338/3. Language: English, Database:
CAPLUS, DOI:10.1038/ncomms1338
Nanoparticles are finding many research and industrial applications, yet their characterization remains a challenge. Their
cores are often polydisperse and coated by a stabilizing shell that varies in size and compn. No single technique can
characterize both the size distribution and the nature of the shell. Advances in anal. ultracentrifugation allow for the extn.
of the sedimentation (s) and diffusion coeffs. (D). Here an approach is reported to transform the s and D distributions of
nanoparticles in soln. into precise mol. wt. (M), d. (pp), and particle diam. (dp) distributions M for mixts. of discrete
nanocrystals is found within 4% of the known quantities. The accuracy and the d. information achieved on nanoparticles
are unparalleled. A single exptl. run is sufficient for full nanoparticle characterization, without the need for stds. or other
auxiliary measurements. The method is of general applicability and its limitations are discussed.
~3 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

17. Mixed-Ligand Nanoparticles as Supramolecular Receptors


By Liu, Xiang; Hu, Ying; Stellacci, Francesco
From Small (2011), 7(14), 1961-1966. Language: English, Database: CAPLUS, DOI:10.1002/smll.201100386
Mixed-ligand-coated Au nanoparticles were synthesized using a naphthalene-terminated thiol (MNT) ligand and
hexanethiol (HT). The mixed ligands self-assemble at the surface of nanoparticles forming a structure that interacts with
PAHs through - interactions. Whereas the corresponding homoligand particles do not interact with PAHs in any
detectable way, the mixed-ligand particles all have good binding ability to PAHs; specifically Au-MNT0.50HT0.50 binds to
pyrene with a binding const. of 6.49 5.71 104 M-1. Overall, mixed ligand-coated Au nanoparticles are versatile
receptors for various PAHs. These easy-to-synthesize and easy-to-tailor particles can be used potentially for the
detection and clean-up of PAH pollutants.
~12 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

18. Effect of Composition on the Catalytic Properties of Mixed-Ligand-Coated Gold Nanoparticles


By Ghosh, Anirban; Basak, Soubir; Wunsch, Benjamin H.; Kumar, Rajiv; Stellacci, Francesco
From Angewandte Chemie, International Edition (2011), 50(34), 7900-7905, S7900/1-S7900/4. Language: English,
Database: CAPLUS, DOI:10.1002/anie.201101821
Effect of compn. on catalytic properties of mixed-ligand-coated gold nanoparticles is discussed, as is esterification of
benzyl alc with acetic acid with prodn. and kinetics for benzyl acetate.
~18 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

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19. Artificial Surface-Modified Si3N4 Nanopores for Single Surface-Modified Gold Nanoparticle Scanning
By Astier, Yann; Datas, Lucien; Carney, Randy; Stellacci, Francesco; Gentile, Francesco; DiFabrizio, Enzo
From Small (2011), 7(4), 455-459. Language: English, Database: CAPLUS, DOI:10.1002/smll.201002113
The use of functionalized Si3N4 nanopores for the detection of neg. charged gold nanoparticles from 2.4 to 8.9 nm diam.
is shown. It is possible to detect the surface mol. interactions through ionic current alterations, whether or not the elec.field driven nanoparticle threads through the pore. This simulation work suggests that electrostatic interactions are
essential to create the initial nanoparticle-nanopore interaction. Once a nanoparticle is engaged into the nanopore,
Brownian motion theory fits the av. off-current time due to the nanopore interaction with the nanoparticle. This has
demonstrated that electrostatic forces are essential to create the initial nanoparticle-nanopore interaction. Brownian
motion theory helps clarify the av. off-current time due to the nanopore interaction with the nanoparticle.
~12 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

20. Wetting of nanometer-scale domains


By Kuna, Jeffrey J.; Stellacci, Francesco; Mwenifumbo, Steve; Stevens, Molly M.
From Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) (2010), 51(1), 16-17. Language:
English, Database: CAPLUS
This study showed that there is an almost linear dependence of work of adhesion on surface compn. for particles coated
with longer hydrophilic and shorter hydrophobic ligand mols. The formation of synthetic surfaces possessing
subnanometer domains using self-assembled monolayers (SAMs) is difficult to achieve on flat surfaces due to the
tendency for dissimilar components of a SAM to phase sep. into domains several nanometers across or larger. It was
found that biocomponent SAMs formed on the surface of a nanoparticle do not undergo conventional phase sepn., but
instead form a stripe-like domains due to the curvature of the underlying surface. In a nanoparticle film system, in which
the nanoparticles were coated with 6-mercaptohexan-1-ol (MHol) and 1-octanethiol (OT), the work of adhesion and thus
surface energy varied non-monotonically with compn. The current hydrophilic ligand, 11-mercaptoundecan-1-ol (MUDol),
is longer than the previous system's hydrophilic ligand, MHol, which is of comparable length to the hydrophobic ligand,
OT. The increased margin in ligand length may preclude or significantly weaken the mol.-scale wetting effects previously
hypothesized to exist since it is known there is substantial disorder in a SAM composed of ligands of two different
lengths. The longer length of the hydrophilic ligand would increase the surface hydroxyl flexibility and reduce the
confinement effect. Addnl., the hydrophobic headgroups would be sheltered by the longer hydrophilic ligands, reducing
the cavitation effect.
~0 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

