Advanced Functional Materials

Cover image for Advanced Functional Materials

July 2, 2014

Volume 24, Issue 25

Pages 3837–4014

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      Metal–Organic Frameworks: Solvent-Mediated Reconstruction of the Metal–Organic Framework HKUST-1 (Cu3(BTC)2) (Adv. Funct. Mater. 25/2014) (page 3837)

      Gerardo Majano, Oliver Martin, Markus Hammes, Stef Smeets, Christian Baerlocher and Javier Pérez-Ramírez

      Version of Record online: 27 JUN 2014 | DOI: 10.1002/adfm.201470162

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      On page 3855, J. Pérez-Ramírez and co-workers demonstrate the reconstruction of water-degraded HKUST-1, one of the most studied metal–organic frameworks, by means of facile, one-step, solvent-assisted treatments. This regeneration process is symbolized by the phoenix, the long-lived bird from Greek mythology that obtains new life by arising from the ashes of its predecessor. Marcel Reich (marcelreich.com) is acknowledged for creating the lovely cover artwork.

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      Water Treatment: Sponge-Templated Preparation of High Surface Area Graphene with Ultrahigh Capacitive Deionization Performance (Adv. Funct. Mater. 25/2014) (page 3838)

      Zhi-Yu Yang, Lin-Jian Jin, Guo-Qian Lu, Qing-Qing Xiao, Yu-Xia Zhang, Lin Jing, Xiao-Xue Zhang, Yi-Ming Yan and Ke-Ning Sun

      Version of Record online: 27 JUN 2014 | DOI: 10.1002/adfm.201470163

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      Capacitive deionization (CDI) is a competent water desalination technique offering an appropriate route to obtain clean water. On page 3917, Y.-M. Yan, K.-N. Sun and co-workers design and prepare a 3D-structured, graphene-based electrode using sponge (polyurethane, PU) as a template. The electrode possesses a large surface area, wide pore size distribution from nanopores to micropores, and low internal resistance, therefore exhibiting a remarkable electrosorptive capacity of 4.95 mg g−1 and a desorption rate of 25 min.

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      Masthead: (Adv. Funct. Mater. 25/2014)

      Version of Record online: 27 JUN 2014 | DOI: 10.1002/adfm.201470167

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      Biomedical Sensors: Materials and Designs for Wireless Epidermal Sensors of Hydration and Strain (Adv. Funct. Mater. 25/2014) (page 3845)

      Xian Huang, Yuhao Liu, Huanyu Cheng, Woo-Jung Shin, Jonathan A. Fan, Zhuangjian Liu, Ching-Jui Lu, Gil-Woo Kong, Kaile Chen, Dwipayan Patnaik, Sang-Heon Lee, Sami Hage-Ali, Yonggang Huang and John A. Rogers

      Version of Record online: 27 JUN 2014 | DOI: 10.1002/adfm.201470165

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      J. A. Rogers and co-workers present an ultrathin, skin-like device for the wireless measurement of the dielectric properties and deformations of the skin. The construction exploits LC resonators with capacitive electrodes that are responsive to skin properties. The material designs offer the potential for compact, epidermal, wireless systems in applications ranging from dermatology and cosmetology to health/wellness monitoring. The image shows the application of lotion onto a skin region that supports a representative device.

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    1. Materials and Designs for Wireless Epidermal Sensors of Hydration and Strain (pages 3846–3854)

      Xian Huang, Yuhao Liu, Huanyu Cheng, Woo-Jung Shin, Jonathan A. Fan, Zhuangjian Liu, Ching-Jui Lu, Gil-Woo Kong, Kaile Chen, Dwipayan Patnaik, Sang-Heon Lee, Sami Hage-Ali, Yonggang Huang and John A. Rogers

      Version of Record online: 2 MAR 2014 | DOI: 10.1002/adfm.201303886

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      An ultrathin, stretchable device capable of soft lamination onto the surface of the skin for wireless measurements of dielectric and surface strain properties is presented. The device uses LC resonators with capacitive electrodes to qualify the skin properties, and is capable of conformal and spontaneous skin integration.

