Advanced Functional Materials

Cover image for Vol. 20 Issue 20

October 22, 2010

Volume 20, Issue 20

Pages 3401–3612

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    1. Self-healing Fibers: Autonomic Recovery of Fiber/Matrix Interfacial Bond Strength in a Model Composite (Adv. Funct. Mater. 20/2010) (page 3401)

      Benjamin J. Blaiszik, Marta Baginska, Scott R. White and Nancy R. Sottos

      Article first published online: 20 OCT 2010 | DOI: 10.1002/adfm.201090089

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      The cover image presents a false-color scanning electron microscopy image of glass composite reinforcement fibers (purple) coated with liquid monomer filled capsules (beige) and solid recrystallized Grubbs' catalyst (purple). On page 3547, Sottos and co-workers demonstrate that single fibers with similar surface functionalization show autonomic recovery of up to 44% of the original interfacial shear strength after full debonding in a model composite system.

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    1. Solar Cells: Performance Optimization of Polymer Solar Cells Using Electrostatically Sprayed Photoactive Layers (Adv. Funct. Mater. 20/2010) (page 3402)

      Joon-Sung Kim, Won-Suk Chung, Kyungkon Kim, Dong Young Kim, Ki-Jung Paeng, Seong Mu Jo and Sung-Yeon Jang

      Article first published online: 20 OCT 2010 | DOI: 10.1002/adfm.201090090

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      This image presents a novel fabrication method for polymer solar cells. Jang and co-workers deposited thin polymer photoactive films by electrodynamic spraying, on page 3538. The morphologies of the resulting photoactive films are optimized to reduce the internal series resistance and to enhance the device efficiency. The performance of such solar cells is comparable to that of solar cells fabricated using the conventional spin-coting method and the facile electrodynamic technique promises continuous large-scale fabrication of polymer solar cells in the future.

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    1. Contents: (Adv. Funct. Mater. 20/2010) (pages 3403–3409)

      Article first published online: 20 OCT 2010 | DOI: 10.1002/adfm.201090091

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      Correction: Controlled Nucleation of GaN Nanowires Grown with Molecular Beam Epitaxy (page 3410)

      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: 20 OCT 2010 | DOI: 10.1002/adfm.201090092

      This article corrects:

      Controlled Nucleation of GaN Nanowires Grown with Molecular Beam Epitaxy

      Vol. 20, Issue 17, 2911–2915, Article first published online: 13 JUL 2010

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    1. Patterning Colloidal Crystals and Nanostructure Arrays by Soft Lithography (pages 3411–3424)

      Junhu Zhang and Bai Yang

      Article first published online: 3 SEP 2010 | DOI: 10.1002/adfm.201000795

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      An overview on recent developments employing soft lithography methods to pattern colloidal crystals and related nanostructure arrays is provided. Lift-up soft lithography and modified microcontact printing methods are applied to fabricate patterned and non-close-packed colloidal crystals with controllable lattice spacing and lattice structure. Combining selective etching, imprinting, and micromolding methods, these colloidal crystal arrays can be employed as templates for nanostructure arrays.

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    1. Enhancing Phosphorescence and Electrophosphorescence Efficiency of Cyclometalated Pt(II) Compounds with Triarylboron (page 3425)

      Zachary M. Hudson, Christina Sun, Michael G. Helander, Hazem Amarne, Zheng-Hong Lu and Suning Wang

      Article first published online: 20 OCT 2010 | DOI: 10.1002/adfm.201090093

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      Triarylboron is found to greatly enhance the photoluminescent quantum yields, electrophosphorescence efficiencies, and electron transport capabilities of cyclometalated N,C-chelate Pt(II) complexes, which leads to significant improvements in the performance of electroluminescent devices based on doped Pt(II) emitters.

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    1. Enhancing Phosphorescence and Electrophosphorescence Efficiency of Cyclometalated Pt(II) Compounds with Triarylboron (pages 3426–3439)

      Zachary M. Hudson, Christina Sun, Michael G. Helander, Hazem Amarne, Zheng-Hong Lu and Suning Wang

      Article first published online: 18 AUG 2010 | DOI: 10.1002/adfm.201000904

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      Triarylboron is found to greatly enhance the photoluminescent quantum yields, electrophosphorescence efficiencies, and electron transport capabilities of cyclometalated N,C-chelate Pt(II) complexes, which leads to significant improvements in the performance of electroluminescent devices based on doped Pt(II) emitters.

