Advanced Functional Materials

Cover image for Vol. 21 Issue 12

June 21, 2011

Volume 21, Issue 12

Pages 2164–2382

  1. Cover Picture

    1. Top of page
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    4. Back Cover
    5. Contents
    6. Corrections
    7. Feature Article
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    9. Full Papers
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    1. Organic Light-Emitting Diodes: Investigating Morphology and Stability of Fac-tris (2-phenylpyridyl)iridium(III) Films for OLEDs (Adv. Funct. Mater. 12/2011) (page 2164)

      Arthur R. G. Smith, Jeremy L. Ruggles, Hamish Cavaye, Paul E. Shaw, Tamim A. Darwish, Michael James, Ian R. Gentle and Paul L. Burn

      Article first published online: 16 JUN 2011 | DOI: 10.1002/adfm.201190040

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      Stable film morphology is critical for durable, high-performance organic light-emitting diodes. On page 2225, Ian R. Gentle, Paul L. Burn, and co-workers use neutron reflectometry to study the out-of-plane structure of blended thin films and multilayer structures. Uniformly blended films of fac-tris(2-phenylpyridyl)iridium(III) [Ir(ppy)3] in 4,4'-bis(N-carbazolyl)biphenyl (CBP) can be formed by evaporation, while 6 wt% films of Ir(ppy)3 in CBP, typically used in OLEDs, were found to phase-separate with moderate heating. Luminescence microscopy shows that phase separation leads to fiber-like structures of CBP (blue) and Ir(ppy)3 (green).

  2. Inside Front Cover

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    1. Energy Materials: Nanoscale Characterization of Energy Generation from Piezoelectric Thin Films (Adv. Funct. Mater. 12/2011) (page 2165)

      Madhu Bhaskaran, Sharath Sriram, Simon Ruffell and Arnan Mitchell

      Article first published online: 16 JUN 2011 | DOI: 10.1002/adfm.201190041

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      A nanoindenter tip, as a tool to characterize electrical energy generation from piezoelectric thin films, is presented by Madhu Bhaskaran and co-workers on page 2251. For the first time, such direct interactions at the nanometer scale are used for controlled in situ characterization of the voltage and current generation of piezoelectric thin films. Quantitative results demonstrate that nanopatterning yields an improved materials platform for integrated micrometer-scale energy-harvesting systems.

  3. Back Cover

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    1. Wireless Strain Monitoring: A Microfluidic, Reversibly Stretchable, Large-Area Wireless Strain Sensor (Adv. Funct. Mater. 12/2011) (page 2166)

      Shi Cheng and Zhigang Wu

      Article first published online: 16 JUN 2011 | DOI: 10.1002/adfm.201190042

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      Shi Cheng and Zhigang Wu demonstrate a new concept of wireless strain sensors, on page 2282, by combining microfluidic stretchable radiofrequency electronics with established integrated circuits. The implemented sensing device is capable of measuring repeated large-area strains of a human joint. The data are transferred wirelessly to a computer system for realtime healthcare or fitness monitoring.

  4. Contents

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    1. Contents: (Adv. Funct. Mater. 12/2011) (pages 2167–2173)

      Article first published online: 16 JUN 2011 | DOI: 10.1002/adfm.201190043

  5. Corrections

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    1. You have free access to this content
      Correction: Functionalization of Chitosan via Atom Transfer Radical Polymerization for Gene Delivery (page 2174)

      Yuan Ping, Cheng-De Liu, Gu-Ping Tang, Jian-Shu Li, Jun Li, Wan-Tai Yang and Fu-Jian Xu

      Article first published online: 16 JUN 2011 | DOI: 10.1002/adfm.201190046

      This article corrects:

      Functionalization of Chitosan via Atom Transfer Radical Polymerization for Gene Delivery

      Vol. 20, Issue 18, 3106–3116, Article first published online: 14 SEP 2010

    2. You have free access to this content
      Correction: A General Approach for Patterning Multiple Types of Cells Using Holey PDMS Membranes and Microfl uidic Channels (page 2174)