    2. Solvent-Mediated Reconstruction of the Metal–Organic Framework HKUST-1 (Cu3(BTC)2) (pages 3855–3865)

      Gerardo Majano, Oliver Martin, Markus Hammes, Stef Smeets, Christian Baerlocher and Javier Pérez-Ramírez

      Version of Record online: 20 FEB 2014 | DOI: 10.1002/adfm.201303678

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      Reconstruction of water-degraded HKUST-1 back into the original material is demonstrated through solvent-assisted liquid- and gas-phase treatments. Up to 94% poro­sity and 85% CO2 sorption capacity could be recovered from a completely collapsed metal–organic framework. The degradation routes affect the physicochemical features and the kinetics of reconstruction. This method opens promising directions for the large-scale application of these materials.

    3. Biocompatible Electromechanical Actuators Composed of Silk-Conducting Polymer Composites (pages 3866–3873)

      Isabella S. Romero, Nathan P. Bradshaw, Jesse D. Larson, Sean Y. Severt, Sandra J. Roberts, Morgan L. Schiller, Janelle M. Leger and Amanda R. Murphy

      Version of Record online: 20 MAR 2014 | DOI: 10.1002/adfm.201303292

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      Durable, biocompatible materials capable of controlled movements are sought after for a variety of drug delivery, surgical, and tissue engineering applications. Methods to synthesize films composed of an interpenetrating network of the biopolymer silk fibroin and poly(pyrrole) are described, and the ability of these materials to function as electromechanical actuators in a biologically relevant environment are demonstrated.

    4. Highly Efficient Multifunctional Supramolecular Gene Carrier System Self-Assembled from Redox-Sensitive and Zwitterionic Polymer Blocks (pages 3874–3884)

      Yuting Wen, Zhongxing Zhang and Jun Li

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/adfm.201303687

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      A convenient supramolecular strategy is demonstrated for building a highly efficient multifunctional gene carrier system. The system is self–assembled and integrated from two polymeric building blocks via host-guest interaction between β-cyclodextrin and adamantyl moieties, possessing the functions of disulfide bond based reduction-responsive degradation, and zwitterionic phosphorylcholine based extracellular stabilization and favorable cellular uptake.

    5. Dielectric Relaxation Processes, Electronic Structure, and Band Gap Engineering of MFU-4-type Metal-Organic Frameworks: Towards a Rational Design of Semiconducting Microporous Materials (pages 3885–3896)

      Pit Sippel, Dmytro Denysenko, Alois Loidl, Peter Lunkenheimer, German Sastre and Dirk Volkmer

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/adfm.201400083

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      Electrical properties of MFU-4 and Co-MFU-4 metal-organic frameworks are investigated by temperature-dependent broad-band dielectric and optical spectroscopy. Density functional theory calculations performed for framework and cluster model compounds give a detailed picture of the frameworks' electronic structures and confirm experimental band gap values. The combined results enable a systematic engineering of MFU-4-type semiconducting microporous materials.

    6. Highly Bright and Compact Alloyed Quantum Rods with Near Infrared Emitting: a Potential Multifunctional Nanoplatform for Multimodal Imaging In Vivo (pages 3897–3905)

      Duyang Gao, Pengfei Zhang, Zonghai Sheng, Dehong Hu, Ping Gong, Chi Chen, Qian Wan, Guanhui Gao and Lintao Cai

      Version of Record online: 1 APR 2014 | DOI: 10.1002/adfm.201304225

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      Near-infrared quantum rods (QRs) with tunable emission and aspect ratio are synthesized as nano-platforms for engineering multifunctional nanoprobes. The as-prepared QRs exhibit great stability and little nonspecific binding. Paramagnetic gadolinium ions can be easily assembled on the QRs to produce multi­functional contrast agents for in vivo lymph node fluorescence and magnetic resonance dual-modal imaging. It provides a general method for designing rod-shape multifunctional nanostructure.

  7. Frontispiece

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      Organic Electronics: Spatial Mapping of Morphology and Electronic Properties of Air-Printed Pentacene Thin Films (Adv. Funct. Mater. 25/2014) (page 3906)

      Shaurjo Biswas, Yongsoo Yang, Christian M. Schlepütz, Nadav Geva, Randall L. Headrick, Ron Pindak, Roy Clarke and Max Shtein

      Version of Record online: 27 JUN 2014 | DOI: 10.1002/adfm.201470166

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      M. Shtein and co-workers use guard flow-enhanced organic vapor jet printing for the additive patterning of pentacene thin fifilms in air, and perform in situ X-ray diffraction to relate process variables, oxidation, structural defects, and electronic properties in thin-film transistor applications. The process structureproperty relationship is quantifified, and the field-effect mobility is extrapolated based on the processing conditions. The schematic shown represents the GF-OVJP process with in situ diffraction and contacts for TFT measurements.

