Small

Cover image for Vol. 6 Issue 23

December 6, 2010

Volume 6, Issue 23

Pages 2621–2768

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Essay
    6. Review Article
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. Mesoporous materials: Why PMO? Towards Functionality and Utility of Periodic Mesoporous Organosilicas (Small 23/2010) (page 2621)

      Wendong Wang, Jennifer E. Lofgreen and Geoffrey A. Ozin

      Article first published online: 3 DEC 2010 | DOI: 10.1002/smll.201090081

      Thumbnail image of graphical abstract

      Writing on the pore wall with a synthetic quill is the idea illustrated in the cover image. This idea captures the role of creative materials chemistry in the development of a novel class of materials called periodic mesoporous organosilica (PMO) since its inception a decade ago. Through the fusion of organic chemistry and inorganic materials chemistry, PMO has grown to possess a variety of new and exciting compositions, properties, and functions. Through a handful of recent trendsetting case histories, the cross-disciplinary applications of PMO in chemistry and physics, materials science and engineering, biology, and medicine are demonstrated in a most powerful way. In doing so, the Review that this image features aims to inspire more collaborative and ambitious endeavors in the second decade of PMO research. For more information, please read the Review “Why PMO? Towards Functionality and Utility of Periodic Mesoporous Organosilicas” by G. A. Ozin and co-workers beginning on page 2634.

  2. Inside Front Cover

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Essay
    6. Review Article
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. Plasmonics: The Effect of Thermal Gradients in SERS Spectroscopy (Small 23/2010) (page 2622)

      Taewook Kang, Soongweon Hong, Yeonho Choi and Luke P. Lee

      Article first published online: 3 DEC 2010 | DOI: 10.1002/smll.201090082

      Thumbnail image of graphical abstract

      While the fundamental understanding of surface-enhanced Raman spectroscopy (SERS) mechanisms has been focused on electromagnetic and chemical enhancement, the effect of thermal gradients in SERS spectroscopy is neglected. The cover image addresses the importance of the photothermal effect in SERS measurements. A strong temperature gradient (∼106 K m−1) is generated by a photothermal effect on nanoplasmonic antenna upon light exposure. The photon-induced resonant excitation of surface plasmons causes electron–phonons coupling and heat dissipation in metal nanoparticles. Consequently, the temperature gradient can force analyte molecules out of confined spaces and form a circular vortex ring due to thermal diffusion and natural convection. The duality of enrichment-depletion by photothermal gradients shows significant SERS intensity changes depending on the position. The critical analysis of thermal gradient effects in SERS substrate, and the interaction of nanoplasmonic antennas and molecules will enable next-generation SERS probes with superior sensitivity. For more information, please read the Communication “The Effect of Thermal Gradients in SERS Spectroscopy” by Y. Choi, L. P. Lee, and co-workers, beginning on page 2649.

  3. Contents

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Essay
    6. Review Article
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. Contents: (Small 23/2010) (pages 2623–2629)

      Article first published online: 3 DEC 2010 | DOI: 10.1002/smll.201090083

  4. Essay

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Essay
    6. Review Article
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. Neurons Are Able to Internalize Soluble Carbon Nanotubes: New Opportunities or Old Risks? (pages 2630–2633)

      Giada Cellot, Laura Ballerini, Maurizio Prato and Alberto Bianco

      Article first published online: 21 SEP 2010 | DOI: 10.1002/smll.201000906

      Thumbnail image of graphical abstract

      Carbon nanotubes (CNT) are increasingly regarded as promising nanovectors to exploit target delivery of specific drugs. However, upgrading CNT from a promising material to an effective biomedical tool in neuroscience requires further investments and investigations. To date, limited and conflicting data exist on neuronal and glial cell reactions to soluble CNT exposure and accumulation.

  5. Review Article

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Essay
    6. Review Article
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. Why PMO? Towards Functionality and Utility of Periodic Mesoporous Organosilicas (pages 2634–2642)

      Wendong Wang, Jennifer E. Lofgreen and Geoffrey A. Ozin

      Article first published online: 18 OCT 2010 | DOI: 10.1002/smll.201000617

      Thumbnail image of graphical abstract

      Writing on the Pore Wall with a Synthetic Quill: Creative synthetic chemistry has endowed the class of periodic mesoporous organosilica materials, dubbed PMO, with a variety of new and exciting compositions, properties, and functions since its inception a decade ago. Using a handful of recent trendsetting case histories, the multidisciplinary applications of PMO materials in chemistry and physics, materials science and engineering, biology, and medicine are demonstrated in a most powerful way. In doing so, this Review aims to inspire more collaborative and ambitious endeavors in the second decade of PMO research.

