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Cover image for Vol. 10 Issue 8

April 24, 2014

Volume 10, Issue 8

Pages 1441–1651

  1. Cover Picture

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    4. Back Cover
    5. Masthead
    6. Contents
    7. Highlights
    8. Reviews
    9. Communications
    10. Frontispiece
    11. Full Papers
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      Plasmonic Nanostars: In Vivo Volumetric Photoacoustic Molecular Angiography and Therapeutic Monitoring with Targeted Plasmonic Nanostars (Small 8/2014) (page 1441)

      Liming Nie, Shouju Wang, Xiaoyong Wang, Pengfei Rong, Ying Ma, Gang Liu, Peng Huang, Guangming Lu and Xiaoyuan Chen

      Version of Record online: 14 APR 2014 | DOI: 10.1002/smll.201470044

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      Induced angiogenesis is a major hallmark of malignant tumor. As reported on page 1585, G. Lu, X. Chen, and co-workers design cyclic Arg-Gly-Asp (RGD) peptide conjugated plasmonic gold nanostars (RGD-GNS) to specifically target integrin avß3 overxpressed on tumor neovasculature. Quantitative volumetric angiography of tumors can be achieved with high resolution and deep penetration by a hemispherical photoacoustic imaging system. It also permits photothermal therapy and sequential therapeutic monitoring.

  2. Inside Front Cover

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    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
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    7. Highlights
    8. Reviews
    9. Communications
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      Thin Films: An All Low-Temperature Fabrication of Macroporous, Electrochemically Addressable Anatase Thin Films (Small 8/2014) (page 1442)

      Michael Schröder, Sébastien Sallard, Matthias Böhm, Marcus Einert, Christian Suchomski, Bernd M. Smarsly, Stephen Mutisya and Massimo F. Bertino

      Version of Record online: 14 APR 2014 | DOI: 10.1002/smll.201470045

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      On page 1566, B. M. Smarsly, M. F. Bertino, and co-workers report a simple lowtemperature approach that allows for the generation of macroporous films of crystalline metal oxides, as exemplified for TiO2 and antimony tin oxide (ATO). The method starts from dispersions containing crystalline metal oxide nanoparticles and polymer beads, the latter acting as porogen. After dip-coating, porous films with ellipsoidal pores with diameters of approx. 50–80 nm can be obtained by subsequent UV treatment, even on flexible substrates.

  3. Back Cover

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    4. Back Cover
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      Self-Assembled Monolayers: Bioinspired Catechol-Terminated Self-Assembled Monolayers with Enhanced Adhesion Properties (Small 8/2014) (page 1656)

      Mireia Guardingo, Elena Bellido, Rosa Miralles-Llumà, Jordi Faraudo, Josep Sedó, Sergio Tatay, Albert Verdaguer, Felix Busqué and Daniel Ruiz-Molina

      Version of Record online: 14 APR 2014 | DOI: 10.1002/smll.201470049

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      The remarkable adhesion to substrates shown by mussel byssus proteins has been mainly attributed to the presence of significant amounts of catechol-like tyrosine in their sequences. As reported on page 1594, D. Ruiz-Molina and co-workers measure the retraction force of an AFM tip in contact with the upward-facing catechol rings of a model compound, self-assembled in monolayers and bound to epitaxial gold surfaces via a thiol group. The results show the importance of spatial and chemical order in catecholic layers with regard to enhanced adhesion.

  4. Masthead

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      Masthead: (Small 8/2014)

      Version of Record online: 14 APR 2014 | DOI: 10.1002/smll.201470048

  5. Contents

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    5. Masthead
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      Contents: (Small 8/2014) (pages 1443–1450)

      Version of Record online: 14 APR 2014 | DOI: 10.1002/smll.201470046

  6. Highlights

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    1. The First Magnetic-Nanoparticle-Free Carbon-Based Contrast Agent of Magnetic-Resonance Imaging-Fluorinated Graphene Oxide (pages 1451–1452)

      Yun Hang Hu

      Version of Record online: 23 DEC 2013 | DOI: 10.1002/smll.201303644

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      Fluorinated graphene oxide (FGO), which can exhibit contrast in T2 mode, is the first carbon-based MRI contrast agent without the incorporation of magnetic nanoparticles. Furthermore, FGO can also be used as a promising agent for the ultrasound imaging and the therapeutic application.