  8. Full Papers

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    1. Spatial Mapping of Morphology and Electronic Properties of Air-Printed Pentacene Thin Films (pages 3907–3916)

      Shaurjo Biswas, Yongsoo Yang, Christian M. Schlepütz, Nadav Geva, Randall L. Headrick, Ron Pindak, Roy Clarke and Max Shtein

      Version of Record online: 3 MAR 2014 | DOI: 10.1002/adfm.201303983

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      Guard flow-enhanced organic vapor jet printing technique enables additive patterning of organic thin films in air, without the use of solvents. During deposition in air, ambient oxygen and moisture are incorporated in the film's “wing” region. This work relates the degree of air exposure to pentacene film's morphology and electronic properties via synchrotron X-ray diffraction and thin-film transistor measurements, respectively.

    2. Sponge-Templated Preparation of High Surface Area Graphene with Ultrahigh Capacitive Deionization Performance (pages 3917–3925)

      Zhi-Yu Yang, Lin-Jian Jin, Guo-Qian Lu, Qing-Qing Xiao, Yu-Xia Zhang, Lin Jing, Xiao-Xue Zhang, Yi-Ming Yan and Ke-Ning Sun

      Version of Record online: 4 MAR 2014 | DOI: 10.1002/adfm.201304091

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      Sponge-templated graphene sheets (STGS) with high specific surface area, wide pore size distribution, and low internal resistance are prepared through a simple annealing method. The as-prepared STGS exhibits promising CDI performance with an ultrahigh electrosorptive capacity of 4.95 mg g−1 and fast desorption rate of 25 min.

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      Magnetite Crystal Orientation in Magnetosome Chains (pages 3926–3932)

      André Körnig, Michael Winklhofer, Jens Baumgartner, Teresa Perez Gonzalez, Peter Fratzl and Damien Faivre

      Version of Record online: 10 MAR 2014 | DOI: 10.1002/adfm.201303737

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      2D-X-ray diffraction analyses of aligned magnetotactic bacteria reveal [111] and [100] fiber textures along the chain direction as a function of cell species. The [100] axis appears unfavorable because it represents a magnetic hard axis in magnetite. Calculations show how this can be turned into an effective easy axis for a given particle elongation.

    4. A Novel Wound Dressing Based on Ag/Graphene Polymer Hydrogel: Effectively Kill Bacteria and Accelerate Wound Healing (pages 3933–3943)

      Zengjie Fan, Bin Liu, Jinqing Wang, Songying Zhang, Qianqian Lin, Peiwei Gong, Limin Ma and Shengrong Yang

      Version of Record online: 17 MAR 2014 | DOI: 10.1002/adfm.201304202

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      A novel application range of graphene hydrogel in wound dressing is exploited. The hydrogels are composed of Ag–graphene composite, AA, and BIS. When the mass ratio of Ag to graphene is 5:1, the hydrogel (Ag5G1) shows strong antibacterial activity, large swelling ratio, excellent biocompatibility, and good extensibility, and it can significantly accelerate the healing rate of artificial wounds in rats.

    5. Synthesis, Structure Transformation, and Electrochemical Properties of Li2MgSi as a Novel Anode for Li-lon Batteries (pages 3944–3952)

      Yongfeng Liu, Ruijun Ma, Yanping He, Mingxia Gao and Hongge Pan

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/adfm.201304287

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      A novel hexagonal Li2MgSi is successfully synthesized through a hydrogen-driven chemical reaction technique, which exhibits significantly improved cycling stability with respect to that of Mg2Si as an anode material for Li-ion batteries. Ball milling induces a polymorphic transformation of Li2MgSi from the hexagonal phase to the cubic phase and further improves the electrochemical lithium storage properties.

    6. Nitrogen-Doped Carbon Networks for High Energy Density Supercapacitors Derived from Polyaniline Coated Bacterial Cellulose (pages 3953–3961)

      Conglai Long, Dongping Qi, Tong Wei, Jun Yan, Lili Jiang and Zhuangjun Fan

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/adfm.201304269

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      An asymmetric supercapacitor based on nitrogen-doped porous carbon networks and 3D flower-like MnO2 as the negative and positive electrode materials, respectively, exhibits a considerably high energy density of 63 Wh kg−1 and an excellent cycling performance with 92% specific capacitance retention after 5000 cycles. Those results offer a low-cost, eco-friendly design of electrode materials for high-performance supercapacitors.

