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Cover image for Vol. 9 Issue 16

August 26, 2013

Volume 9, Issue 16

Pages 2653–2825

  1. Cover Picture

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      Drug Delivery: Photosensitizer-Incorporated Quadruplex DNA-Gated Nanovechicles for Light-Triggered, Targeted Dual Drug Delivery to Cancer Cells (Small 16/2013) (page 2653)

      Cuie Chen, Li Zhou, Jie Geng, Jinsong Ren and Xiaogang Qu

      Article first published online: 16 AUG 2013 | DOI: 10.1002/smll.201370091

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      A light-operated vehicle for targeted intracellular drug delivery has been constructed by J. Ren, X. Qu, and co-workers using photosensitizer-incorporated G-quadruplex DNAcapped mesoporous silica nanoparticles. Upon light irradiation, the photosensitizer generates reactive oxygen species, causing the DNA capping to be cleaved and allowing the cargo (drugs) to be released. This platform, described in detail on page 2793, makes it possible to develop a drug-carrier system for a synergistic combination of chemotherapy and photodynamic therapy for the treatment of cancer with a high spatial/temporal control.

  2. Inside Front Cover

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      Multicolor Emission: Multicolor Emission of Hybrid Block Copolymer–Quantum Dot Microspheres by Controlled Spatial Isolation of Quantum Dots (Small 16/2013) (page 2654)

      Kang Hee Ku, Minsoo P. Kim, Kwanyeol Paek, Jae Man Shin, Sunhaeng Chung, Se Gyu Jang, Weon-Sik Chae, Gi-Ra Yi and Bumjoon J. Kim

      Article first published online: 16 AUG 2013 | DOI: 10.1002/smll.201370092

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      Multicolor-emitting hybrid microspheres of block copolymers (BCPs) and quantum dots (QDs) are fabricated by B. J. Kim and co-workers with their nanostructures controlled in all three dimensions. On page 2667, location control and separation of the QDs within the microspheres are achieved using supramolecular assemblies of BCP micelles. Through ratiometric control of site-isolated, different-colored QDs, a full-color display without undesired Förster resonance energy transfer between the QDs is achieved.

  3. Back Cover

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      Microfluidics: High Throughput-Per-Footprint Inertial Focusing (Small 16/2013) (page 2828)

      Ata Tuna Ciftlik, Maxime Ettori and Martin A. M. Gijs

      Article first published online: 16 AUG 2013 | DOI: 10.1002/smll.201370093

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      The integration of microfluidic structures and microelectronic chips is made feasible by M. A. M. Gijs and co-workers. On page 2764, they determine the effect of Reynolds numbers on focusing, the entry length required for the laminar flow to develop, and the pressure resistance of the microfluidic channels. This enables maximisation of the ‘throughput-per-footprint’ (TPFP), allowing the channels to be scaled down to the required sizes without compromising the flow throughput.

  4. Masthead

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      Masthead: (Small 16/2013)

      Article first published online: 16 AUG 2013 | DOI: 10.1002/smll.201370094

  5. Contents

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    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Communications
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      Contents: (Small 16/2013) (pages 2655–2661)

      Article first published online: 16 AUG 2013 | DOI: 10.1002/smll.201370095

  6. Communications

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    7. Communications
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    1. Lanthanide-Based, Near-Infrared Luminescent and Magnetic Lipoparticles: Monitoring Particle Integrity (pages 2662–2666)

      Sara Lacerda, Célia S. Bonnet, Agnès Pallier, Sandrine Villette, Frédéric Foucher, Frances Westall, Frédéric Buron, Franck Suzenet, Chantal Pichon, Stéphane Petoud and Éva Tóth

      Article first published online: 2 APR 2013 | DOI: 10.1002/smll.201201923

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      Near-infrared emitting, magnetic particles for combined optical and MR detection based on liposomes or artificial lipoproteins are presented. They provide a novel strategy for the luminescence sensitization of lanthanide cations (Yb3+, Nd3+) without covalent bonds between the chromophore and the lanthanide, and provide an unambiguous tool for monitoring the integrity of the liponanoparticles, via emission in the NIR region.

    2. Multicolor Emission of Hybrid Block Copolymer–Quantum Dot Microspheres by Controlled Spatial Isolation of Quantum Dots (pages 2667–2672)

      Kang Hee Ku, Minsoo P. Kim, Kwanyeol Paek, Jae Man Shin, Sunhaeng Chung, Se Gyu Jang, Weon-Sik Chae, Gi-Ra Yi and Bumjoon J. Kim

      Article first published online: 7 FEB 2013 | DOI: 10.1002/smll.201202839

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      Multicolor emitting microspheres with three dimensionally controlled nanostructures are produced via a simple and efficient method. Location control and separation of the quantum dots (QDs) within the microspheres are achieved by a supramolecular assembly of block copolymer micelles to control the Förster resonance energy transfer efficiency between the different-colored QDs.

