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Copyright 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Early View (Online Version of Record published before inclusion in an issue)


Editor-in-Chief: Jos Oliveira; Deputy Editor: Mary Farrell Online ISSN: 1613-6829 Associated Title(s): Advanced Energy Materials, Advanced Engineering Materials, Advanced Functional Materials, Advanced Healthcare Materials, Advanced Materials 1. Review Articles 1. Design and Assembly of Rotaxane-Based Molecular Switches and Machines Wenlong Yang, Yongjun Li, Huibiao Liu, Lifeng Chi and Yuliang Li Article first published online: 20 JAN 2012 | DOI: 10.1002/smll.201101738

Recent progress in the constructionof functional smart molecular machines based on conjugated organic molecules with photo-electronic activity is summarized. Additionally, light is shed on how the novel functions of molecular machines are extended, and examples of the ways in which conjugated organic molecules have been, or can be, applied to the design and process of intelligentized systems are presented.

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2. Full Papers 1. Functionalization of Amorphous SiO2 and 6H-SiC(0001) Surfaces with Benzo[ghi]perylene-1,2dicarboxylic Anhydride via an APTES Linker Deb Kumar Bhowmick, Steffen Linden, Andr Devaux, Luisa De Cola and Helmut Zacharias Article first published online: 19 JAN 2012 | DOI: 10.1002/smll.201101941

Functionalization of SiC with a fluorescent dye is achieved in two steps. On the hydroxyl-terminated substrate, a silanization reaction first covalenty binds a 3-aminopropyl triethoxysilane (APTES) linker molecule at which the perylene dye is subsequently attached. Spatially resolved fluorescence lifetime measurements indicate that the dye is electronically isolated from the substrate. Furthermore, the formation of HH complexes is observed. Abstract Full Article (HTML) PDF(1016K) References Request Permissions 2. Self-Assembly of a Dendron-Attached Tetrathiafulvalene: Gel Formation and Modulation in the Presence of Chloranil and Metal Ions

Xingyuan Yang, Guanxin Zhang, Liqiang Li, Deqing Zhang, Lifeng Chi and Daoben Zhu Article first published online: 19 JAN 2012 | DOI: 10.1002/smll.201101917

Molecular gels of a dendron-attached tetrathiafulvalene (TTF) can be modulated by varying the oxidation state of the tetrathiafulvalene through oxidation with the ensemble of chloranil and Sc3+/Pb2+ and reduction with magnesium. The dendron-substituted TTF 1 can self-assemble in several solvents to form gels which exhibit a rope-like framework or interwoven nanofibers, depending on the polarity of the solvent from which the gel is formed.

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3. Communications 1. Facile Modification of Silica Substrates Provides a Platform for Direct-Writing Surface Click Chemistry Sabine Oberhansl, Michael Hirtz, Anna Lagunas, Ramon Eritja, Elena Martinez, Harald Fuchs and
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Josep Samitier Article first published online: 18 JAN 2012 | DOI: 10.1002/smll.201101875

Please click here: A facile two-step functionalization strategy for silicon oxide-based substrates generates a stable platform for surface click chemistry via direct writing. The suitability of the obtained substrates is proven by patterning with two different direct-writing techniques and three different molecules. Abstract Full Article (HTML) PDF(369K) References Supporting Information Request Permissions 2. Dipolar-Modulated Charge-Doped Trilayer Organic Semiconductor nn Heterojunction

Jianing Liu, Katharina Ditte, Wei Jiang, Zhaohui Wang and Cornelia Denz Article first published online: 18 JAN 2012 | DOI: 10.1002/smll.201101776

A novel dipolar-modulated charge-doped trilayer nn organic heterojunction with a bidirectional tunable energy band discontinuity is constructed. The rectifying mechanism of the trilayer is similar to the rectifying and inverse-rectifying characteristics from np and pn junctions, respectively. Zero-bias optoelectronic behavior and persistent photoconductivity are discovered. These results show that what are viewed as technological hurdles in the development of an organic nn heterojunction should, in fact, lead to a better approach in organic optoelectronics.

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4. Full Papers 1. A Cell-Delivered and Cell-Activated SN38-Dextran Prodrug Increases Survival in a Murine
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Disseminated Pancreatic Cancer Model Matthew T. Basel, Sivasai Balivada, Tej B. Shrestha, Gwi-Moon Seo, Marla M. Pyle, Masaaki Tamura, Stefan H. Bossmann and Deryl L. Troyer Article first published online: 11 JAN 2012 | DOI: 10.1002/smll.201101879

Monocyte/macrophage-like cells (Raw264.7) are shown to migrate specifically to intraperitoneal tumors when injected intraperitoneally. These cells can be engineered to express a TetOn regulated intracellular carboxylesterase, loaded with an irinotecan-like prodrug, and used to deliver and activate the prodrug specifically at a tumor site when given with doxycycline. Abstract Full Article (HTML) PDF(773K) References Supporting Information Request Permissions 2. Hydrogel Nanoparticles with Covalently Linked Coomassie Blue for Brain Tumor Delineation Visible to the Surgeon

Guochao Nie, Hoe Jin Hah, Gwangseong Kim, Yong-Eun Koo Lee, Ming Qin, Tanvi S. Ratani, Panagiotis Fotiadis, Amber Miller, Akiko Kochi, Di Gao, Thomas Chen, Daniel A. Orringer, Oren Sagher, Martin A. Philbert and Raoul Kopelman Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101607

Hydrogel nanoparticles containing a high concentration of visible dye by covalent linkage, with PEGylated surface and conjugated tumor targeting moiety, enable visual delineation of brain tumors in vitro and in vivo. This technology enables color-guided tumor resection in real time, with no need for extra equipment or special lighting conditions.