    2. Non-Volatile Organic Memory Elements Based on Carbon-Nanotube-Enabled Vertical Field-Effect Transistors (pages 3440–3445)

      Bo Liu, Mitchell A. McCarthy and Andrew G. Rinzler

      Article first published online: 18 AUG 2010 | DOI: 10.1002/adfm.201001175

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      The simple addition of a charge storage layer to the carbon-nanotube-enabled vertical field-effect transistor yields a non-volatile memory element. The devices exhibit a large, fully gate-sweep-programmable hysteresis in the cyclic transfer curves exhibiting on/off ratios > 4 orders of magnitude. The high aspect ratio carbon nanotubes facilitate charge injection into the charge storage layer, realizing the strong memory effect without sacrificing mobility in the vertical channel.

    3. Electrospinning Derived One-Dimensional LaOCl: Ln3+ (Ln = Eu/Sm, Tb, Tm) Nanofibers, Nanotubes and Microbelts with Multicolor-Tunable Emission Properties (pages 3446–3456)

      Guogang Li, Zhiyao Hou, Chong Peng, Wenxin Wang, Ziyong Cheng, Chunxia Li, Hongzhou Lian and Jun Lin

      Article first published online: 23 AUG 2010 | DOI: 10.1002/adfm.201001114

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      One-dimensional LaOCl:Ln3+ (Ln = Eu/Sm, Tb, Tm) nanofibers, nanotubes, and quasi-1D microbelts are successfully prepared by a sol–gel/electrospinning process and subsequent heat treatment. Under the low-voltage electron beam excitation, a variety of luminescent colors are efficiently adjusted in a wide color area for mono- and co-doped LaOCl:Ln3+ phosphors.

    4. Solution-Processed Zinc Oxide as High-Performance Air-Stable Electron Injector in Organic Ambipolar Light-Emitting Field-Effect Transistors (pages 3457–3465)

      Michael C. Gwinner, Yana Vaynzof, Kulbinder K. Banger, Peter K. H. Ho, Richard H. Friend and Henning Sirringhaus

      Article first published online: 23 AUG 2010 | DOI: 10.1002/adfm.201000785

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      Electron injectionin organic field-effect transistors (OFETs) is approached in a novel way. Modification of gold electrodes with a solution-deposited and patterned zinc oxide (ZnO) layer allows unstable low-work-function metals to be avoided. Ambipolar light-emitting OFETs based on poly(9,9-dioctylfluorene-alt-benzothiadiazole) and poly(9,9-dioctylfluorene) with electron-injecting gold/ZnO and hole-injecting gold electrodes show substantially lower electron threshold voltages and higher currents than devices with bare gold.

    5. Direct Observation of Capacitor Switching Using Planar Electrodes (pages 3466–3475)

      Nina Balke, Martin Gajek, Alexander K. Tagantsev, Lane W. Martin, Ying-Hao Chu, Ramamoorthy Ramesh and Sergei V. Kalinin

      Article first published online: 17 AUG 2010 | DOI: 10.1002/adfm.201000475

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      Planar capacitor structures formed by a ferroelectric film embedded between two electrodes are used to investigate the details of polarization switching. Scanning probe microscopy is used to observe the domain growth from one electrode to the other during the capacitor switching. Studies of the kinetics of domain evolution allows clear visualization of nucleation sites, as well as forward and lateral growth stages of domain formation.

    6. Photoinduced Degradation of Polymer and Polymer–Fullerene Active Layers: Experiment and Theory (pages 3476–3483)

      Matthew O. Reese, Alexandre M. Nardes, Benjamin L. Rupert, Ross E. Larsen, Dana C. Olson, Matthew T. Lloyd, Sean E. Shaheen, David S. Ginley, Garry Rumbles and Nikos Kopidakis

      Article first published online: 23 AUG 2010 | DOI: 10.1002/adfm.201001079

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      The mechanism of photoinduced degradation in bulk heterojunctions of P3HT and PCBM is studied using contactless photoconductivity, spectroscopy, structural characterization at the molecular and film level, and quantum chemical calculations. While PCBM is found to stabilize P3HT films exposed to air, the fullerene cage undergoes a series of oxidations leading to significant deterioration of the photoconductivity of the material.

