Advanced Materials

Cover image for Vol. 25 Issue 4

January 25, 2013

Volume 25, Issue 4

Pages 493–639

  1. Cover Picture

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      Graphene: Super Gas Barrier and Selectivity of Graphene Oxide-Polymer Multilayer Thin Films (Adv. Mater. 4/2013) (page 493)

      You-Hao Yang, Laura Bolling, Morgan A. Priolo and Jaime C. Grunlan

      Article first published online: 18 JAN 2013 | DOI: 10.1002/adma.201370020

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      A flexible and transparent gas barrier remains a key challenge for high performance food and flexible electronics packaging. A transparent nanobrick wall of graphene oxide nanoplatelets and polyethylenimine (< 100 nm thick), deposited using the layer-by-layer assembly technique, reduces the oxygen permeability of PET film by orders of magnitude, as reported by Jaime C. Grunlan and co-workers on page 503. The cover image, by graphic designer David Feagan, conceptually highlights the ability of this nanobrick wall to block the passage of oxygen.

  2. Inside Front Cover

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      Stimuli Responsive Materials: Biopsy with Thermally-Responsive Untethered Microtools (Adv. Mater. 4/2013) (page 494)

      Evin Gultepe, Jatinder S. Randhawa, Sachin Kadam, Sumitaka Yamanaka, Florin M. Selaru, Eun J. Shin, Anthony N. Kalloo and David H. Gracias

      Article first published online: 18 JAN 2013 | DOI: 10.1002/adma.201370021

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      The first biopsy with untethered, sub-millimeter scale grippers is described by David H. Gracias and co-workers on page 514. The cover shows the retrieval of cells from the bile duct of a live pig using thermally responsive tether-free m-grippers. The retrieved tissue was of a high enough quality and quantity to enable both histological and molecular biology analyses which forms the basis of diagnostics. Image created by Martin Rietveld.

  3. Back Cover

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      Lithium-Ion Batteries: Highly Conductive and Strain-Released Hybrid Multilayer Ge/Ti Nanomembranes with Enhanced Lithium-Ion-Storage Capability (Adv. Mater. 4/2013) (page 644)

      Chenglin Yan, Wang Xi, Wenping Si, Junwen Deng and Oliver G. Schmidt

      Article first published online: 18 JAN 2013 | DOI: 10.1002/adma.201370022

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      Chenglin Yan, Wang Xi, and co-workers report on page 539 a novel hybrid tubular structure composed of multilayer Ge and Ti nanomembranes with superior reversible capacity by a strain released method. The high conductivity, fast lithium ion diffusion and good volume tolerance of the material are evaluated by single tube devices. The proof of concept in this work paves the way for integration of microbatteries for chip-scale applications.

  4. Masthead

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    1. Masthead: (Adv. Mater. 4/2013)

      Article first published online: 18 JAN 2013 | DOI: 10.1002/adma.201370023

  5. Contents

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    1. Contents: (Adv. Mater. 4/2013) (pages 495–502)

      Article first published online: 18 JAN 2013 | DOI: 10.1002/adma.201370024

  6. Correction

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  7. Communications

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    1. Super Gas Barrier and Selectivity of Graphene Oxide-Polymer Multilayer Thin Films (pages 503–508)

      You-Hao Yang, Laura Bolling, Morgan A. Priolo and Jaime C. Grunlan

      Article first published online: 1 OCT 2012 | DOI: 10.1002/adma.201202951

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      Super gas barrier thin films, fabricated with layer-by-layer assembly of polyethylenimine and graphene oxide, exhibit significantly reduced oxygen and carbon dioxide transmission rates. This thin film's nanobrick wall structure also provides high gas selectivity for hydrogen.

    2. Electric Control of the Giant Rashba Effect in Bulk GeTe (pages 509–513)

      Domenico Di Sante, Paolo Barone, Riccardo Bertacco and Silvia Picozzi

      Article first published online: 16 OCT 2012 | DOI: 10.1002/adma.201203199

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      Relativistic effects, including the Rashba effect, are increasingly seen as key ingredients in spintronics. A link between Rashba physics and the field of ferroelectrics is established by predicting giant Rashba spin-splitting in bulk GeTe (see the Figure showing the band-structure as well as in-plane and out- of-plane spin polarization for a constant energy cut).