21. Monolayer-coated surfaces as catalytic platforms for organic reactions


By Stellacci, Francesco; Wunsch, Benjamin
From PCT Int. Appl. (2009), WO 2009143406 A2 20091126, Language: English, Database: CAPLUS
This invention provides a method for increasing the activity of catalysts. The method requires the introduction of the
catalyst into nano-structured surfaces. The catalysts are introduced as functional groups in mols. forming a monolayer
on a surface. A mixed monolayer of catalyst and inert mols. generates ordered domains of mols. on the surface. The
catalyst is confined in regions of 0.5 nm to 3 nm in size and is surrounded by an inert material. The presence of such
ordered domains that commensurate in size with the reactants, enhance the performance of the catalyst and increase
the rate of the reaction.
~0 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

22. Statistical analysis of scanning tunneling microscopy images of 'striped' mixed monolayer protected gold
nanoparticles
By Hu, Ying; Wunsch, Benjamin H.; Sahni, Sahil; Stellacci, Francesco
From Journal of Scanning Probe Microscopy (2009), 4(1), 24-35. Language: English, Database: CAPLUS,
DOI:10.1166/jspm.2009.1004

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Recent studies based on scanning tunneling microscopy (STM) have shown that when gold nanoparticles are coated
with binary mixts. of ligand mols. ribbon-like domains of alternating compn. spontaneously form in the particles ligand
shell. The presence of these domains has been linked to many surface properties, such as protein nonspecific
adsorption, cell membrane permeation, or soly. Here we present a detailed report on the methods and procedures used
to acquire and analyze STM images of these ligand coated nanoparticles. We develop a novel statistical approach to
analyze the images and differentiate them from images generated by feedback loop artifact. We conclude with a
discussion of the potentials and problems of this technique.
~11 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

23. Nanoparticles having sub-nanometer features


By Stellacci, Francesco; Jackson, Alicia M.
From U.S. Pat. Appl. Publ. (2009), US 20090246527 A1 20091001, Language: English, Database: CAPLUS
An article has a surface, at least a portion of which has a local radius of curvature of 1000 nm. The article may be a
nanoparticle or a surface, a portion of which has a roughness characterized by a radius of curvature of 1000 nm. A
monolayer coating disposed on the surface includes a plurality of ligands organized into ordered domains having a
characteristic size of 10 nm.
~2 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

24. Monodispersed organic monolayer coated calcium-containing nanoparticles


By Stellacci, Francesco; Uzun, Oktay; Cox, Sherman
From PCT Int. Appl. (2009), WO 2009111437 A2 20090911, Language: English, Database: CAPLUS
A method for the synthesis of monodispersed, org.-monolayer coated, calcium-contg. nanoparticles is presented. A
biphasic liq. system comprises an aq. phase of bare particles and an org. phase contg. org. mols. with carboxylic acid
end group is mixed. The carboxylic acid group binds to the surface of the calcium-contg. particles and the particles are
coated with a monolayer of org. mols. The exposed surface of the coated particles is more hydrophobic than the surface
of the bare particle and the particles are extd. to the org. phase. The process changes the geometry of the particles and
decreases the size distribution in a population of particles. Acid neutralizers tablets (antacids) and acid neutralizing
processes in natural water reservoirs and in industrial water are important for the relief of acid assocd. pain for people
with ulcers or with gastroesophageal reflux disease, or acid indigestion. Calcium carbonate is often used as an antacid.
~2 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

25. The role of phase separated nanodomains in the solubility of mixed-monolayer-protected metal nanoparticles
By Centrone, Andrea; Penzo, Erika; Jackson, Alicia M.; Stellacci, Francesco
From AIChE Annual Meeting, Conference Proceedings, Philadelphia, PA, United States, Nov. 16-21, 2008 (2008),
187/1-187/2. Language: English, Database: CAPLUS
We present that, when Au nanoparticles are coated with a binary mixt. of immiscible ligands, ordered ribbon-like domains
of alternating compn. spontaneously form and that their width is comparable to the size of a single solvent mol. When
ribbon-like domains arise in the ligand shell, the enthalpy of mixing for mixed ligand nanoparticles depends on the
domain spacing (which can be varied through the stoichiometric ratio of the ligands used in the synthesis). Probably the
ligand shell domains favor the wetting of the different solvents when their sizes and chem. groups match the solvent
mols. size and chem. functionality thus contributing to the total nanoparticle soly.
~0 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

26. Electrophysiological study of single gold nanoparticle/-hemolysin complex formation: a nanotool to slow down
ssDNA through the -hemolysin nanopore
By Astier, Yann; Uzun, Oktay; Stellacci, Francesco
From Small (2009), 5(11), 1273-1278. Language: English, Database: CAPLUS, DOI:10.1002/smll.200801779

