Advanced Functional Materials

Cover image for Vol. 20 Issue 17

September 9, 2010

Volume 20, Issue 17

Pages 2743–2957

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    1. Porous Structures: In situ Porous Structures: A Unique Polymer Erosion Mechanism in Biodegradable Dipeptide-Based Polyphosphazene and Polyester Blends Producing Matrices for Regenerative Engineering (Adv. Funct. Mater. 17/2010)

      Meng Deng, Lakshmi S. Nair, Syam P. Nukavarapu, Sangamesh G. Kumbar, Tao Jiang, Arlin L. Weikel, Nicholas R. Krogman, Harry R. Allcock and Cato T. Laurencin

      Article first published online: 8 SEP 2010 | DOI: 10.1002/adfm.201090073

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      C. T. Laurencin et al. illustrate a unique polymer erosion mechanism through which polymer matrices evolve from a solid coherent film to an assemblage of microspheres with 3D interconnected porous structures imbued with both micropores and nanopores, as reported on page 2794. The tissue in-growth of this dynamic pore forming scaffold attests to the utility of this system for developing solid matrices that balance degradation with tissue formation.

  2. Inside Front Cover

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    1. Conjugated Polymers: High-Resolution Scanning Near-Field Optical Lithography of Conjugated Polymers (Adv. Funct. Mater. 17/2010)

      Daniel Credgington, Oliver Fenwick, Ana Charas, Jorge Morgado, Klaus Suhling and Franco Cacialli

      Article first published online: 8 SEP 2010 | DOI: 10.1002/adfm.201090074

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      The image is a visualization of the scanning near-field optical lithography system in action, showing the optical fiber probe attached to a quartz tuning fork. The probe is held above a sample comprising a PPV-precursor film deposited onto a quartz substrate. The precursor is being patterned using laser light delivered through the fiber, the pattern in this case being somewhat familiar. The scattered substrates show example AFM images (not to the same scales) of other patterned conjugated polymer films, as presented by F. Cacialli et al. on page 2842.

  3. Contents

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    1. Contents: (Adv. Funct. Mater. 17/2010) (pages 2743–2749)

      Article first published online: 8 SEP 2010 | DOI: 10.1002/adfm.201090075

  4. Feature Article

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    1. Organically Functionalized Mesoporous Silica by Co-structure-Directing Route (pages 2750–2768)

      Chuanbo Gao and Shunai Che

      Article first published online: 26 JUL 2010 | DOI: 10.1002/adfm.201000074

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      A co-structure-directing route leads to functional mesoporous silicas with diverse structures, porous properties, morphologies and functionalities, which are reviewed with mechanisms discussed in detail. Organic functional groups are distributed in a regular way following the arrangement of surfactant headgroups, which is a distinct feature of these materials.

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    1. A Molecular Brush Approach to Enhance Quantum Yield and Suppress Nonspecific Interactions of Conjugated Polyelectrolyte for Targeted Far-Red/Near-Infrared Fluorescence Cell Imaging

      Kan-Yi Pu, Kai Li and Bin Liu

      Article first published online: 8 SEP 2010 | DOI: 10.1002/adfm.201090076

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      A molecular brush composed of a red-fluorescent conjugated polymer backbone and dense PEG grafting chains is synthesized via click chemistry to serve as an efficient far-red/near infrared fluorescent probe. This molecular brush overcomes the intrinsic drawbacks of conjugated polyelectrolytes to possess high quantum yield with minimal nonspecific interactions in biological media, allowing for targeted cancer cell imaging in a high-contrast, selective and nonviral manner.

  6. Full Papers

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    1. A Molecular Brush Approach to Enhance Quantum Yield and Suppress Nonspecific Interactions of Conjugated Polyelectrolyte for Targeted Far-Red/Near-Infrared Fluorescence Cell Imaging (pages 2770–2777)

      Kan-Yi Pu, Kai Li and Bin Liu

      Article first published online: 2 JUL 2010 | DOI: 10.1002/adfm.201000495

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      A molecular brush composed of a red-fluorescent conjugated polymer backbone and dense PEG grafting chains is synthesized via click chemistry to serve as an efficient far-red/near infrared fluorescent probe. This molecular brush overcomes the intrinsic drawbacks of conjugated polyelectrolytes to possess high quantum yield with minimal nonspecific interactions in biological media, allowing for targeted cancer cell imaging in a high-contrast, selective and nonviral manner.

