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Cover image for Vol. 10 Issue 3

February 12, 2014

Volume 10, Issue 3

Pages 417–616

  1. Cover Picture

    1. Top of page
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    3. Inside Front Cover
    4. Masthead
    5. Contents
    6. Reviews
    7. Frontispiece
    8. Communications
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    10. Full Papers
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      Cancer Therapy: Development of Novel Tumor-Targeted Theranostic Nanoparticles Activated by Membrane-Type Matrix Metalloproteinases for Combined Cancer Magnetic Resonance Imaging and Therapy (Small 3/2014) (page 417)

      Celina Ansari, Grigory A. Tikhomirov, Su Hyun Hong, Robert A. Falconer, Paul M. Loadman, Jason H. Gill, Rosalinda Castaneda, Florette K. Hazard, Ling Tong, Olga D. Lenkov, Dean W. Felsher, Jianghong Rao and Heike E. Daldrup-Link

      Article first published online: 4 FEB 2014 | DOI: 10.1002/smll.201470016

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      Cancer cells overexpress matrix-type metalloproteinases (MMPs, shown as pacmen). MMPs cleave the peptide linker connecting anticancer prodrug to the dextran coated magnetic nanoparticle. After the cleavage, the drug becomes toxic (active drug shown in purple). As J. Rao, H. E. Daldrup-Link, and co-workers describe on page 566, this tumor specific drug release reduces the side-effects of cancer therapy. The magnetic core of the nanoparticles allows for MRI monitoring of their distribution in the body.

  2. Inside Front Cover

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Masthead
    5. Contents
    6. Reviews
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
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      Self-Assembly: Sacrificial-Post Templating Method for Block Copolymer Self-Assembly (Small 3/2014) (page 418)

      Amir Tavakkoli K. G., Samuel M. Nicaise, Adam F. Hannon, Kevin W. Gotrik, Alfredo Alexander-Katz, Caroline A. Ross and Karl K. Berggren

      Article first published online: 4 FEB 2014 | DOI: 10.1002/smll.201470017

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      Block copolymer (BCP) thin films self-assemble to form nanoscale patterns, as K. K. Berggren and co-workers report on page 493. On a smooth substrate, the polystyrene-block-poly(dimethylsiloxane) copolymer forms randomly oriented inplane cylinders with a 35-nm period (images on the left). A set of sacrifical nanoposts made of poly(methyl methacrylate) directed the self-assembly to form (center top to bottom): square arrays of spheres or holes, and square and hexagonal meshes with bimodal hole-size distributions. The posts and the polystyrene are removed by etching and the final pattern consists of oxidized poly(dimethylsiloxane)

  3. Masthead

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    3. Inside Front Cover
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      Masthead: (Small 3/2014)

      Article first published online: 4 FEB 2014 | DOI: 10.1002/smll.201470021

  4. Contents

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Masthead
    5. Contents
    6. Reviews
    7. Frontispiece
    8. Communications
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    10. Full Papers
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      Contents: (Small 3/2014) (pages 419–425)

      Article first published online: 4 FEB 2014 | DOI: 10.1002/smll.201470018

  5. Reviews

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    4. Masthead
    5. Contents
    6. Reviews
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    8. Communications
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    10. Full Papers
    1. Nanoprobes Visualizing Gliomas by Crossing the Blood Brain Tumor Barrier (pages 426–440)

      Xihui Gao and Cong Li

      Article first published online: 17 SEP 2013 | DOI: 10.1002/smll.201301673

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      The difficulty to precisely delineate the irregular margins of malignant gliomas leads to their incomplete resection and disproportionately high recurrence and mortality. Nanoprobes show promise in visualizing gliomas with up-regulated sensitivity, targeting specificity and intracerebral delivery efficiency. This Review addresses recent developments in the field of nanoprobes to define gliomas by crossing the blood brain tumor barrier.