  6. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Essay
    6. Review Article
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. Layer-by-layer assembly: Layer-By-Layer Technique for Producing Porous Nanostructured 3D Constructs Using Moldable Freeform Assembly of Spherical Templates (Small 23/2010) (page 2643)

      Praveen Sher, Catarina A. Custódio and João. F. Mano

      Article first published online: 3 DEC 2010 | DOI: 10.1002/smll.201090084

      Thumbnail image of graphical abstract

      The frontispiece shows a new easy and versatile layer-by-layer (LbL)-based methodology to develop 3D nanometer-scale structures from a macrotemplate arrangement of random wax spheres. This method, based on the dropwise addition of polyelectrolyte solutions, displays a new “in-situ binding” feature, which brings the freeform assembly of spherical templates into moldable 3D geometries held together without any binder. The highlight of this step is the simultaneous coating of multilayers acting as joints between the spheres, which after leaching lead to the formation of an interconnected structure. Good cell adhesion and proliferation indicate their potential application in tissue engineering. For more information, please read the Communication “Layer-By-Layer Technique for Producing Porous Nanostructured 3D Constructs Using Moldable Freeform Assembly of Spherical Templates” by P. Sher, C. A. Custódio, and J. F. Mano, beginning on page 2643.

  7. Communications

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Essay
    6. Review Article
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. Layer-By-Layer Technique for Producing Porous Nanostructured 3D Constructs Using Moldable Freeform Assembly of Spherical Templates (pages 2644–2648)

      Praveen Sher, Catarina A. Custódio and João. F. Mano

      Article first published online: 11 OCT 2010 | DOI: 10.1002/smll.201001066

      Thumbnail image of graphical abstract

      An easy and versatile layer-by-layer approach using a “perfusion technique” is developed. The ability of the technique to precisely assemble random template particles into moldable 3D architectures along with simultaneous production of multilayers is displayed. A stable porous interconnected nanostructured 3D system is formed

    2. The Effect of Thermal Gradients in SERS Spectroscopy (pages 2649–2652)

      Taewook Kang, Soongweon Hong, Yeonho Choi and Luke P. Lee

      Article first published online: 3 SEP 2010 | DOI: 10.1002/smll.201000996

      Thumbnail image of graphical abstract

      The importance of the photothermal effect in surface enhanced Raman scattering (SERS) measurements is addressed. Strong temperature gradient (≈106 K m−1) induced by photothermal effect can force molecules to move. Finally, redistributed molecules can result in a nonuniform SERS intensity.

    3. Tunable Nano/Micropores for Particle Detection and Discrimination: Scanning Ion Occlusion Spectroscopy (pages 2653–2658)

      G. Seth Roberts, Darby Kozak, Will Anderson, Murray F. Broom, Robert Vogel and Matt Trau

      Article first published online: 26 OCT 2010 | DOI: 10.1002/smll.201001129

      Thumbnail image of graphical abstract

      Conventional pore technologies are limited in the size range of structures they can analyze by the fixed size of the pore. A novel stretchable pore which can be tuned to optimize the pore size to a particular experimental system is applied here to distinguish between nanoparticle populations of similar size and to detect DNA modification of nanoparticles.

    4. High-Speed Programming of Nanowire-Gated Carbon-Nanotube Memory Devices (pages 2659–2663)

      Guillaume Agnus, Arianna Filoramo, Stéphane Lenfant, Dominique Vuillaume, Jean-Philippe Bourgoin and Vincent Derycke

      Article first published online: 27 OCT 2010 | DOI: 10.1002/smll.201001293

      Thumbnail image of graphical abstract

      Resistanceprogramming of carbon-nanotube-based optoelectronic memory devices at sub-microsecond speed is demonstrated. The use of silicon nanowires as programming electrodes allows study of the scaling rules of the programming speed and the charge-retention mechanism. Such fast and nonvolatile memory elements have potential for the development of adaptive circuits.

