Advanced Materials

Cover image for Vol. 25 Issue 36

September 25, 2013

Volume 25, Issue 36

Pages 4953–5114

  1. Cover Picture

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    10. Frontispiece
    11. Communications
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      Microstructures: 3D Printing of Free Standing Liquid Metal Microstructures (Adv. Mater. 36/2013) (page 4953)

      Collin Ladd, Ju-Hee So, John Muth and Michael D. Dickey

      Version of Record online: 24 SEP 2013 | DOI: 10.1002/adma.201370225

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      A direct-write method for writing 3D freestanding, liquid-metal microcomponents from the binary eutectic alloy of gallium and indium at room temperature is described in work by Prof. Michael Dickey, Prof. John Muth, and co-workers on page 5081. The smallest components fabricated by the technique are of the order of 10 μm in size, and smaller–sized structures may be possible. The technique allows the formation of mechanically stable structures and is capable of printing wires, spheres, arches, and interconnects.

  2. Inside Front Cover

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    9. Communications
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      Supercapacitors: Freestanding Mesoporous VN/CNT Hybrid Electrodes for Flexible All-Solid-State Supercapacitors (Adv. Mater. 36/2013) (page 4954)

      Xu Xiao, Xiang Peng, Huanyu Jin, Tianqi Li, Chengcheng Zhang, Biao Gao, Bin Hu, Kaifu Huo and Jun Zhou

      Version of Record online: 24 SEP 2013 | DOI: 10.1002/adma.201370226

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      On page 5091 Prof. Jun Zhou, Prof. Kaifu Huo, and co-workers demonstrate high-performance all-solid-state supercapacitors based on flexible, free-standing mesoporous vanadium nitride nanowire (MVNN)/carbon nanotube hybrid electrodes. The MVNNs are synthesized by way of a hydrothermal synthesis followed by thermal nitridation under an ammonia atmosphere. The devices show a stable performance and high volumetric capacitance, along with high volume energy and power density. These electrodes have potential applications in portable/wearable electronics.

  3. Back Cover

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      Metamaterials: 3D Soft Metamaterials with Negative Poisson's Ratio (Adv. Mater. 36/2013) (page 5116)

      Sahab Babaee, Jongmin Shim, James C. Weaver, Elizabeth R. Chen, Nikita Patel and Katia Bertoldi

      Version of Record online: 24 SEP 2013 | DOI: 10.1002/adma.201370227

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      A new class of 3D metamaterial with a negative Poisson ratio is designed by Prof. Katia Bertoldi and co-workers, as described in the Communication on page 5044. The buckling-induced auxetic properties of these materials are demonstrated through experimental studies and finite element simulations, which exhibit excellent agreement. The design rules can be applied to various length scales, reconfiguration is based on application of different stimuli, and the auxetic behavior is retained over a wide range of applied strain.

  4. Masthead

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    1. Masthead: (Adv. Mater. 36/2013)

      Version of Record online: 24 SEP 2013 | DOI: 10.1002/adma.201370228

  5. Contents

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    11. Communications
  6. Editorials

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      Advanced Materials 25 Years On (pages 4962–4965)

      Dr. Peter Gregory

      Version of Record online: 24 SEP 2013 | DOI: 10.1002/adma.201303702

  7. Reviews

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    11. Communications
    1. 25th Anniversary Article: Understanding the Lithiation of Silicon and Other Alloying Anodes for Lithium-Ion Batteries (pages 4966–4985)

      Matthew T. McDowell, Seok Woo Lee, William D. Nix and Yi Cui

      Version of Record online: 22 AUG 2013 | DOI: 10.1002/adma.201301795

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      Due to its extremely high theoretical lithium storage capacity, silicon is an attractive anode material for next-generation lithium-ion batteries. However, complex volume changes and phase transformations during the lithium-silicon reaction can lead to capacity decay with cycling. In this review, we discuss fundamental studies that have been conducted to understand volume changes, phase transformations, stress evolution, mechanical properties, and fracture behavior of nanostructured Si anodes for lithium-ion batteries.

    2. 25th Anniversary Article: Colloidal Quantum Dot Materials and Devices: A Quarter-Century of Advances (pages 4986–5010)

      Jin Young Kim, Oleksandr Voznyy, David Zhitomirsky and Edward H. Sargent

      Version of Record online: 4 SEP 2013 | DOI: 10.1002/adma.201301947

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      Colloidal quantum dots offer a compelling combination of low-cost and large-area solution processing and spectral tunability via the quantum size effect. These materials are promising in a wide range of optoelectronic applications. The quarter-century-long history of the colloidal quantum dot field is reviewed, beginning with early discoveries in synthesis and physical chemistry, through foundational advances in materials processing, chemistry, and understanding, and concluding with an account of recent breakthroughs that have produced record-setting solar cells.