  6. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Masthead
    5. Contents
    6. Reviews
    7. Frontispiece
    8. Communications
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    10. Full Papers
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      Polymersomes: Third-Party ATP Sensing in Polymersomes: A Label-Free Assay of Enzyme Reactions in Vesicular Compartments (Small 3/2014) (page 441)

      Umit Hakan Yildiz, Hans-Peter M. De Hoog, Zhikang Fu, Nikodem Tomczak, Atul N. Parikh, Madhavan Nallani and Bo Liedberg

      Article first published online: 4 FEB 2014 | DOI: 10.1002/smll.201470019

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      Polymersomes are encapsulated with a fluorescent reporter and a non-labeled enzyme for sensing of adenosine triphosphate (ATP). As B. Liedberg and co-workers report on page 442, passive diffusion of exogenously added ATP through the membrane is sensed by monitoring the ATPinduced fluorescence quenching of the reporter polymer followed by partial recovery of its emission due to hydrolysis of reporter-bound ATP by alkaline phosphatase.

  7. Communications

    1. Top of page
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    3. Inside Front Cover
    4. Masthead
    5. Contents
    6. Reviews
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    8. Communications
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    10. Full Papers
    1. Third-Party ATP Sensing in Polymersomes: A Label-Free Assay of Enzyme Reactions in Vesicular Compartments (pages 442–447)

      Umit Hakan Yildiz, Hans-Peter M. De Hoog, Zhikang Fu, Nikodem Tomczak, Atul N. Parikh, Madhavan Nallani and Bo Liedberg

      Article first published online: 21 AUG 2013 | DOI: 10.1002/smll.201300060

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      Submicrometer, porous polymeric vesicles, composed of an amphiphilic di-block copolymer, polystyrene-b-polyisocyanoalanine (2-thiophene-3-yl-ethyl) amide, are used to encapsulate an enzyme, alkaline phosphatase, and a fluorescent reporter polymer poly 1(3((4methylthiophen-3-yl)oxy) propyl) quinuclidin-1-ium. Passive diffusion of exogenously added adenosine triphosphate (ATP) through the membrane was sensed by monitoring the ATP-induced fluorescence quenching of the reporter polymer followed by partial recovery of its emission due to hydrolysis of reporter-bound ATP by alkaline phosphatase.

    2. Highly Elastic and Superstretchable Graphene Oxide/Polyacrylamide Hydrogels (pages 448–453)

      Huai-Ping Cong, Ping Wang and Shu-Hong Yu

      Article first published online: 9 SEP 2013 | DOI: 10.1002/smll.201301591

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      Graphene oxide (GO)/polyacrylamide (PAM) hydrogels with highly elastic and superstretchable mechanical behavior is fabricated by the synergistic effects of a Ca2+-induced GO crosslinking network, chemically crosslinked PAM network, and entanglements between these networks via hydrogen-bonding interactions. This new nanocomposite material may broaden the applications of hydrogels in the biomedical field and take us closer to artificial biotissues.

    3. Probing Lateral Charge Transport in Single Molecule Layers: How Charge is Transported Over Long Distances in Fullerene Self-Assembled Monolayers (pages 454–461)

      Galina V. Dubacheva, Mélanie Devynck, Guillaume Raffy, Lionel Hirsch, André Del Guerzo and Dario M. Bassani*

      Article first published online: 9 SEP 2013 | DOI: 10.1002/smll.201300502

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      The lateral conductance of a single monolayer of fullerene on an insulating substrate is investigated using conduction atomic force microscopy. The quadratic dependence of the of I(V) observed contrasts the exponential fall-off of the current as a function of distance. A similar behavior is observed for an anthracene monolayer, which is found to be ca. 104 times less conducting than the fullerene monolayer under similar conditions.

    4. Sub-Diffraction Limit Imaging of Inorganic Nanowire Networks Interfacing Cells (pages 462–468)

      Juhun Park, Jinwoo Lee, Seon Namgung, Kwang Heo, Hyungwoo Lee, Sungchul Hohng and Seunghun Hong

      Article first published online: 3 SEP 2013 | DOI: 10.1002/smll.201301214

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      Sub-diffraction limit imaging of SnO2 nanowires (NWs) interfacing cells is studied using stochastic optical reconstruction microscopy. This method allows the estimation of the dimension of the NWs with a rather high resolution compared with previous imaging methods. In addition, since this strategy is compatible with biological environments, the NWs can be imaged with cell membrane proteins simultaneously and the effect of the NWs on the cell adhesion efficiency can be analyzed.