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Single-monolayer-protected gold nanoparticles can be captured in the -hemolysin nanopore (see image). Singlenanopore ion conductance studies of the nanoparticle/nanopore complex are described. The effect of the nanoparticle
size, charge, and surface coating on ssDNA threading speed through the nanopore/nanoparticle complex is discussed.
~9 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

27. Surface-structure-regulated cell-membrane penetration by monolayer-protected nanoparticles


By Verma, Ayush; Uzun, Oktay; Hu, Yuhua; Hu, Ying; Han, Hee-Sun; Watson, Nicki; Chen, Suelin; Irvine, Darrell J.;
Stellacci, Francesco
From Nature Materials (2008), 7(7), 588-595. Language: English, Database: CAPLUS, DOI:10.1038/nmat2202
Nanoscale objects are typically internalized by cells into membrane-bounded endosomes and fail to access the cytosolic
cell machinery. Whereas some biomacromols. may penetrate or fuse with cell membranes without overt membrane
disruption, no synthetic material of comparable size has shown this property yet. Cationic nano-objects pass through cell
membranes by generating transient holes, a process assocd. with cytotoxicity. Studies aimed at generating cellpenetrating nanomaterials have focused on the effect of size, shape and compn. Here, we compare membrane
penetration by two nanoparticle isomers' with similar compn. (same hydrophobic content), one coated with subnanometre
striations of alternating anionic and hydrophobic groups, and the other coated with the same moieties but in a random
distribution. We show that the former particles penetrate the plasma membrane without bilayer disruption, whereas the
latter are mostly trapped in endosomes. Our results offer a paradigm for analyzing the fundamental problem of cellmembrane-penetrating bio- and macro-mols. The structural organization of surface groups on nanoparticles is proven to
be important for cell membrane penetration. Nanoparticles coated with alternating ribbon-like arrangements of
hydrophobic and anionic ligands penetrate membranes without causing disruption. These design rules may have
implications for toxicity issues and drug delivery applications of nanomaterials. The structural organization of surface
groups on nanoparticles is proven to be important for cell membrane penetration. Nanoparticles coated with alternating
ribbon-like arrangements of hydrophobic and anionic ligands penetrate membranes without causing disruption. These
design rules may have implications for toxicity issues and drug delivery applications of nanomaterials.
~511 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

28. Effect of Ligand Shell Structure on the Interaction between Monolayer-Protected Gold Nanoparticles
By Hu, Ying; Uzun, Oktay; Dubois, Cedric; Stellacci, Francesco
From Journal of Physical Chemistry C (2008), 112(16), 6279-6284. Language: English, Database: CAPLUS,
DOI:10.1021/jp709895z
Here the authors present a comparative anal. of 2 types of equally monodisperse Au nanoparticles (8 nm in diam.), one
coated only with dodecanethiol ligands and the other coated with a mixt. of dodecanethiol and 4-methylbenzenethiol
ligands. The former particles ('homoligand') have a homogeneous coating, while the latter ones ('rippled') show a striated
structure composed of phase-sepd. ribbon-like domains of alternating compn. A combined scanning tunneling and TEM
study shows that homoligand nanoparticles interdigitate into one another less than rippled particles and readily form
hexagonally packed supracrystals, while rippled particles are trapped in more disordered glassy arrangements.
~20 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

29. Fabrication of water soluble chains using divalent metal nanoparticles


By Uzun, Oktay; Stellacci, Francesco
From Abstracts of Papers, 235th ACS National Meeting, New Orleans, LA, United States, April 6-10, 2008 (2008),
PMSE-141. Language: English, Database: CAPLUS
Nanostructured materials reveal unique electronic and optical properties that are related to their size and shape. They
can simultaneously provide scaffolds for devices and serve as building blocks for the creation of two- and threedimensional systems. The existing methodologies for the fabrication of nanoparticle assemblies are less established
than what conventional mol. synthesis can offer. We developed a new approach that is based on the functionalization of
the polar singularities that must form when a curved surface is coated with ordered monolayers, such as a phase-sepd.
mixt. of ligands. This simple method can allow us to place reactive mols. specifically at two diametrically opposed
positions in the mol. coating of metal nanoparticles and thus, creating nanoparticle based bi-functional reactive
monomers.
~0 Citings

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Page 10

Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

30. Fabrication of water soluble chains using divalent metal nanoparticles


By Uzun, Oktay; Stellacci, Francesco
From PMSE Preprints (2008), 98, 230-231. Language: English, Database: CAPLUS
Nanostructured materials reveal unique electronic and optical properties that are related to their size and shape. They
can simultaneously provide scaffolds for devices and serve as building blocks for the creation of two- and threedimensional systems. The existing methodologies for the fabrication of nanoparticle assemblies are less established
than what conventional mol. synthesis can offer. We developed a new approach that is based on the functionalization of
the polar singularities that must form when a curved surface is coated with ordered monolayers, such as a phase-sepd.
mixt. of ligands. This simple method can allow us to place reactive mols. specifically at two diametrically opposed
positions in the mol. coating of metal nanoparticles and thus, creating nanoparticle based bi-functional reactive
monomers.
~0 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