    3. A Near-Infrared Fluorescent Nanosensor (AuC@Urease) for the Selective Detection of Blood Urea (pages 2673–2677)

      Lakshmi V. Nair, Divya S. Philips, Ramapurath S. Jayasree and Ayyappanpillai Ajayaghosh

      Article first published online: 27 FEB 2013 | DOI: 10.1002/smll.201300213

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      The use of a nanosensor (AuC@Urease) based on an NIR-emitting gold cluster and urease enzyme selectively detects urea in whole blood. The detection is based on an enzyme-specific conversion of urea to ammonium ions which facilitates pH-induced aggregation of AuC, leading to fluorescence quenching. This method does not interfere with urease inactive analytes or the autofluorescence of blood as confirmed by comparable urea levels obtained by AuC@Urease and standard clinical methods within an error limit of ±3%.

    4. Transport Phenomena and Conduction Mechanism of Individual Cross-Junction SnO2 Nanobelts (pages 2678–2683)

      Zheng Guo, Xing Chen, Jin-Huai Liu and Xing-Jiu Huang

      Article first published online: 19 MAR 2013 | DOI: 10.1002/smll.201200672

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      Electrical characteristics of individual cross-junction nanodevices consisting of two SnO2 nanobelts are systematically investigated. The source–drain current along one nanobelt under constant source–drain voltage is not linearly varied with the ‘gate’ voltage applied on the terminal of the other one. The absolute increments for the source–drain and ‘gate’ current gradually increase as the gate voltage deviates from 0 V.

    5. Electrospun Silicon Nanoparticle/Porous Carbon Hybrid Nanofibers for Lithium-Ion Batteries (pages 2684–2688)

      Xiaosi Zhou, Li-Jun Wan and Yu-Guo Guo

      Article first published online: 6 MAR 2013 | DOI: 10.1002/smll.201202071

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      Si–C hybrid nanofibers with a core-shell structure of Si nanoparticles confined in porous carbon nanofibers are fabricated by a single-nozzle electrospinning technique. The as-obtained Si nanoparticles/porous carbon hybrid nanofibers exhibit excellent properties in terms of cycling performance and rate capabilities for application as anode materials for lithium-ion batteries.

    6. Facile Synthesis of Luminescent AgInS2–ZnS Solid Solution Nanorods (pages 2689–2695)

      Xuyong Yang, Yuxin Tang, Swee Tiam Tan, Michel Bosman, Zhili Dong, Kheng Swee Leck, Yun Ji, Hilmi Volkan Demir and Xiao Wei Sun

      Article first published online: 16 APR 2013 | DOI: 10.1002/smll.201202656

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      Highly luminescent semiconducting AgInS2–ZnS solid solution nanorods are successfully prepared by a facile one-pot solvothermal method. The resulting solid solution nanorods with length of 32 ± 5 nm are formed by fast growth of the AgInS2-rich solid solution head, followed by slow growth of the ZnS-rich solid solution tail. Photoluminescence studies on the solid solution nanorods reveal strong photoluminescence with peak emission wavelengths tunable from 650 to 700 nm.

    7. Two-Phase Synthesis of Small Thiolate-Protected Au15 and Au18 Nanoclusters (pages 2696–2701)

      Qiaofeng Yao, Yong Yu, Xun Yuan, Yue Yu, Jianping Xie and Jim Yang Lee

      Article first published online: 28 FEB 2013 | DOI: 10.1002/smll.201203112

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      A one-pot two-phase method for the direct synthesis of small Au (Au15 and Au18) nanoclusters (NCs) of high purity is developed. A mild reductant is combined with two equilibria (i.e., equilibrium partition and aggregation–dissociation equilibrium) to provide a constant reaction environment for the formation of monodisperse small Au NCs. The pH sensitivity of the aggregation–dissociation equilibrium is used to tailor the cluster size.