    5. Nano-Structured Polymer-Silica Composite Derived from a Marine Diatom via Deactivation Enhanced Atom Transfer Radical Polymerization Grafting (pages 469–473)

      Jacqueline O'Connor, Yvonne Lang, Joshua Chao, Hongliang Cao, Liam Collins, Brian J. Rodriguez, Peter Dockery, David P. Finn, Wenxin Wang and Abhay Pandit

      Article first published online: 19 AUG 2013 | DOI: 10.1002/smll.201301146

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      A diatom frustule is functionalized with an alkyl halide to allow the growth of a polymer from its surface via deactivation enhanced atom transfer radical polymerization. The diatom core is partially dissolved to form a more translational platform. This method can be used to create an array of nano-structured composites derived from the species-specific diatom architecture.

    6. Synthesis for Yolk-shell-structured Metal Sulfide Powders with Excellent Electrochemical Performances for Lithium-ion Batteries (pages 474–478)

      Seung Ho Choi and Yun Chan Kang

      Article first published online: 1 SEP 2013 | DOI: 10.1002/smll.201301483

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      Yolk-shell-structured metal sulfide powders are developed for the first time. The yolk-shell SnS powders with a distinctive SnS@void@SnS configuration exhibit superior electrochemical properties for lithium-ion batteries even at high current densities due to their unique structure. The simple two-step process introduced in this manuscript can be applied to the preparation of various types of yolk-shell-structured metal sulfide powders.

    7. Periodic AuAg-Ag2S Heterostructured Nanowires (pages 479–482)

      Xun Hong, Zongyou Yin, Zhanxi Fan, Yee-Yan Tay, Junze Chen, Yaping Du, Can Xue, Hongyu Chen and Hua Zhang

      Article first published online: 16 SEP 2013 | DOI: 10.1002/smll.201302304

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      AuAg-Ag2S heterostructured nanowires consisting of periodic AuAg alloy and Ag2S nanocrytals are synthesized in a simple, one-pot reaction. After the AuAg alloy nanowire with a diameter of 2–3 nm is synthesized, it is converted to AuAg-Ag2S heterostructured nanowire by addition of sulfur. The diffusion of Au and Ag in the Ag2S nanocrystals and the subsequent Ostwald ripening process are the key reasons for the formation of heterostructured nanowires. This new type of hybrid nanostructure undergoes photoinduced charge separation and may have photocatalytic applications.

  8. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Masthead
    5. Contents
    6. Reviews
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. You have free access to this content
      Solar Cells: Highly Electrocatalytic Activity of RuO2 Nanocrystals for Triiodide Reduction in Dye-Sensitized Solar Cells (Small 3/2014) (page 483)

      Yu Hou, Zu Peng Chen, Dong Wang, Bo Zhang, Shuang Yang, Hai Feng Wang, P. Hu, Hui Jun Zhao and Hua Gui Yang

      Article first published online: 4 FEB 2014 | DOI: 10.1002/smll.201470020

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      Using a new two-step strategy, ruthenium dioxide (RuO2) nanocrystals are successfully synthesized and exploited as counter electrode catalysts, which exhibit promising electrocatalytic activity towards triiodide reduction. By virtue of firstprinciple calculations, the catalytic mechanism of electrocatalysis for triiodide reduction is systematically investigated by H. F. Wang, H. G. Yang, and co-workers on page 484. It is found that the electrochemical triiodide reduction reaction on RuO2 catalyst surfaces can be significantly enhanced, owing to the ideal combination of good electrocatalytic activity and high electrical conductivity.