      Bo Yuan, Yong Li, Dong Wang, Yunyan Xie, Yingyi Liu, Li Cui, Fuquan Tu, Hao Li, Hang Ji, Wei Zhang and Xingyu Jiang

      Article first published online: 16 JUN 2011 | DOI: 10.1002/adfm.201190047

      This article corrects:

      A General Approach for Patterning Multiple Types of Cells Using Holey PDMS Membranes and Microfluidic Channels

      Vol. 20, Issue 21, 3715–3720, Article first published online: 14 OCT 2010

  6. Feature Article

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    1. Nanostructured Tungsten Oxide – Properties, Synthesis, and Applications (pages 2175–2196)

      Haidong Zheng, Jian Zhen Ou, Michael S. Strano, Richard B. Kaner, Arnan Mitchell and Kourosh Kalantar-zadeh

      Article first published online: 24 MAY 2011 | DOI: 10.1002/adfm.201002477

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      Tungsten oxides (WOx) are unique functional materials that can be obtained in a vast variety of nanostructured forms. This Feature Article presents a comprehensive review on the properties of WOx that goes beyond chromism and photocatalysis, for which they are usually investigated for. This is followed by a survey of their synthesis methods and implementations for different applications.

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    1. ORGANIC FIELD-EFFECT TRANSISTORS: Physicochemically Stable Polymer-Coupled Oxide Dielectrics for Multipurpose Organic Electronic Applications (Adv. Funct. Mater. 12/2011) (page 2197)

      Se Hyun Kim, Mi Jang, Hoichang Yang, John E. Anthony and Chan Eon Park

      Article first published online: 16 JUN 2011 | DOI: 10.1002/adfm.201190044

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      Hoichang Yang, John E. Anthony, Chan Eon Park, and co-workers describe a new chemically linked polymer-coupling method for the surface modification of oxide dielectrics that enables multipurpose organic electronic applications. Ultrathin polymer layers are chemically coupled on oxide dielectrics with chlorosilane-terminated polystyrene. The polystyrene brush layer is physicochemically stable and provides a hydrophobic and smooth surface to induce highly ordered crystalline structures of vacuum- and solutionprocessable organic semiconductors. on page 2198

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    1. Physicochemically Stable Polymer-Coupled Oxide Dielectrics for Multipurpose Organic Electronic Applications (pages 2198–2207)

      Se Hyun Kim, Mi Jang, Hoichang Yang, John E. Anthony and Chan Eon Park

      Article first published online: 12 APR 2011 | DOI: 10.1002/adfm.201002054

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      Ultrathin polymer layers were chemically coupled on oxide dielectrics with chlorosilane-terminated polystyrene (PS). The PS-brush layer was physicochemically stable and provided a smooth, hydrophobic surface to induce highly ordered crystalline structures of vacuum- and solution-processable organic semiconductors. In particular, PS-coupled AlOx nanodielectrics allowed solution-processable organic field-effect transistors to operate at a gate voltage of approximately –1 V, with a field-effect mobility of ∼1.26 cm2 V−1 s−1.

    2. “Brick-and-Mortar” Self-Assembly Approach to Graphitic Mesoporous Carbon Nanocomposites (pages 2208–2215)

      Pasquale F. Fulvio, Richard T. Mayes, Xiqing Wang, Shannon M. Mahurin, John C. Bauer, Volker Presser, John McDonough, Yury Gogotsi and Sheng Dai

      Article first published online: 20 APR 2011 | DOI: 10.1002/adfm.201002641

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      Ordered mesoporous carbons having graphitic carbon nanoparticles are prepared in a one-pot synthesis route by “brick-and-mortar” self-assembly using onion-like carbons, or carbon black (“bricks”) and phenolic resin (“mortar”) in the presence of triblock copolymers. Mesopore widths, electrical series resistance, and capacitance can be tailored by brick selection and contents in final nanocomposites.

