Recent progress in creating complex and multiplexed surface-grafted macromolecular architectures.

Surface-grafted macromolecules, including polymers, DNA, peptides, etc., are versatile modifications to tailor the interfacial functions in a wide range of fields. In this review, we aim to provide an overview of the most recent progress in engineering surface-grafted chains for the creation of complex and multiplexed surface architectures over micro- to macro-scopic areas. A brief introduction to surface grafting is given first. Then the fabrication of complex surface architectures is summarized with a focus on controlled chain conformations, grafting densities and three-dimensional structures. Furthermore, recent advances are highlighted for the generation of multiplexed arrays with designed chemical composition in both horizontal and vertical dimensions. The applications of such complicated macromolecular architectures are then briefly discussed. Finally, some perspective outlooks for future studies and challenges are suggested. We hope that this review will be helpful to those just entering this field and those in the field requiring quick access to useful reference information about the progress in the properties, processing, performance, and applications of functional surface-grafted architectures.

[1]  Zijian Zheng,et al.  Construction of 3D polymer brushes by dip-pen nanodisplacement lithography: understanding the molecular displacement for ultrafine and high-speed patterning. , 2015, Small.

[2]  Zijian Zheng,et al.  High-resolution, large-area, serial fabrication of 3D polymer brush structures by parallel dip-pen nanodisplacement lithography. , 2012, Small.

[3]  Egor M. Larin,et al.  Surface patterning of nanoparticles with polymer patches , 2016, Nature.

[4]  Dianzeng Jia,et al.  Microfluidically mediated atom-transfer radical polymerization. , 2019, Chemical communications.

[5]  Wei-min Liu,et al.  Continuous Surface Polymerization via Fe(II)‐Mediated Redox Reaction for Thick Hydrogel Coatings on Versatile Substrates , 2018, Advanced materials.

[6]  K. Ijiro,et al.  A Strategy for Finely Aligned Gold Nanorod Arrays using Polymer Brushes as a Template. , 2020, Langmuir : the ACS journal of surfaces and colloids.

[7]  C. Hawker,et al.  Fabrication of complex three-dimensional polymer brush nanostructures through light-mediated living radical polymerization. , 2013, Angewandte Chemie.

[8]  R. Jordan,et al.  Surface-Initiated Cu(0)-Mediated CRP for the Rapid and Controlled Synthesis of Quasi-3D Structured Polymer Brushes. , 2019, ACS macro letters.

[9]  C. Stafford,et al.  Quantifying Strain via Buckling Instabilities in Surface Modified Polymer Brushes. , 2020, Macromolecules.

[10]  V. Vasilevskaya,et al.  Self-Assembly into Strands in Amphiphilic Polymer Brushes. , 2016, Langmuir : the ACS journal of surfaces and colloids.

[11]  C. Mirkin,et al.  Large-Area Patterning of Metal Nanostructures by Dip-Pen Nanodisplacement Lithography for Optical Applications. , 2017, Small.

[12]  S. Minko,et al.  Robust, Solvent-Free, Catalyst-Free Click Chemistry for the Generation of Highly Stable Densely Grafted Poly(ethylene glycol) Polymer Brushes by the Grafting To Method and Their Properties , 2016 .

[13]  Zhong-yuan Lu,et al.  Tethering solvophilic blocks to the ends of polymer brushes: an effective method for adjusting surface patterns. , 2019, Soft matter.

[14]  M. Damha,et al.  High‐Density RNA Microarrays Synthesized In Situ by Photolithography , 2018, Angewandte Chemie.

[15]  Xin Jia,et al.  “ anywhere ” under sunlight : a universal surface-initiated polymerization from polydopamine-coated surfaces † , 2014 .

[16]  J. Kaar,et al.  Reduced Enzyme Dynamics upon Multipoint Covalent Immobilization Leads to Stability-Activity Tradeoff. , 2020, Journal of the American Chemical Society.

[17]  Bin Zhao,et al.  Fabrication of 2D Block Copolymer Brushes via a Polymer-Single-Crystal-Assisted-Grafting-to Method. , 2020, Macromolecular rapid communications.

[18]  Andy T. Tek,et al.  Surface Initiated Polymer Thin Films for the Area Selective Deposition and Etching of Metal Oxides. , 2020, ACS nano.

[19]  O. Soppera,et al.  Nitroxide Mediated Photopolymerization: A Versatile Tool for the Fabrication of Complex Multilayer Polyfunctional Copolymer Nanostructures , 2014 .