  7. Reviews

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    1. What Have We Learnt About the Mechanisms of Rapid Water Transport, Ion Rejection and Selectivity in Nanopores from Molecular Simulation? (pages 1453–1465)

      Michael Thomas, Ben Corry and Tamsyn A. Hilder

      Version of Record online: 25 JAN 2014 | DOI: 10.1002/smll.201302968

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      This Review elucidates the physical mechanisms which act to produce the remarkable rapid water transport, and ion rejection/selectivity properties observed in nanopores. Particular emphasis is given to atomistic simulations, as they have the potential to provide fundamental insights which are more difficult to obtain through experiment.

  8. Communications

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    1. High-Performance and Tailorable Pressure Sensor Based on Ultrathin Conductive Polymer Film (pages 1466–1472)

      Qi Shao, Zhiqiang Niu, Michael Hirtz, Lin Jiang, Yuanjun Liu, Zhaohui Wang and Xiaodong Chen

      Version of Record online: 25 JAN 2014 | DOI: 10.1002/smll.201303601

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      A highly sensitive and tailorable pressure sensor is designed based on the variation of contact resistance between an Au covered micropillar array and a conductive polymer film. The sensitivity of such pressure sensors can be tuned from 0.03 kPa−1 to 17 kPa−1 at pressures less than 1 kPa, and a limit of detection of 2 Pa has been demonstrated.

    2. Reductive Deprotection of Monolayer Protected Nanoclusters: An Efficient Route to Supported Ultrasmall Au Nanocatalysts for Selective Oxidation (pages 1473–1478)

      Sayantani Das, Anandarup Goswami, Mahdi Hesari, Jafar F. Al-Sharab, Eliška Mikmeková, Flavio Maran and Tewodros Asefa

      Version of Record online: 15 JAN 2014 | DOI: 10.1002/smll.201302854

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      The synthesis and investigation of the catalytic properties of Au nanoparticles (AuNPs) is an area of intense research. Despite much effort being made to this field, attaining both high catalytic activity and selectivity at the same time remains elusive. Herein a new mild reductive thiolate-deprotection strategy is reported to prepare nanoporous silica-supported ultrasmall AuNP catalysts that show very efficient catalytic activity and high selectivity for oxidation reactions.

    3. Graphite Oxide Nanoparticles with Diameter Greater than 20 nm Are Biocompatible with Mouse Embryonic Stem Cells and Can Be Used in a Tissue Engineering System (pages 1479–1484)

      I-Ning E. Wang, Joshua T. Robinson, Grace Do, Guosong Hong, Danny R. Gould, Hongjie Dai and Phillip C. Yang

      Version of Record online: 23 DEC 2013 | DOI: 10.1002/smll.201303133

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      Graphite oxide sheets demonstrate size-dependent uptake and toxicity towards embryonic stem cells. Graphite oxide sheets larger than 20 nm are biocompatible and can be safely used with mouse embryonic stem cells, while graphite oxide sheets smaller than 20 nm in diameter reduced cell proliferation and increased cell toxicity.

    4. Combined Chemical and Physical Encoding with Silk Fibroin-Embedded Nanostructures (pages 1485–1489)

      Abrin L. Schmucker, Matthew B. Dickerson, Matthew Rycenga, Bryan F. Mangelson, Keith A. Brown, Rajesh R. Naik and Chad A. Mirkin

      Version of Record online: 23 DEC 2013 | DOI: 10.1002/smll.201302923

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      Nanostructures spun into regenerated silk fibroin fibers encode physical and chemical information. These materials are composed of Raman enhancing nanoscale structures whose location in a linear array and chemical functionality endow them with a tunable identity or code. These structures remain functional after being electrospun into fibroin fibers and report a unique spectroscopic signature to prove the authenticity of a material through their code and by uniquely linking it to the composition of the host material.