    2. Photoswitchable Gas Permeation Membranes Based on Liquid Crystals (pages 2778–2785)

      Eric Głowacki, Karen Horovitz, Ching W. Tang and Kenneth L. Marshall

      Article first published online: 9 JUL 2010 | DOI: 10.1002/adfm.201000551

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      Light-actuated gas permeation membranes are fabricated from liquid crystals (LC’s) imbibed into porous plastic membranes. Diffusion of nitrogen can be tuned through different LC compositions, LC alignment, and isothermal photogenerated nematic–isotropic phase transitions afforded by a mesogenic azobenzene dye. Our goal is to create a novel membrane system to achieve tunability of mass transfer controllable by external stimuli.

    3. Squaraine-Doped Functional Nanoprobes: Lipophilically Protected Near-Infrared Fluorescence for Bioimaging (pages 2786–2793)

      Yong-Deok Lee, Chang-Keun Lim, Sehoon Kim, Ick Chan Kwon and Jungahn Kim

      Article first published online: 13 JUL 2010 | DOI: 10.1002/adfm.201000650

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      Dual lipophilization of intraparticle matrix and dye dopants greatly stabilizes near-infrared fluorescence from self-assembled polymer nanoprobes in aqueous milieux. Hydrophobically stabilized optical signal, along with tiny size and capability of surface functionalization, renders the nanoprobes applicable to bioimaging applications.

    4. In situ Porous Structures: A Unique Polymer Erosion Mechanism in Biodegradable Dipeptide-Based Polyphosphazene and Polyester Blends Producing Matrices for Regenerative Engineering (pages 2794–2806)

      Meng Deng, Lakshmi S. Nair, Syam P. Nukavarapu, Sangamesh G. Kumbar, Tao Jiang, Arlin L. Weikel, Nicholas R. Krogman, Harry R. Allcock and Cato T. Laurencin

      Article first published online: 9 JUL 2010 | DOI: 10.1002/adfm.201000968

      Thumbnail image of graphical abstract

      A unique polymer erosion process through which polymer matrices evolve from a solid coherent film to an assemblage of microspheres with 3D interconnected porous structures. The in situ porous structures result from unique hydrogen bonding in the blend promoting a three-stage degradation mechanism. Furthermore, the tissue in-growth of this dynamic pore forming scaffold attests to its utility in regenerative medicine.

    5. Time–Temperature–Transformation (TTT) Diagrams for Crystallization of Metal Oxide Thin Films (pages 2807–2814)

      Jennifer L. M. Rupp, Barbara Scherrer, Nina Schäuble and Ludwig J. Gauckler

      Article first published online: 26 JUL 2010 | DOI: 10.1002/adfm.201000377

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      The integration of functional metal oxide thin films in MEMS devices requires distinctive thermokinetic engineering of the oxide films. As-deposited oxide thin films exhibit amorphous or biphasic amorphous-crystalline microstructures that actively change during MEMS processing and also under device operation. Primary time-temperature-transformation diagrams are proposed to offer a distinctive mapping of the crystallization of the metal oxide film to allow for better MEMS integration in the future.

    6. Multifunctional Au-Coated TiO2 Nanotube Arrays as Recyclable SERS Substrates for Multifold Organic Pollutants Detection (pages 2815–2824)

      Xuanhua Li, Guangyu Chen, Liangbao Yang, Zhen Jin and Jinhuai Liu

      Article first published online: 21 JUL 2010 | DOI: 10.1002/adfm.201000792

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      A multifunctional Au-coated TiO2 nanotube array is made via synthesis of a TiO2 nanotube array through a ZnO template, followed by deposition of Au particles onto the TiO2 surface. Such arrays exhibit excellent advantages, such as a high-performance SERS ability together with photocatalytic properties, for a recyclable SERS substrate, suggesting promising applications in the detection of organic pollutants.

    7. Conjugated-Polymer-Based Lateral Heterostructures Defined by High-Resolution Photolithography (pages 2825–2832)

      Jui-Fen Chang, Michael C. Gwinner, Mario Caironi, Tomo Sakanoue and Henning Sirringhaus

      Article first published online: 22 JUL 2010 | DOI: 10.1002/adfm.201000436

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      Solution processing of polymer semiconductors enables large-area electronics manufacturing, but also restricts the realization of advanced device architectures such as lateral heterostructures. A degradation-free, high-resolution photolithographic method is demonstrated for patterning polymer semiconductors and exemplified this with high-performance field-effect transistors (FETs) in bottom- and top-gate architectures, as well as ambipolar light-emitting FETs based on a lateral heterojunction between two polymers.