[20]  V. Studer,et al.  A New Approach to Design Artificial 3D Microniches with Combined Chemical, Topographical, and Rheological Cues , 2018 .

[21]  Eric Huang,et al.  Microfluidic impact printer with interchangeable cartridges for versatile non-contact multiplexed micropatterning. , 2013, Lab on a chip.

[22]  N. Spencer,et al.  Oxygen Tolerant and Cytocompatible Iron(0)-Mediated ATRP Enables the Controlled Growth of Polymer Brushes from Mammalian Cell Cultures. , 2020, Journal of the American Chemical Society.

[23]  Zijian Zheng,et al.  Polymer Brush Electrets , 2013 .

[24]  Richard A. Vaia,et al.  Multi-component hierarchically structured polymer brushes , 2012 .

[25]  Zijian Zheng,et al.  3D-patterned polymer brush surfaces , 2011 .

[26]  A. Alleyne,et al.  Block copolymer assembly on nanoscale patterns of polymer brushes formed by electrohydrodynamic jet printing. , 2014, ACS nano.

[27]  Zijian Zheng,et al.  Massively parallel patterning of complex 2D and 3D functional polymer brushes by polymer pen lithography. , 2014, ACS applied materials & interfaces.

[28]  Mark A. Skylar-Scott,et al.  Voxelated soft matter via multimaterial multinozzle 3D printing , 2019, Nature.

[29]  George C Schatz,et al.  Apertureless cantilever-free pen arrays for scanning photochemical printing. , 2015, Small.

[30]  Zev J. Gartner,et al.  Interrogating cellular fate decisions with high-throughput arrays of multiplexed cellular communities , 2016, Nature Communications.

[31]  P. Braun,et al.  Polymer brushes patterned with micrometer-scale chemical gradients using laminar co-flow. , 2014, ACS applied materials & interfaces.

[32]  Shilin Huang,et al.  Lossless Fast Drop Self‐Transport on Anisotropic Omniphobic Surfaces: Origin and Elimination of Microscopic Liquid Residue , 2019, Advanced materials.

[33]  Zhiqiang Cheng,et al.  Kinetic and high-throughput profiling of epigenetic interactions by 3D-carbene chip-based surface plasmon resonance imaging technology , 2017, Proceedings of the National Academy of Sciences.

[34]  J. Gautrot,et al.  Surface-initiated polymer brushes in the biomedical field: applications in membrane science, biosensing, cell culture, regenerative medicine and antibacterial coatings. , 2014, Chemical reviews.

[35]  W. Tan,et al.  Multicolor and Erasable DNA Photolithography , 2014, ACS nano.

[36]  Tailoring cryo-electron microscopy grids by photo-micropatterning for in-cell structural studies , 2019, Nature Methods.

[37]  E. Thormann,et al.  Salt-Induced Control of the Grafting Density in Poly(ethylene glycol) Brush Layers by a Grafting-to Approach. , 2018, Langmuir : the ACS journal of surfaces and colloids.

[38]  F. Breitling,et al.  Miniaturized and Automated Synthesis of Biomolecules—Overview and Perspectives , 2019, Advanced materials.

[39]  B. Li,et al.  Capillary Microfluidic-Assisted Surface Structuring. , 2020, ACS macro letters.

[40]  Will R. Gutekunst,et al.  Metal-Free Removal of Polymer Chain Ends Using Light. , 2016, Macromolecules.

[41]  Adam B. Braunschweig,et al.  Controlled-Height Brush Polymer Patterns via Surface-Initiated Thiol-Methacrylate Photopolymerizations. , 2019, ACS macro letters.

[42]  K. Hölz,et al.  Multi-level patterning nucleic acid photolithography , 2019, Nature Communications.

[43]  Andreas B. Dahlin,et al.  Strongly stretched protein resistant poly(ethylene glycol) brushes prepared by grafting-to. , 2015, ACS applied materials & interfaces.

[44]  T. Okano,et al.  Artificial cilia as autonomous nanoactuators: Design of a gradient self-oscillating polymer brush with controlled unidirectional motion , 2016, Science Advances.

[45]  N. Spencer,et al.  Modulation of Surface-Initiated ATRP by Confinement: Mechanism and Applications , 2017, Macromolecules.

[46]  Sarah Hurst Petrosko,et al.  Evolution of Dip-Pen Nanolithography (DPN): From Molecular Patterning to Materials Discovery. , 2020, Chemical reviews.