    5. Programmed Nanopatterning of Organic/Inorganic Nanoparticles Using Nanometer-Scale Wells Embedded in a DNA Origami Scaffold (pages 2664–2667)

      Akinori Kuzuya, Naohiro Koshi, Mayumi Kimura, Kentaro Numajiri, Takahiro Yamazaki, Toshiyuki Ohnishi, Fuminori Okada and Makoto Komiyama

      Article first published online: 11 NOV 2010 | DOI: 10.1002/smll.201001484

      Thumbnail image of graphical abstract

      Gold nanoparticles are selectively patterned into nanoarrays by using a punched DNA origami scaffold with nanometer-sized periodical wells. By simply adding unmodified gold nanoparticle into the solution of the punched origami scaffold, exactly one particle is captured selectively in a thiolated well. The capture is completely chemoselective such that an alternating streptavidin/gold nanoparticle heteroarray with a 26 nm period is successfully prepared.

    6. Active Guidance of 3D Microstructures (pages 2668–2672)

      Sung Hoon Lee, Sung-Eun Choi, Austen James Heinz, Wook Park, Sangkwon Han, Yoonseok Jung and Sunghoon Kwon

      Article first published online: 9 NOV 2010 | DOI: 10.1002/smll.201001248

      Thumbnail image of graphical abstract

      A new method for sorting loaded microstructures using a platform known as active rail is presented. Active rail actively sorts grooved hydrogel microstructures at channel branch sites through pneumatic activation of a flexible rail. This paper provides a sorting mechanism that is capable of continuous flow reconfigurable multibranch guidance, and it demonstrates stacking of microstructures for combinatorial multicompartment chemical delivery.

    7. Photoluminescent Smart Hydrogels with Reversible and Linear Thermoresponses (pages 2673–2677)

      Yingnan Jiang, Xudong Yang, Cheng Ma, Chuanxi Wang, Hui Li, Fengxia Dong, Xiaoming Zhai, Kui Yu, Quan Lin and Bai Yang

      Article first published online: 10 NOV 2010 | DOI: 10.1002/smll.201001151

      Thumbnail image of graphical abstract

      Smart hydrogels are designed and synthesized to exhibit sensitive, linear, and reversible photoluminescence (PL) responses to temperature change in the range of 10 to 50°C.The Eu-doped core/shell nanoparticle hydrogels consist of poly[styrene-co-(N-isopropylacrylamide)] (PS-co-PNIPAM)/PNIPAM.

    8. Gd-Labeled Microparticles in MRI: In vivo Imaging of Microparticles After Intraperitoneal Injection (pages 2678–2682)

      Jeremy L. Steinbacher, Sherrill A. Lathrop, Kai Cheng, Jedd M. Hillegass, Kelly J. Butnor, Risto A. Kauppinen, Brooke T. Mossman and Christopher C. Landry

      Article first published online: 10 NOV 2010 | DOI: 10.1002/smll.201001447

      Thumbnail image of graphical abstract

      To visualize the biodistribution of porous silica microparticles in vivo, known ligands are used to immobilize gadolinium in the pores for use as MRI contrast agents. MRI studies with rodents show that a fraction of the microparticles administered by intraperitoneal injection passed through the kidneys by an unknown mechanism and are, surprisingly, excreted via the urine. Analysis of the urine with SEM and energy dispersive spectroscopy corroborated the MRI results.

    9. Polymer Nanotubules Obtained by Layer-by-Layer Deposition within AAO-Membrane Templates with Sub-100-nm Pore Diameters (pages 2683–2689)

      Younghyun Cho, Woo Lee, Young Kuk Jhon, Jan Genzer and Kookheon Char

      Article first published online: 11 NOV 2010 | DOI: 10.1002/smll.201001212

      Thumbnail image of graphical abstract

      Well definedpolymeric nanotubules with diameters less than 100 nm are prepared through the template-assisted layer-by-layer method by controlling the ratio of polymer dimension to pore size. The molecular weight of the polymers, the chain conformation, and the aggregation condition are finely tuned by adjusting the valency of salts as well as solution pH to prevent pore blockage originating from the polymer multilayer deposited at the top surface of the templates.