    7. Heteroepitaxial Patterned Growth of Vertically Aligned and Periodically Distributed ZnO Nanowires on GaN Using Laser Interference Ablation (pages 3484–3489)

      Dajun Yuan, Rui Guo, Yaguang Wei, Wenzhuo Wu, Yong Ding, Zhong Lin Wang and Suman Das

      Article first published online: 23 AUG 2010 | DOI: 10.1002/adfm.201001058

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      The figure shows a scanning electron microscope image of vertically aligned ZnO nanowire arrays produced through heteroepitaxial growth on GaN substrates patterned through laser interference ablation. The micrograph shows 45° tilted views of aligned individual ZnO nanowires with uniform diameter, height, and 2 μm period on a portion of a growth area spanning one square centimeter. The inset image is an enlarged view of the nanowires (scale bar is 1 μm).

    8. Atomically Defined Rare-Earth Scandate Crystal Surfaces (pages 3490–3496)

      Josée E. Kleibeuker, Gertjan Koster, Wolter Siemons, David Dubbink, Bouwe Kuiper, Jeroen L. Blok, Chan-Ho Yang, Jayakanth Ravichandran, Ramamoorthy Ramesh, Johan E. ten Elshof, Dave H. A. Blank and Guus Rijnders

      Article first published online: 23 AUG 2010 | DOI: 10.1002/adfm.201000889

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      Expanding the numberof atomically flat perovskite-type oxides: controlled selective wet etching of rare-earth scandates results in single-terminated, well-defined surfaces. Using the powerful combination of time-of-flight mass spectroscopy and the morphology study of SrRuO3 thin-film growth, complete ScO2-termination of the surfaces is established.

    9. Poly[oligo(ethylene glycol) methacrylate-co-glycidyl methacrylate] Brush Substrate for Sensitive Surface Plasmon Resonance Imaging Protein Arrays (pages 3497–3503)

      Weihua Hu, Yingshuai Liu, Zhisong Lu and Chang Ming Li

      Article first published online: 27 AUG 2010 | DOI: 10.1002/adfm.201001159

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      A POEGMA-co-GMA polymer brush prepared via SI-ATRP possesses a high protein loading capacity of 1.8 monolayers and efficient resistance to nonspecific protein adsorption. Using it as a unique supporting layer, label-free and multiplexed SPRi detection of AFP, CEA and HBsAg in human serum was achieved at satisfying detection limits (50, 20, and 100 ng mL−1, respectively) and with excellent specificity.

    10. FeCl3-Based Few-Layer Graphene Intercalation Compounds: Single Linear Dispersion Electronic Band Structure and Strong Charge Transfer Doping (pages 3504–3509)

      Da Zhan, Li Sun, Zhen Hua Ni, Lei Liu, Xiao Feng Fan, Yingying Wang, Ting Yu, Yeng Ming Lam, Wei Huang and Ze Xiang Shen

      Article first published online: 27 AUG 2010 | DOI: 10.1002/adfm.201000641

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      Iron chloride intercalated few-layer graphene are successfully prepared and systematically studied by Raman spectroscopy. Raman spectra of such few-layer graphene intercalation compounds (FLGIC) clearly reveal the single-layer graphene-like electronic structure and strong charge transfer induced doping effect. Such properties are further confirmed by first principle calculations. The successful fabrication of FLGIC opens a new way to modify properties of graphene for future applications.

  8. Frontispiece

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    1. Tunable Dielectric Function in Electric-Responsive Glass with Tree-Like Percolating Pathways of Chargeable Conductive Nanoparticles (page 3510)

      Alberto Paleari, Sergio Brovelli, Roberto Lorenzi, Marco Giussani, Alessandro Lauria, Natalia Mochenova and Norberto Chiodini

      Article first published online: 20 OCT 2010 | DOI: 10.1002/adfm.201090094

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      Electrically driven, responsive nanomaterials are demonstrated, focusing on the rational design of a nanostructured glass with tunable dielectric function obtained by injection and accumulation of charge on semiconductor nanocrystals. This leads to electrically controlled switching of semiconducting nanophases to charged polarizable states. Charge transport and capacitance data demonstrate the role of the nanophase and confirm the polarization effect enabled by the tree-like percolation mechanisms.

  9. Full Papers

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    1. Tunable Dielectric Function in Electric-Responsive Glass with Tree-Like Percolating Pathways of Chargeable Conductive Nanoparticles (pages 3511–3518)

      Alberto Paleari, Sergio Brovelli, Roberto Lorenzi, Marco Giussani, Alessandro Lauria, Natalia Mochenova and Norberto Chiodini

      Article first published online: 17 AUG 2010 | DOI: 10.1002/adfm.201000449

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      Electrically driven, responsive nanomaterials are demonstrated, focusing on the rational design of a nanostructured glass with tunable dielectric function obtained by injection and accumulation of charge on semiconductor nanocrystals. This leads to electrically controlled switching of semiconducting nanophases to charged polarizable states. Charge transport and capacitance data demonstrate the role of the nanophase and confirm the polarization effect enabled by the tree-like percolation mechanisms.