[47]  I. Manners,et al.  Tailored multifunctional micellar brushes via crystallization-driven growth from a surface , 2019, Science.

[48]  K. Hinrichs,et al.  Mussel‐Inspired Polymer Carpets: Direct Photografting of Polymer Brushes on Polydopamine Nanosheets for Controlled Cell Adhesion , 2016, Advanced materials.

[49]  Daewha Hong,et al.  Antifouling Surface Coating Using Droplet-Based SI-ARGET ATRP of Carboxybetaine under Open-Air Conditions. , 2019, Langmuir : the ACS journal of surfaces and colloids.

[50]  S. Minko,et al.  Tunable plasmonic nanostructures from noble metal nanoparticles and stimuli-responsive polymers , 2012 .

[51]  Adam B. Braunschweig,et al.  Towards scanning probe lithography-based 4D nanoprinting by advancing surface chemistry, nanopatterning strategies, and characterization protocols. , 2016, Chemical Society reviews.

[52]  M. C. Stuart,et al.  Emerging applications of stimuli-responsive polymer materials. , 2010, Nature materials.

[53]  Olivia J. Scheideler,et al.  Recapitulating complex biological signaling environments using a multiplexed, DNA-patterning approach , 2020, Science Advances.

[54]  Eric Henderson,et al.  Microfabricated "Biomolecular Ink Cartridges"—Surface patterning tools (SPTs) for the printing of multiplexed biomolecular arrays , 2006 .

[55]  A. Goto,et al.  Multistimuli Responsive Reversible Cross-Linking-Decross-Linking of Concentrated Polymer Brushes. , 2020, ACS applied materials & interfaces.

[56]  R. Haag,et al.  Biospecific Monolayer Coating for Multivalent Capture of Circulating Tumor Cells with High Sensitivity , 2019, Advanced Functional Materials.

[57]  P. Braun,et al.  General Method for Forming Micrometer-Scale Lateral Chemical Gradients in Polymer Brushes , 2014 .

[58]  P. Taboada,et al.  Submicron Patterning of Polymer Brushes: An Unexpected Discovery from Inkjet Printing of Polyelectrolyte Macroinitiators. , 2016, Journal of the American Chemical Society.

[59]  Liqiang Li,et al.  Surface-grafting polymers: from chemistry to organic electronics , 2020, Materials Chemistry Frontiers.

[60]  E. Gulari,et al.  Individually addressable parallel peptide synthesis on microchips , 2002, Nature Biotechnology.

[61]  K. Matyjaszewski,et al.  Brush-modified materials: Control of molecular architecture, assembly behavior, properties and applications , 2020 .

[62]  Omar Azzaroni,et al.  Practical use of polymer brushes in sustainable energy applications: interfacial nanoarchitectonics for high-efficiency devices. , 2019, Chemical Society reviews.

[63]  J. Genzer,et al.  Opto-mechanical scission of polymer chains in photosensitive diblock-copolymer brushes. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[64]  Feng Zhou,et al.  Grafting robust thick zwitterionic polymer brushes via subsurface-initiated ring-opening metathesis polymerization for anti-microbial and anti-biofouling. , 2019, ACS applied materials & interfaces.

[65]  Shuang Hou,et al.  Programming Thermoresponsiveness of NanoVelcro Substrates Enables Effective Purification of Circulating Tumor Cells in Lung Cancer Patients , 2014, ACS nano.

[66]  J. Genzer,et al.  Enhanced Stability of Surface-Tethered Diblock Copolymer Brushes with a Neutral Polymer Block and a Weak Polyelectrolyte Block: Effects of Molecular Weight and Hydrophobicity of the Neutral Block , 2017 .

[67]  Harm-Anton Klok,et al.  Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes. , 2017, Chemical reviews.

[68]  Peng-Yuan Wang,et al.  Decoration of Material Surfaces with Complex Physicochemical Signals for Biointerface Applications. , 2020, ACS biomaterials science & engineering.

[69]  Badriprasad Ananthanarayanan,et al.  Stimuli-sensitive intrinsically disordered protein brushes , 2014, Nature Communications.

[70]  H. Klok,et al.  Complex polymer topologies and polymer—nanoparticle hybrid films prepared via surface-initiated controlled radical polymerization , 2020 .

[71]  R. Bar-Ziv,et al.  DNA condensation in one dimension. , 2016, Nature nanotechnology.