    8. Hierarchical Cu2S Microsponges Constructed from Nanosheets for Efficient Photocatalysis (pages 2702–2708)

      Yong Liu, Yonghui Deng, Zhenkun Sun, Jing Wei, Gengfeng Zheng, Abdullah M. Asiri, Sher Bahader Khan, Mohammed M. Rahman and Dongyuan Zhao

      Article first published online: 18 FEB 2013 | DOI: 10.1002/smll.201300197

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      3D porous hierarchical Cu2S microsponges (HCMs) constructed from 2D ultrathin active nanosheets (∼1.5 nm) with nearly 99% exposed (111) facets are fabricated by a simple hydrothermal route. The as-prepared HCMs possess an improved visible-light-harvesting ability, high surface area, low electron–hole recombination, and excellent photocatalytic activity for phenol degradation under visible light irradiation.

    9. Photoassisted Preparation of Cobalt Phosphate/Graphene Oxide Composites: A Novel Oxygen-Evolving Catalyst with High Efficiency (pages 2709–2714)

      Jingqi Tian, Haiyan Li, Abdullah M. Asiri, Abdulrahman O. Al-Youbi and Xuping Sun

      Article first published online: 18 FEB 2013 | DOI: 10.1002/smll.201203202

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      Cobalt phosphate (CoPi) nanoplates can be integrated with graphene oxide (GO) by photochemical deposition from an aqueous solution under visible-light illumination using GO as a photocatalyst. The use of the CoPi/GO composites as an oxygen-evolving catalyst with high efficiency is demonstrated. Integrating CoPi with GO leads to reduction of the overvoltage and enhancement of the photocurrent.

    10. Size-Controllable Synthesis and Functionalization of Ultrafine Polymeric Nanoparticles (pages 2715–2719)

      Mengjun Chen, Wantai Yang and Meizhen Yin

      Article first published online: 26 FEB 2013 | DOI: 10.1002/smll.201203130

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      A facile approach to ultrafine hydrophilic polymeric nanoparticles within 10 nm is developed by anhydrous or aqueous inverse microemulsion polymerization of N,N-dimethylacrylamide. Since auto- precipitation of products occurs without any demulsifiers, the recycling of surfactants is feasible. The auto-precipitation mechanism is proposed and discussed. Functionalization of the nanoparticles is achieved by employing them as nanoreactors to form hybrids with titanium tetraisopropoxide.

  7. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Communications
    8. Frontispiece
    9. Full Papers
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      Carbon Nanotubes: Biodegradation of Single-Walled Carbon Nanotubes by Eosinophil Peroxidase (Small 16/2013) (page 2720)

      Fernando T. Andón, Alexandr A. Kapralov, Naveena Yanamala, Weihong Feng, Arjang Baygan, Benedict J. Chambers, Kjell Hultenby, Fei Ye, Muhammet S. Toprak, Birgit D. Brandner, Andrea Fornara, Judith Klein-Seetharaman, Gregg P. Kotchey, Alexander Star, Anna A. Shvedova, Bengt Fadeel and Valerian E. Kagan

      Article first published online: 16 AUG 2013 | DOI: 10.1002/smll.201370096

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      B. Fadeel, V. E. Kagan, and co-workers report on page 2721 the interaction of one oxidized single-walled carbon nanotube (SWCNT) with two molecules of eosinophil peroxidase (EPO), one of the major human oxidant generating enzymes. Their study demonstrates that human EPO (in vitro) and murine EPO of ex vivo activated eosinophils catalyses the oxidative biodegradation of SWCNTs. Molecular modeling studies reveal two binding sites for SWCNTs on EPO, one located at the same side as the catalytic site and the other on the distal side of EPO. Eosinophils are key players of the innate immune system and these results are relevant to potential respiratory exposures to carbon nanotubes. Image courtesy of Dr. L. Szekely, Karolinska Institute, Stockholm.

  8. Full Papers

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    2. Cover Picture
    3. Inside Front Cover
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    5. Masthead
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    7. Communications
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    9. Full Papers
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    11. Full Papers
    1. Biodegradation of Single-Walled Carbon Nanotubes by Eosinophil Peroxidase (pages 2721–2729)

      Fernando T. Andón, Alexandr A. Kapralov, Naveena Yanamala, Weihong Feng, Arjang Baygan, Benedict J. Chambers, Kjell Hultenby, Fei Ye, Muhammet S. Toprak, Birgit D. Brandner, Andrea Fornara, Judith Klein-Seetharaman, Gregg P. Kotchey, Alexander Star, Anna A. Shvedova, Bengt Fadeel and Valerian E. Kagan

      Article first published online: 27 FEB 2013 | DOI: 10.1002/smll.201202508

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      Human eosinophil peroxidase (EPO) is able to degrade SWCNTs in vitro in the presence of H2O2. EPO is one of the major oxidant-generating enzymes present in human lungs during inflammatory states. The biodegradation of SWCNTs is evidenced also in an ex vivo culture system using primary murine eosinophils stimulated to undergo degranulation. These results are relevant to potential respiratory exposure to carbon nanotubes.