      Corrected by:

      Correction: 25th Anniversary Article: Colloidal Quantum Dot Materials and Devices: A Quarter-Century of Advances

      Vol. 27, Issue 26, 3849, Version of Record online: 6 JUL 2015

    3. 25th Anniversary Article: Engineering Hydrogels for Biofabrication (pages 5011–5028)

      Jos Malda, Jetze Visser, Ferry P. Melchels, Tomasz Jüngst, Wim E. Hennink, Wouter J. A. Dhert, Jürgen Groll and Dietmar W. Hutmacher

      Version of Record online: 23 AUG 2013 | DOI: 10.1002/adma.201302042

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      Hydrogels are attractive cell carriers for regenerative medicine as they recapitulate several features of the natural extracellular matrix. However, biofabrication of three-dimensional complex, tissue-like structures with high shape fidelity dictates narrow boundaries for the physical properties of the hydrogels applied. This review focuses on strategies and new developments that address these physicochemical challenges.

    4. 25th Anniversary Article: Dynamic Interfaces for Responsive Encapsulation Systems (pages 5029–5043)

      Ekaterina V. Skorb and Helmuth Möhwald

      Version of Record online: 3 SEP 2013 | DOI: 10.1002/adma.201302142

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      Significant advances of dynamic interfaces for responsive encapsulation systems are discussed. Methods for encapsulation with prolonged storage and controllable release are discussed. The most essential advances of the systems presented are multifunctionality and responsiveness to a multitude of stimuli. Specific examples of advanced applications – drug delivery, diagnostics, tissue engineering, lab-on-chip and organ-on-chip, bio-sensors, membranes, templates for synthesis, optical systems, and antifouling, self-healing materials and coatings – are provided.

  8. Communications

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    5. Masthead
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    7. Editorials
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    10. Frontispiece
    11. Communications
    1. 3D Soft Metamaterials with Negative Poisson's Ratio (pages 5044–5049)

      Sahab Babaee, Jongmin Shim, James C. Weaver, Elizabeth R. Chen, Nikita Patel and Katia Bertoldi

      Version of Record online: 22 JUL 2013 | DOI: 10.1002/adma.201301986

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      Buckling is exploited to design a new class of three-dimensional metamaterials with negative Poisson's ratio. A library of auxetic building blocks is identified and procedures are defined to guide their selection and assembly. The auxetic properties of these materials are demonstrated both through experiments and finite element simulations and exhibit excellent qualitative and quantitative agreement.

    2. Red, Green and Blue Reflections Enabled in an Optically Tunable Self-Organized 3D Cubic Nanostructured Thin Film (pages 5050–5054)

      Tsung-Hsien Lin, Yannian Li, Chun-Ta Wang, Hung-Chang Jau, Chun-Wei Chen, Cheng-Chung Li, Hari Krishna Bisoyi, Timothy J. Bunning and Quan Li

      Version of Record online: 1 AUG 2013 | DOI: 10.1002/adma.201300798

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      A new light-driven chiral molecular switch doped in a stable blue phase (BP) liquid crystal allows wide optical tunability of three-dimensional cubic nanostructures with a selective reflection wavelength that is reversibly tuned through the visible region. Moreover, unprecedented reversible light-directed red, green, and blue reflections of the self-organized three-dimensional cubic nanostructure in a single film are demonstrated for the first time. Additionally, unusual isothermal photo-stimulated less ordered BP II to more ordered BP I phase transition was observed in the system.

    3. Hydration and Dynamic State of Nanoconfined Polymer Layers Govern Toughness in Nacre-mimetic Nanocomposites (pages 5055–5059)

      Tuukka Verho, Mikko Karesoja, Paramita Das, Lahja Martikainen, Reidar Lund, Angel Alegría, Andreas Walther and Olli Ikkala

      Version of Record online: 2 AUG 2013 | DOI: 10.1002/adma.201301881

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      Biological high-performance composites inspire to create new tough, strong, and stiff structural materials. We show a brittle-to-ductile transition in a self-assembled nacre-inspired poly(vinyl alcohol)/nanoclay composite based on a hydration-induced glass-to-rubber transition in the 2D-nanoconfined poly(vinyl alcohol) layers. The findings open routes to design dissipative toughening mechanisms to combine stiffness and strength in nanocomposites.