[72]  Jeffrey S. Moore,et al.  Spatially Selective and Density-Controlled Activation of Interfacial Mechanophores. , 2019, Journal of the American Chemical Society.

[73]  N. Gianneschi,et al.  Polymer brush hypersurface photolithography , 2020, Nature Communications.

[74]  Changyou Gao,et al.  A complementary density gradient of zwitterionic polymer brushes and NCAM peptides for selectively controlling directional migration of Schwann cells. , 2015, Biomaterials.

[75]  Emre H. Discekici,et al.  Simultaneous Preparation of Multiple Polymer Brushes under Ambient Conditions using Microliter Volumes. , 2018, Angewandte Chemie.

[76]  C. Mirkin,et al.  Solution-Phase Photochemical Nanopatterning Enabled by High-Refractive-Index Beam Pen Arrays. , 2017, ACS nano.

[77]  Deborah E Leckband,et al.  Poly(N-isopropyl acrylamide) brush topography: dependence on grafting conditions and temperature. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[78]  P. Bastiaens,et al.  Configurable low-cost plotter device for fabrication of multi-color sub-cellular scale microarrays. , 2014, Small.

[79]  K. A. Brown,et al.  Liquid-Phase Beam Pen Lithography. , 2016, Small.

[80]  J. Rühe,et al.  Highly Selective Capture Surfaces on Medical Wires for Fishing Tumor Cells in Whole Blood. , 2017, Analytical chemistry.

[81]  Hao Qi,et al.  Towards controlled polymer brushes via a self-assembly-assisted-grafting-to approach , 2016, Nature Communications.

[82]  Huan H. Cao,et al.  Controlled DNA Patterning by Chemical Lift-Off Lithography: Matrix Matters. , 2015, ACS nano.

[83]  Jiaxi Cui,et al.  Phototriggered Growth and Detachment of Polymer Brushes with Wavelength Selectivity. , 2018, ACS macro letters.

[84]  A. Welle,et al.  Replication of Polymer Based Peptide Microarrays by Multi Step Transfer , 2016 .

[85]  Yi Wang,et al.  Biomimicking Nano-Micro Binary Polymer Brushes for Smart Cell Orientation and Adhesion Control. , 2016, Small.

[86]  P. Gopalan,et al.  Phase Behavior of Mixed Polymer Brushes Grown from Ultrathin Coatings. , 2019, ACS macro letters.

[87]  S. Inagi,et al.  Electrochemically mediated atom transfer radical polymerization from a substrate surface manipulated by bipolar electrolysis: fabrication of gradient and patterned polymer brushes. , 2015, Angewandte Chemie.

[88]  Christopher Y. Li,et al.  Terraced and Smooth Gradient Polymer Brushes via a Polymer Single-Crystal Assisted Grafting-To Method. , 2018, Angewandte Chemie.

[89]  F. Breitling,et al.  A Trifunctional Linker for Purified 3D Assembled Peptide Structure Arrays , 2018 .

[90]  H. Schönherr,et al.  Block Copolymer Brushes for Completely Decoupled Control of Determinants of Cell-Surface Interactions. , 2016, Angewandte Chemie.

[91]  B. Cui,et al.  Electron Beam Lithography on Irregular Surface Using Grafted PMMA Monolayer as Resist , 2017 .

[92]  K. Lam,et al.  Combinatorial Peptide Microarray Synthesis Based on Microfluidic Impact Printing , 2018, ACS combinatorial science.

[93]  C. Barner‐Kowollik,et al.  2D laser lithography on silicon substrates via photoinduced copper-mediated radical polymerization. , 2018, Chemical communications.

[94]  K. Matyjaszewski,et al.  Biocatalytic "Oxygen-Fueled" Atom Transfer Radical Polymerization. , 2018, Angewandte Chemie.

[95]  K. A. Brown,et al.  Nanocombinatorics with Cantilever-Free Scanning Probe Arrays. , 2019, ACS nano.

[96]  R. Bar-Ziv,et al.  Emergent properties of dense DNA phases toward artificial biosystems on a surface. , 2014, Accounts of chemical research.

[97]  Alexandra M. Greiner,et al.  Micropatterning: Interdigitated Multicolored Bioink Micropatterns by Multiplexed Polymer Pen Lithography (Small 19/2013) , 2013 .

[98]  N. Spencer,et al.  Fabrication and Interfacial Properties of Polymer Brush Gradients by Surface-Initiated Cu(0)-Mediated Controlled Radical Polymerization , 2017 .