      Corrected by:

      Correction: Correction: Electric Control of the Giant Rashba Effect in Bulk GeTe

      Vol. 25, Issue 27, 3625–3626, Article first published online: 12 JUL 2013

    3. Biopsy with Thermally-Responsive Untethered Microtools (pages 514–519)

      Evin Gultepe, Jatinder S. Randhawa, Sachin Kadam, Sumitaka Yamanaka, Florin M. Selaru, Eun J. Shin, Anthony N. Kalloo and David H. Gracias

      Article first published online: 9 OCT 2012 | DOI: 10.1002/adma.201203348

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      Thermally activated, untethered microgrippers can reach narrow conduits in the body and be used to excise tissue for diagnostic analyses. As depicted in the figure, the feasibility of an in vivo biopsy of the porcine bile duct using untethered microgrippers is demonstrated.

    4. Biomimetic Reflectors Fabricated Using Self-Organising, Self-Aligning Liquid Crystal Polymers (pages 520–523)

      Ariosto Matranga, Sarwat Baig, Jessica Boland, Christopher Newton, Timothy Taphouse, Gary Wells and Stephen Kitson

      Article first published online: 8 NOV 2012 | DOI: 10.1002/adma.201203182

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      The photograph shows a polymer reflector that mimics the colour and underlying molecular structure of a golden beetle. It is formed from self-organizing layers of photopolymerised liquid crystal. These require an aligning layer, but we show that a layer of the material can be used as to self-align subsequent coatings, enabling the construction of complex structures by sequential coating of engineered materials.

    5. Effect of Selenophene in a DPP Copolymer Incorporating a Vinyl Group for High-Performance Organic Field-Effect Transistors (pages 524–528)

      Il Kang, Tae Kyu An, Jung-a Hong, Hui-Jun Yun, Ran Kim, Dae Sung Chung, Chan Eon Park, Yun-Hi Kim and Soon-Ki Kwon

      Article first published online: 2 NOV 2012 | DOI: 10.1002/adma.201202867

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      A new polymeric semiconductor, PDPPDTSE, is reported which is composed of a diketopyrrolopyrrole moiety and selenophenylene vinylene selenophene, with a high field-effect mobility achieved through intermolecular donor–acceptor interactions. The field-effect mobility of OFET devices based on PDPPDTSE by spin-casting is 4.97 cm2 V−1 s−1, which is higher than predecessor polymeric semiconductors.

    6. Antibacterial Strategies from the Sea: Polymer-Bound Cl-Catechols for Prevention of Biofilm Formation (pages 529–533)

      Luis García-Fernández, Jiaxi Cui, Cristina Serrano, Zahid Shafiq, Radu A. Gropeanu, Verónica San Miguel, Jagoba Iturri Ramos, Miao Wang, Gunther K. Auernhammer, Sandra Ritz, Ali A. Golriz, Rüdiger Berger, Manfred Wagner and Aránzazu del Campo

      Article first published online: 9 NOV 2012 | DOI: 10.1002/adma.201203362

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      Inspired by the amino acid 2-chloro-4,5-dihydroxyphenylalanine (Cl-DOPA), present in the composition of the proteinaceous glue of the sandcastle worm Phragmatopoma californica, a simple strategy is presented to confer antifouling properties to polymer surfaces using (but not releasing) a bioinspired biocide. Cl-Dopamine is used to functionalize polymer materials and hydrogel films easily, to prevent biofilm formation on them.

    7. A Single-Device Universal Logic Gate Based on a Magnetically Enhanced Memristor (pages 534–538)

      Mirko Prezioso, Alberto Riminucci, Patrizio Graziosi, Ilaria Bergenti, Rajib Rakshit, Raimondo Cecchini, Anna Vianelli, Francesco Borgatti, Norman Haag, M. Willis, Alan J. Drew, William P. Gillin and Valentin A. Dediu

      Article first published online: 23 OCT 2012 | DOI: 10.1002/adma.201202031

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      Memristors are one of the most promising candidates for future information and communications technology (ICT) architectures. Two experimental proofs of concept are presented based on the intermixing of spintronic and memristive effects into a single device, a magnetically enhanced memristor (MEM). By exploiting the interaction between the memristance and the giant magnetoresistance (GMR), a universal implication (IMP) logic gate based on a single MEM device is realized.

    8. Highly Conductive and Strain-Released Hybrid Multilayer Ge/Ti Nanomembranes with Enhanced Lithium-Ion-Storage Capability (pages 539–544)

      Chenglin Yan, Wang Xi, Wenping Si, Junwen Deng and Oliver G. Schmidt

      Article first published online: 26 OCT 2012 | DOI: 10.1002/adma.201203458

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      Highly conductive and hybridized microtubes relying on strain-released ultrathin Ti/Ge bilayer nanomembranes are reported. These hybrid multilayer microtubes show a remarkably enhanced reversible capacity up to 1495 mA h g−1 with a high first-cycle Coulombic efficiency of 85%, and demonstrate an excellent capacity of ≈930 mA h g−1 after 100 cycles.