    4. Rapidly–Dissolvable Microneedle Patches Via a Highly Scalable and Reproducible Soft Lithography Approach (pages 5060–5066)

      Katherine A. Moga, Lissett R. Bickford, Robert D. Geil, Stuart S. Dunn, Ashish A. Pandya, Yapei Wang, John H. Fain, Christine F. Archuleta, Adrian T. O'Neill and Joseph M. DeSimone

      Version of Record online: 29 JUL 2013 | DOI: 10.1002/adma.201300526

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      Microneedle devices for transdermal drug delivery have recently become an attractive method to overcome the diffusion-limiting epidermis and effectively transport therapeutics to the body. Here, we demonstrate the fabrication of highly reproducible and completely dissolvable polymer microneedles on flexible water-soluble substrates. These biocompatible microneedles (made by using a soft lithography process known as PRINT) showed efficacy in piercing both murine and human skin samples and delivering a fluorescent drug surrogate to the tissue.

    5. Caged Pt Nanoclusters Exhibiting Corrodibility to Exert Tumor-Inside Activation for Anticancer Chemotherapeutics (pages 5067–5073)

      Chih-Te Chien, Jia-Ying Yan, Wan-Ching Chiu, Te-Haw Wu, Chia-Yeh Liu and Shu-Yi Lin

      Version of Record online: 2 AUG 2013 | DOI: 10.1002/adma.201302363

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      We report on caged Pt nanoclusters that are able to exert tumor-inside activation for anticancer chemotherapeutics and to minimize systemic toxicity. By shrinking the Pt size to 1 nm, it possesses corrodibility for dissolution in weakly acidic organelles to release toxic Pt ions. The therapeutic effect in exerting tumor-inside activation is confirmed in vivo by post-modifying a pH-cleavable PEG corona and mixing it with a tumor-homing peptide for tumour suppression.

  9. Frontispiece

    1. Top of page
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    5. Masthead
    6. Contents
    7. Editorials
    8. Reviews
    9. Communications
    10. Frontispiece
    11. Communications
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      A Bi2WO6-Based Hybrid Photocatalyst with Broad Spectrum Photocatalytic Properties under UV, Visible, and Near-Infrared Irradiation (Adv. Mater. 36/2013) (page 5074)

      Jian Tian, Yuanhua Sang, Guangwei Yu, Huaidong Jiang, Xiaoning Mu and Hong Liu

      Version of Record online: 24 SEP 2013 | DOI: 10.1002/adma.201370230

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      By assembling Bi2WO6 nanosheets on TiO2 nanobelts, Bi2WO6-TiO2 nanobelt surface heterostructures with enhanced broad spectrum (UV, visible, and nearinfrared light) photocatalytic properties are constructed by Prof. Hong Liu and co-workers, on page 5075. Such nanomaterials have potential as a photofunctional material for waste-water cleaning utilizing natural solar light.

  10. Communications

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    1. A Bi2WO6-Based Hybrid Photocatalyst with Broad Spectrum Photocatalytic Properties under UV, Visible, and Near-Infrared Irradiation (pages 5075–5080)

      Jian Tian, Yuanhua Sang, Guangwei Yu, Huaidong Jiang, Xiaoning Mu and Hong Liu

      Version of Record online: 15 JUL 2013 | DOI: 10.1002/adma.201302014

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      Near-infrared active photocatalytic properties of Bi2WO6 nanosheets owing to the oxygen vacancies of the Bi2WO6 nanosheets are reported. The broad spectrum photocatalyst, Bi2WO6-TiO2 nanobelt heterostructures, are obtained by assembling Bi2WO6 nanocrystals on TiO2 nanobelts. The active light band of the novel hybrid photocatalyst with high photocatalytic activity covers full-spectrum solar light including the UV, visible, and near-infrared ranges.

    2. 3D Printing of Free Standing Liquid Metal Microstructures (pages 5081–5085)

      Collin Ladd, Ju-Hee So, John Muth and Michael D. Dickey

      Version of Record online: 4 JUL 2013 | DOI: 10.1002/adma.201301400

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      This paper describes a method to direct-write 3D liquid metal microcomponents at room temperature. The thin oxide layer on the surface of the metal allows the formation of mechanically stable structures strong enough to stand against gravity and the large surface tension of the liquid. The method is capable of printing wires, arrays of spheres, arches, and interconnects.