[99]  Christof M Niemeyer,et al.  DNA Surface Technology: From Gene Sensors to Integrated Systems for Life and Materials Sciences. , 2018, Angewandte Chemie.

[100]  T. Chen,et al.  Spatiotemporal control of polymer brush formation through photoinduced radical polymerization regulated by DMD light modulation. , 2019, Lab on a chip.

[101]  Zheng‐Hong Luo,et al.  Role of External Field in Polymerization: Mechanism and Kinetics. , 2020, Chemical reviews.

[102]  Lloyd M. Smith,et al.  Enzymatic fabrication of high-density RNA arrays. , 2014, Angewandte Chemie.

[103]  A. C. Jamison,et al.  Robust Thick Polymer Brushes Grafted from Gold Surfaces Using Bidentate Thiol-Based Atom-Transfer Radical Polymerization Initiators. , 2016, ACS applied materials & interfaces.

[104]  Xiaolong Wang,et al.  Fabrication of arbitrary three-dimensional polymer structures by rational control of the spacing between nanobrushes. , 2011, Angewandte Chemie.

[105]  Zijian Zheng,et al.  Functional polymer surfaces for controlling cell behaviors , 2017 .

[106]  Tao Chen,et al.  Wafer-scale synthesis of defined polymer brushes under ambient conditions , 2015 .

[107]  H. Klok,et al.  Reversibly Cross-Linking Polymer Brushes Using Interchain Disulfide Bonds , 2020 .

[108]  Jens Bauer,et al.  Multiscale Origami Structures as Interface for Cells. , 2015, Angewandte Chemie.

[109]  Lindsey C. Szymczak,et al.  Peptide Arrays: Development and Application. , 2018, Analytical chemistry.

[110]  V. Somoza,et al.  Next-Generation o-Nitrobenzyl Photolabile Groups for Light-Directed Chemistry and Microarray Synthesis** , 2015, Angewandte Chemie.

[111]  Guangzhao Zhang,et al.  Liquid-mediated three-dimensional scanning probe nanosculpting. , 2013, Small.

[112]  J. Lahann,et al.  Substrate-Independent Micropatterning of Polymer Brushes Based on Photolytic Deactivation of Chemical Vapor Deposition Based Surface-Initiated Atom-Transfer Radical Polymerization Initiator Films. , 2018, ACS applied materials & interfaces.

[113]  K. Niikura,et al.  DNA Brush-Directed Vertical Alignment of Extensive Gold Nanorod Arrays with Controlled Density , 2017, ACS omega.

[114]  E. N. Govorun,et al.  Surfactant-Induced Patterns in Polymer Brushes. , 2017, Langmuir : the ACS journal of surfaces and colloids.

[115]  A. Goto,et al.  Facile Fabrication of Concentrated Polymer Brushes with Complex Patterning by Photocontrolled Organocatalyzed Living Radical Polymerization. , 2018, Angewandte Chemie.

[116]  F. Bischoff,et al.  High-flexibility combinatorial peptide synthesis with laser-based transfer of monomers in solid matrix material , 2016, Nature Communications.

[117]  K. Eichhorn,et al.  Chain Extension of Stimuli‐Responsive Polymer Brushes: A General Strategy to Overcome the Drawbacks of the “Grafting‐To” Approach , 2013 .

[118]  J. Genzer,et al.  Light-Induced Reversible Change of Roughness and Thickness of Photosensitive Polymer Brushes. , 2016, ACS applied materials & interfaces.

[119]  Harald Fuchs,et al.  A Versatile Microarray Platform for Capturing Rare Cells , 2015, Scientific Reports.

[120]  R. Chapman,et al.  An Oxygen-Tolerant PET-RAFT Polymerization for Screening Structure-Activity Relationships. , 2018, Angewandte Chemie.

[121]  M. Kamperman,et al.  Recent Developments and Practical Feasibility of Polymer‐Based Antifouling Coatings , 2020, Advanced Functional Materials.

[122]  D. Scaini,et al.  Quantification of Circulating Cancer Biomarkers via Sensitive Topographic Measurements on Single Binder Nanoarrays , 2017, ACS omega.

[123]  Xungai Wang,et al.  Solvent-driven migration of highly polar monomers into hydrophobic PDMS produces a thick graft layer via subsurface initiated ATRP for efficient antibiofouling. , 2020, Chemical communications.

[124]  B. Cui,et al.  Grafted Polystyrene Monolayer Brush as Both Negative and Positive Tone Electron Beam Resist. , 2017, Langmuir : the ACS journal of surfaces and colloids.

