Copper-Mediated Living Radical Polymerization (Atom Transfer Radical Polymerization and Copper(0) Mediated Polymerization): From Fundamentals to Bioapplications,Chemical Reviews

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Copper-Mediated Living Radical Polymerization (Atom Transfer Radical Polymerization and Copper(0) Mediated Polymerization): From Fundamentals to Bioapplications
Chemical Reviews ( IF 51.4 ) Pub Date : 2015-11-04 00:00:00 , DOI: 10.1021/acs.chemrev.5b00396
Cyrille Boyer ₁ , Nathaniel Alan Corrigan ₁ , Kenward Jung ₁ , Diep Nguyen ₁ , Thuy-Khanh Nguyen ₁ , Nik Nik M. Adnan ₁ , Susan Oliver ₁ , Sivaprakash Shanmugam ₁ , Jonathan Yeow ₁

Affiliation

This article is part of the Frontiers in Macromolecular and Supramolecular Science special issue.

Cyrille Boyer (front row, left) received his Ph.D. from the University of Montpellier II (Ecole Nationale Superieure de Chimie de Montpellier, France) in 2006. At the end of 2006, he joined the Centre for Advanced Macromolecular Design (CAMD) as a senior research fellow. In 2013, Cyrille was promoted to Associate Professor at the University of New South Wales and received the UNSW Research Excellence Award at the Faculty of Engineering and was a finalist of NSW innovation award in 2014. Cyrille’s research interests mainly cover the use of photoredox catalysts to perform living radical polymerization and polymer postmodification, hybrid organic–inorganic nanoparticles for imaging, and energy storage. Cyrille has published over 150 research articles, including eight patents, which have gathered over 5000 citations. Nathaniel Corrigan (back row, left) was born in Lismore, NSW, Australia in 1991. He completed his Bachelor of Chemical Engineering at the UNSW-Australia in 2014, with his honors project investigating catalyst-free visible light-induced RAFT polymerizations. He is currently undertaking a Ph.D. under the supervision of A/Prof. Cyrille Boyer at UNSW-Australia, with his research focusing on photoredox catalysis for polymerizations as well as other visible light-induced polymerizations. Kenward Jung (back row, second from right) is a Ph.D. student at the Centre for Advanced Macromolecular Design, UNSW-Australia. His research interests are based in the field of polymer chemistry with a particular emphasis on the external regulation of controlled polymerizations and the development of “green” processes for macromolecular design. A major focal point of his research is the development of photoregulated polymerizations in heterogeneous systems. Diep Nguyen (front row, second from right) earned her B.S. in Education of Chemistry from Hue University of Education and M.S. from Vietnam National University of Science. She is currently a Ph.D. student in the research group of A/Prof. Cyrille Boyer at UNSW-Australia. Her Ph.D. involves the design and synthesis of macromolecules for the delivery of carbon monoxide for antimicrobial applications. Thuy-Khanh Nguyen (front row, second from left) received her B.Sc. from James Cook University (Townsville, Australia) in 2009. She worked as a research assistant at the Oxford University Clinical Research Unit (Ho Chi Minh City, Vietnam) from 2010–2011. Nguyen completed her M.Sc. in Infectious Diseases, Drug Discovery and Vaccinology from the National University of Singapore (Singapore) in 2013. She then spent about one year working as a research officer at Vela Diagnostics (Singapore). Since March 2014, Nguyen has been a Ph.D. student at the Australian Centre for Nanomedicine (ACN) and Centre for Advanced Macromolecular Design (CAMD), UNSW-Australia. Her research interests are focused on macromolecular design for drug delivery, nitric oxide, and biofilm dispersal. Nik Nik M. Adnan (front row, right) earned his B.E. at UNSW-Australia. He is currently a Ph.D. student at the Australian Centre for Nanomedicine (ACN) and Centre for Advanced Macromolecular Design (CAMD), UNSW Australia, under the guidance of Cyrille Boyer. His research focuses on the fabrication of therapeutic nanomaterials for biomedical application, mainly on the light-responsive hybrid nanomaterials as cancer phototherapy and drug delivery agents. Susan Oliver (front row, middle) received her B.Sc.