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5. Communications 1. Nanoengineered Metal Surface Capsules: Construction of a Metal-Protection System


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Daria V. Andreeva, Dmitry V. Sviridov, Admir Masic, Helmuth Mhwald and Ekaterina V. Skorb Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201102365

Sonochemically formed metal capsules, which can protect a metal surface and release active compounds, are presented. The capsules are formed by modifying a metal surface into having a porous sponge layer; this layer is continuous with the bulk metal allowing for excellent adhesion. The porosity of the sponge layer and polyelectrolyte complexes allows active compounds to be stored and released depending on external stimuli. These porous capsules open up prospects in metal nanoengineering and surface protection as well as in encapsulation and polyelectrolyte applications. Abstract Full Article (HTML) PDF(1210K) References Supporting Information Request Permissions 2. Neuronal Architectures with Axo-dendritic Polarity above Silicon Nanowires

Sophie Roth, Ghislain Bugnicourt, Mariano Bisbal, Sylvie Gory-Faur, Jacques Brocard and Catherine Villard Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201102325

An approach is developped to gain control over the polarity of neuronal networks at the cellular level by physically constraining cell development by the use of micropatterns. It is demonstrated that the position and path of individual axons, the cell extension that propagates the neuron output signal, can be chosen with a success rate higher than 85%. This allows the design of small living computational blocks above silicon nanowires. Abstract Full Article (HTML) PDF(717K) References Supporting Information Request Permissions 3. New Design Concepts for the Fabrication of Nanometric Gap Structures: Electrochemical Oxidation of OTS Mono- and Bilayer Structures

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Tamara S. Druzhinina, Stephanie Hoeppener and Ulrich S. Schubert Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101842

A reliable nanofabrication concept to engineer metallic nanometric gap structures and to incorporate silver nanoparticles within the gaps utilizing a combination of self-assembly strategies and electrochemical oxidation lithography is developed. The approach uses the differences in oxidation kinetics of n-octadecyltrichlorosilane (OTS) monolayer and bilayer structures. The processes are investigated in detail and form the basis for a new nanofabrication process.

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6. Full Papers 1. Standing Arrays of Gold Nanorods End-Tethered with Polymer Ligands Alla Petukhova, Jesse Greener, Kun Liu, Dmytro Nykypanchuk, Renaud Nicola, Krzysztof Matyjaszewski and Eugenia Kumacheva Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101297

Solution-based side-by-side assembly of 2D superlattices of gold nanorods end-functionalized with a small amount of polymer paves the way for producing standing nanorod arrays. Abstract Full Article (HTML) PDF(1090K) References Supporting Information Request Permissions 2. Highly Size- and Shape-Controlled Synthesis of Silver Nanoparticles via a Templated Tollens Reaction

Ruggero Dondi, Wu Su, Gerry A. Griffith, Graham Clark and Glenn A. Burley Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101474

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A mild, facile one-step synthetic strategy for the preparation of size- and shape-controlled silver nanoparticles (AgNPs) is presented. The AgNPs prepared by this strategy exhibit remarkable stability in high salt aqueous buffer systems up to 2.8 M NaCl for a period of at least 24 h. The high degree of sizeand shape-control of these AgNPs is achieved by the development of novel multifunctional triazole sugar ligands, which mediate the nucleation, growth, and passivation phases of AgNP preparation in the presence of the Tollens reagent as the silver source. Abstract Full Article (HTML) PDF(484K) References Supporting Information Request Permissions 3. Engineered Redox-Responsive PEG Detachment Mechanism in PEGylated Nano-Graphene Oxide for Intracellular Drug Delivery

Huiyun Wen, Chunyan Dong, Haiqing Dong, Aijun Shen, Wenjuan Xia, Xiaojun Cai, Yanyan Song, Xuequan Li, Yongyong Li and Donglu Shi Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101613

A PEGylated nano-graphene oxide (NGO-SS-mPEG) with redox-responsive polyethylene glycol (PEG) detachment mechanism can rapidly release encapsulated payload under tumor-relevant glutathione (GSH) levels. The specially engineered delivery system addresses the critical issues related to NGO of physiological stability and drug delivery in a tumor-selective and controlled fashion. Abstract Full Article (HTML) PDF(1216K) References Supporting Information Request Permissions 4. Predictive Gold Nanocluster Formation Controlled by Metal-Ligand Complexes

John M. Pettibone and Jeffrey W. Hudgens Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101777