  9. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Masthead
    5. Contents
    6. Reviews
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. Highly Electrocatalytic Activity of RuO2 Nanocrystals for Triiodide Reduction in Dye-Sensitized Solar Cells (pages 484–492)

      Yu Hou, Zu Peng Chen, Dong Wang, Bo Zhang, Shuang Yang, Hai Feng Wang, P. Hu, Hui Jun Zhao and Hua Gui Yang

      Article first published online: 19 JUN 2013 | DOI: 10.1002/smll.201300653

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      In a new two-step strategy, ruthenium dioxide (RuO2) nanocrystals are synthesized and exploited as counter-electrode catalysts. The mechanism of electrocatalysis for triiodide reduction is investigated systematically by first-principles calculations. The electrochemical triiodide reduction reaction on RuO2 catalyst surfaces can be enhanced significantly, owing to the ideal combination of good electrocatalytic activity and high electrical conductivity.

    2. Sacrificial-Post Templating Method for Block Copolymer Self-Assembly (pages 493–499)

      Amir Tavakkoli K. G., Samuel M. Nicaise, Adam F. Hannon, Kevin W. Gotrik, Alfredo Alexander-Katz, Caroline A. Ross and Karl K. Berggren

      Article first published online: 10 JUL 2013 | DOI: 10.1002/smll.201301066

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      The sacrificial post-templating method in block copolymer self-assembly, with the help of majority-block-functionalized posts, achieves several morphologies and structures on a single substrate without template incorporation. This method is applied to direct the assembly of a monolayer and bilayer of block copolymer microdomains. Arrays of different templates produce square and hexagonal lattices of spheres and perforated lamellae. Furthermore, bimodal hole sizes and density multiplication are achieved.

    3. Electrostatic Control of Structure in Self-Assembled Membranes (pages 500–505)

      Ronit Bitton, Lesley W. Chow, R. Helen Zha, Yuri S. Velichko, E. Thomas Pashuck and Samuel I. Stupp

      Article first published online: 11 SEP 2013 | DOI: 10.1002/smll.201300254

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      Hierarchical self-assembly of heparin-binding peptide amphiphiles with oppositely charged, high molecular weight polyelectrolytes at the solution interface depends strongly on aggregation strength. Strong aggregation of peptide amphiphiles with polyelectrolytes leads to micron-thick membranes with aligned nanofibers (right), while weak aggregation leads to non-fibrous membranes containing cubic symmetry and nanoscale periodicities (left).

    4. Size-Controlled Soft-Template Synthesis of Carbon Nanodots toward Versatile Photoactive Materials (pages 506–513)

      Woosung Kwon, Gyeongjin Lee, Sungan Do, Taiha Joo and Shi-Woo Rhee

      Article first published online: 9 SEP 2013 | DOI: 10.1002/smll.201301770

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      Size-controlled soft-template synthesis of carbon nanodots (CNDs) as novel photoactive materials is reported. The size dependence of the optical properties is revealed. To explore the potential of the CNDs as photoactive materials, CND-based optoelectronic devices including multicolored light-emitting diodes and air-stable organic solar cells are successfully demonstrated.

    5. Controlling Mechanical Properties of Cell-Laden Hydrogels by Covalent Incorporation of Graphene Oxide (pages 514–523)

      Chaenyung Cha, Su Ryon Shin, Xiguang Gao, Nasim Annabi, Mehmet R. Dokmeci, Xiaowu (Shirley) Tang and Ali Khademhosseini

      Article first published online: 11 OCT 2013 | DOI: 10.1002/smll.201302182

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      Methacrylate is chemically grafted on the graphene oxide (GO) surface. Higher concentrations of the resulting methacrylated graphene oxide (MeGO) can be stably dispersed and conjugated within the hydrogels which improved fracture strength as compared with GO. In addition, cells maintain high viability within MeGO-linked hydrogels. Therefore, covalent incorporation of GO induces proper interfacial bonding between GO and the polymeric network, and ultimately improves the quality of cell-laden hydrogels.