(Hons) in industrial chemistry from UNSW-Australia and worked for a number of years in industry, primarily in the pharmaceutical area. She is currently a Ph.D. student working with Cyrille Boyer at the Australian Centre for Nanomedicine (ACN) and Centre for Advanced Macromolecular Design (CAMD). Her research involves enhancing the therapeutic effects of polyphenolic compounds with macromolecules. Sivaprakash Shanmugam (back row, second from left) earned his B.S. in Biochemistry, with a minor in Chemistry, from Case Western Reserve University in 2013. He is currently a postgraduate student pursuing his Ph.D. in Chemical Engineering at UNSW-Australia under the direction of A/Prof. Cyrille Boyer. His research focuses on the development of spatial, temporal, and sequence control of light-mediated RAFT polymerization. Jonathan Yeow (back row, right) is currently undertaking his Ph.D. as part of the Centre for Advanced Macromolecular Design at the University of New South Wales with a focus on biomedical applications of self-assembled polymeric nanoparticles. He received his Bachelor Science (Chemistry) and Bachelor Engineering (Mechanical) (Biomedical) degrees from the University of Sydney in 2013. His research focuses on the implementation of advanced self-assembly techniques to generate polymeric nanoparticles for drug delivery and imaging applications. Apolar solvents include anisole, toluene, etc. Polar solvents include acetonitrile, methanol, water, etc. Disproportionation solvents include DMSO, perfluoro-alcohol, water, etc. Figure 1. Normal, reverse, and SR&NI ATRP. X = (pseudo) halogen, R = alkyl. Red indicates the initial system components. Figure 2. Common ligands used in ATRP and Cu(0)-mediated polymerization with corresponding K_ATRP values for the reaction between ethyl 2-bromoisobutyrate and Cu(I) complexes in acetonitrile at 22 °C. The value for the DMCBCy complex was estimated on the basis of the differences in reactivities of the Cu(I) complexes of Me₆TREN and DMCBCy toward methyl chloroacetate and those of the Cu(I) complex of Me₆TREN toward methyl chloroacetate and ethyl 2-bromoisobutyrate. The value for the TPMA* complex is estimated on the basis of the differences in reactivities of the CuI complexes of TPMA and TPMA* toward MBrP and those of the Cu(I) complex of TPMA toward MBrP and ethyl 2-bromoisobutyrate. Data from refs 100 and 101. Figure 3. AGET, ARGET, ICAR, and SARA ATRP. *In SARA ATRP, the reducing agent is Cu(0) and the oxidized agent is Cu^I–L. Figure 4. Proposed mechanism of SET-LRP by Percec and co-workers. Reprinted with permission from ref 13. Copyright 2011 American Chemical Society. Figure 5. Representative colors of copper-mediated polymerization: (A) Cu(0)-wire-catalyzed copper-mediated polymerization of MA (12.5 cm of 20 gauge wire is wrapped around the stirring bar); reaction conditions, [MA]₀/[MBP]₀/[Me₆TREN]₀ = 222/1/0.1. (B) Cu(I)Br/Me₆TREN-catalyzed polymerization of MA in MeCN; reaction conditions, [MA]₀/[MBP]₀/[Cu(I)Br]₀/[Me₆TREN]₀ = 222/1/0.1/0.1. (C) Cu(I)Br/bpy-catalyzed ATRP of MA in toluene, [MA]₀/[MBP]₀/[Cu(I)Br]₀/[bpy]₀ = 222/1/1/1. (D) Cu(I)Br/bpy-catalyzed ATRP of MA in acetonitrile, [MA]₀/[MBP]₀/[Cu(I)Br]₀/[bpy]₀ = 222/1/1/1. Reprinted with permission from ref 15. Copyright 2011 American Chemical Society. Figure 6. ln([M]₀/[M]) vs time and percentage of bromine-functionalized chain vs conversion (%) for the Cu(0)/Me₆TREN-catalyzed polymerization of MA initiated with methyl-2-bromopropionate (MBP) at 25 °C in pure DMSO and acetonitrile. Experimental condition: [MA]₀/[MBP]₀/[Cu(0)]₀/[Me₆TREN]₀ = 222/1/0.1/0.1, and Cu(0) < 75 mm. Reprinted with permission from ref 155. Copyright 2008 American Chemical Society. Figure 7. eATRP mechanism. ^aAdapted from ref 278. Copyright 2011 Wiley. ^aAdapted from ref 278. Copyright 2011 Wiley. ^a(A) Thio–bromo coupling, (B) bromo–amine coupling, (C) ATNRC, (D) ATR,C (E) CuAAc “click” chemistry, and (F) methanethiosulfonate-mediated thiol–ene and thiol–disulfide exchange reactions. ^a(A) Thio–bromo coupling, (B) bromo–amine coupling, (C) ATNRC, (D) ATR,C (E) CuAAc “click” chemistry, and (F) methanethiosulfonate-mediated thiol–ene and thiol–disulfide exchange reactions. Figure 8. (Left) Self-assembly of diblock copolymers to give micelles with spherical, cylindrical, or vesicle structures. As the length of the green insoluble block increases relative to the blue soluble block, cylindrical and vesicle-like structures are more likely to form as the cpp increases.(329) Reproduced with permission from ref 329. Copyright 2013 PCCP Owner Societies. (Right) Range of morphologies produced by self-assembly of a PS-b-PAA in water; LCM = large compound micelles; HHH = hexagonally packed hollow hoop.(332) Reproduced with permission from ref 332. Copyright 2012 The Royal Society of Chemistry. Figure 9. Schematic illustration of drug-loaded polymeric micelles with acid–base drug–polymer interactions.(354) Reprinted with permission from ref 354. Copyright 2007 American Chemical Society. Figure 10. Structure and mechanism for complexation of PDMAEA-b-PImPAA-b-PnBuA with siRNA and delivery to cytosol via endosomal escape.(355) Reprinted with permission from ref 355. Copyright 2013 American Chemical Society. Figure 11. (Left) Schematic illustration of self-assembly of PTX loaded mixed micelles. (Right) The normalized signal intensity recorded in the rabbit liver of (a) small molecule gadolinium chelate, (b) mixed micelles without FA, and (c) FA-conjugated mixed micelles.(357) Reproduced with permission from ref 357. Copyright 2012 The Royal Society of Chemistry. Figure 12. Common examples of stimuli-responsive monomers that can be polymerized by copper-mediated living radical polymerization. pH-responsive monomers: (C1) DMAEMA = 2-(dimethylamino)ethyl methacrylate, (C2) DMAEA = 2-(dimethylamino)ethyl acrylate, (C3) DEAEMA = 2-(diethylamino)ethyl methacrylate, (C4) DPAEMA = 2-(diisopropylamino)ethyl methacrylate, (C5) 2VP = 2-vinylpyridine, (C6) 4VP = 4-vinylpyridine, (C7) MAA = methacrylic acid, (C8) AA = acrylic acid, (C9) VBzA = 4-vinylbenzoic acid, (C10) MEMA-Hyd = 2-hydrazinyl-2-oxoethyl methacrylate (hydrazide precursor); temperature-responsive monomers: (C11) NIPAAm = N-isopropylacrylamide, (C12) OEGMA = oligo(ethylene glycol) methyl ether methacrylate, (C13) OEGA = oligo(ethylene glycol) methyl ether acrylate, (C14) MEO₂MA = OEGMA where n = 2, (C15) MEDSA = [2-(Methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, (C16) THPMA = tetrahydropyranyl methacrylate; light-responsive monomers: (C17) NBMA = ortho-nitrobenzyl methacrylate, (C18) DEACouMA = (7-(diethylamino)-2-oxo-2H-chromen-4-yl)methyl methacrylate, 7-(diethylamino)coumarin-based methacrylate, (C19) PMPMA = p-methoxyphenacyl methacrylate, (C20) CouHEMA = 2-((4-methyl-2-oxo-2H-chromen-7-yl)oxy)ethyl methacrylate; glucose-responsive monomers: (C21) 4VPBA = (4-vinylphenyl)boronic acid, (C22) pBDEMA = (5-ethyl-2-phenyl-1,3,2-dioxaborinan-5-yl)methyl methacrylate; CO₂-responsive monomers: (C23) ADAm = (N-amidino)dodecyl acrylamide; and redox-sensitive monomer: (C24) MAEFc = 2-(methacryloyloxy) ethyl ferrocene-carboxylate. Figure 13. (Left) Schematic illustration of micelle formation/disassembly in response to environmental pH. (Right) Transmission electron microscope (TEM) image of negatively stained micelles.(366) Adapted with permission from ref 366. Copyright 2006 American Chemical Society. Figure 14. (A) Schematic illustration of the pH-sensitive release of curcumin from PCL-b-PDEAEMA-b-PMEDSA. (B) Blood plasma retention times of curcumin-loaded micelles and curcumin alone in vivo.(368) Adapted with permission from ref 368. Copyright 2014 The Royal Society of Chemistry. Figure 15. Fluorescence intensity of (A) PEG-b-PDEAEMA and (B) PEG-b-PCL micelles as a function of pH using N-phenyl-2-naphthylamine as a hydrophobic probe.