  8. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Essay
    6. Review Article
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. Drug delivery: Logic-Embedded Vectors for Intracellular Partitioning, Endosomal Escape, and Exocytosis of Nanoparticles (Small 23/2010) (page 2690)

      Rita E. Serda, Aaron Mack, Anne L. van de Ven, Silvia Ferrati, Kenneth Dunner Jr., Biana Godin, Ciro Chiappini, Matthew Landry, Louis Brousseau, Xuewu Liu, Andrew J. Bean and Mauro Ferrari

      Article first published online: 3 DEC 2010 | DOI: 10.1002/smll.201090085

      Thumbnail image of graphical abstract

      Cell-derived vectors containing nanoparticles represent a means for cell-to-cell communication, biobarrier crossing, and dissemination of nanoparticle-encapsulated signals. The frontispiece image shows a pseudocolored transmission electron microscopy image with a membrane-enclosed vesicle containing iron oxide nanoparticles. These nanoparticle-loaded vectors were expelled from the cell following cellular internalization of logic-embedded vectors; that is, vectors that direct their own cellular and intracellular fate based on particle properties, such as size and surface chemistry. Other cellular destinations include the lysosome and cytoplasm. For more information, please read the Full Paper “Logic-Embedded Vectors for Intracellular Partitioning, Endosomal Escape, and Exocytosis of Nanoparticles” by R. E. Serda and co-workers, beginning on page 2690.

  9. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Essay
    6. Review Article
    7. Frontispiece
    8. Communications
    9. Frontispiece
    10. Full Papers
    1. Logic-Embedded Vectors for Intracellular Partitioning, Endosomal Escape, and Exocytosis of Nanoparticles (pages 2691–2700)

      Rita E. Serda, Aaron Mack, Anne L. van de Ven, Silvia Ferrati, Kenneth Dunner Jr., Biana Godin, Ciro Chiappini, Matthew Landry, Louis Brousseau, Xuewu Liu, Andrew J. Bean and Mauro Ferrari

      Article first published online: 18 OCT 2010 | DOI: 10.1002/smll.201000727

      Thumbnail image of graphical abstract

      Logic-embedded vectors (LEVs) are multiparticle drug-delivery systems with the ability to localize components at multiple intracellular sites. LEVs consisting of porous silicon nanocarriers and iron oxide nanoparticles are internalized by phagocytosis and undergo intracellular partitioning to diverse intracellular locations, which include the cytosol and membrane-bound compartments compatible with cellular secretion.

    2. Flexible Replication Technique for High-Aspect-Ratio Nanostructures (pages 2701–2707)

      Adriana Szeghalmi, Kornelia Sklarek, Michael Helgert, Robert Brunner, Wilfried Erfurth, Ulrich Gosele and Mato Knez

      Article first published online: 11 NOV 2010 | DOI: 10.1002/smll.201000169

      Thumbnail image of graphical abstract

      Polymer replicas of high-aspect-ratio nanostructured templates are presented. The adhesion between the replica and the master is disrupted by selectively removing a sacrificial layer deposited by atomic layer deposition. Polystyrene nanostructures with aspect ratios up to 1:13 are easily obtained. (Scale bar of image: 1000 nm)

    3. Surface-Induced Synthesis and Self-Assembly of Metal Suprastructures (pages 2708–2715)

      Shaozhou Li, Xiao Huang, Hai Li, Hui Cai, Chee Lip Gan, Freddy Boey and Hua Zhang

      Article first published online: 26 OCT 2010 | DOI: 10.1002/smll.201001084

      Thumbnail image of graphical abstract

      Thesynthesis of a series of self-assembled suprastructures of Ag nanoparticles (AgNPs) is studied sytematically in borosilicate glassware heavily cleaned with aqua regia. These structures are mostly formed from the crystallographically iso-oriented AgNPs. It is demonstrated that the surface energy of glassware can affect both chemical and shape-controlled synthesis.

    4. Self-Organized Ce1-xGdxO2-y Nanowire Networks with Very Fast Coarsening Driven by Attractive Elastic Interactions (pages 2716–2724)

      Marta Gibert, Patricia Abellán, Alessandro Benedetti, Teresa Puig, Felip Sandiumenge, Alberto García and Xavier Obradors

      Article first published online: 9 NOV 2010 | DOI: 10.1002/smll.201001237

      Thumbnail image of graphical abstract

      A new pathtowards self-organized epitaxial nanowire networks produced by high-throughput solution methods is reported, which has wide potential for many materials and functionalities. A thermodynamic driving force and a very fast effective growth rate are the key elements met in anisotropically strained Ce1-xGdxO2-y nanowires.