    3. Organic Proton-Conducting Molecules as Solid-State Separator Materials for Fuel Cell Applications (pages 2216–2224)

      Lucía Jiménez-García, Anke Kaltbeitzel, Volker Enkelmann, Jochen S. Gutmann, Markus Klapper and Klaus Müllen

      Article first published online: 20 APR 2011 | DOI: 10.1002/adfm.201002357

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      Organic proton-conducting molecules are presented as alternative materials to state-of-the-art polymers used as electrolytes in proton-exchanging membrane (PEM) fuel cells. A series of phosphonic acid-containing molecules possessing a carbon-rich hydrophobic core and a hydrophilic periphery is synthesized. This study provides insights into the proton-conducting properties of this novel class of materials and the mechanisms responsible for proton transport.

    4. Investigating Morphology and Stability of Fac-tris (2-phenylpyridyl)iridium(III) Films for OLEDs (pages 2225–2231)

      Arthur R. G. Smith, Jeremy L. Ruggles, Hamish Cavaye, Paul E. Shaw, Tamim A. Darwish, Michael James, Ian R. Gentle and Paul L. Burn

      Article first published online: 25 MAR 2011 | DOI: 10.1002/adfm.201002365

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      The out-of-plane and surface morphology of vacuum-deposited phosphorescent small molecule OLED films is studied using neutron reflectometry. The thermal stability of an Ir(ppy)3:CBP emissive layer can be improved by increasing the Ir(ppy)3 concentration. In a TCTA/Ir(ppy)3:CBP/BCP multilayer, thermal annealing causes the migration of BCP throughout the Ir(ppy)3:CBP layer.

    5. Phase-Change Materials: Vibrational Softening upon Crystallization and Its Impact on Thermal Properties (pages 2232–2239)

      Toshiyuki Matsunaga, Noboru Yamada, Rie Kojima, Shinichi Shamoto, Masugu Sato, Hajime Tanida, Tomoya Uruga, Shinji Kohara, Masaki Takata, Peter Zalden, Gunnar Bruns, Ilya Sergueev, Hans Christian Wille, Raphaël Pierre Hermann and Matthias Wuttig

      Article first published online: 26 APR 2011 | DOI: 10.1002/adfm.201002274

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      Crystallization of amorphous solids is usually accompanied by significant changes of transport properties, such as an increase in thermal conductivity. Phase-change materials, however, reveal a remarkably low thermal conductivity in the crystalline state. This phenomenon is caused by the change of bonding upon crystallization which leads to an increase of the sound velocity and a softening of the optical modes.

    6. Dynamic Stability of Organic Conducting Polymers and Its Replication in Electrical Conduction and Degradation Mechanisms (pages 2240–2250)

      Emmanuel F. C. Chimamkpam, Thomas Schweizer, Roland Hauert, Andreas Schilling and José M. F. Ferreira

      Article first published online: 26 APR 2011 | DOI: 10.1002/adfm.201002185

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      The dynamic stability of organic conducting polymer materials, described in terms of thermally induced host–guest motional behavior, is mirrored in their electrical conduction mechanisms and provides information about homo­geneity, mechanical state, and degradation. For lifetime prognosis of organic electronic devices, complementary models on dynamic stability and electrical conduction mechanism “connect the dots” starting from the preparative history of a given sample.

    7. Nanoscale Characterization of Energy Generation from Piezoelectric Thin Films (pages 2251–2257)

      Madhu Bhaskaran, Sharath Sriram, Simon Ruffell and Arnan Mitchell

      Article first published online: 4 APR 2011 | DOI: 10.1002/adfm.201002663

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      The use of nanoindentation to characterize in situ the voltage and current generation of piezoelectric thin films and nanoislands is reported. This work presents the controlled observation of nanoscale piezoelectric voltage and current generation. The influence of size on energy generation parameters is reported, demonstrating that nanoislands can exhibit more effective current generation than continuous films.