    7. Scaling Behavior of Resistive Switching in Epitaxial Bismuth Ferrite Heterostructures (pages 3962–3969)

      Abhimanyu Rana, Haidong Lu, Kashinath Bogle, Qi Zhang, Rama Vasudevan, Vishal Thakare, Alexei Gruverman, Satishchandra Ogale and Nagarajan Valanoor

      Version of Record online: 18 MAR 2014 | DOI: 10.1002/adfm.201400110

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      Resistive switching of (001) epitaxial multi­ferroic BiFeO3/La0.67Sr0.33MnO3/SrTiO3 heterostructures is investigated for varying lengths scales in both the thickness and lateral directions. Macroscale current–voltage analyses in conjunction with local conduction atomic force microscopy reveal that whilst both the local and global resistive states are strongly driven by polarization direction, the type of conduction mechanism is different for each distinct thickness regime.

    8. Engineering of Mixed Host for High External Quantum Efficiency above 25% in Green Thermally Activated Delayed Fluorescence Device (pages 3970–3977)

      Bo Seong Kim and Jun Yeob Lee

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/adfm.201303730

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      High quantum efficiency above 25% in thermally activated delayed fluorescence device is achieved using mixed hosts without any exciplex formation between host materials. A combination of mCP and BmPyPb is effective to improve the quantum efficiency up to 28.6%.

    9. Electron Barrier Formation at the Organic-Back Contact Interface is the First Step in Thermal Degradation of Polymer Solar Cells (pages 3978–3985)

      I. T. Sachs-Quintana, Thomas Heumüller, William R. Mateker, Darian E. Orozco, Rongrong Cheacharoen, Sean Sweetnam, Christoph J. Brabec and Michael D. McGehee

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/adfm.201304166

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      Thermal degradation near operating temperatures occurs at the metal-organic interface if the polymer T g is near the operating temperature. The degradation is reversed by peeling off and reapplying the metal electrode. X-ray photoelectron spectroscopy measurements reveal a larger amount of polymer adheres to electrodes peeled from aged devices than electrodes peeled from fresh devices. Using an inverted device suppresses degradation.

    10. Optimization of the Power Conversion Efficiency of Room Temperature-Fabricated Polymer Solar Cells Utilizing Solution Processed Tungsten Oxide and Conjugated Polyelectrolyte as Electrode Interlayer (pages 3986–3995)

      Lie Chen, Chen Xie and Yiwang Chen

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/adfm.201304256

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      Solution processed polymer solar cell with outstanding efficiency and stability is fabricated at room temperature. Spin-coating conjugated polyelectrolyte-ionic liquid-crystal complex at cathode and tungsten oxide together with ter(ethyleneoxide)-substituted PBDTT-TT-TEG at anode achieves optimized efficiency 7.8%, which further increases to 8.5% after inserting ZnO as cathode interlayer. This is best PCE for PBDTTT-C-T:PC70BM-based cells with solution processed interlayers reported to date.

    11. An Effective Approach for the Development of Reliable YBCO Bulk Cryomagnets with High Trapped Field Performances (pages 3996–4004)

      Driss Kenfaui, Pierre-Frédéric Sibeud, Eric Louradour, Xavier Chaud and Jacques G. Noudem

      Version of Record online: 24 MAR 2014 | DOI: 10.1002/adfm.201304083

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      High-performance YBa2Cu3O7-δbulk superconductors with improved reliability and thermal transfer ability are fabricated in short time. The approach taken here is based on the insertion of a metal wires network into the holes of YBa2Cu3O7-δ drilled single grains progressively annealed at high temperature under oxygen pressure. The achieved microstructure is pore-free and crack-free, and the thermal exchange markedly fostered inside the superconductor.

    12. Electrospun Polyaniline Fibers as Highly Sensitive Room Temperature Chemiresistive Sensors for Ammonia and Nitrogen Dioxide Gases (pages 4005–4014)

      Yuxi Zhang, Jae Jin Kim, Di Chen, Harry L. Tuller and Gregory C. Rutledge

      Version of Record online: 1 APR 2014 | DOI: 10.1002/adfm.201400185

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      Electrospun polyaniline fibers are fabricated and evaluated as chemiresistive gas sensors. The fibers exhibit remarkable changes in measured resistances for ammonia and nitrogen dioxide sensing, with short characteristic response times. A time-dependent reaction-diffusion model is used to extract physical parameters from fitting experimental data, and to illustrate the selection of optimal material design parameters for gas sensing by nanofibers.

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