[125]  Barbara Pui Chan,et al.  Parallel, Multi-Material Electrohydrodynamic 3D Nanoprinting. , 2020, Small.

[126]  Christopher K. Ober,et al.  50th Anniversary Perspective: Polymer Brushes: Novel Surfaces for Future Materials , 2017 .

[127]  Blair K. Brettmann,et al.  Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes , 2017, Science Advances.

[128]  J. Rühe,et al.  THE SURFACE SCIENCE OF MICROARRAY GENERATION - A CRITICAL INVENTORY. , 2019, ACS applied materials & interfaces.

[129]  R. Bar-Ziv,et al.  Dendritic and nanowire assemblies of condensed DNA polymer brushes. , 2014, Journal of the American Chemical Society.

[130]  Zijian Zheng,et al.  Arbitrary and Parallel Nanofabrication of 3D Metal Structures with Polymer Brush Resists. , 2015, Small.

[131]  Emre H. Discekici,et al.  Simple Benchtop Approach to Polymer Brush Nanostructures Using Visible-Light-Mediated Metal-Free Atom Transfer Radical Polymerization. , 2016, ACS Macro Letters.

[132]  Haeshin Lee,et al.  Polydopamine Surface Chemistry: A Decade of Discovery. , 2018, ACS applied materials & interfaces.

[133]  Mir Jalil Razavi,et al.  Nanoscale Surface Creasing Induced by Post-polymerization Modification. , 2015, ACS nano.

[134]  V. Studer,et al.  Multiprotein Printing by Light‐Induced Molecular Adsorption , 2016, Advanced materials.

[135]  M. Sussman,et al.  Maskless fabrication of light-directed oligonucleotide microarrays using a digital micromirror array , 1999, Nature Biotechnology.

[136]  Emre H. Discekici,et al.  Engineering Surfaces through Sequential Stop‐Flow Photopatterning , 2016, Advanced materials.

[137]  Marco Mende,et al.  A Low‐Cost Laser‐Based Nano‐3D Polymer Printer for Rapid Surface Patterning and Chemical Synthesis of Peptide and Glycan Microarrays , 2019, Advanced Materials Technologies.

[138]  C. Ober,et al.  Synthesis, Processing, and Characterization of Helical Polypeptide Rod-Coil Mixed Brushes. , 2018, ACS macro letters.

[139]  Feng Zhou,et al.  Brushing up functional materials , 2019, NPG Asia Materials.

[140]  Tejal A Desai,et al.  Programmed synthesis of three-dimensional tissues , 2015, Nature Methods.

[141]  C. Stafford,et al.  Buckling Instabilities in Polymer Brush Surfaces via Postpolymerization Modification. , 2017, Macromolecules.

[142]  A. Goto,et al.  Effective Synthesis of Patterned Polymer Brushes with Tailored Multiple Graft Densities. , 2019, ACS applied materials & interfaces.

[143]  Hong Chen,et al.  Multi-Stimulus Responsive Biointerfaces with Switchable Bioadhesion and Surface Functions. , 2020, ACS applied materials & interfaces.

[144]  Alexandra M. Greiner,et al.  Interdigitated multicolored bioink micropatterns by multiplexed polymer pen lithography. , 2013, Small.

[145]  Hongwei Ma,et al.  A facile method for permanent and functional surface modification of poly(dimethylsiloxane). , 2007, Journal of the American Chemical Society.

[146]  G. Fredrickson,et al.  Exploring Lateral Microphase Separation in Mixed Polymer Brushes by Experiment and Self-Consistent Field Theory Simulations , 2012 .

[147]  P. Gopalan,et al.  Substrate-Independent Approach to Dense Cleavable Polymer Brushes by Nitroxide-Mediated Polymerization. , 2018, ACS macro letters.

[148]  L. Ionov,et al.  Programmable patterning of protein bioactivity by visible light. , 2014, Nano letters.

[149]  Nathan J. Rebello,et al.  Effect of Grafting Density of Random Copolymer Brushes on Perpendicular Alignment in PS-b-PMMA Thin Films , 2017 .

[150]  Phillip Stafford,et al.  Scalable high-density peptide arrays for comprehensive health monitoring , 2014, Nature Communications.

[151]  Feng Zhou,et al.  Tapping the potential of polymer brushes through synthesis. , 2015, Accounts of chemical research.

[152]  L. Korley,et al.  Polymer-Grafted Nanoparticles , 2020 .