    8. Controlling Interface Intermixing and Properties of SrTiO3-Based Superlattices (pages 2258–2263)

      Teruyasu Mizoguchi, Hiromichi Ohta, Hak-Sung Lee, Nobuaki Takahashi and Yuichi Ikuhara

      Article first published online: 20 APR 2011 | DOI: 10.1002/adfm.201100230

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      The intermixing behaviour at nonpolar heterointerfaces in SrTiO3-based superlattices is studied. Nb is confined to a unit-cell thickness without intermixing, while Ba diffuses to the adjoining Nb-doped SrTiO3 layers. The intermixing behavior is dependent on the migration energy, the vacancy-formation energy and the Fermi energy. A way of controlling atomic-scale intermixing at nonpolar heterointerfaces is found and the property improvements demonstrated.

    9. Highly Sensitive Glucose Biosensors Based on Organic Electrochemical Transistors Using Platinum Gate Electrodes Modified with Enzyme and Nanomaterials (pages 2264–2272)

      Hao Tang, Feng Yan, Peng Lin, Jianbin Xu and Helen L. W. Chan

      Article first published online: 26 APR 2011 | DOI: 10.1002/adfm.201002117

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      Glucose sensors based on organic electrochemical transistors are suitable for disposable applications. The sensitivity of the device is dramatically improved by modifying the Pt gate electrode with glucose oxidase, chitosan, and Pt nanoparticles, or multiwall carbon nanotubes. The glucose sensor shows a detection limit down to 5 nM and relatively high selectivity and stability.

    10. Towards Integrated Molecular Electronic Devices: Characterization of Molecular Layer Integrity During Fabrication Processes (pages 2273–2281)

      Amr M. Mahmoud, Adam Johan Bergren, Nikola Pekas and Richard L. McCreery

      Article first published online: 20 APR 2011 | DOI: 10.1002/adfm.201002496

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      The integration of molecular electronics devices may require harsh conditions that can damage soft molecular materials. We show that the use of carbon–carbon bonds to anchor molecular layers leads to excellent stability in response to direct top contact deposition, high temperatures (up to 400 °C), photolithographic processing, and packaging.

    11. A Microfluidic, Reversibly Stretchable, Large-Area Wireless Strain Sensor (pages 2282–2290)

      Shi Cheng and Zhigang Wu

      Article first published online: 22 MAR 2011 | DOI: 10.1002/adfm.201002508

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      A novel concept of self-contained large-area wireless strain sensors, based on multi-layer microfluidic stretchable radiofrequency electronics (μFSRFEs), is proposed and evaluated. Compared to existing solutions, the presented device is capable of remotely detecting repeated high tensile dynamic or static strains of up to 15% over very large surfaces or movable parts.

    12. Evaluation of the Biocompatibility of PLACL/Collagen Nanostructured Matrices with Cardiomyocytes as a Model for the Regeneration of Infarcted Myocardium (pages 2291–2300)

      Shayanti Mukherjee, Jayarama Reddy Venugopal, Rajeswari Ravichandran, Seeram Ramakrishna and Michael Raghunath

      Article first published online: 26 APR 2011 | DOI: 10.1002/adfm.201002434

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      A scalable, nanotopographically controlled in-vitro model of poly(L-lactic acid)-co-poly(ϵ-caprolactone)/collagen nanofibers is fabricated that mimics the native myocardial environment for cardiomyocytes, inspired by microscopic analysis of the ventricular organization in native tissue. Guided by nanoscale mechanical cues provided by the underlying random nanofibrous scaffold, the tissue constructs display anisotropic rearrangement of cells, characteristic of the native cardiac tissue.

    13. A Composite Formation Route to Well-Crystalline Manganese Oxide Nanocrystals: High Catalytic Activity of Manganate–Alumina Nanocomposites (pages 2301–2310)

      Tae Woo Kim, Hana Yoo, In Young Kim, Hyung-Wook Ha, Ah Reum Han, Jong-San Chang, Ji Sun Lee and Seong-Ju Hwang

      Article first published online: 26 APR 2011 | DOI: 10.1002/adfm.201100218

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      Porous manganese oxide–alumina nanocomposites are synthesized by the reaction between permanganate anions and aluminum oxyhydroxide cations. The nanoscale mixing of the manganate with alumina makes the improvement of its crystallinity via calcination possible without detectable enlargement of particles. The resulting nanocomposites with high crystallinity and a nanometer-level particle size show extremely high catalytic activity for the oxidation of olefin molecules.