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Selective reduction of gold-diphosphine complexes produces predictable nascent gold nanoclusters that can be separated into two classes. Class I complexes produce nascent neutral clusters and Class II produce cationic, ligated Au8 and Au10 nanoclusters. Predictable nascent products allow further tunable control of metal nuclearity through postreduction, size-selective processing, when desired. Abstract Full Article (HTML) PDF(622K) References Supporting Information Request Permissions 5. Tuning Ratios, Densities, and Supramolecular Spacing in Bifunctional DNA-Modified Gold Nanoparticles

Julin A. Daz, David M. Grewer and Julianne M. Gibbs-Davis Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101922

Strategies for controlling the composition and loading of multiple functional groups on DNAmodified gold nanoparticles are compared using fluorescence spectroscopy, different DNA constructs, and fluorophore small-molecule labels. To dial in distances between the fluorophores, hybridization of an adjuster strand to branched DNA or Y-DNA complexes is shown to further modulate supramolecular spacing. Abstract Full Article (HTML) PDF(978K) References Supporting Information Request Permissions 6. Synthesis of Nanoamorphous Germanium and Its Transformation to Nanocrystalline Germanium

mer Dag, Eric J. Henderson and Geoffrey A. Ozin Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101993

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Two oxide-based precursors in a water/alcohol solution, one acting as a reducing agent ((CH3CH2O) 3SiH) and the other as a germanium source (Ge(OCH2CH3)4), react very slowly to form colloidally stable amorphous nanoparticles of germanium encapsulated by a shell of silica (na-Ge/SiO2). Evaporation of the solvent yields monoliths of na-Ge/SiO2, which can be annealed to form nanocrystalline germanium (nc-Ge) embedded in a silica matrix (nc-Ge/SiO2), from which freestanding, colloidally stable nc-Ge can be obtained by chemical etching of the encapsulating silica matrix.

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7. Communications 1. Pulling Tethers from Pore-Spanning Bilayers: Towards Simultaneous Determination of Local Bending Modulus and Lateral Tension of Membranes Marta Kocun and Andreas Janshoff Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101557

Nanotubes from pore-spanning membranes: a site-specific experimental procedure is introduced that allows determination of the lateral tension and bending modulus of pore-spanning bilayers in a single force cycle comprising indentation followed by nanotube formation upon retraction. With this technique, a quantitative mapping of intrinsic local elastic properties comes into reach. Abstract Full Article (HTML) PDF(681K) References Supporting Information Request Permissions 2. Electrospun Fiber Template for Replica Molding of Microtopographical Neural Growth Guidance

Yingyi Liu, Yi Sun, Hao Yan, Xiyu Liu, Wei Zhang, Zhuo Wang and Xingyu Jiang Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101199

A method for replica molding electrospun (ES) fibers on the surface of polydimethylsiloxane
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(PDMS) is developed for culturing and guiding of cells, instead of ES fibers. With this method, microgrooves and microstructures composed of microgrooves can be obtained. PDMS is integrated into the microfluidic chip as a substrate to successfully pattern and guide neurites on the PDMS surface with microgrooves. Abstract Full Article (HTML) PDF(778K) References Supporting Information Request Permissions 3. Binary Assembly of Colloidal Semiconductor Nanorods with Spherical Metal Nanoparticles

Yasutaka Nagaoka, Tie Wang, Jared Lynch, Derek LaMontagne and Y. Charles Cao Article first published online: 9 JAN 2012 | DOI: 10.1002/smll.201101902

Binary assemblies of CdSe/CdS semiconductor nanorods are prepared with spherical metal nanoparticles intercalated into aligned, parallel nanorod arrays. Mechanistic studies suggest that the formation of these binary assemblies is a kinetically limited process. Organic additives with suitable polarity and strong affinity to spherical nanoparticles that have both a high dielectric constant and a large Hamaker constant play an important roles.

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8. Full Papers 1. Importance of Nanoparticle Size in Colorimetric and SERS-Based Multimodal Trace Detection of Ni(II) Ions with Functional Gold Nanoparticles eljka Krpeti, Luca Guerrini, Iain A. Larmour, John Reglinski, Karen Faulds and Duncan Graham Article first published online: 5 JAN 2012 | DOI: 10.1002/smll.201101980

Design of functionalized gold nanoparticles and their assembly for SERS/colorimetric detection of Ni (II) is described. This systematic study emphasizes the importance of the nanoparticle core size in controlled particle assembly and sensor-response tunability, demonstrating how lower detection limits can be achieved by carefully selecting the particle core size and surface chemistry, promoting the feasibility of a multimodal approach.
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Abstract Full Article (HTML) PDF(467K) References Supporting Information Request Permissions 2. Single-Molecule Conductance of -Conjugated Rotaxane: New Method for Measuring Stipulated Electric Conductance of -Conjugated Molecular Wire Using STM Break Junction

Manabu Kiguchi, Shigeto Nakashima, Tomofumi Tada, Satoshi Watanabe, Susumu Tsuda, Yasushi Tsuji and Jun Terao Article first published online: 5 JAN 2012 | DOI: 10.1002/smll.201102075

Covering a single -conjugated wire with an -cyclodextrin molecule is a promising technique for suppressing conductance fluctuations. The peak in the conductance histogram of the covered molecular junction is sharper than that of the uncovered junction. The covering technique has two prominent effects: the suppression of intramolecular motion, and the elimination of intermolecular interactions.