    6. Cationic Bovine Serum Albumin Based Self-Assembled Nanoparticles as siRNA Delivery Vector for Treating Lung Metastatic Cancer (pages 524–535)

      Jianfeng Han, Qin Wang, Zhirong Zhang, Tao Gong and Xun Sun

      Article first published online: 19 SEP 2013 | DOI: 10.1002/smll.201301992

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      Cationic bovine serum albumin based self-assembled nanoparticles are developed to deliver therapeutic siRNA to treat lung metastatic cancer. Interaction between the vehicles and the negatively charged blood components mediates an immediate aggregate formation. This aggregation leads to a primary lung accumulation via the filter effect of capillary beds and the simultaneous dissolution of the aggregates facilitates efficient intracellular siRNA delivery within the lung.

    7. Insights into Stabilization of a Viral Protein Cage in Templating Complex Nanoarchitectures: Roles of Disulfide Bonds (pages 536–543)

      Feng Li, Huiling Chen, Lingzhi Ma, Kun Zhou, Zhi-Ping Zhang, Chun Meng, Xian-En Zhang and Qiangbin Wang

      Article first published online: 9 SEP 2013 | DOI: 10.1002/smll.201300860

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      The origin of robustness: Cysteines at position 9 (C9) and C104 of the major capsid protein (VP1) of simian virus 40 are found to play essential roles in stablizing the viral protein cage as scaffold for assembly of inorganic nanoparticles. The presence of an inorganic core also helps the assembly and stabilization of the protein cage.

    8. Active Targeting Using HER-2-Affibody-Conjugated Nanoparticles Enabled Sensitive and Specific Imaging of Orthotopic HER-2 Positive Ovarian Tumors (pages 544–555)

      Minati Satpathy, Liya Wang, Rafal Zielinski, Weiping Qian, Malgorzata Lipowska, Jacek Capala, Gee Young Lee, Hong Xu, Y. Andrew Wang, Hui Mao and Lily Yang

      Article first published online: 27 AUG 2013 | DOI: 10.1002/smll.201301593

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      HER-2 targeted dual optical and magnetic resonance (MR) imaging nanoparticles are developed by conjugating a near infrared dye (NIR-830) labeled HER-2 affibody to magnetic iron oxide nanoparticles. Target specificity of the nanoparticles and sensitivity of optical and MR imaging of ovarian tumors as small as 1 mm in diameter have been demonstrated in an orthotopic human ovarian cancer xenograft model.

    9. Gadolinium-Conjugated Gold Nanoshells for Multimodal Diagnostic Imaging and Photothermal Cancer Therapy (pages 556–565)

      Andrew J. Coughlin, Jeyarama S. Ananta, Nanfu Deng, Irina V. Larina, Paolo Decuzzi and Jennifer L. West

      Article first published online: 23 SEP 2013 | DOI: 10.1002/smll.201302217

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      When conjugated to gadolinium, near-infrared resonant gold-silica nanoshells can be employed for image-guided photothermal ablation of cancer. These particle conjugates demonstrate positive contrast across length scales with a variety of imaging modes, including magnetic resonance, X-ray, optical coherence tomography, reflectance confocal microscopy, and two-photon luminescence.

    10. Development of Novel Tumor-Targeted Theranostic Nanoparticles Activated by Membrane-Type Matrix Metalloproteinases for Combined Cancer Magnetic Resonance Imaging and Therapy (pages 566–575)

      Celina Ansari, Grigory A. Tikhomirov, Su Hyun Hong, Robert A. Falconer, Paul M. Loadman, Jason H. Gill, Rosalinda Castaneda, Florette K. Hazard, Ling Tong, Olga D. Lenkov, Dean W. Felsher, Jianghong Rao and Heike E. Daldrup-Link

      Article first published online: 27 AUG 2013 | DOI: 10.1002/smll.201301456

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      The design and characterization of novel multifunctional “theranostic” nanoparticles (TNPs) is described for enzyme-specific drug activation at tumor sites and simultaneous in vivo magnetic resonance imaging (MRI) of drug delivery. TNPs consist of iron oxide core for MR imaging, MMP-14 cleavable peptide linker for specific activation in tumors, and a prodrug that is non-toxic unless activated.