    3. Enhanced Thermoelectric Properties of Pb-doped BiCuSeO Ceramics (pages 5086–5090)

      Jin-Le Lan, Yao-Chun Liu, Bin Zhan, Yuan-Hua Lin, Boping Zhang, Xun Yuan, Wenqing Zhang, Wei Xu and C.-W. Nan

      Version of Record online: 30 JUL 2013 | DOI: 10.1002/adma.201301675

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      A high-performance thermoelectric oxyselenide BiCuSeO ceramic with ZT > 1.1 at 823 K and higher average ZT value (ZTave ≈0.8) is obtained. The heavy doping element and nanostructures can effectively tune its electronic structure, hole concentration, and thermal conductivity, resulting in substantially enhanced mobility, power factor, and thus ZT value. This work provides a path to high-performance thermoelectric ceramics.

    4. Freestanding Mesoporous VN/CNT Hybrid Electrodes for Flexible All-Solid-State Supercapacitors (pages 5091–5097)

      Xu Xiao, Xiang Peng, Huanyu Jin, Tianqi Li, Chengcheng Zhang, Biao Gao, Bin Hu, Kaifu Huo and Jun Zhou

      Version of Record online: 4 JUL 2013 | DOI: 10.1002/adma.201301465

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      High-performance all-solid-state supercapacitors (SCs) are fabricated based on thin, lightweight, and flexible freestanding MVNN/CNT hybrid electrodes. The device shows a high volume capacitance of 7.9 F/cm3, volume energy and power density of 0.54 mWh/cm3 and 0.4 W/cm3 at a current density of 0.025 A/cm3. By being highly flexible, environmentally friendly, and easily connectable in series and parallel, the all-solid-state SCs promise potential applications in portable/wearable electronics.

    5. The Memristive Properties of a Single VO2 Nanowire with Switching Controlled by Self-Heating (pages 5098–5103)

      Sung-Hwan Bae, Sangmin Lee, Hyun Koo, Long Lin, Bong Hyun Jo, Chan Park and Zhong Lin Wang

      Version of Record online: 2 AUG 2013 | DOI: 10.1002/adma.201302511

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      A two-terminal memristor memory based on a single VO2 nanowire is reported that can not only provide switchable resistances in a large range of about four orders of magnitude but can also maintain the resistances by a low bias voltage. The phase transition of the single VO2 nanowire was driven by the bias voltage of 0.34 V without using any heat source. The memristive behavior of the single VO2 nanowire was confirmed by observing the switching and non-volatile properties of resistances when voltage pulses and low bias voltage were applied, respectively. Furthermore, multiple retainable resistances in a large range of about four orders of magnitude can be utilized by controlling the number and the amount of voltage pulses under the low bias voltage. This is a key step towards the development of new low-power and two-terminal memory devices for next-generation non-volatile memories.

    6. Restoration of Superhydrophobicity in Crushed Polymer Films by Treatment with Water: Self-Healing and Recovery of Damaged Topographic Features Aided by an Unlikely Source (pages 5104–5108)

      Uttam Manna and David M. Lynn

      Version of Record online: 13 AUG 2013 | DOI: 10.1002/adma.201302217

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      The crushing of superhydrophobic polymer multilayers destroys micro/nanoscale topographic features critical for the maintenance of superhydrophobicity. We demonstrate that these surface features can be recovered, and that superhydrophobicity can be fully restored, by treatment of damaged films with liquid water. These polymer-based films can also sustain other forms of severe abuse without loss of superhydrophobicity. This combination of features addresses several important practical issues associated with the durability of artificial superhydrophobic surfaces.

    7. Aligned Carbon Nanotube-Silicon Sheets: A Novel Nano-architecture for Flexible Lithium Ion Battery Electrodes (pages 5109–5114)

      Kun Fu, Ozkan Yildiz, Hardik Bhanushali, Yongxin Wang, Kelly Stano, Leigang Xue, Xiangwu Zhang and Philip D. Bradford

      Version of Record online: 1 AUG 2013 | DOI: 10.1002/adma.201301920

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      Aligned carbon nanotube sheets provide an engineered scaffold for the deposition of a silicon active material for lithium ion battery anodes. The sheets are low-density, allowing uniform deposition of silicon thin films while the alignment allows unconstrained volumetric expansion of the silicon, facilitating stable cycling performance. The flat sheet morphology is desirable for battery construction.

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