    8. Polymer Scaffolds for Small-Diameter Vascular Tissue Engineering (pages 2833–2841)

      Haiyun Ma, Jiang Hu and Peter X. Ma

      Article first published online: 22 JUL 2010 | DOI: 10.1002/adfm.201000922

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      Novel biodegradable poly(L-lactic acid) (PLLA) scaffolds are built by utilizing the different thermal conductivities of the mold materials. The scaffolds with gradient oriented tubular microstructures can be employed in the tissue engineering of small-diameter blood vessels because of their certain structural similarities to natural blood vessels and pore design, which facilitates tissue regeneration.

    9. High-Resolution Scanning Near-Field Optical Lithography of Conjugated Polymers (pages 2842–2847)

      Daniel Credgington, Oliver Fenwick, Ana Charas, Jorge Morgado, Klaus Suhling and Franco Cacialli

      Article first published online: 6 JUL 2010 | DOI: 10.1002/adfm.201000202

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      The image shows a schematic of the scanning near-field optical lithography (SNOL) probe, overlaid by MM2-minimized oligomers analogous to the polymer precursors and polymer structures referred to in this communication, surrounded by reproductions of the images of the main structures demonstrated.

    10. Tris(8-hydroxyquinoline-5-sulfonate)aluminum Intercalated Mg–Al Layered Double Hydroxide with Blue Luminescence by Hydrothermal Synthesis (pages 2848–2856)

      Shuangde Li, Jun Lu, Min Wei, David G. Evans and Xue Duan

      Article first published online: 26 JUL 2010 | DOI: 10.1002/adfm.201000200

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      Blue luminescent materials (DDS−AQS(x%)/LDH) are prepared by hydrothermally co-intercalating tris(8-hydroxyquinoline-5-sulfonate)aluminum (AQS3−) and dodecyl sulfonate (DDS) into Mg–Al layered double hydroxides (LDHs). The cyan–blue luminescence transition upon intercalation can be attributed to the isomerization of meridianal to facial AQS through the ligand flip driven by host–guest electrostatic interaction and the dispersion effect of DDS

    11. A Graphene Oxide˙Streptavidin Complex for Biorecognition – Towards Affinity Purification (pages 2857–2865)

      Zunfeng Liu, Linhua Jiang, Federica Galli, Igor Nederlof, René C. L. Olsthoorn, Gerda E. M. Lamers, Tjerk. H. Oosterkamp and Jan Pieter Abrahams

      Article first published online: 13 JUL 2010 | DOI: 10.1002/adfm.201000761

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      A novel method is described for preparing graphene oxide (GO)•streptavidin complexes that can be used for affinity purification. The complex shows strong biotin-recognition capability and excellent loading capacity. Capturing biotinylated DNA, fluorophores, and Au NPs on the GO•streptavidin complexes demonstrates its usefulness as a docking matrix for affinity purification, specifically well suited for direct imaging by EM and AFM.

  7. Frontispiece

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Feature Article
    6. Frontispiece
    7. Full Papers
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    1. Self-Propagating Domino-like Reactions in Oxidized Graphite

      Franklin Kim, Jiayan Luo, Rodolfo Cruz-Silva, Laura J. Cote, Kwonnam Sohn and Jiaxing Huang

      Article first published online: 8 SEP 2010 | DOI: 10.1002/adfm.201090077

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      Rapid, self-propagating reduction of graphite oxide films can be trigged by a local hot spot. In the presence of potassium salts, violent, catastrophic domino-like, reduction–combustion reactions are observed that rapidly burned up the material. Such domino-like reactions can be guided to produce functional nanoparticle/graphene hybrids using graphite oxide as an in situ power source.