    9. Fragmentation of Poly(lactic acid) Nanosheets and Patchwork Treatment for Burn Wounds (pages 545–551)

      Yosuke Okamura, Koki Kabata, Manabu Kinoshita, Hiromi Miyazaki, Akihiro Saito, Toshinori Fujie, Shinya Ohtsubo, Daizoh Saitoh and Shinji Takeoka

      Article first published online: 1 NOV 2012 | DOI: 10.1002/adma.201202851

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      Freestanding poly(L-lactic acid) (PLLA) nanosheets are mass-produced by a simple combination of a spin-coating-assisted multi-layering process and a peeling technique. The resulting PLLA nanosheets are fragmented by homogenization and then reconstructed into a “patchwork” sheet on various surfaces without any adhesive reagents. The patchwork is shown to offer excellent protection against burn wound infection with Pseudomonas aeruginosa, and may therefore be an alternative to conventional burn therapy for prevention of infection.

    10. On-Demand Patterning of Nanostructured Pentacene Transistors by Scanning Thermal Lithography (pages 552–558)

      Joseph E. Shaw, Paul N. Stavrinou and Thomas D. Anthopoulos

      Article first published online: 9 NOV 2012 | DOI: 10.1002/adma.201202877

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      Thermal scanning lithography is used to pattern semiconducting nanoribbon-like pentacene structures with ultrahigh spatial resolution onto arbitrary substrates in air. The method allows control of the pentacene crystal growth direction and domain-size distribution. By combining these quasi-one-dimensional nanoribbon-like structures with conductive electrodes and a suitable gate dielectric, functional p-channel transistors are demonstrated.

    11. High-Mobility Field Effect Transistors Based on Supramolecular Charge Transfer Nanofibres (pages 559–564)

      Abhay A. Sagade, K. Venkata Rao, Umesha Mogera, Subi J. George, Ayan Datta and Giridhar U. Kulkarni

      Article first published online: 7 NOV 2012 | DOI: 10.1002/adma.201203926

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      Self-assembled charge transfer supramolecular nanofibres of coronene tetracarboxylate (CS) and dodecyl substituted unsymmetric viologen derivative (DMV) behave as active channel in field effect transistors exhibiting high mobility. These devices work in ambient conditions and can regenerate in the presence of a single drop of water.

  8. Frontispiece

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    1. Holographic Molecularly Imprinted Polymers for Label-Free Chemical Sensing (Adv. Mater. 4/2013) (page 565)

      Yannick Fuchs, Olivier Soppera, Andrew G. Mayes and Karsten Haupt

      Article first published online: 18 JAN 2013 | DOI: 10.1002/adma.201370025

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      A new material combining a molecularly imprinted polymer for specific analyte recognition, and a holographic structure for optochemical sensing is described by Karsten Haupt, Olivier Soppera, and co-workers on page 566. The material is obtained in one step through photo-polymerization with interfering laser beams, resulting in a holographic molecularly imprinted polymer film that is hierarchically structured at four length scales. Specific binding of the target analyte testosterone is measured by diffraction analysis.

  9. Communication

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    1. Holographic Molecularly Imprinted Polymers for Label-Free Chemical Sensing (pages 566–570)

      Yannick Fuchs, Olivier Soppera, Andrew G. Mayes and Karsten Haupt

      Article first published online: 18 OCT 2012 | DOI: 10.1002/adma.201203204

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      Holographic molecularly imprinted polymer films for the use in chemical sensors are obtained in one step through photopolymerization with interfering laser beams. This results in hierarchical structuring at four length scales: micrometer-scale patterning of millimeter- to centimeter- size polymer objects with holographic optical properties, exhibiting nanometer-scale porosity and specific molecular recognition properties at the molecular scale through self-assembly. Specific binding of the target analyte testosterone is measured by diffraction analysis.

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    1. Solution-Processed Fullerene-Based Organic Schottky Junction Devices for Large-Open-Circuit-Voltage Organic Solar Cells (Adv. Mater. 4/2013) (page 571)

      Bin Yang, Fawen Guo, Yongbo Yuan, Zhengguo Xiao, Yunzhang Lu, Qingfeng Dong and Jinsong Huang

      Article first published online: 18 JAN 2013 | DOI: 10.1002/adma.201370026

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      The Schottky-junction structure has been broadly applied in inorganic photovoltaic devices but has not yet been successfully applied in organic photovoltaic devices. Jinsong Huang and co-workers report on page 572 fullerene-based Schottky-junction devices that can output a much larger open-circuit voltage (∼0.95 V) than most bulk heterojunction (BHJ) organic photovoltaic devices. The efficiencies of the fullerene based Schottky-junction devices are shown to be larger than those of the state-of-the-art BHJ devices under certain conditions.