    5. Direct Fabrication of Hexagonally Ordered Ridged Nanoarchitectures via Dual Interference Lithography for Efficient Sensing Applications (pages 1490–1494)

      Hwan Chul Jeon, Tae Yoon Jeon, Tae Soup Shim and Seung-Man Yang

      Version of Record online: 19 DEC 2013 | DOI: 10.1002/smll.201302860

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      Novel, large-area uniform hexagonally-ordered ridged nanoarchitectures (HORNs) can be fabricated using dual interference lithography derived from a novel prism and substrate beneath a spin-coated photoresist (PR) film. The metallic HORN arrays provide tunable SERS effects with large-scale sample homogeneity that depends on the number of stacks present along the z-direction, which is determined by the PR film thickness. Furthermore, the HORN structures show significant potential for use in particle-based or fluorescence-based sensing platforms by forming a free suspension of ridged nanoparticles or achieving highly intensified fluorescence signals, respectively.

    6. Ultrasensitive and Closed-Tube Colorimetric Loop-Mediated Isothermal Amplification Assay Using Carboxyl-Modified Gold Nanoparticles (pages 1495–1499)

      Jacky K. F. Wong, Shea Ping Yip and Thomas M. H. Lee

      Version of Record online: 13 MAR 2014 | DOI: 10.1002/smll.201302348

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      LAMP ends up in purple/red: The incorporation of 11-mercaptoundecanoic acid-modified gold nanoparticles into loop-mediated isothermal amplification (LAMP) reaction enables as few as 200 copies of a target DNA sequence to be detected by the naked eye. The color is controlled by magnesium ion-templated aggregation, and in the presence of the target, the LAMP reaction by-product pyrophosphate ion leads to particle deaggregation.

    7. DNA-Regulated Upconverting Nanoparticle Signal Transducers for Multivalued Logic Operation (pages 1500–1503)

      Xiang Ran, Fang Pu, Jinsong Ren and Xiaogang Qu

      Version of Record online: 30 JAN 2014 | DOI: 10.1002/smll.201303138

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      Upconversion applied in logic gate: The Upconversion nanoparticles (UCNPs) give multi emissions when excited by midrange IR radiation. A ternary logic system is designed which combines the unique characters of UCNPs with the ensemble of DNA. By regulating the emission of UCNPs, this logic system involvs more than two states, and the density of information can be increased.

  9. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Back Cover
    5. Masthead
    6. Contents
    7. Highlights
    8. Reviews
    9. Communications
    10. Frontispiece
    11. Full Papers
    1. You have free access to this content
      Biosensors: Selective Detection of Target Proteins by Peptide-Enabled Graphene Biosensor (Small 8/2014) (page 1504)

      Dmitriy Khatayevich, Tamon Page, Carolyn Gresswell, Yuhei Hayamizu, William Grady and Mehmet Sarikaya

      Version of Record online: 14 APR 2014 | DOI: 10.1002/smll.201470047

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      Depiction of the graphene FET-based bionanosensor functionalized with two engineered chimeric peptides, bio-GrBP5, and SS-GrBP5, which undergo spatially controlled self-assembly on the sensor surface to bind to target protein (SA) with enhanced molecular selectivity. This novel peptide-enabled graphene FET tool described on page 1505 by M. Sarikaya and co-workers has potential to address a wide range of bio-sensing problems, such as studying ligand-receptor interactions and clinical detection of biomarkers.