    11. Beyond the Hybridization Effects in Plasmonic Nanoclusters: Diffraction-Induced Enhanced Absorption and Scattering (pages 576–583)

      Mohsen Rahmani, Andrey E. Miroshnichenko, Dang Yuan Lei, Boris Luk'yanchuk, Michael I. Tribelsky, Arseniy I. Kuznetsov, Yuri S. Kivshar, Yan Francescato, Vincenzo Giannini, Minghui Hong and Stefan A. Maier

      Article first published online: 3 SEP 2013 | DOI: 10.1002/smll.201301419

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      Young's interference among plasmonic structures comes into being when two or three nanoparticles with separation on the order of the wavelength are illuminated simultaneously by a plane wave. It leads to the redistribution of the Poynting vectors field and the formation of near-field subwavelength optical vortices. The phenomenon provides a new physical mechanism for the enhancement of absorption and scattering of light by nano-objects.

    12. Size Controlled Synthesis of Silicon Nanocrystals Using Cationic Surfactant Templates (pages 584–590)

      Keith Linehan and Hugh Doyle

      Article first published online: 11 SEP 2013 | DOI: 10.1002/smll.201301189

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      Highly monodisperse Si nanocrystals (2–6 nm) are synthesized by solution-phase reduction of SiCl4 within inverse micelles. Alkyl-terminated nanocrystals with mean diameters from 2 to 6 nm are produced by varying the cationic surfactants used, confirmed by TEM and FTIR. Si nanocrystals exhibit strong blue emission, with a highest quantum yield of 12% for the smallest NCs.

    13. A Dual-Responsive Mesoporous Silica Nanoparticle for Tumor-Triggered Targeting Drug Delivery (pages 591–598)

      Dong Xiao, Hui-Zhen Jia, Jing Zhang, Chen-Wei Liu, Ren-Xi Zhuo and Xian-Zheng Zhang

      Article first published online: 17 SEP 2013 | DOI: 10.1002/smll.201301926

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      A novel pH- and redox- dual-responsive mesoporous silica nanoparticle is demonstrated for tumor-triggered targeting drug delivery in tumor cells. Upon the acidic condition, the targeting property is switched on for enhanced tumor cell internalization. Once entering tumor cell, the loaded drug can be released quickly due to the removal of peptide capping. This intelligent tumor-triggered targeting mesoporous silica nanoparticle (TTTMSN) will find great potential for cancer treatment.

    14. Theranostic GO-Based Nanohybrid for Tumor Induced Imaging and Potential Combinational Tumor Therapy (pages 599–608)

      Si-Yong Qin, Jun Feng, Lei Rong, Hui-Zhen Jia, Si Chen, Xiang-Ji Liu, Guo-Feng Luo, Ren-Xi Zhuo and Xian-Zheng Zhang

      Article first published online: 3 SEP 2013 | DOI: 10.1002/smll.201301613

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      A novel theranostic system based on a GO-PEI(Peptide-DOX)-PEG nanohybrid is designed to achieve fluorescent imaging and targeted combinational therapy of tumor cells. Once triggered by the MMP2 enzyme over-expressed in tumor cells, the peptide cleavage permits the liberation of initially locked DOX for targeted chemotherapy and concurrent DOX fluorescence recovery for in situ tumor cell imaging, while co-delivered genes further promote therapeutic efficacy.

    15. Synergistic Modulation of Surface Interaction to Assemble Metal Nanoparticles into Two-Dimensional Arrays with Tunable Plasmonic Properties (pages 609–616)

      Lin Jiang, Changji Zou, Zhonghan Zhang, Yinghui Sun, Yueyue Jiang, Wanru Leow, Bo Liedberg, Shuzhou Li and Xiaodong Chen

      Article first published online: 6 SEP 2013 | DOI: 10.1002/smll.201302126

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      Synergistic modulation of nanoparticles assembly: The inter-particle and substrate-particle interaction provides synergistic modulation of 2D uniform arrays of Au nanoparticles on a substrate, which results in a wide range of inter-particle distances between the nanoparticles on the substrate.

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