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      Effects of Thermal Annealing Upon the Morphology of Polymer–Fullerene Blends (pages 3519–3529)

      Eric Verploegen, Rajib Mondal, Christopher J. Bettinger, Seihout Sok, Michael F. Toney and Zhenan Bao

      Article first published online: 18 AUG 2010 | DOI: 10.1002/adfm.201000975

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      In situ grazing incidence X-ray scattering is used to systematically characterize the thin film morphology of polymer–fullerene bulk heterojunction blends during the thermal annealing process. This work provides insight into the nature and dynamics of the crystallization processes of P3HT – PCBM blends that can be used to guide the optimization of the processing conditions for organic solar cell devices.

    3. Anomalous Raman Scattering of Colloidal Yb3+,Er3+ Codoped NaYF4 Nanophosphors and Dynamic Probing of the Upconversion Luminescence (pages 3530–3537)

      Jingning Shan, Mruthunjaya Uddi, Nan Yao and Yiguang Ju

      Article first published online: 18 AUG 2010 | DOI: 10.1002/adfm.201000933

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      Size-dependent Raman spectra and dynamic upconversion luminescence of the colloidal Yb3+,Er3+ codoped NaYF4 nanophosphors are investigated. Anomalous line narrowing of the Raman scattering with decreasing the particle size and fluorescence decays indicate that the surface effects instead of the phonon confinement are dominant in affecting the energy transfer of an upconversion process.

    4. Performance Optimization of Polymer Solar Cells Using Electrostatically Sprayed Photoactive Layers (pages 3538–3546)

      Joon-Sung Kim, Won-Suk Chung, Kyungkon Kim, Dong Young Kim, Ki-Jung Paeng, Seong Mu Jo and Sung-Yeon Jang

      Article first published online: 4 AUG 2010 | DOI: 10.1002/adfm.201000433

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      Polymer solar cells (PSCs) are fabricated using a novel film deposition method, the electrostatic spray (e-spray) technique. The performance of PSCs is primarily influenced by the inherent film morphology of the e-sprayed films, and is optimized by reducing the internal resistance. The performance of the e-sprayed PSCs is comparable to that of the PSCs fabricated using the spin-coating method under identical conditions.

    5. Autonomic Recovery of Fiber/Matrix Interfacial Bond Strength in a Model Composite (pages 3547–3554)

      Benjamin J. Blaiszik, Marta Baginska, Scott R. White and Nancy R. Sottos

      Article first published online: 18 AUG 2010 | DOI: 10.1002/adfm.201000798

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      Autonomic self-healing of interfacial damage in a model single-fiber composite is achieved through sequestration of ca. 1.5-μm-diameter dicyclopentadiene (DCPD) healing-agent-filled capsules and recrystallized Grubbs’ catalyst to the fiber/matrix interface. When damage initiates at the interface, the capsules on the fiber surface rupture, and healing agent is released into the crack plane where it contacts the catalyst, initiating polymerization. Up to 44% average recovery of interfacial shear strength is achieved.

    6. An Organic Hole Transport Layer Enhances the Performance of Colloidal PbSe Quantum Dot Photovoltaic Devices (pages 3555–3560)

      Chih-Yin Kuo, Ming-Shin Su, Yu-Chien Hsu, Hui-Ni Lin and Kung-Hwa Wei

      Article first published online: 18 AUG 2010 | DOI: 10.1002/adfm.201001047

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      A photovoltaic device incorporating a PEDOT:PSS hole transport layer and PbSe QDs exhibits a solar power conversion efficiency of 2.4%, substantially enhanced (by 60%) relative to that of a standard PbSe QD device. The corresponding solar device life time, measured in terms of the time required to reach 80% of the normalized efficiency, is improved six-fold.