  10. Full Papers

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    5. Masthead
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    7. Highlights
    8. Reviews
    9. Communications
    10. Frontispiece
    11. Full Papers
    1. Selective Detection of Target Proteins by Peptide-Enabled Graphene Biosensor (pages 1505–1513)

      Dmitriy Khatayevich, Tamon Page, Carolyn Gresswell, Yuhei Hayamizu, William Grady and Mehmet Sarikaya

      Version of Record online: 26 MAR 2014 | DOI: 10.1002/smll.201302188

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      Graphene nanobiosensors are functionalized with multifunctional, self-assembling peptides that selectively detect specific proteins from a complex solution. The two peptides, that is, passivating and probing, impart specific function and required physiochemical properties to the surface of graphene. The novel peptide-enabled gFET device has potential to address a wide range of bio-sensing problems, such as studying ligand-receptor interactions and clinical detection of biomarkers.

    2. Extended Nanofluidic Immunochemical Reaction with Femtoliter Sample Volumes (pages 1514–1522)

      Kentaro Shirai, Kazuma Mawatari and Takehiko Kitamori

      Version of Record online: 16 DEC 2013 | DOI: 10.1002/smll.201302709

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      An extended nanofluidics-based quantitative immunochemical reaction capable of high capture efficiency using a femtoliter sample volume is achieved. A patterning method using a photolithography with vacuum ultraviolet light and low-temperature bonding enables the patterning of functional groups for antibody immobilization before bonding, resulting in an immunochemical reaction space of only 86 fL.

    3. Crucial Role of Anions on Arrangement of Cu2S Nanocrystal Superstructures (pages 1523–1528)

      Yansong Xiong, Ke Deng, Yuying Jia, Liangcan He, Lin Chang, Linjie Zhi and Zhiyong Tang

      Version of Record online: 27 JAN 2014 | DOI: 10.1002/smll.201303434

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      The arrays of Cu2S nanowires and the superlattice of Cu2S nanoparticles are fabricated by classic solventless thermolysis reaction of copper thiolate. Anions are found to play the key role in the arrangement of Cu2S nanocrystal superstructures. In the presence of Cl ions, Cu2S nanowire arrays are prepared; otherwise superlattices of Cu2S nanoparticles are produced.

    4. Transition Metal-Depleted Graphenes for Electrochemical Applications via Reduction of CO2 by Lithium (pages 1529–1535)

      Hwee Ling Poh, Zdenek Sofer, Jan Luxa and Martin Pumera

      Version of Record online: 16 DEC 2013 | DOI: 10.1002/smll.201303002

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      The fabrication of transition metal-depleted graphene is described, by using ultrapure CO2 (with benefits of low cost and easy availability) and elemental lithium to reduce CO2 to form graphene. Such a preparation method produces graphene of high purity with electrochemical behavior that is not dominated by any residual transition metal impurities, which would dramatically alter its electrochemical properties.

    5. Ultrasmall Fe3O4 Nanoparticle/MoS2 Nanosheet Composites with Superior Performances for Lithium Ion Batteries (pages 1536–1543)

      Yu Chen, Bohang Song, Xiaosheng Tang, Li Lu and Junmin Xue

      Version of Record online: 21 DEC 2013 | DOI: 10.1002/smll.201302879

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      A composite anode consisting of MoS2 nanosheets and ultrasmall Fe3O4 nanoparticles is fabricated for lithium ion battery application. MoS2 nanosheets provide high reversible capacity while Fe3O4 nanoparticles play a crucial role as spacers to stabilize the MoS2 nanosheets. Thus, excellent cyclic and rate performances are achieved by this composite.