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9. Communications 1. Conjugated Polymers for Light-Activated Antifungal Activity Chengfen Xing, Gaomai Yang, Libing Liu, Qiong Yang, Fengting Lv and Shu Wang Article first published online: 5 JAN 2012 | DOI: 10.1002/smll.201101825

A cationic polythiopheneporphyrin (PTP) dyad is shown to exhibit efficient light-activated antifungal activity. Higher singlet oxygen (1O2) generation efficiency can be attained from PTP upon photoexcitation due to the light-harvesting properties of the polymer backbone and efficient energy transfer from the polythiophene to the porphyrin units. PTP can be used for treating fungal infections in lower doses of irradiation light and polymer concentration.
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10. Full Papers 1. Auger Recombination Suppression in Nanocrystals with Asymmetric ElectronHole Confinement Juan I. Climente, Jose L. Movilla and Josep Planelles Article first published online: 5 JAN 2012 | DOI: 10.1002/smll.201101740

Core/shell nanocrystals in which electrons and holes have different spatial locations display reduced Auger relaxation rates. A two-band Kane Hamiltonian is used to understand the observed experimental behavior. It is shown that certain shell thicknesses lead to strongly suppressed Auger recombination, regardless of the core size.

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11. Communications 1. Self-Fluorescence of Chemically Crosslinked MRI Nanoprobes to Enable Multimodal Imaging of Therapeutic Cells Hyun Min Kim, Young-Woock Noh, Hye Sun Park, Mi Young Cho, Kwan Soo Hong, Hyunseung Lee, Da Hye Shin, Jongeun Kang, Moon-Hee Sung, Haryoung Poo and Yong Taik Lim Article first published online: 5 JAN 2012 | DOI: 10.1002/smll.201102361

Old chemistry for novel materials: Self-fluorescent high-relaxivity T2-weighted magnetic resonance imaging (MRI) contrast agents are produced. They are a novel type of MR/optical dual-modality in vivo imaging nanoprobe using glutaraldehyde crosslinking chemistry, and they are used to label and monitor therapeutic cells both in vitro and in vivo.

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Request Permissions 2. Optical Identification of Single- and Few-Layer MoS2 Sheets

Hai Li, Gang Lu, Zongyou Yin, Qiyuan He, Hong Li, Qing Zhang and Hua Zhang Article first published online: 5 JAN 2012 | DOI: 10.1002/smll.201101958

A simple approach is developed to identify the layer number of 2D MoS2 sheets. By using an optical imaging method combined with image analysis software, a high-contrast image of the MoS2 sheets can be extracted from the red (R) channel of the color optical microscopy image. The value of the intensity difference in the grayscale image of the R channel between MoS2 sheets (13 layers) and the SiO2 substrate can be used to identify the layer number of the sheet.

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12. Full Papers 1. Subcellular Tracking of Drug Release from Carbon Nanotube Vehicles in Living Cells Bin Kang, Jun Li, Shuquan Chang, Mingzhu Dai, Chao Ren, Yaodong Dai and Da Chen Article first published online: 5 JAN 2012 | DOI: 10.1002/smll.201101714

The subcellular release of anticancer drug DOX from carbon nanotube vehicles in living cells is directly observed under a confocal microscope using a unique two-dye labeling approach. Imaging clearly shows the time-dependent process of drug transportation into cells and release to the cell nucleus. The drug DOX detaches from SWNTs inside the lysosomes to yield free molecules to escape into the cytoplasm and finally into the cell nucleus, while the vehicle SWNTs are trapped inside lysosomes, without entering the nucleus.

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13. Communications 1. Metallic Nanobowls by Galvanic Replacement Reaction on Heterodimeric Nanoparticles Yonatan Ridelman, Gurvinder Singh, Ronit Popovitz-Biro, Sharon G. Wolf, Sanjib Das and Rafal Klajn

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Article first published online: 3 JAN 2012 | DOI: 10.1002/smll.201101882

Well-defined metallic nanobowls can be prepared by extending the concept of a protecting group to colloidal synthesis. Magnetic nanoparticles are employed as protecting groups during the galvanic replacement of silver with gold. The replacement reaction is accompanied by spontantous dissociation of the protecting groups, leaving behind metallic nanobowls.