    14. Modification of Exciton Lifetime by the Metal Cathode in Phosphorescent OLEDs, and Implications on Device Efficiency and Efficiency Roll-off Behavior (pages 2311–2317)

      Dandan Song, Suling Zhao and Hany Aziz

      Article first published online: 20 APR 2011 | DOI: 10.1002/adfm.201002585

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      Interactions with a metal layer ∼30–100 nm away, as is typically the case in PhOLEDs, is found to result in an increase in the spontaneous emission decay rate of triplet excitons, causing the exciton lifetime to become shorter as the distance between the phosphorescent material and the metal becomes smaller, thereby influencing device efficiency and efficiency roll-off behaviour.

  9. Frontispiece

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    1. MEMBRANES: Tailoring the Separation Behavior of Hybrid Organosilica Membranes by Adjusting the Structure of the Organic Bridging Group (Adv. Funct. Mater. 12/2011) (page 2318)

      Hessel L. Castricum, Goulven G. Paradis, Marjo C. Mittelmeijer-Hazeleger, Robert Kreiter, Jaap F. Vente and Johan E. ten Elshof

      Article first published online: 16 JUN 2011 | DOI: 10.1002/adfm.201190045

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      Energy-efficient molecular separations under harsh industrial conditions can be realized with organically linked silica membranes. A generic approach to tailor the separation selectivity is presented by Hessel L. Castricum and co-workers. The image shows that membrane properties can be tuned by adjusting the size, shape, and electronic structure of the organic bridging group in order to enable separations of a wide range of molecular mixtures. on page 2319

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    1. Tailoring the Separation Behavior of Hybrid Organosilica Membranes by Adjusting the Structure of the Organic Bridging Group (pages 2319–2329)

      Hessel L. Castricum, Goulven G. Paradis, Marjo C. Mittelmeijer-Hazeleger, Robert Kreiter, Jaap F. Vente and Johan E. ten Elshof

      Article first published online: 12 APR 2011 | DOI: 10.1002/adfm.201002361

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      The permeability and separation selectivity of hybrid organosilica membranes is tailored by the size, shape, and electronic structure of the organic bridging group. The separation of hydrogen and water can be achieved with short CH2 and C2H4 bridges, while CO2 separation is enhanced by applying larger organic groups (benzene, octane). A polymeric character and concomitant selectivity towards nonpolar molecules is obtained with flexible octane bridges.

    2. Additive-Free Dispersion of Single-Walled Carbon Nanotubes and Its Application for Transparent Conductive Films (pages 2330–2337)

      Wen-Bin Liu, Songfeng Pei, Jinhong Du, Bilu Liu, Libo Gao, Yang Su, Chang Liu and Hui-Ming Cheng

      Article first published online: 2 MAY 2011 | DOI: 10.1002/adfm.201002257

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      An approach to prepare additive-free dispersions of SWCNTs with the aid of functionalized carbonaceous byproducts is reported. The majority of SWCNTs dispersed are present in small bundles or individually, and the structure and properties of the SWCNTs are preserved. SWCNT transparent conductive films with high electrical and optical performance are fabricated using these dispersions.

    3. Engineering of Ultra-Hydrophobic Functional Coatings Using Controlled Aggregation of Bicomponent Core/Shell Janus Particles (pages 2338–2344)

      Sebastian Berger, Leonid Ionov and Alla Synytska

      Article first published online: 20 APR 2011 | DOI: 10.1002/adfm.201100155

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      The engineering of ultra-hydrophobic functional coatings using controlled aggregation of bicomponent polymeric Janus particles is presented. This is possible due to their ability to self-assemble and form hierarchical structured aggregates in dispersions. The obtained findings could be very important for the design of novel materials with advanced properties.