31. Relationship Between Structure and Solubility of Thiol-Protected Silver Nanoparticles and Assemblies
By Bauer, Christina A.; Stellacci, Francesco; Perry, Joseph W.
From Topics in Catalysis (2008), 47(1-2), 32-41. Language: English, Database: CAPLUS, DOI:10.1007/s11244-0079032-5
The soly. of alkylthiol-coated Ag nanoparticles and the energetics of the ligand disordering were studied. Calorimetry
measurements provided correlations between the nature of the ligands and the enthalpy of the ligand disordering, which
have guided the improvement of nanoparticle soly. and dispersion in org. media.
~22 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

32. Entropy-Mediated Patterning of Surfactant-Coated Nanoparticles and Surfaces


By Singh, Chetana; Ghorai, Pradip K.; Horsch, Mark A.; Jackson, Alicia M.; Larson, Ronald G.; Stellacci, Francesco;
Glotzer, Sharon C.
From Physical Review Letters (2007), 99(22), 226106/1-226106/4. Language: English, Database: CAPLUS,
DOI:10.1103/PhysRevLett.99.226106
The authors perform atomistic and mesoscale simulations to explain the origin of exptl. obsd. stripelike patterns formed
by immiscible ligands coadsorbed on the surfaces of Au and Ag nanoparticles. When the conformational entropy gained
via this morphol. is sufficient, microphase-sepd. stripelike patterns form. When the entropic gain is not sufficient, the
authors instead predict bulk phase-sepd. Janus particles. The authors also show corroborating exptl. results that confirm
simulational predictions that stripes form on flat surfaces as well as on curved nanoparticle surfaces.
~10 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

33. Nanoparticles having sub-nanometer features


By Stellacci, Francesco; Jackson, Alicia M.
From PCT Int. Appl. (2007), WO 2007100787 A2 20070907, Language: English, Database: CAPLUS
An article has a surface, at least a portion of which has a local radius of curvature of 1000 nm. The article may be a
nanoparticle or a surface, a portion of which has a roughness characterized by a radius of curvature of 1000 nm. A
monolayer coating disposed on the surface includes a plurality of ligands organized into ordered domains having a
characteristic size of 10 nm.
~0 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

34. Divalent Metal Nanoparticles

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By DeVries, Gretchen A.; Brunnbauer, Markus; Hu, Ying; Jackson, Alicia M.; Long, Brenda; Neltner, Brian T.; Uzun,
Oktay; Wunsch, Benjamin H.; Stellacci, Francesco
From Science (Washington, DC, United States) (2007), 315(5810), 358-361. Language: English, Database: CAPLUS,
DOI:10.1126/science.1133162
Nanoparticles can be used as the building blocks for materials such as supracrystals or ionic liqs. However, they lack the
ability to bond along specific directions as atoms and mols. do. We report a simple method to place target mols.
specifically at two diametrically opposed positions in the mol. coating of metal nanoparticles. The approach is based on
the functionalization of the polar singularities that must form when a curved surface is coated with ordered monolayers,
such as a phase-sepd. mixt. of ligands. The mols. placed at these polar defects have been used as chem. handles to
form nanoparticle chains that in turn can generate self-standing films.
~432 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

35. Low temperature scanning tunneling microscopy images of 'rippled' mixed monolayer protected nanoparticles
By Jackson, Alicia M.; Miwa, Jill; Rosei, Federico; Stellacci, Francesco
From Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) (2006), 47(2), 864-865.
Language: English, Database: CAPLUS
Nanoparticles of Au coated with a mixt. of 1-nonanethiol and mercaptohexanol (molar ratio: 2:1) were prepd. using a
slight variation of the Schiffrin method. The ligand shell ordering in the samples was studied at low temp. and UHV
conditions using a high-resoln. scanning tunneling microscope. The microstructure of the coated Au nanoparticles is
depicted and described. Some of the nanoparticles form highly defined ribbon-like domains or ripples. The data for the
ripple spacing measured with the UHV HR-STM are nearly identical with data obtained in a DI multimode Nanoscope IIIa
STM under ambient conditions.
~0 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

36. From Homoligand- to Mixed-Ligand- Monolayer-Protected Metal Nanoparticles: A Scanning Tunneling Microscopy
Investigation
By Jackson, Alicia M.; Hu, Ying; Silva, Paulo Jacob; Stellacci, Francesco
From Journal of the American Chemical Society (2006), 128(34), 11135-11149. Language: English, Database:
CAPLUS, DOI:10.1021/ja061545h
The ligand shell that coats, protects, and imparts a large no. of
properties to gold nanoparticles is a 2-D self-assembled
monolayer wrapped around a 3-D metallic core. Here we
present a study of the mol. packing of ligand shells on gold
nanoparticles based on the anal. of scanning tunneling
microscopy (STM) images. We discuss methods for optimal
nanoparticle sample prepn. in relation to STM imaging
conditions. We show that the packing of a self-assembled
monolayer composed solely of octanethiols on gold
nanoparticles depends on the particle's diam. with an av.
headgroup spacing of 5.4 , which is different from that of
similar monolayers formed on flat Au(111) surfaces (5.0 ). In
the case of nanoparticles coated with mixts. of ligands-known
to phase sep. into randomly shaped and ordered domains on
flat surfaces-we find that phase sepn. leads to the formation of
concentric, ribbonlike domains of alternating compn. The
spacing of these domains depends on the ligand shell compn.
We find that, for a given compn., the spacing increases with
diam. in a manner characterized by discontinuous transitions at
"crit." particle sizes. We discuss possible interpretations for the
obsd. trends in our data.
~128 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