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14. Full Papers 1. Probing Access Resistance of Solid-State Nanopores with a Scanning-Probe Microscope Tip Changbae Hyun, Ryan Rollings and Jiali Li Article first published online: 28 DEC 2011 | DOI: 10.1002/smll.201101337

A novel apparatus that integrates solid-state nanopore ionic current measurement with a scanning probe microscope is constructed and used to characterize the access resistance of solid-state nanopores. The apparatus is capable of recording the current blockage 3D map caused by the probe tip Is(x,y,z) in salt solution. Access resistance is an important parameter for understanding the nanopore translocation process of single DNA and protein molecules.<?br?> Abstract Full Article (HTML) PDF(665K) References Supporting Information Request Permissions 2. Transparent and Conducting GrapheneRNA-Based Nanocomposites

Faranak Sharifi, Reg Bauld, M. Shafiq Ahmed and Giovanni Fanchini Article first published online: 27 DEC 2011 | DOI: 10.1002/smll.201101537
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Different mechanisms of adhesion occur on graphene surfaces for the two types of RNA investigated: RNA VI forms aggregates whereas RNA IX uniformly covers the graphene surface. Such differences lead to the formation of different types of transparent and conducting grapheneRNA composites, with the best crossover between transparency and electric performance for nanocrystalline graphite dispersed in RNA VI.

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15. Concepts 1. Unconventional Layer-by-Layer Assembly: Surface Molecular Imprinting and Its Applications Huaping Xu, Monika Schnhoff and Xi Zhang Article first published online: 27 DEC 2011 | DOI: 10.1002/smll.201101884

Preassembling singly charged, uncharged, or water-repellent building blocks in an unconventional layer-by-layer fashion enhances the ability for advanced functionality, in particular, surface molecular imprinting, of the resulting multilayer film.

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16. Communications 1. Efficient Gene Delivery to Mesenchymal Stem Cells by an Ethylenediamine-Modified Polysaccharide from Mulberry Leaves Wen-Wen Deng, Xia Cao, Miao Wang, Yan Yang, Wei-Yan Su, Ya-Wei Wei, Zhen Ou-Yang, JiangNan Yu and Xi-Ming Xu Article first published online: 27 DEC 2011 | DOI: 10.1002/smll.201101554

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A polysaccharide of mulberry leaves (MPS) is isolated from mulberry leaves and cationized by grafting ethylenediamine onto the MPS backbone to obtain the cationic polysaccharide of mulberry leaves (CMPS). The plasmid DNA/CMPS nanoparticles are prepared by combining plasmid DNA with CMPS and used to transfect mesenchymal stem cells, which results in significantly higher transfection efficiency than when Lipofectamine 2000 is used. Abstract Full Article (HTML) PDF(712K) References Request Permissions 2. Effect of Protein Adsorption on the Fluorescence of Ultrasmall Gold Nanoclusters

Li Shang, Stefan Brandholt, Florian Stockmar, Vanessa Trouillet, Michael Bruns and G. Ulrich Nienhaus Article first published online: 27 DEC 2011 | DOI: 10.1002/smll.201101353

The interaction of proteins with ultrasmall gold nanoclusters (Au NCs) is investigated. Upon protein association, the fluorescence of Au NCs is significantly enhanced and, concomitantly, their luminescence lifetime is prolonged. The results stress the importance of investigating the behavior of fluorescent metal NCs in complex biological environment for advancing their bio-nanotechnology applications.

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17. Full Papers 1. Shape Changes of Pt Nanoparticles Induced by Deposition on Mesoporous Silica Lisandro J. Giovanetti, Jos M. Ramallo-Lpez, Michael Foxe, Louis C. Jones, Matthias M. Koebel, Gabor A. Somorjai, Aldo F. Craievich, Miquel B. Salmeron and Flix G. Requejo Article first published online: 23 DEC 2011 | DOI: 10.1002/smll.201101293

2 nm Pt nanoparticles (NPs) are impregnated in mesoporous silica substrates (SBA-15). A change in


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the Fourier transformation indicates the deformation of the Pt NPs in contact with the SBA-15 surface, from spherical to flat morphology.

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18. Communications 1. Three-Dimensional Obstacles for Bacterial Surface Motility Claudia Meel, Nadzeya Kouzel, Enno R. Oldewurtel and Berenike Maier Article first published online: 20 DEC 2011 | DOI: 10.1002/smll.201101362

Twitching motility enables bacteria to move over surfaces using type IV pili as grappling hooks. Here it is shown that the motility of the round Neisseria gonorrhoeae as well as of rod-shaped Myxococcus xanthus is guided by elevations with dimension and depth corresponding to the size of the bacteria.

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19. Full Papers 1. Covalent Layer-by-Layer Assembly of Redox Active Molecular Multilayers on Silicon (100) by Photochemical Thiol-Ene Chemistry Christian Schulz, Susann Nowak, Roland Frhlich and Bart Jan Ravoo Article first published online: 20 DEC 2011 | DOI: 10.1002/smll.201101822

Covalently bound redox active layers are fabricated onto silicon (100) using decaallylferrocene in a layer-by-layer assembly with sequential photochemical thiol-ene reactions. The layer growth is linear for at least sixteen layers. The molar density of ferrocene for each layer is 6 1011 mol cm2.

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20. Communications 1. Size-Controllable DNA Rings with Copper-Ion Modification Junwye Lee, Shogo Hamada, Rashid Amin, Sunho Kim, Atul Kulkarni, Taesung Kim, Yonghan Roh, Satoshi Murata and Sung Ha Park Article first published online: 19 DEC 2011 | DOI: 10.1002/smll.201101561

Cu2+-modified DNA nanostructures are investigated using differently sized DNA rings that are composed of core and extension motifs. Chemical reduction and current measurements are adopted for verifying Cu2+ modification, and the results provide clear evidence for the co-ordination of Cu2+ in DNA structures.