    6. Surface Coating-Dependent Cytotoxicity and Degradation of Graphene Derivatives: Towards the Design of Non-Toxic, Degradable Nano-Graphene (pages 1544–1554)

      Yingjie Li, Liangzhu Feng, Xiaoze Shi, Xiaojing Wang, Yinlong Yang, Kai Yang, Teng Liu, Guangbao Yang and Zhuang Liu

      Version of Record online: 21 DEC 2013 | DOI: 10.1002/smll.201303234

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      This work carefully studies how surface coatings affect the cytotoxicity and extracellular biodegradation of graphene oxide (GO). Surface coating of GO sheets with biocompatible macromolecules, although greatly attenuates their toxicity, would inhibit their enzyme-induced degradation. A disulfide linker is then introduced during polymer coating of GO, resulting in a new type of functionalized GO with negligible toxicity and considerable degradability, promising for further biomedical applications.

    7. Tunable Reverse-Biased Graphene/Silicon Heterojunction Schottky Diode Sensor (pages 1555–1565)

      Amol Singh, Md. Ahsan Uddin, Tangali Sudarshan and Goutam Koley

      Version of Record online: 23 DEC 2013 | DOI: 10.1002/smll.201302818

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      Graphene/Si Schottky diode sensors operated in reverse bias exhibits orders of magnitude higher molecular detection sensitivity and lower power dissipation compared to both forward bias operation and graphene chemiresistor. Changing the Schottky barrier height (SBH) at the heterointerface by adsorbed molecules and reverse bias enables very high response and sensing tunability, respectively.

    8. An All Low-Temperature Fabrication of Macroporous, Electrochemically Addressable Anatase Thin Films (pages 1566–1574)

      Michael Schröder, Sébastien Sallard, Matthias Böhm, Marcus Einert, Christian Suchomski, Bernd M. Smarsly, Stephen Mutisya and Massimo F. Bertino

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/smll.201300970

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      Porous TiO2 films (pore size: approx. 100 nm) are obtained in an all-room-temperature process, using preformed TiO2 nanoparticles and poly(styrene) beads as template, followed by UV treatment.

    9. Topical Delivery of Avastin to the Posterior Segment of the Eye In Vivo Using Annexin A5-associated Liposomes (pages 1575–1584)

      Benjamin M. Davis, Eduardo M. Normando, Li Guo, Lisa A. Turner, Shereen Nizari, Paul O'Shea, Stephen E. Moss, Satyanarayana Somavarapu and M. Francesca Cordeiro

      Version of Record online: 5 MAR 2014 | DOI: 10.1002/smll.201303433

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      Annexin A5 significantly enhances uptake and transcytosis of liposomal drug carrier systems across multi-layered corneal epithelial barriers. Using a combination of in vitro and in vivo assays, it is demonstrated that Annexin A5 coated liposomes can be employed to deliver physiologically significant concentrations of Avastin to the posterior of the rat and rabbit eye after topical instillation.

    10. In Vivo Volumetric Photoacoustic Molecular Angiography and Therapeutic Monitoring with Targeted Plasmonic Nanostars (pages 1585–1593)

      Liming Nie, Shouju Wang, Xiaoyong Wang, Pengfei Rong, Ying Ma, Gang Liu, Peng Huang, Guangming Lu and Xiaoyuan Chen

      Version of Record online: 22 OCT 2013 | DOI: 10.1002/smll.201302924

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      Induced angiogenesis is one major hallmark of malignant tumor. Using cyclic RGD peptide conjugated gold nanostars (RGD-GNS), quantitative volumetric angiography of tumor can be achieved with high resolution and deep penetration depth by a hemispherical photoacoustic imaging system. This unique theranostic platform also enables photothermal therapy and subsequent therapeutic monitoring.

    11. Bioinspired Catechol-Terminated Self-Assembled Monolayers with Enhanced Adhesion Properties (pages 1594–1602)

      Mireia Guardingo, Elena Bellido, Rosa Miralles-Llumà, Jordi Faraudo, Josep Sedó, Sergio Tatay, Albert Verdaguer, Felix Busqué and Daniel Ruiz-Molina

      Version of Record online: 19 DEC 2013 | DOI: 10.1002/smll.201302406

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      Highly packed catechol monolayers with a large density and smaller roughness are studied by AFM force-distance curves. These experiments afford adhesion force values higher and much more monodisperse than those reported for polydopamine-like polymeric materials. These results are unique giving valuable information on the effect of molecular organization on the adhesive properties of interphases. Such information is crucial for the development of improved materials and interphases engineered at the molecular level, by chemical design.