37. Size fractionation of metal nanoparticles by membrane filtration

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By Akthakul, Ariya; Hochbaum, Allon I.; Stellacci, Francesco; Mayes, Anne M.


From Advanced Materials (Weinheim, Germany) (2005), 17(5), 532-535. Language: English, Database: CAPLUS,
DOI:10.1002/adma.200400636
A thin film composite nanofiltration membrane was fabricated by coating a conventional ultrafiltration membrane with a
self-assembling amphiphilic graft copolymer. The membranes were used in the fractionation of gold nanoparticles to
achieve a well-defined particle cutoff diam. and decreased size dispersion.
~76 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

38. Ligand coated metal nanoparticles new tools for nanofabrication and for fluorescence imaging
By Stellacci, Francesco; Perry, Joseph W.
From Abstracts, 31st Northeast Regional Meeting of the American Chemical Society, Saratoga Springs, NY, United
States, June 15-18 (2003), 65. Language: English, Database: CAPLUS
Ligand-coated metal nanoparticles are powerful new materials for nano-electronic and photonic applications. They can
be readily synthesized and their stability and soly. allows them to be cast in complex composite materials or selfassembled into ordered films. It will be demonstrated that it is possible to induce the growth of these nanoparticles with
the proper excitation conditions. More importantly, conductive metal features can be obtained in composite materials
consisting of a polymer matrix doped with ligand-coated metal nanoparticles, suitable reducing dyes, and metal salts, via
either linear or non-linear optical excitation. 3D silver, copper and gold structures fabricated using two-photon absorption
that are characterized with various techniques will be presented. The synthesis and characterization of silver
nanoparticles with fluorescent chromophores covalently bond to their metallic core will be presented. The fluorescence
properties of these particles and of their fractal aggregates will be compared. It will be shown that chromophores selfassembled on metal nanoparticle fractal clusters can show two-photon induced fluorescence enhancements as high as
five orders of magnitude.".
~0 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

39. One- and two-photon induced growth of ligand coated nanoparticles for 2 + 3D metal patterning
By Stellacci, Francesco; Bauer, Christina A.; Meyer-Friedrichsen, Timo; Wenseleers, Wim; Alain, Valerie; Kuebler,
Stephen M.; Pond, Stephanie J.; Zhang, Yadong; Marder, Seth R.; Perry, Joseph W.
From Proceedings of SPIE-The International Society for Optical Engineering (2002), 4809(Nanoscale Optics and
Applications), 62-68. Language: English, Database: CAPLUS, DOI:10.1117/12.453771
Ligand-coated metallic nanoparticles are powerful new materials for nanoelectronic and photonics applications. They
can be readily synthesized and their stability and soly. allows them to be cast in complex composite materials or selfassembled into quasi-ordered films. The authors demonstrate that, in the presence of reducing dyes with a large twophoton cross-section and metal salts, it is possible to induce the growth of metal nanoparticles in composite films under
optical excitation or irradn. with electrons. The authors demonstrate further that continuous metal structures can be
obtained via laser irradn. of the composites and that, with two-photon excitation, 3D structures can be fabricated. Silver,
copper, and gold microstructures have been fabricated via two-photon excitation. The compn. of the authors polymeric
precursor is described in detail. In order to achieve highly-homogeneous solid-state solns. of nanoparticles dissolved in
poly(vinylcarbazole) (PVK), the authors synthesized tailor-made nanoparticles on which the authors have introduced a
mixt. of carbazoyl-terminated octylthiol and simple octylthiols. Preliminary expts. on electron-beam lithog. show that thin
films of nanoparticles doped with suitable dyes and metal salts are efficient precursors form metal structures.
~4 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

40. Ultrabright supramolecular beacons based on the self-assembly of two-photon chromophores on metal nanoparticles
By Stellacci, Francesco; Bauer, Christina A.; Meyer-Friedrichsen, Timo; Wenseleers, Wim; Marder, Seth R.; Perry,
Joseph W.
From Journal of the American Chemical Society (2003), 125(2), 328-329. Language: English, Database: CAPLUS,
DOI:10.1021/ja0281277
Silver nanoparticles coated with a self-assembled layer of 2500 chromophoric alkylthiol ligands, that exhibit a huge per
particle two-photon absorption cross section (2.7 10-45 cm4 s photon-1) and a high fluorescence quantum yield (0.33),
are reported. Polyfunctionalized variants of these nanoparticles have been produced that show reasonable soly. in
water/ethanol mixts. By virtue of the large no. of tethered chromophores, these particles act as strongly two-photon
absorbing nanobeacons and may have applications in fluorescence imaging and sensing.