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21. Full Papers 1. Imbricate Scales as a Design Construct for Microsystem Technologies Seok Kim, Yewang Su, Agustin Mihi, Seungwoo Lee, Zhuangjian Liu, Tanmay K. Bhandakkar, Jian Wu, Joseph B. Geddes III, Harley T. Johnson, Yongwei Zhang, Jung-Ki Park, Paul V. Braun, Yonggang Huang and John A. Rogers Article first published online: 19 DEC 2011 | DOI: 10.1002/smll.201101832

An imbricate architecturedesign for microsystems is presented. It offers fault-tolerant, multifunctional capabilities in layouts that can provide mechanical flexibility even with full, 100% areal coverage of rigid plates. Such designs are implemented in flexible heterogeneous photonic surfaces including combinations of silicon, photonic, and plasmonic scales using a manufacturing approach based on transfer printing.

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References Supporting Information Request Permissions 2. Parameters Affecting the Efficient Delivery of Mesoporous Silica Nanoparticle Materials and Gold Nanorods into Plant Tissues by the Biolistic Method

Susana Martin-Ortigosa, Justin S. Valenstein, Wei Sun, Lorena Moeller, Ning Fang, Brian G. Trewyn, Victor S.-Y. Lin and Kan Wang Article first published online: 16 DEC 2011 | DOI: 10.1002/smll.201101294

Biolistic-mediated delivery of mesoporous silica nanoparticles (MSNs) and DNA to plant cells is performed via two strategies: gold plating the surfaces of MSNs to increase momentum during bombardment, and co-bombardment of the MSNs with 0.6 m gold particles. In both cases, a CaCl2/spermidine-based protocol is used to coat DNA onto the particles. Abstract Full Article (HTML) PDF(489K) References Request Permissions 3. Cargo-Towing Fuel-Free Magnetic Nanoswimmers for Targeted Drug Delivery

Wei Gao, Daniel Kagan, On Shun Pak, Corbin Clawson, Susana Campuzano, Erdembileg ChuluunErdene, Erik Shipton, Eric E. Fullerton, Liangfang Zhang, Eric Lauga and Joseph Wang Article first published online: 15 DEC 2011 | DOI: 10.1002/smll.201101909

Fuel-free nanomotors are essential for future in-vivo biomedical applications. The first example of towing drug-loaded magnetic polymeric particles using magnetically driven fuel free flexible nanomotors is described. The effect of the cargo size upon the swimming performance is evaluated experimentally and compared to a theoretical model. Potential applications of these cargo-towing motors are demonstrated by using the directed delivery of drug-loaded microparticles to HeLa cancer cells in biological media.

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22. Highlights 1. Chemical Reaction on a Solid Surface with Nanoconfined Geometry Lin Jiang, Yinghui Sun and Xiaodong Chen Article first published online: 15 DEC 2011 | DOI: 10.1002/smll.201102275

Linear alkane polymerization is achieved on the Au(110) surface with 1D constrained nanochannels, which play a key role in the selective CH activation and CC bond coupling.

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23. Full Papers 1. Layer-by-Layer Formation of Block-Copolymer-Derived TiO2 for Solid-State Dye-Sensitized Solar Cells Stefan Guldin, Pablo Docampo, Morgan Stefik, Gen Kamita, Ulrich Wiesner, Henry J. Snaith and Ullrich Steiner Article first published online: 15 DEC 2011 | DOI: 10.1002/smll.201102063

Fabrication of sufficiently thick mesoporous TiO2 photoelectrodes with morphology control on the 10 nm length scale is essential for solid-state dye-sensitized solar cells (ss-DSC). This study of the temporal evolution of block-copolymer-directed mesoporous TiO2 films during annealing and calcination enables the build-up of sufficiently thick films for high-performance ssDSC devices.

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24. Communications 1. Dynamic Preconcentration of Gold Nanoparticles for Surface-Enhanced Raman Scattering in a Microfluidic System
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Kwang Bok Kim, Ji-Hyung Han, Hyoungseon Choi, Hee Chan Kim and Taek Dong Chung Article first published online: 15 DEC 2011 | DOI: 10.1002/smll.201101771

A reversible preconcentration of gold nanoparticles (AuNPs) can be used for chemical analysis based on surface-enhanced Raman scattering in a microfluidic system. AuNPs homogeneously dispersed in solution are locally preconcentrated by charge-selective ion extraction through a pair of negatively charged polyelectrolyte plugs. This phenomenon creates dynamic hot spots among the preconcentrated AuNPs, which can also be redispersed as required.