[153]  Y. Ikada,et al.  Polymer surface with graft chains , 2003 .

[154]  Mir Jalil Razavi,et al.  The Formation and Evolution of Creased Morphologies Using Reactive Diffusion in Ultrathin Polymer Brush Platforms , 2017 .

[155]  K. A. Brown,et al.  Beam pen lithography as a new tool for spatially controlled photochemistry, and its utilization in the synthesis of multivalent glycan arrays. , 2014, Chemical science.

[156]  Zijian Zheng,et al.  Size-tunable, highly sensitive microelectrode arrays enabled by polymer pen lithography. , 2017, Soft matter.

[157]  J. Genzer,et al.  Making polymer brush photosensitive with azobenzene containing surfactants , 2015 .

[158]  C. Mirkin,et al.  Polymer-Pen Chemical Lift-Off Lithography. , 2017, Nano letters.

[159]  Chad A. Mirkin,et al.  Catalyst discovery through megalibraries of nanomaterials , 2018, Proceedings of the National Academy of Sciences.

[160]  M. W. Tsui,et al.  Massively Multiplexed Tip-Based Photochemical Lithography under Continuous Capillary Flow , 2018 .

[161]  Alexandra M. Greiner,et al.  Click‐Chemistry Based Multi‐Component Microarrays by Quill‐Like Pens , 2014 .

[162]  S. P. Fodor,et al.  Light-directed, spatially addressable parallel chemical synthesis. , 1991, Science.

[163]  A. Chilkoti,et al.  In Pursuit of Zero 2.0: Recent Developments in Nonfouling Polymer Brushes for Immunoassays , 2019, Advanced materials.

[164]  J. Lai,et al.  Reversibly photoswitchable gratings prepared from azobenzene-modified tethered poly(methacrylic acid) brush as colored actuator , 2020 .

[165]  C. Niemeyer,et al.  DNA-SMART: Biopatterned Polymer Film Microchannels for Selective Immobilization of Proteins and Cells. , 2017, Small.

[166]  T. Okano,et al.  Fabrication of Micropatterned Self-Oscillating Polymer Brush for Direction Control of Chemical Waves. , 2017, Small.

[167]  Chad A Mirkin,et al.  On-Tip Photo-Modulated Molecular Printing. , 2015, Angewandte Chemie.

[168]  Xiaolong Wang,et al.  Bio-Inspired Renewable Surface-Initiated Polymerization from Permanently Embedded Initiators. , 2016, Angewandte Chemie.

[169]  E. Kumacheva,et al.  Helicoidal Patterning of Nanorods with Polymer Ligands. , 2019, Angewandte Chemie.

[170]  R. Chapman,et al.  Up in the air: oxygen tolerance in controlled/living radical polymerisation. , 2018, Chemical Society reviews.

[171]  M. S. Onses,et al.  Writing chemical patterns using electrospun fibers as nanoscale inkpots for directed assembly of colloidal nanocrystals. , 2019, Nanoscale.

[172]  G. Leggett Light-directed nanosynthesis: near-field optical approaches to integration of the top-down and bottom-up fabrication paradigms. , 2012, Nanoscale.

[173]  Wei‐Ssu Liao,et al.  Surface functional DNA density control by programmable molecular defects. , 2018, Chemical communications.

[174]  A. Sidorenko,et al.  Binary Polymer Brushes of Strongly Immiscible Polymers. , 2015, ACS applied materials & interfaces.

[175]  G. Fredrickson,et al.  Self-assembly in a mixed polymer brush with inhomogeneous grafting density composition , 2013 .

[176]  C. Liu,et al.  “On silico” peptide microarrays for high-resolution mapping of antibody epitopes and diverse protein-protein interactions , 2011, Nature Medicine.

[177]  N. Seeman,et al.  Cinnamate-based DNA photolithography , 2013, Nature materials.

[178]  A. Khokhlov,et al.  Self-assembly in densely grafted macromolecules with amphiphilic monomer units: diagram of states. , 2017, Soft matter.

[179]  Daniel T. Kovari,et al.  Self-regenerating giant hyaluronan polymer brushes , 2019, Nature Communications.

[180]  Haojun Liang,et al.  DNA Polymer Brush Patterning through Photocontrollable Surface-Initiated DNA Hybridization Chain Reaction. , 2015, Small.

[181]  K. Lam,et al.  Microfluidic Print-to-Synthesis Platform for Efficient Preparation and Screening of Combinatorial Peptide Microarrays. , 2018, Analytical chemistry.