    5. Nanogeometry Matters: Unexpected Decrease of Capillary Adhesion Forces with Increasing Relative Humidity (pages 2725–2730)

      Mariana Köber, Enrique Sahagún, Pedro García-Mochales, Fernando Briones, Monica Luna and Juan José Sáenz

      Article first published online: 11 NOV 2010 | DOI: 10.1002/smll.201001297

      Thumbnail image of graphical abstract

      A counterintuitive monotonous decrease of the capillary adhesion forces between hydrophilic surfaces with increasing relative humidity is presented for the whole humidity range. It is shown, experimentally as well as theoretically, that this unexpected result is related to the actual shape of the asperity at the nanometer scale.

    6. Structural and Electronic Properties of Extremely Long Perylene Bisimide Nanofibers Formed through a Stoichiometrically Mismatched, Hydrogen-Bonded Complexation (pages 2731–2740)

      Shiki Yagai, Tomohiro Seki, Haruno Murayama, Yusuke Wakikawa, Tadaaki Ikoma, Yoshihiro Kikkawa, Takashi Karatsu, Akihide Kitamura, Yoshihito Honsho and Shu Seki

      Article first published online: 10 NOV 2010 | DOI: 10.1002/smll.201001344

      Thumbnail image of graphical abstract

      Extremely long nanofibers, whose lengths reach the millimeter regime, are generated via co-aggregation of a melamine-appended perylene bisimide semiconductor and a substituted cyanurate, both of which are ditopic triple-hydrogen-bonding building blocks. Microscopy and X-ray diffraction studies suggest that hydrogen-bonded polymeric chains are formed along the long axis of the nanofibers by the 1:2 complexation of the two components, which further stack along the short axis of the nanofibers.

    7. Rapid Delivery of Drug Carriers Propelled and Navigated by Catalytic Nanoshuttles (pages 2741–2747)

      Daniel Kagan, Rawiwan Laocharoensuk, Maria Zimmerman, Corbin Clawson, Shankar Balasubramanian, Dae Kang, Daniel Bishop, Sirilak Sattayasamitsathit, Liangfang Zhang and Joseph Wang

      Article first published online: 27 OCT 2010 | DOI: 10.1002/smll.201001257

      Thumbnail image of graphical abstract

      The use of catalytic nanoshuttles to transport and release common polymeric and liposomal drug carriers is presented. This nanomotor delivery may help address current nanoparticle drug delivery obstacles.

    8. High-On/Off-Ratio Graphene Nanoconstriction Field-Effect Transistor (pages 2748–2754)

      Ye Lu, Brett Goldsmith, Douglas R. Strachan, Jong Hsien Lim, Zhengtang Luo and A. T. Charlie Johnson

      Article first published online: 27 OCT 2010 | DOI: 10.1002/smll.201001324

      Thumbnail image of graphical abstract

      High-on/off-ratio graphene transistors are fabricated using feedback-controlled electromigration to create etch masks for features down to 10 nm. By creating single constriction transistors rather than nanoribbons or quantum dots, the on-state resistance of the graphene is relatively high (50 kΩ), while large on/off ratios are maintained, even at room temperature.

    9. A Biodegradable and Biocompatible Regular Nanopattern for Large-Scale Selective Cell Growth (pages 2755–2761)

      Lucia Csaderova, Elena Martines, Krishna Seunarine, Nikolaj Gadegaard, Chris D. W. Wilkinson and Mathis O. Riehle

      Article first published online: 11 NOV 2010 | DOI: 10.1002/smll.201000193

      Thumbnail image of graphical abstract

      A selective cell response to polymer nanopillars is demonstrated by fibroblasts (hTert) and endothelia (b.End3). Whereas the hTert do not proliferate, b.End3 do so forming a monolayer. This is evident in the Coomassie-stained cells (left: hTERT; right: b.End3) on poly-ϵ-caprolactone with a central 1 cm2 pattern of 100-nm-wide, 110-nm-high nanopillars spaced 300 nm apart. The blue color indicates the presence of cells. Scale bar: 5 mm.

    10. Encapsulation and Release of Molecular Cargos via Temperature-Induced Vesicle-To-Micelle Transitions (pages 2762–2768)

      Qi Chen, Holger Schönherr and G. Julius Vancso

      Article first published online: 11 NOV 2010 | DOI: 10.1002/smll.201001348

      Thumbnail image of graphical abstract

      A temperature change is used as an external stimulus to induce a vesicle-to-micelle transition of block copolymer aggregates. This transition allows the release of fluorogenic substrates from inside the vesicles and the hydrolysis of the substrates catalyzed by enzymes, as well as the subsequent partial encapsulation of the product to prevent unwanted subsequent reactions.

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