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~67 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

41. Five orders-of-magnitude enhancement of two-photon absorption for dyes on silver nanoparticle fractal clusters
By Wenseleers, Wim; Stellacci, Francesco; Meyer-Friedrichsen, Timo; Mangel, Timo; Bauer, Christina A.; Pond,
Stephanie J. K.; Marder, Seth R.; Perry, Joseph W.
From Journal of Physical Chemistry B (2002), 106(27), 6853-6863. Language: English, Database: CAPLUS,
DOI:10.1021/jp014675f
Strong enhancement of the two-photon absorption of org. mols. near silver nanoparticle fractal clusters has been obsd.
and has been exploited to yield composite materials with very strong two-photon absorption and two-photon-excited
fluorescence properties. Measurements on cluster films coated with a chromophoric polymer or with thiol-bound
chromophores give spatially-averaged enhancements of 1000 and 20,000, resp. Two-photon fluorescence microscopy
studies show that the enhancements are spatially inhomogeneous, with peak-enhancement factors of 10,000
(polymer/cluster) and 160,000 (thiol chromophore/cluster), and excitation frequency-dependent. These results are in
accord with theor. predictions of local-field effects due to strong localization of collective plasmon modes in fractal metal
clusters, and demonstrate an approach to ultrasensitive two-photon processes.
~149 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

42. Laser and electron-beam induced growth of nanoparticles for 2D and 3D metal patterning
By Stellacci, Francesco; Bauer, Christina A.; Meyer-Friedrichsen, Timo; Wenseleers, Wim; Alain, Valerie; Kuebler,
Stephen M.; Pond, Stephanie J. K.; Zhang, Yadong; Marder, Seth R.; Perry, Joseph W.
From Advanced Materials (Weinheim, Germany) (2002), 14(3), 194-198. Language: English, Database: CAPLUS,
DOI:10.1002/1521-4095(20020205)14:3<194::AID-ADMA194>3.0.CO;2-W
Defined continuous metal patterns were grown by laser or electron beam irradn. of composite materials contg. the
corresponding metal nanoparticles. Excitation by 1- or 2-photon absorption resulted in 1-step laser writing of continuous
Ag, Cu, and Au metal microstructures in 1D, 2D, and 3D patterns. The electron beam irradn. of ultrathin films of a dyeattached-metal nanoparticle composite allowed for high-sensitive writing of lines and pads demonstrating the applicability
of such materials for direct electron beam lithog. of a metal. The samples were investigated by SEM, TEM , and optical
absorption spectroscopy. A polymer/nanocomposite material for the direct writing of Ag metal was designed and
fabricated based on the photoreductive growth of the nanoparticles. It consisted of AgBF4 as a precursor for the metal
nanoparticles, a photoreducing dye (I; R1 = R2 = C11H23) as the sensitizer, ligand-coated Ag nanoparticles as seeds (I;
R1 = Me, R2 = C11H22SH) and polyvinylcarbazole as the host polymer and sacrificial reducing agent.

~130 Citings
Copyright 2015 American Chemical Society (ACS). All Rights Reserved.

43. Contact angle and adsorption energies of nanoparticles at the air-liquid interface determined by neutron reflectivity
and molecular dynamics
By Reguera Javier; Ponomarev Evgeniy; Geue Thomas; Stellacci Francesco; Bresme Fernando; Moglianetti Mauro
From Nanoscale (2015), 7(13), 5665-73, Language: English, Database: MEDLINE

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Understanding how nanomaterials interact with interfaces is essential to control their self-assembly as well as their
optical, electronic, and catalytic properties. We present here an experimental approach based on neutron reflectivity
(NR) that allows the in situ measurement of the contact angles of nanoparticles adsorbed at fluid interfaces. Because
our method provides a route to quantify the adsorption and interfacial energies of the nanoparticles in situ, it
circumvents problems associated with existing indirect methods, which rely on the transport of the monolayers to
substrates for further analysis. We illustrate the method by measuring the contact angle of hydrophilic and
hydrophobic gold nanoparticles, coated with perdeuterated octanethiol (d-OT) and with a mixture of d-OT and
mercaptohexanol (MHol), respectively. The contact angles were also calculated via atomistic molecular dynamics
(MD) computations, showing excellent agreement with the experimental data. Our method opens the route to quantify
the adsorption of complex nanoparticle structures adsorbed at fluid interfaces featuring different chemical
compositions.
~0 Citings
Copyright 2015 U.S. National Library of Medicine.