[182]  N. Spencer,et al.  Reversible Light-Switching of Enzymatic Activity on Orthogonally Functionalized Polymer Brushes. , 2017, ACS Applied Materials and Interfaces.

[183]  T. Fukuda,et al.  Controlled Synthesis of Concentrated Polymer Brushes with Ultralarge Thickness by Surface-Initiated Atom Transfer Radical Polymerization under High Pressure , 2020 .

[184]  Xiangcheng Pan,et al.  Oxygen-Initiated and Regulated Controlled Radical Polymerization under Ambient Conditions. , 2018, Angewandte Chemie.

[185]  I. Szleifer,et al.  Self-organized polyelectrolyte end-grafted layers under nanoconfinement. , 2014, ACS nano.

[186]  Blair K. Brettmann,et al.  Giant Hyaluronan Polymer Brushes Display Polyelectrolyte Brush Polymer Physics Behavior. , 2019, ACS macro letters.

[187]  B. Spengler,et al.  Combinatorial Synthesis of Peptoid Arrays via Laser-Based Stacking of Multiple Polymer Nanolayers. , 2019, Macromolecular rapid communications.

[188]  Junbai Li,et al.  Complex polymer brush gradients based on nanolithography and surface-initiated polymerization. , 2012, Chemical Society reviews.

[189]  Zijian Zheng,et al.  Proceedings of the Chemical Society. June/July 1959 , 1959 .

[190]  Kato L. Killops,et al.  Advancements and challenges of patterning biomolecules with sub-50 nm features , 2013 .

[191]  H. Fuchs,et al.  Combinatorial Synthesis of Macromolecular Arrays by Microchannel Cantilever Spotting (µCS) , 2018, Advanced materials.

[192]  H. Fuchs,et al.  Multi-color polymer pen lithography for oligonucleotide arrays. , 2016, Chemical communications.

[193]  Chad A. Mirkin,et al.  Desktop Nanofabrication with Massively Multiplexed Beam Pen Lithography , 2013, Nature Communications.

[194]  I. Luzinov,et al.  Polymer brushes by the "grafting to" method. , 2011, Macromolecular rapid communications.

[195]  G. López,et al.  Nanopatterned Polymer Brushes for Triggered Detachment of Anchorage‐Dependent Cells , 2014 .

[196]  R. Bar-Ziv,et al.  Gene Expression on DNA Biochips Patterned with Strand-Displacement Lithography. , 2018, Angewandte Chemie.

[197]  Wufang Yang,et al.  Facile preparation of structured zwitterionic polymer substrate via sub-surface initiated atom transfer radical polymerization and its synergistic marine antifouling investigation , 2019, European Polymer Journal.

[198]  Bárbara Santos Gomes,et al.  The increasing dynamic, functional complexity of bio-interface materials , 2018 .

[199]  T. Chen,et al.  Patterned polymer brushes. , 2012, Chemical Society reviews.

[200]  A. Kuzuya,et al.  Reversible changes in the orientation of gold nanorod arrays on polymer brushes , 2020, Nanoscale advances.

[201]  Adam B. Braunschweig,et al.  Optimization of 4D polymer printing within a massively parallel flow-through photochemical microreactor , 2016 .

[202]  P. Gopalan,et al.  A single-component inimer containing cross-linkable ultrathin polymer coating for dense polymer brush growth. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[203]  J. Genzer,et al.  Light-Induced Structuring of Photosensitive Polymer Brushes , 2019, ACS Applied Polymer Materials.

[204]  Lei Xie,et al.  Controlled Growth of Ultra-Thick Polymer Brushes via Surface-Initiated Atom Transfer Radical Polymerization with Active Polymers as Initiators. , 2019, Macromolecular rapid communications.

[205]  S. Demirci,et al.  A switchable polymer brush system for antifouling and controlled detection. , 2017, Chemical communications.

[206]  F. Bischoff,et al.  Purification of High‐Complexity Peptide Microarrays by Spatially Resolved Array Transfer to Gold‐Coated Membranes , 2013, Advanced materials.

[207]  Changyou Gao,et al.  Preparation of an Arg-Glu-Asp-Val Peptide Density Gradient on Hyaluronic Acid-Coated Poly(ε-caprolactone) Film and Its Influence on the Selective Adhesion and Directional Migration of Endothelial Cells. , 2016, ACS applied materials & interfaces.