    2. Enhanced Field-Emission Behavior of Layered MoS2 Sheets (pages 2730–2734)

      Ranjit V. Kashid, Dattatray J. Late, Stanley S. Chou, Yi-Kai Huang, Mrinmoy De, Dilip S. Joag, Mahendra A. More and Vinayak P. Dravid

      Article first published online: 21 FEB 2013 | DOI: 10.1002/smll.201300002

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      Field emission studies of few-layer MoS2 sheets show that the turn-on field required to draw a current density of 10 μA/cm2 is 3.5 V/μm. The turn-on value is comparable with MoS2 nanoflower-, graphene-, and carbon nanotube-based field emitters. The low turn-on field value is due to the high field-enhancement factor (∼1138) associated with the nanometric sharp edges of the MoS2 sheets. It is possible to orient the layered MoS2 sheets for achieving a higher field enhancement factor, resulting in a high current density obtainable at the lower field.

    3. Broad-Spectrum Antibacterial Activity of Carbon Nanotubes to Human Gut Bacteria (pages 2735–2746)

      Hanqing Chen, Bing Wang, Di Gao, Ming Guan, Lingna Zheng, Hong Ouyang, Zhifang Chai, Yuliang Zhao and Weiyue Feng

      Article first published online: 6 MAR 2013 | DOI: 10.1002/smll.201202792

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      Carbon nanotubes (CNT)s can selectively lyse the walls and membranes of human gut bacteria, depending on not only the length and surface functional groups of CNTs, but also the shapes of bacteria. The mechanism of antibacterial activity is associated with their diameter-dependent piercing and length-dependent wrapping. CNTs have potential as effective, selective, and broad-spectrum antibacterial agents, especially against drug-resistant bacteria.

    4. Synergetic Material and Structure Optimization Yields Robust Spider Web Anchorages (pages 2747–2756)

      Nicola M. Pugno, Steven W. Cranford and Markus J. Buehler

      Article first published online: 15 APR 2013 | DOI: 10.1002/smll.201201343

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      How does a spider attach a web to the environment, in spite of unknown conditions? The answer is the unique attachment disc, a clustered network of piriform silk fibers that mechanically anchors a web. Through integrated theoretical, computational, and experimental analysis, the clever mechanism by which this structure provides a self-optimizing strong and robust attachment is elucidated.

    5. Biodegradable Nanocapsules as siRNA Carriers for Mutant K-Ras Gene Silencing of Human Pancreatic Carcinoma Cells (pages 2757–2763)

      Guimiao Lin, Rui Hu, Wing-Cheung Law, Chih-Kuang Chen, Yucheng Wang, Hui Li Chin, Quoc Toan Nguyen, Cheng Kee Lai, Ho Sup Yoon, Xiaomei Wang, Gaixia Xu, Ling Ye, Chong Cheng and Ken-Tye Yong

      Article first published online: 20 FEB 2013 | DOI: 10.1002/smll.201201716

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      Cationic poly(lactic acid) (CPLA)-based degradable nanocapsules (NCs) are utilized as novel carriers of siRNA for effective gene silencing of pancreatic cancer cells. These CPLA-NCs can readily form nanoplexes with K-Ras siRNA and over 90% transfection efficiency is achieved using the nanoplexes.

    6. High Throughput-Per-Footprint Inertial Focusing (pages 2764–2773)

      Ata Tuna Ciftlik, Maxime Ettori and Martin A. M. Gijs

      Article first published online: 18 FEB 2013 | DOI: 10.1002/smll.201201770

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      Integration of microfluidic structures and microelectronic chips is appealing only if the required downscaling for microfluidics does not compromise the fluidic throughput. Here, such integration of microfluidic inertial focusing is feasible by exploring the scaling laws of throughput-per-footprint (TPFP). This study reveals the interplay between theory, the effect of Reynolds numbers between 75 and 1500 on focusing, the entry length for the laminar flow to develop, and pressure resistance of the microchannels, in maximizing TPFP.

    7. Systematic Engineering of Uniform, Highly Efficient, Targeted and Shielded Viral-Mimetic Nanoparticles (pages 2774–2783)

      Zahra Karjoo, Helen O. McCarthy, Parin Patel, Faranak Salman Nouri and Arash Hatefi

      Article first published online: 7 MAR 2013 | DOI: 10.1002/smll.201300077

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      Design parameters are described for the reproducible production of targeted and shielded nanoparticles that are highly efficient, safe, customizable and uniform, and meet the criteria for reproducibility. Therefore, they exhibit all the major necessary characteristics for in vivo translation.