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25. Full Papers 1. Nanoscale Localization Sampling Based on Nanoantenna Arrays for Super-resolution Imaging of Fluorescent Monomers on Sliding Microtubules Kyujung Kim, Junichiro Yajima, Youngjin Oh, Wonju Lee, Shinsuke Oowada, Takayuki Nishizaka and Donghyun Kim Article first published online: 14 DEC 2011 | DOI: 10.1002/smll.201101840

Sub-diffraction-limited imaging of fluorescent monomers on sliding microtubules in vitro is performed by nanoscale localization sampling (NLS). NLS is based on periodic nanohole antenna arrays that create local hot spots through surface plasmon localization. A fourfold improvement in spatial resolution is achieved by imaging rhodamine-labeled microtubules at 76 nm resolution in the direction of movement and 135 nm orthogonally. Abstract Full Article (HTML) PDF(1341K) References Supporting Information Request Permissions 2. Highly Wrinkled Cross-Linked Graphene Oxide Membranes for Biological and Charge-Storage Applications

Lena A. L. Tang, Wong Cheng Lee, Hui Shi, Ethel Y. L. Wong, Anton Sadovoy, Sergey Gorelik,
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Jonathan Hobley, Chwee Teck Lim and Kian Ping Loh Article first published online: 13 DEC 2011 | DOI: 10.1002/smll.201101690

Highly wrinkled graphene oxide membranes are formed at the waterair interface by a cross-linking reaction. The corrugation of the membrane can be controlled by the temperature and concentration of the cross-linking species. The corrugated graphene oxide membrane is a good scaffold for the growth of human mesenchymal stem cells and promotes spontaneous stem-cell differentiation into oesteoblast lineage. The corrugated film structure reduces face-to-face stacking of the graphene and good capacitance values (211 F g1) can be obtained when the film is used in supercapacitors.

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26. Communications 1. Graphene Audio Voltage Amplifier Erica Guerriero, Laura Polloni, Laura Giorgia Rizzi, Massimiliano Bianchi, Giovanni Mondello and Roman Sordan Article first published online: 9 DEC 2011 | DOI: 10.1002/smll.201102141

A graphene audio voltage amplifier is fabricated by overlapping the gate with source/drain contacts. The fabricated complementary amplifier has a voltage gain of 3.7 (11.4 dB) at 10 kHz, a total harmonic distortion in the audio frequency range of <1%, a unity-gain frequency of 360 kHz, and a 3 dB bandwidth of 70 kHz. Abstract Full Article (HTML) PDF(495K) References Supporting Information Request Permissions 2. Controlled Assemblies of Gold Nanorods in PVA Nanofiber Matrix as Flexible Free-Standing SERS Substrates by Electrospinning

Chuan-Ling Zhang, Kong-Peng Lv, Huai-Ping Cong and Shu-Hong Yu Article first published online: 9 DEC 2011 | DOI: 10.1002/smll.201102230

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Under control: Controlled assemblies of gold nanorods in a poly(vinyl alcohol) (PVA) nanofiber matrix with tunable optical properties can be achieved by using electrospinning. The resultant assemblies can be used as substrates for surface-enhanced Raman spectroscopy (SERS). This work provides a facile way to control alignment of anisotropic nanostructures in a polymer nanofiber matrix and generates new assemblies with interesting properties.

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27. Reviews 1. Physical Aspects of Cell Culture Substrates: Topography, Roughness, and Elasticity Aftin M. Ross, Zhongxiang Jiang, Martin Bastmeyer and Joerg Lahann Article first published online: 9 DEC 2011 | DOI: 10.1002/smll.201100934

The cellular environment plays a significant role in cell phenotype and function. As such, physical properties of cell culture substrates including topography, roughness, and elasticity may be utilized to investigate the influence of these physical cues on the cellular response. In this review, strategies for modulating the physical properties of surfaces, the influence of these changes on cell responses, and the promise and limitations of these surfaces in in-vitro settings are highlighted, with a particular emphasis on elastic substrates.

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28. Full Papers 1. Diameter-Dependent Thermal Transport in Individual ZnO Nanowires and its Correlation with Surface Coating and Defects Cong Tinh Bui, Rongguo Xie, Minrui Zheng, Qingxin Zhang, Chorng Haur Sow, Baowen Li and John T. L. Thong Article first published online: 9 DEC 2011 | DOI: 10.1002/smll.201102046
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Thermal transport properties of individual zinc oxide nanowires are characterized using a suspended micro-electrothermal device. It is found that the thermal conductivities of the nanowires are dramatically reduced by at least one order of magnitude compared to bulk values. An empirical relationship for assessing diameter-dependent thermal properties is observed, which shows an approximately linear dependence of the thermal conductivity on the cross-section area of the nanowires in the measured diameter range. Abstract Full Article (HTML) PDF(2045K) References Supporting Information Request Permissions 2. Designer Hydrophilic Regions Regulate Droplet Shape for Controlled Surface Patterning and 3D Microgel Synthesis

Matthew J. Hancock, Fumiki Yanagawa, Yun-Ho Jang, Jiankang He, Nezamoddin N. Kachouie, Hirokazu Kaji and Ali Khademhosseini Article first published online: 9 DEC 2011 | DOI: 10.1002/smll.201101745