  8. Full Papers

    1. Top of page
    2. Cover Picture
    3. Inside Front Cover
    4. Contents
    5. Feature Article
    6. Frontispiece
    7. Full Papers
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    1. Self-Propagating Domino-like Reactions in Oxidized Graphite (pages 2867–2873)

      Franklin Kim, Jiayan Luo, Rodolfo Cruz-Silva, Laura J. Cote, Kwonnam Sohn and Jiaxing Huang

      Article first published online: 9 JUL 2010 | DOI: 10.1002/adfm.201000736

      Thumbnail image of graphical abstract

      Rapid, self-propagating reduction of graphite oxide films can be trigged by a local hot spot. In the presence of potassium salts, violent, catastrophic domino-like, reduction–combustion reactions are observed that rapidly burned up the material. Such domino-like reactions can be guided to produce functional nanoparticle/graphene hybrids using graphite oxide as an in situ power source.

    2. Porous Silicon-Based Optical Microsensors for Volatile Organic Analytes: Effect of Surface Chemistry on Stability and Specificity (pages 2874–2883)

      Anne M. Ruminski, Brian H. King, Jarno Salonen, Jay L. Snyder and Michael J. Sailor

      Article first published online: 9 JUL 2010 | DOI: 10.1002/adfm.201000575

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      600-μm diameter porous photonic crystals, electrochemically etched from silicon, are chemically modified and attached to the tips of optical fibers. Surface modifications consisting of hydride, oxide, hydrocarbon, and carbide species are studied; the response to various VOC analytes depends on the surface chemistry on the porous Si particle.

    3. Molecular Origins of the Mechanical Behavior of Hybrid Glasses (pages 2884–2892)

      Mark S. Oliver, Geraud Dubois, Mark Sherwood, David M. Gage and Reinhold H. Dauskardt

      Article first published online: 9 JUL 2010 | DOI: 10.1002/adfm.201000558

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      Molecular Modeling of Deformation and Fracture of Hybrid Glasses. The impact of network structure on the mechanical properties of two ethane-bridged hybrid glasses (Et-OCS and Et-OCS(Me)) is elucidated using a combination of molecular modeling and experimental characterization. A novel fracture model for predicting the complex 3-D fracture path in these materials at the atomic scale is presented.

    4. A Transparent, Flexible, Low-Temperature, and Solution-Processible Graphene Composite Electrode (pages 2893–2902)

      Haixin Chang, Guangfeng Wang, An Yang, Xiaoming Tao, Xuqing Liu, Youde Shen and Zijian Zheng

      Article first published online: 13 JUL 2010 | DOI: 10.1002/adfm.201000900

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      A transparent, flexible, low-temperature, and solution-processible graphene composite electrode (GCE) is fabricated based on large-size, highly soluble, chemically derived graphene. The performance of organic light-emitting diodes (OLEDs) based on a GCE anode is comparable, if not superior, to that of OLEDs made with an ITO anode.

    5. Ultrathin, Organic, Semiconductor/Polymer Blends by Scanning Corona-Discharge Coating for High-Performance Organic Thin-Film Transistors (pages 2903–2910)

      Hee Joon Jung, Yu Jin Shin, Youn Jung Park, Sung Cheol Yoon, Dong Hoon Choi and Cheolmin Park

      Article first published online: 6 JUL 2010 | DOI: 10.1002/adfm.201000032

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      A new, direct coating process, scanning corona-discharge coating (SCDC), is described for making thin tri-isopropylsilylethynyl pentacene (TIPS-PEN) single-crystal/amorphous-polymer films. Organic thin-film transistors fabricated by SCDC show a high OTFT performance with a maximum field-effect mobility of approximately 0.23 cm2 V−1 s−1, which is comparable with that obtained with a single-crystalline, ribbon-like TIPS-PEN active channel.

    6. Controlled Nucleation of GaN Nanowires Grown with Molecular Beam Epitaxy (pages 2911–2915)

      Kris A. Bertness, Aric W. Sanders, Devin M. Rourke, Todd E. Harvey, Alexana Roshko, John B. Schlager and Norman A. Sanford

      Article first published online: 13 JUL 2010 | DOI: 10.1002/adfm.201000381

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      GaN nanowires are grown with near perfect size and placement control with catalyst-free molecular beam epitaxy. This new methodology for selective epitaxy on silicon substrates achieved periodic array structures and dimension control to better than 2%, which in turn enables a number of photonic and sensor applications.