44. Protein-nanoparticle interactions: the effects of surface compositional and structural heterogeneity are scale
dependent
By Huang Rixiang; Carney Randy P; Stellacci Francesco; Lau Boris L T
From Nanoscale (2013), 5(15), 6928-35, Language: English, Database: MEDLINE
Nanoparticles (NPs) in the biological environment are exposed to a large variety and concentration of proteins.
Proteins are known to adsorb in a 'corona' like structure on the surface of NPs. In this study, we focus on the effects of
surface compositional and structural heterogeneity on protein adsorption by examining the interaction of selfassembled monolayer coated gold NPs (AuNPs) with two types of proteins: ubiquitin and fibrinogen. This work was
designed to systematically investigate the role of surface heterogeneity in nanoparticle-protein interaction. We have
chosen the particles as well as the proteins to provide different types (in distribution and length-scale) of heterogeneity.
The goal was to unveil the role of heterogeneity and of its length-scale in the particle-protein interaction. Dynamic light
scattering and circular dichroism spectroscopy were used to reveal different interactions at pH above and below the
isoelectric points of the proteins, which is related to the charge heterogeneity on the protein surface. At pH 7.4, there
was only a monolayer of proteins adsorbed onto the NPs and the secondary structure of proteins remained intact. At
pH 4.0, large aggregates of nanoparticle-protein complexes were formed and the secondary structures of the proteins
were significantly disrupted. In terms of interaction thermodynamics, results from isothermal titration calorimetry
showed that ubiquitin adsorbed differently onto (1) AuNPs with charged and nonpolar terminals organized into nanoscale structure (66-34 OT), (2) AuNPs with randomly distributed terminals (66-34 brOT), and (3) AuNPs with
homogeneously charged terminals (MUS). This difference in adsorption behavior was not observed when AuNPs
interacted with fibrinogen. The results suggested that the interaction between the proteins and AuNPs was influenced
by the surface heterogeneity on the AuNPs, and this influence depends on the scale of surface heterogeneity and the
size of the proteins.
~3 Citings
Copyright 2015 U.S. National Library of Medicine.

45. Electrical method to quantify nanoparticle interaction with lipid bilayers


By Carney Randy P; Astier Yann; Carney Tamara M; Voitchovsky Kislon; Jacob Silva Paulo H; Stellacci Francesco
From ACS nano (2013), 7(2), 932-42, Language: English, Database: MEDLINE
Understanding as well as rapidly screening the interaction of nanoparticles with cell membranes is of central
importance for biological applications such as drug and gene delivery. Recently, we have shown that "striped" mixedmonolayer-coated gold nanoparticles spontaneously penetrate a variety of cell membranes through a passive pathway.
Here, we report an electrical approach to screen and readily quantify the interaction between nanoparticles and bilayer
lipid membranes. Membrane adsorption is monitored through the capacitive increase of suspended planar lipid
membranes upon fusion with nanoparticles. We adopt a Langmuir isotherm model to characterize the adsorption of
nanoparticles by bilayer lipid membranes and extract the partition coefficient, K, and the standard free energy gain by
this spontaneous process, for a variety of sizes of cell-membrane-penetrating nanoparticles. We believe that the
method presented here will be a useful qualitative and quantitative tool to determine nanoparticle interaction with lipid
bilayers and consequently with cell membranes.
~3 Citings
Copyright 2015 U.S. National Library of Medicine.

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46. Determination of monolayer-protected gold nanoparticle ligand-shell morphology using NMR


By Liu Xiang; Yu Miao; Kim Hyewon; Mameli Marta; Stellacci Francesco
From Nature communications (2012), 31182, Language: English, Database: MEDLINE
It is accepted that the ligand shell morphology of nanoparticles coated with a monolayer of molecules can be partly
responsible for important properties such as cell membrane penetration and wetting. When binary mixtures of
molecules coat a nanoparticle, they can arrange randomly or separate into domains, for example, forming Janus,
patchy or striped particles. To date, there is no straightforward method for the determination of such structures. Here
we show that a combination of one-dimensional and two-dimensional NMR can be used to determine the ligand shell
structure of a series of particles covered with aliphatic and aromatic ligands of varying composition. This approach is a
powerful way to determine the ligand shell structure of patchy particles; it has the limitation of needing a whole series
of compositions and ligands' combinations with NMR peaks well separated and whose shifts due to the surrounding
environment can be large enough.
~0 Citings
Copyright 2015 U.S. National Library of Medicine.

47. Determination of nanoparticle size distribution together with density or molecular weight by 2D analytical
ultracentrifugation
By Carney Randy P; Kim Jin Young; Qian Huifeng; Jin Rongchao; Mehenni Hakim; Stellacci Francesco; Bakr Osman
M
From Nature communications (2011), 2335, Language: English, Database: MEDLINE
Nanoparticles are finding many research and industrial applications, yet their characterization remains a challenge.
Their cores are often polydisperse and coated by a stabilizing shell that varies in size and composition. No single
technique can characterize both the size distribution and the nature of the shell. Advances in analytical
ultracentrifugation allow for the extraction of the sedimentation (s) and diffusion coefficients (D). Here we report an
approach to transform the s and D distributions of nanoparticles in solution into precise molecular weight (M), density
((P)) and particle diameter (d(p)) distributions. M for mixtures of discrete nanocrystals is found within 4% of the
known quantities. The accuracy and the density information we achieve on nanoparticles are unparalleled. A single
experimental run is sufficient for full nanoparticle characterization, without the need for standards or other auxiliary
measurements. We believe that our method is of general applicability and we discuss its limitations.
~7 Citings
Copyright 2015 U.S. National Library of Medicine.