  9. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
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    5. Masthead
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      Liquid Crystals: Colloid-in-Liquid Crystal Gels that Respond to Biomolecular Interactions (Small 16/2013) (page 2784)

      Ankit Agarwal, Sumyra Sidiq, Shilpa Setia, Emre Bukusoglu, Juan J. de Pablo, Santanu Kumar Pal and Nicholas L. Abbott

      Article first published online: 16 AUG 2013 | DOI: 10.1002/smll.201370097

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      The response of a thin film of a gel comprised of liquid crystal (LC) and colloids that is immersed in water is reported on page 2785 by S. K. Pal, N. L. Abbott, and co-workers. The time-lapse polarized light micrographs are shown in the image in a clockwise direction.

  10. Full Papers

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    1. Colloid-in-Liquid Crystal Gels that Respond to Biomolecular Interactions (pages 2785–2792)

      Ankit Agarwal, Sumyra Sidiq, Shilpa Setia, Emre Bukusoglu, Juan J. de Pablo, Santanu Kumar Pal and Nicholas L. Abbott

      Article first published online: 2 APR 2013 | DOI: 10.1002/smll.201202869

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      Formation of colloid-in-liquid crystal gels that are stable upon exposure to aqueous solutions of amphiphiles is reported. The gels can be driven through ordering transitions via interfacial interactions of synthetic and biological adsorbates. The gels also respond optically to enzymatic processes at their interfaces.

    2. Photosensitizer-Incorporated Quadruplex DNA-Gated Nanovechicles for Light-Triggered, Targeted Dual Drug Delivery to Cancer Cells (pages 2793–2800)

      Cuie Chen, Li Zhou, Jie Geng, Jinsong Ren and Xiaogang Qu

      Article first published online: 23 JAN 2013 | DOI: 10.1002/smll.201201916

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      A novel light-operated vehicle for targeted intracellular drug delivery is constructed using photosensitizer-incorporated G-quadruplex DNA-capped mesoporous silica nanoparticles. Upon light irradiation, the photosensitizer generates ROS, causing the DNA capping to be cleaved and allowing cargo to be released. Importantly, this platform makes it possible to develop a drug-carrier system for the synergistic combination of chemotherapy and PDT for cancer treatment with spatial/temporal control.

    3. Hierarchically Nanoperforated Graphene as a High Performance Electrode Material for Ultracapacitors (pages 2801–2809)

      Dattakumar Mhamane, Anil Suryawanshi, Sreekuttan M. Unni, Chandrashekhar Rode, Sreekumar Kurungot and Satishchandra Ogale

      Article first published online: 18 APR 2013 | DOI: 10.1002/smll.201202670

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      A high specific capacitance (Cs) value is obtained for a symmetric ultracapacitor (UC) cell in 1 M H2SO4 electrolyte by using hierarchically nanoperforated graphene nanosheets (HPGN) as an electrode material. Nanoperforations are introduced in graphene by simple stirring in silica nanoparticle dispersion followed by HF treatment. The HPGN is shown to deliver a remarkably high energy density (68.43 Wh kg−1) as compared to earlier reports for graphene-based materials.

    4. Graphene-Bonded and -Encapsulated Si Nanoparticles for Lithium Ion Battery Anodes (pages 2810–2816)

      Yang Wen, Yujie Zhu, Alex Langrock, Ayyakkannu Manivannan, Sheryl H. Ehrman and Chunsheng Wang

      Article first published online: 26 FEB 2013 | DOI: 10.1002/smll.201202512

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      A unique graphene-bonded and -encapsulated Si nanocomposite synthesized using a one-step aerosol technique exhibits a remarkable cycling stability as anode in a Li ion battery, revealing a promising technology for Si anode development.

    5. Wafer-Scale Patterning of Reduced Graphene Oxide Electrodes by Transfer-and-Reverse Stamping for High Performance OFETs (pages 2817–2825)

      Joong Suk Lee, Nam Hee Kim, Moon Sung Kang, Hojeong Yu, Dong Ryoul Lee, Joon Hak Oh, Suk Tai Chang and Jeong Ho Cho

      Article first published online: 16 APR 2013 | DOI: 10.1002/smll.201300538

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      Reproducible and effective wafer-scale patterning of reduced graphene oxide (rGO) electrodes by transfer-and-reverse stamping method is reported. The highly defined rGO micropatterns with various shapes are readily formed on rigid or flexible hydrophobized substrates and serve as the electrodes for high-performance n- and p-type OFETs and complementary inverters.

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