    4. Hollow Two-Layered Chiral Nanoparticles Consisting of Optically Active Helical Polymer/Silica: Preparation and Application for Enantioselective Crystallization (pages 2345–2350)

      Bo Chen, Jianping Deng and Wantai Yang

      Article first published online: 26 APR 2011 | DOI: 10.1002/adfm.201100113

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      Multilayer chiral core/shell nanoparticles are afforded by a combination of radical polymerization of n-butyl acrylate (to form the PBA core), catalytic polymerization of substituted acetylene (PSA middle layer) and sol–gel process of TEOS (outer shell). Removing the PBA cores provides hollow chiral nanoparticles, which act as chiral nucleation sites inducing enantioselective crystallization of D- or L-alanine enantiomer with enantiomeric efficiency of ca. 80%.

    5. Growth of Topological Insulator Bi2Se3 Thin Films on SrTiO3 with Large Tunability in Chemical Potential (pages 2351–2355)

      Guanhua Zhang, Huajun Qin, Jun Chen, Xiaoyue He, Li Lu, Yongqing Li and Kehui Wu

      Article first published online: 20 APR 2011 | DOI: 10.1002/adfm.201002667

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      The position of the surface chemical potential is critical to the properties of 3-dimensional topological insulators. High quality topological insulator Bi2Se3 thin films can be grown on carefully treated SrTiO3 substrate. This enables large tunability in chemical potential of the film, and even the reversal of the sign of the Hall resistivity by using a back gate.

    6. Electrospinning Preparation and Drug-Delivery Properties of an Up-conversion Luminescent Porous NaYF4:Yb3+, Er3+@Silica Fiber Nanocomposite (pages 2356–2365)

      Zhiyao Hou, Chunxia Li, Pingan Ma, Guogang Li, Ziyong Cheng, Chong Peng, Dongmei Yang, Piaoping Yang and Jun Lin

      Article first published online: 20 APR 2011 | DOI: 10.1002/adfm.201100193

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      Electrospinning derived α-NaYF4:Yb3+, Er3+ decorated silica fibers, which combine porous structure and red up-conversion luminescence, can be used as a drug-delivery vehicle. The IBU-loaded silica fiber system shows a controlled release property for IBU. In addition, the up-conversion emission intensities of the drug carrier system vary with the amount of IBU released.

    7. Asymmetric Supercapacitors Based on Graphene/MnO2 and Activated Carbon Nanofiber Electrodes with High Power and Energy Density (pages 2366–2375)

      Zhuangjun Fan, Jun Yan, Tong Wei, Linjie Zhi, Guoqing Ning, Tianyou Li and Fei Wei

      Article first published online: 20 APR 2011 | DOI: 10.1002/adfm.201100058

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      A novel asymmetric supercapacitor based on graphene/MnO2 and activated carbon nanofibers (ACN) as the positive and negative electrodes, respectively, has been developed in aqueous Na2SO4 electrolyte solution. More interestingly, the asymmetric supercapacitor exhibits a maximum energy density of 51.1 Wh kg−1 and excellent cycling durability, with 97% specific capacitance retained even after 1000 cycles.

    8. Highly Efficient, Solution-Processed, Single-Layer, Electrophosphorescent Diodes and the Effect of Molecular Dipole Moment (pages 2376–2382)

      Hameed A. Al-Attar, Gareth C. Griffiths, Tom N. Moore, Mustafa Tavasli, Mark A. Fox, Martin R. Bryce and Andrew P. Monkman

      Article first published online: 2 MAY 2011 | DOI: 10.1002/adfm.201100324

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      A new family of electrophosphorescent dopants based on a series of tris-cyclometalated iridium(III) complexes of 2-(carbazol-3-yl)-4/5-R-pyridine ligands with varying molecular dipole strengths are used to fabricate highly efficient, solution-processed, single-layer devices with efficiencies of up to 40 cd A−1. The molecular dipole moments of these complexes are correlated with the optical and electrical performance of the organic light-emitting diodes.

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