    12. M-shaped Grating by Nanoimprinting: A Replicable, Large-Area, Highly Active Plasmonic Surface-Enhanced Raman Scattering Substrate with Nanogaps (pages 1603–1611)

      Zhendong Zhu, Benfeng Bai, Huigao Duan, Haosu Zhang, Mingqian Zhang, Oubo You, Qunqing Li, Qiaofeng Tan, Jia Wang, Shoushan Fan and Guofan Jin

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/smll.201302436

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      M for Nano: An M-shaped plasmonic nanograting with nanogaps is proposed and fabricated by using room-temperature nanoimprinting and anisotropic reactive-ion etching, and enables strong field localization in the nanogaps. Surface-enhanced Raman scattering (SERS) experiments show an average SERS enhancement factor as high as 5×108 by using the M-grating substrate, which reveals its potential as a replicable, large-area, highly active SERS substrate.

    13. First Demonstration of Gold Nanorods-Mediated Photodynamic Therapeutic Destruction of Tumors via Near Infra-Red Light Activation (pages 1612–1622)

      Raviraj Vankayala, Yu-Kuan Huang, Poliraju Kalluru, Chi-Shiun Chiang and Kuo Chu Hwang

      Version of Record online: 16 DEC 2013 | DOI: 10.1002/smll.201302719

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      Gold nanorods (Au NRs)-mediated photodynamic therapy effects on destruction of tumors were demonstrated upon single photon NIR light excitation without additional organic photosensitizers, and simultaneously act as fluorescent markers.

    14. RNAi-Microsponges Form through Self-Assembly of the Organic and Inorganic Products of Transcription (pages 1623–1633)

      Kevin E. Shopsowitz, Young Hoon Roh, Zhou J. Deng, Stephen W. Morton and Paula T. Hammond

      Version of Record online: 19 DEC 2013 | DOI: 10.1002/smll.201302676

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      The structure of microsponges formed during rolling circle transcription is elucidated. These particles consist of RNA adsorbed onto the surface of nanocrystalline magnesium pyrophosphate sheets that self-assemble as RNA and pyrophosphate are produced during transcription. This unique composite structure allows for high loadings of RNA capable of mediating RNAi.

    15. Aragonite Nanorods in Calcium Carbonate/Polymer Hybrids Formed through Self-Organization Processes from Amorphous Calcium Carbonate Solution (pages 1634–1641)

      Satoshi Kajiyama, Tatsuya Nishimura, Takeshi Sakamoto and Takashi Kato

      Version of Record online: 14 JAN 2014 | DOI: 10.1002/smll.201302745

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      Nanostructured inorganic/polymer hybrids based on aragonite nanorods derived from aqueous suspensions of amorphous calcium carbonate (ACC) are prepared. ACC stabilized by an acidic polymer is crystallized gradually in a matrix of polymer films under ambient conditions. Thin-film hybrids composed of layers for calcite nanoparticles and aligned aragonite nanorods spontaneously develop in the polymer matrix.

    16. Tuning Cellular Response to Nanoparticles via Surface Chemistry and Aggregation (pages 1642–1651)

      Jie An Yang, Samuel E. Lohse and Catherine J. Murphy

      Version of Record online: 9 DEC 2013 | DOI: 10.1002/smll.201302835

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      By first mixing gold nanoparticles (Au NPs) with serum proteins then buffer, Au NP aggregation, commonly observed through direct addition to cell media, is prevented. Cells in cell media with non-aggregated Au NPs exhibit better cell viability and lower uptake of Au NPs. F-actin disruption appears to be related to Au NP uptake and surface chemistry.

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