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    1. Solution-Processed Fullerene-Based Organic Schottky Junction Devices for Large-Open-Circuit-Voltage Organic Solar Cells (pages 572–577)

      Bin Yang, Fawen Guo, Yongbo Yuan, Zhengguo Xiao, Yunzhang Lu, Qingfeng Dong and Jinsong Huang

      Article first published online: 2 NOV 2012 | DOI: 10.1002/adma.201203080

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      A solution-processed fullerene-based organic Schottky junction photovoltaic device is fabricated to produce a large open circuit voltage, 0.85–0.95 V, which is higher than that of most organic bulk-heterojunction devices. A power conversion efficiency of 5% is achieved in fullerene-derivative [6,6]-phenyl-C71-butyric acid methylester-based Schottky junction devices.

    2. Soft Conductive Elastomer Materials for Stretchable Electronics and Voltage Controlled Artificial Muscles (pages 578–583)

      Hristiyan Stoyanov, Matthias Kollosche, Sebastian Risse, Rémi Waché and Guggi Kofod

      Article first published online: 23 OCT 2012 | DOI: 10.1002/adma.201202728

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      Block copolymer elastomer conductors (BEC) are mixtures of block copolymers grafted with conducting polymers, which are found to support very large strains, while retaining a high level of conductivity. These novel materials may find use in stretchable electronics. The use of BEC is demonstrated in a capacitive strain sensor and in an artificial muscle of the dielectric elastomer actuator type, supporting more than 100% actuation strain and capacity strain sensitivity up to 300%.

    3. CO2-Responsive “Smart” Single-Walled Carbon Nanotubes (pages 584–590)

      Zanru Guo, Yujun Feng, Shuai He, Meizhen Qu, Honglin Chen, Hanbin Liu, Yufeng Wu and Yu Wang

      Article first published online: 7 NOV 2012 | DOI: 10.1002/adma.201202991

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      A new type of “smart” single-walled carbon nanotubes is created by wrapping a pyrene-labeled CO2-responsive polymer via π–π stacking. The polymer/SWNT hybrids not only undergo a hydrophobic–hydrophilic transition upon CO2 stimulus of CO2 in a mixed solvent, but also exhibit switchable dispersion/aggregation states upon the alternate bubbling of CO2 and N2 in pure water.

    4. Highly Compression-Tolerant Supercapacitor Based on Polypyrrole-mediated Graphene Foam Electrodes (pages 591–595)

      Yang Zhao, Jia Liu, Yue Hu, Huhu Cheng, Chuangang Hu, Changcheng Jiang, Lan Jiang, Anyuan Cao and Liangti Qu

      Article first published online: 18 OCT 2012 | DOI: 10.1002/adma.201203578

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      Deformation-tolerant devices are vital for the development of high-tech electronics of unconventional forms. In this study, a highly compressible supercapacitor has been fabricated by using newly developed polypyrrole-mediated graphene foam as electrode. The assembled supercapacitor performs based on the unique and robust foam electrodes achieves superb compression tolerance without significant variation of capacitances under long-term compressive loading and unloading processes.

    5. High Quantum Efficiency in Solution and Vacuum Processed Blue Phosphorescent Organic Light Emitting Diodes Using a Novel Benzofuropyridine-Based Bipolar Host Material (pages 596–600)

      Chil Won Lee and Jun Yeob Lee

      Article first published online: 8 NOV 2012 | DOI: 10.1002/adma.201203180

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      High quantum efficiency in solution and vacuum processed blue phosphorescent organic light emitting diodes are achieved using a new benzofuropyridine based bipolar host material. High quantum efficiencies of 18.0% and 23.0% are obtained in soluble and vacuum evaporable blue devices.

    6. Light Induced Nanowire Assembly: The Electrostatic Alignment of Semiconductor Nanowires into Functional Macroscopic Yarns (pages 601–605)

      Nattasamon Petchsang, Matthew P. McDonald, Louise E. Sinks and Masaru Kuno

      Article first published online: 2 OCT 2012 | DOI: 10.1002/adma.201202722

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      The electrostatic alignment and directed assembly of semiconductor nanowires into macroscopic, centimeter-long yarns is demonstrated. Different morphologies can be produced, including longitudinally segmented/graded yarns or mixed composition fibers. Nanowire yarns display long range photoconductivities and open up exciting opportunities for potential use in future nanowire-based textiles or in solar photovoltaics.