    7. Integrating Ionic Gate and Rectifier Within One Solid-State Nanopore via Modification with Dual-Responsive Copolymer Brushes (pages 3561–3567)

      Wei Guo, Hongwei Xia, Liuxuan Cao, Fan Xia, Shutao Wang, Guangzhao Zhang, Yanlin Song, Yugang Wang, Lei Jiang and Daoben Zhu

      Article first published online: 23 AUG 2010 | DOI: 10.1002/adfm.201000989

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      A dual-functional single-pore nanofluidic device with both steric exclusion induced ionic gating function and charge selectivity based ion rectifying function is demonstrated. The compound nanofluidic device returns two distinctive feedback signals: the changes in ion permeability and the changes in ionic rectifying capability, in response to separate input stimuli, temperature, and pH. The functionalities are realized by fabricating copolymer brushes onto one cone-shaped solid-state nanopore.

    8. Electrodeposition on Nanofibrous Polymer Scaffolds: Rapid Mineralization, Tunable Calcium Phosphate Composition and Topography (pages 3568–3576)

      Chuanglong He, Guiyong Xiao, Xiaobing Jin, Chenghui Sun and Peter X. Ma

      Article first published online: 30 JUL 2010 | DOI: 10.1002/adfm.201000993

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      Flowers of bone-like mineral are grown on biodegradable polymer nanofibers under an electric field. A fast electrodeposition technique is developed in this work to fabricate mineralized nanofibrous polymer scaffolds with mineral composition, content, and topography that are tunable by varying the processing parameters. The resulting scaffold mimics the extracellular matrix of natural bone and can provide an advanced interface for bone regeneration.

    9. Stretchable, Transparent Zinc Oxide Thin Film Transistors (pages 3577–3582)

      Kyungyea Park, Deok-Kyou Lee, Byung-Sung Kim, Haseok Jeon, Nae-Eung Lee, Dongmok Whang, Hoo-Jeong Lee, Youn Jea Kim and Jong-Hyun Ahn

      Article first published online: 18 AUG 2010 | DOI: 10.1002/adfm.201001107

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      Stretchable and transparent zinc oxide thin film transistor arrays are fabricated on rubber substrates using a wavy structural configuration that can provide high flexibility and stretchability. These design and fabrication methods offer the possibility of developing a new format of stretchable electronics.

    10. Copolymer Networks Based on Poly(ω-pentadecalactone) and Poly(ϵ-caprolactone)Segments as a Versatile Triple-Shape Polymer System (pages 3583–3594)

      Jörg Zotzmann, Marc Behl, Yakai Feng and Andreas Lendlein

      Article first published online: 26 AUG 2010 | DOI: 10.1002/adfm.201000478

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      The domains of multiphase copolymer networks obtained by linking star-shaped precursors that have segments of poly(ω-pentadecalactone) (red) and poly(ε-caprolactone) (yellow) with a diisocyanate (black) act as stimuli-sensitive switches, which enable a triple-shape effect. This triple-shape effect could be obtained by two-step programming at Thigh as well as a one-step deformation at Thigh or, most impressively, at ambient temperature.

    11. Anchoring Hydrous RuO2 on Graphene Sheets for High-Performance Electrochemical Capacitors (pages 3595–3602)

      Zhong-Shuai Wu, Da-Wei Wang, Wencai Ren, Jinping Zhao, Guangmin Zhou, Feng Li and Hui-Ming Cheng

      Article first published online: 23 AUG 2010 | DOI: 10.1002/adfm.201001054

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      Hydrous ruthenium oxide/graphene sheet composites (ROGSCs) are prepared by combining a sol–gel method and low-temperature annealing. ROGSC-based electrochemical capacitors display high specific capacitance (570 F g−1 for 38.3 wt% Ru), enhanced rate capability, excellent electrochemical stability (˜97.9% after 1000 cycles), and high energy density (20.1 Wh kg−1) or power density (10000 W kg−1), due to positive synergistic effect.

    12. Ferritin–Polymer Conjugates: Grafting Chemistry and Integration into Nanoscale Assemblies (pages 3603–3612)

      Yunxia Hu, Debasis Samanta, Sangram S. Parelkar, Sung Woo Hong, Qian Wang, Thomas P. Russell and Todd Emrick

      Article first published online: 23 AUG 2010 | DOI: 10.1002/adfm.201000958

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      Poly(methacryloyloxyethyl phosphorylcholine) (polyMPC) and poly(PEG methacrylate) (polyPEGMA) chains are grafted onto the nanocages by atom transfer radical polymerization (ATRP), and the polymer grafting to the nanocage surface is the enabling feature for generating clean assemblies of ferritin with diblock copolymers, and for masking the ferritin nanocages from antibody recognition.

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