Droplets conform to hydrophilic regions with hydrophobic boundaries at the macroscale and microscale. Shaped droplets of prepolymer solution become shaped microgels once crosslinked. Sedimenting microparticles contained in a microdroplet form a gradient deposition pattern. Finite element simulations provide a computational design platform for shaped droplets and corresponding surface patterning and microgels. Abstract Full Article (HTML) PDF(3050K) References Supporting Information Request Permissions 3. Flexible Pillared Graphene-Paper Electrodes for High-Performance Electrochemical Supercapacitors

Gongkai Wang, Xiang Sun, Fengyuan Lu, Hongtao Sun, Mingpeng Yu, Weilin Jiang, Changsheng Liu and Jie Lian Article first published online: 8 DEC 2011 | DOI: 10.1002/smll.201101719
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Flexible graphene paper infiltrated by carbon black (CB) nanoparticles using a vacuum filtration method is developed as a high-performance electrode material for supercapacitors. The self-restacking of graphene sheets is mitigated by the introduction of carbon black as a spacer. The pillared graphene paper-based supercapacitors exhibit excellent electrochemical performance and cyclic stability compared with undoped graphene paper.

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29. Communications 1. Branched and 4-Arm Starlike -Helical Peptide Structures with Enhanced Antimicrobial Potency and Selectivity Nikken Wiradharma, Shao-Qiong Liu and Yi-Yan Yang Article first published online: 8 DEC 2011 | DOI: 10.1002/smll.201101672

Linear, 2-arm branched, and 4-arm starlike peptides are designed and their antimicrobial and hemolytic activities are characterized. Branching molecular designs are demonstrated to enhance antimicrobial activity and reduce undesired hemolysis, leading to better selectivity towards microbes over mammalian cells. This unique strategy can also be applied to optimize the molecular structures of other types of macromolecular antimicrobials such as polymers.

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30. Full Papers 1. Exosomes as Extrapulmonary Signaling Conveyors for Nanoparticle-Induced Systemic Immune Activation Motao Zhu, Yiye Li, Jian Shi, Weiyue Feng, Guangjun Nie and Yuliang Zhao Article first published online: 6 DEC 2011 | DOI: 10.1002/smll.201101708

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Nanoparticle (NP)-induced exosomes are conveyors in the signaling induction of systemic immunostimulation. Respiratory exposure of magnetic iron oxide nanoparticles (MIONs) can induce exosome secretion from antigen-presenting cells (APCs, probably alveolar macrophages) in the alveolar region. These exosomes sequentially fast transfer to an extrapulmonary site, and extrapulmonarytransferred exosomes are capable of remarkable activation of systemic T cells.

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31. Communications 1. A Novel Assay for Quantifying the Number of Plasmids Encapsulated by Polymer Nanoparticles Nupura S. Bhise, Ron B. Shmueli, Jose Gonzalez and Jordan J. Green Article first published online: 5 DEC 2011 | DOI: 10.1002/smll.201101718

Polymeric nanoparticles are promising for gene therapy and stem cell reprogramming using nonviral vectors. A novel assay utilizing nanoparticle tracking analysis is developed to easily quantify the number of plasmids within polymeric nanoparticles while in aqueous solution. Particles effective at cotransfecting primary human fibroblasts are approximately 100 nm in diameter and contain around 100 plasmids per particle.

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32. Reviews 1. Chemical Approaches toward Graphene-Based Nanomaterials and their Applications in Energy-Related Areas Bin Luo, Shaomin Liu and Linjie Zhi Article first published online: 25 NOV 2011 | DOI: 10.1002/smll.201101396

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With a focus on chemical and thermal approaches toward the production of well-defined graphenebased nanomaterials, this paper gives a brief overview of the recent exciting research results and the potential applications of graphene nanomaterials in energy-related areasincluding solar cells, lithium ion secondary batteries, supercapacitors, and catalysiswhich have attracted great attention all over the world. Abstract Full Article (HTML) PDF(1772K) References Request Permissions 2. Bicelles: Lipid Nanostructured Platforms with Potential Dermal Applications

Lucyanna Barbosa-Barros, Gelen Rodrguez, Clara Barba, Mercedes Ccera, Laia Rubio, Joan Estelrich, Carmen Lpez-Iglesias, Alfonso de la Maza and Olga Lpez Article first published online: 23 NOV 2011 | DOI: 10.1002/smll.201101545

Bicelles have the ability to penetrate through the narrow intercellular spaces of the stratum corneum of the skin to reinforce its lipid lamellae. Their structure also allows for the incorporation of different molecules that can be carried through the skin layers.

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33. Communications 1. Molecular Cloisonn: Multicomponent Organic Alternating Nanostructures at Vicinal Surfaces with Tunable Length Scales Dingyong Zhong, Lifeng Chi, Haiming Guo, Dongxia Shi and Harald Fuchs Article first published online: 4 OCT 2011 | DOI: 10.1002/smll.201100822

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By careful management of the adsorption preference of organic molecules at faceted vicinal surfaces, organic alternating structures can be extended to multilayers and multicomponent with tunable size scales ranging from several to a few tens nanometers.

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