    7. An Ion-Induced Low-Oil-Adhesion Organic/Inorganic Hybrid Film for Stable Superoleophobicity in Seawater (pages 606–611)

      Li-Ping Xu, Jing Zhao, Bin Su, Xueli Liu, Jitao Peng, Yibiao Liu, Hongliang Liu, Gao Yang, Lei Jiang, Yongqiang Wen, Xueji Zhang and Shutao Wang

      Article first published online: 7 NOV 2012 | DOI: 10.1002/adma.201203461

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      Superoleophobicity under seawater: An ion-induced low-oil-adhesion film with underwater superoleophobicity is prepared by a typical layer-by-layer (LBL) method. Under an artificial marine environment with high ion-strength, the prepared polyelectrolytes/AuNPs hybrid film becomes rougher and possesses a higher water ratio, which in turn endows the film with superoleophobicity and low underwater oil adhesion. The as-prepared film shows excellent environmental stability in artificial seawater. This study provides a new strategy for controlling the self-cleaning property and accelerating the development of stable underwater superoleophobic films.

    8. On the Origin of Chirality in Nanoplasmonic Gyroid Metamaterials (pages 612–617)

      Sang Soon Oh, Angela Demetriadou, Sebastian Wuestner and Ortwin Hess

      Article first published online: 26 OCT 2012 | DOI: 10.1002/adma.201202788

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      Metallic single gyroids, a new class of self-assembled nanoplasmonic metamaterials, are analyzed on the basis of a tri-helical metamaterial model. The physical mechanisms underlying the chiral optical behavior of the nanoplasmonic single gyroid are identified and it is shown that the optical chirality in this metallic structure is primarily determined by structural chirality and the connectivity of helices along the main cubic axes.

    9. First-Principles Calculations of Lithium-Ion Migration at a Coherent Grain Boundary in a Cathode Material, LiCoO2 (pages 618–622)

      Hiroki Moriwake, Akihide Kuwabara, Craig A. J. Fisher, Rong Huang, Taro Hitosugi, Yumi H. Ikuhara, Hideki Oki and Yuichi Ikuhara

      Article first published online: 2 NOV 2012 | DOI: 10.1002/adma.201202805

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      Results of theoretical calculations are reported, examining the effect of a coherent twin boundary on the electrical properties of LiCoO2. This study suggests that internal interfaces in LiCoO2 strongly affect the battery voltage, battery capacity, and power density of this material, which is of particular concern if it is used in all-solid-state Li-ion batteries.

    10. Flexible and Stretchable Polymers with Embedded Magnetic Nanostructures (pages 623–629)

      Marco Donolato, Christopher Tollan, Jose Maria Porro, Andreas Berger and Paolo Vavassori

      Article first published online: 26 OCT 2012 | DOI: 10.1002/adma.201203072

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      A novel pathway is presented to transfer and embed functional patterned magnetic nanostructures into flexible and stretchable polymeric membranes. The geometrical and magnetic properties are maintained through the process, realized even directly inside a microfluidic channel. These results pave the way to the realization of smart biomedical systems and devices based on the integration of magnetic nanostructures into new classes of substrates.

    11. Single-Step Formation of Graphene on Dielectric Surfaces (pages 630–634)

      Wei Xiong, Yun Shen Zhou, Li Jia Jiang, Amitabha Sarkar, Masoud Mahjouri-Samani, Zhi Qiang Xie, Yang Gao, Natale Joseph Ianno, Lan Jiang and Yong Feng Lu

      Article first published online: 8 NOV 2012 | DOI: 10.1002/adma.201202840

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      The direct formation of graphene on various dielectric surfaces is successful via a single-step rapid thermal processing (RTP) of substrates coated with amorphous carbon (C) and nickel (Ni) thin films. High-quality graphene is obtained uniformly on the whole surface of wafers with a controlled number of graphene layers. The monolayer graphene exhibits a low sheet resistance and a high optical transmittance in the visible range.

    12. MFU-4 – A Metal-Organic Framework for Highly Effective H2/D2 Separation (pages 635–639)

      Julia Teufel, Hyunchul Oh, Michael Hirscher, Mohammad Wahiduzzaman, Lyuben Zhechkov, Agnieszka Kuc, Thomas Heine, Dmytro Denysenko and Dirk Volkmer

      Article first published online: 8 NOV 2012 | DOI: 10.1002/adma.201203383

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      The metal-organic framework, MFU-4, possessing small cavities and apertures, is exploited for quantum sieving of hydrogen isotopes. Quantum mechanically, a molecule confined in a small cavity shows an increase in effective size depending on the particle mass, which leads to a faster deuterium adsorption from a H2/D2 isotope mixture.

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