48. Surface-structure-regulated cell-membrane penetration by monolayer-protected nanoparticles


By Verma Ayush; Uzun Oktay; Hu Yuhua; Hu Ying; Han Hee-Sun; Watson Nicki; Chen Suelin; Irvine Darrell J; Stellacci
Francesco
From Nature materials (2008), 7(7), 588-95, Language: English, Database: MEDLINE
Nanoscale objects are typically internalized by cells into membrane-bounded endosomes and fail to access the
cytosolic cell machinery. Whereas some biomacromolecules may penetrate or fuse with cell membranes without overt
membrane disruption, no synthetic material of comparable size has shown this property yet. Cationic nano-objects
pass through cell membranes by generating transient holes, a process associated with cytotoxicity. Studies aimed at
generating cell-penetrating nanomaterials have focused on the effect of size, shape and composition. Here, we
compare membrane penetration by two nanoparticle 'isomers' with similar composition (same hydrophobic content),
one coated with subnanometre striations of alternating anionic and hydrophobic groups, and the other coated with the
same moieties but in a random distribution. We show that the former particles penetrate the plasma membrane
without bilayer disruption, whereas the latter are mostly trapped in endosomes. Our results offer a paradigm for
analysing the fundamental problem of cell-membrane-penetrating bio- and macro-molecules.
~93 Citings
Copyright 2015 U.S. National Library of Medicine.

49. Entropy-mediated patterning of surfactant-coated nanoparticles and surfaces


By Singh Chetana; Ghorai Pradip K; Horsch Mark A; Jackson Alicia M; Larson Ronald G; Stellacci Francesco; Glotzer
Sharon C
From Physical review letters (2007), 99(22), 226106, Language: English, Database: MEDLINE

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We perform atomistic and mesoscale simulations to explain the origin of experimentally observed stripelike patterns
formed by immiscible ligands coadsorbed on the surfaces of gold and silver nanoparticles. We show that when the
conformational entropy gained via this morphology is sufficient, microphase-separated stripelike patterns form. When
the entropic gain is not sufficient, we instead predict bulk phase-separated Janus particles. We also show
corroborating experimental results that confirm our simulational predictions that stripes form on flat surfaces as well as
on curved nanoparticle surfaces.
~2 Citings
Copyright 2015 U.S. National Library of Medicine.

50. Divalent metal nanoparticles


By Devries Gretchen A; Brunnbauer Markus; Hu Ying; Jackson Alicia M; Long Brenda; Neltner Brian T; Uzun Oktay;
Wunsch Benjamin H; Stellacci Francesco
From Science (New York, N.Y.) (2007), 315(5810), 358-61, Language: English, Database: MEDLINE
Nanoparticles can be used as the building blocks for materials such as supracrystals or ionic liquids. However, they
lack the ability to bond along specific directions as atoms and molecules do. We report a simple method to place
target molecules specifically at two diametrically opposed positions in the molecular coating of metal nanoparticles.
The approach is based on the functionalization of the polar singularities that must form when a curved surface is
coated with ordered monolayers, such as a phase-separated mixture of ligands. The molecules placed at these polar
defects have been used as chemical handles to form nanoparticle chains that in turn can generate self-standing films.
~2 Citings
Copyright 2015 U.S. National Library of Medicine.

51. From homoligand- to mixed-ligand- monolayer-protected metal nanoparticles: a scanning tunneling microscopy
investigation
By Jackson Alicia M; Hu Ying; Silva Paulo Jacob; Stellacci Francesco
From Journal of the American Chemical Society (2006), 128(34), 11135-49, Language: English, Database: MEDLINE
The ligand shell that coats, protects, and imparts a large number of properties to gold nanoparticles is a 2-D selfassembled monolayer wrapped around a 3-D metallic core. Here we present a study of the molecular packing of
ligand shells on gold nanoparticles based on the analysis of scanning tunneling microscopy (STM) images. We
discuss methods for optimal nanoparticle sample preparation in relation to STM imaging conditions. We show that the
packing of a self-assembled monolayer composed solely of octanethiols on gold nanoparticles depends on the
particle's diameter with an average headgroup spacing of 5.4 A, which is different from that of similar monolayers
formed on flat Au(111) surfaces (5.0 A). In the case of nanoparticles coated with mixtures of ligands-known to phase
separate into randomly shaped and ordered domains on flat surfaces-we find that phase separation leads to the
formation of concentric, ribbonlike domains of alternating composition. The spacing of these domains depends on the
ligand shell composition. We find that, for a given composition, the spacing increases with diameter in a manner
characterized by discontinuous transitions at "critical" particle sizes. We discuss possible interpretations for the
observed trends in our data.
~2 Citings
Copyright 2015 U.S. National Library of Medicine.