    7. Preparation and Memory Performance of a Nanoaggregated Dispersed Red 1-Functionalized Poly (N-vinylcarbazole) Film via Solution-Phase Self-Assembly (pages 2916–2922)

      Xiao-Dong Zhuang, Yu Chen, Gang Liu, Bin Zhang, Koon-Gee Neoh, En-Tang Kang, Chun-Xiang Zhu, Yong-Xi Li and Li-Juan Niu

      Article first published online: 9 JUL 2010 | DOI: 10.1002/adfm.201000258

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      A write-once, read-many-times memory device is fabricated by spin-coating a pre-assembled solution of PVDR as the active layer sandwiched between an aluminum electrode and an indium-tin-oxide electrode. This device shows very good memory performance, with an ON/OFF current ratio of more than 105, which is high enough to ensure a low misreading rate through the precise control of the ON and OFF states. The stability of the nanoaggregated PVDR device is much higher than that of non-nanoaggregated PVDR devices.

    8. Multifunctional Triphenylamine/Oxadiazole Hybrid as Host and Exciton-Blocking Material: High Efficiency Green Phosphorescent OLEDs Using Easily Available and Common Materials (pages 2923–2929)

      Youtian Tao, Qiang Wang, Chuluo Yang, Cheng Zhong, Jingui Qin and Dongge Ma

      Article first published online: 9 JUL 2010 | DOI: 10.1002/adfm.201000669

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      A simple triphenylamine/oxadiazole hybrid can function as efficient bipolar host and exciton blocking material for PHOLEDs. Together with the use of TPBI as electron transporting layer and NPB as hole transporting layer, the charge carrier balance can be manipulated. Accordingly, the best EL performance can be achieved with a maximum EQE of 23.7% and a maximum power efficiency of 105 lm W−1 for a (ppy)2Ir(acac) based green PHOLED and 20.6% and 61.7 lm W−1 for a (fbi)2Ir(acac) based yellow PHOLED.

    9. Air-Operable, High-Mobility Organic Transistors with Semifluorinated Side Chains and Unsubstituted Naphthalenetetracarboxylic Diimide Cores: High Mobility and Environmental and Bias Stress Stability from the Perfluorooctylpropyl Side Chain (pages 2930–2944)

      Byung Jun Jung, Kyusang Lee, Jia Sun, Andreas G. Andreou and Howard E. Katz

      Article first published online: 9 JUL 2010 | DOI: 10.1002/adfm.201000655

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      An N,N′-bis(3-(perfluoroctyl)propyl)-1,4,5,8-naphthalenetetracarboxylic diimide (8–3-NTCDI)-based organic thin-ilm transistor (OTFT) on an octadecyltrimethoxysilane (OTS)-treated Si/SiO2 substrate shows apparent electron mobility approaching 0.7 cm2 V-1s-1 in air. The transistor on hexamethyldisilazane (HMDS) is more stable against gate bias stress than that on OTS with mobility comparable to amorphous Si TFTs. This performance is promising for use in display backplanes.

    10. Triplet Exciton and Polaron Dynamics in Phosphorescent Dye Blended Polymer Photovoltaic Devices (pages 2945–2950)

      Chang-Lyoul Lee, In-Wook Hwang, Clare Chisu Byeon, Bok Hyeon Kim and Neil C. Greenham

      Article first published online: 22 JUL 2010 | DOI: 10.1002/adfm.201000763

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      The photo-physical interactions between MEH-PPV, PtOEP, and PCBM are schematically shown in the figure. The rate and probability of exciton dissociation between PtOEP and PCBM are much faster and higher than that of the triplet-triplet energy transfer between PtOEP and MEH-PPV. It suggests that simple blending of the phosphorescent dye does not assure a positive triplet effect in bulk heterojunction photovoltaic devices.

    11. High-Performance All-Polymer White-Light-Emitting Diodes Using Polyfluorene Containing Phosphonate Groups as an Efficient Electron-Injection Layer (pages 2951–2957)

      Baohua Zhang, Chuanjiang Qin, Junqiao Ding, Lei Chen, Zhiyuan Xie, Yanxiang Cheng and Lixiang Wang

      Article first published online: 15 NOV 2010 | DOI: 10.1002/adfm.201000538

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      An efficient electron injector with a structure of PF-EP/LiF/Al is successfully developed and used to fabricate high-performance all-polymer PWLEDs based on a three-color white single polymer WP-B5G5R2. The optimized device exhibits the highest external quantum efficiency, forward viewing luminous efficiency and power efficiency of 6.7%, 15.4 cd A−1 and 11.4 lm W−1 at 347 cd m−2, respectively, rendering great potential of low-cost large-area solution-processed manufacturing for efficient PWLEDs.

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