(369) Adapted with permission from ref 369. Copyright 2006 American Chemical Society. Figure 16. (Left) Structure of POEGA-g-P2VP graft copolymer. (Right) TEM images of self-assembled morphologies of POEGA-g-P2VP at different pH values: (A) pH 6.5, (B) pH 8.0, (C) pH 9.0, and (D) pH 10.0.(372) Adapted with permission from ref 372. Copyright 2011 John Wiley and Sons. Figure 17. Schematic illustration of the “schizophrenic” behavior of a poly(VBAz)-b-poly(DEAEMA) diblock.(375) Adapted with permission from ref 375. Copyright 2002 John Wiley and Sons. Figure 18. (Left) Structure of a PEG-b-(PGlyA-co-(PGlyA-g-Pyr)) diblock copolymer. (Right) Release kinetics of acetal bound pyrene from polymeric micelles at different pH values.(376) Adapted with permission from ref 376. Copyright 2007 John Wiley and Sons. Figure 19. (Left) T₁-weighted spin–echo MR images recorded for aqueous solution of non-cross-linked micelles and CCL micelles at pH 5.0 and 7.4. (Right) Proton relaxation rates for core cross-linked micelles at pH 6.0 and 7.4.(380) Adapted with permission from ref 380. Copyright 2013 John Wiley and Sons. Figure 20. (Left) Variation in LCST transitions as a function of the ratio between the DMA and NIPAAm comonomers. (Right) Release kinetics of encapsulated Amphotericin B above (38 °C) and below the LCST transition of the P(NIPAAm-co-DMA)-b-PLA-b-P(NIPAAm-co-DMA) micelles.(387) Reproduced with permission from ref 387. Copyright 2014 The Royal Society of Chemistry. Figure 21. (Left) Structures of monomers used in thermoresponsive, degradable POEGMA-co-MEO₂MA-co-BMDO. (Right) Gel permeation chromatography (GPC) trace of polymer before and after hydrolysis in alkaline conditions.(391) Reprinted with permission from ref 391. Copyright 2007 American Chemical Society. Figure 22. (Left) In vitro cumulative DOX release profiles from DOX-MZF-micelles at 20, 37, and 43 °C under an AMF (treated for 5 min every 24 h). (Right) Cell viability of Hep G2 cells after 24 h under different treatment conditions.(395) Reproduced with permission from ref 395. Copyright 2015 The Royal Society of Chemistry. Figure 23. Light-induced photolysis of coumarin from micelle leading to disassociation/aggregation.(401) Adapted with permission from ref 401. Copyright 2009 John Wiley and Sons. Figure 24. (A) Schematic illustration of the release of 5-FU from the coumarin side chains under high energy UV irradiation. (B) Release profile of 5-FU bound drug with and without UV irradiation at 254 nm.(406) Adapted with permission from ref 406. Copyright 2011 American Chemical Society. Figure 25. (a) Reversible photoinduced cross-linking of pendant coumarin moieties and (b) schematic illustration of micellization and reversible cross-linking.(412) Adapted with permission from ref 412. Copyright 2007 American Chemical Society. Figure 26. (A) Structures of SP and azobenzene and their reversible photoisomerism. (B) SEM images of self-assembled PAA-b-poly(AzoMA) vesicles forming micelle-like aggregates under UV irradiation. Subsequent visible light irradiation reforms the vesicle structure.(417) Reprinted with permission from ref 417. Copyright 2004 American Chemical Society. Figure 27. Examples of light-responsive moieties positioned at the junction between two polymer blocks: (A) truxillic acid(420) and (B) ortho-nitrobenzyl(421) moieties positioned at the junction between polymer blocks P1 and P2. Figure 28. (Left) Schematic illustration of the response of a phenylboronic acid functionalized micelle to glucose. (Right) Release of insulin over time at different glucose concentrations.(429) Adapted with permission from ref 429. Copyright 2009 American Chemical Society. Figure 29. (a) Self-assembly of thiol-reactive thermoresponsive PEG-b-P(MEO₂MA-co-EEO₂MA-co-coumarin) and intracellular trafficking of micellar nanoparticles. Upon cellular internalization, Michael addition reaction of α,β-unsaturated ketone moieties with thiols in the reductive cytosol milieu leads to micelle-to-unimer transition, accompanied by concomitant emission turn-on and release of physically encapsulated drugs. (b) Chemical structure of thiol-reactive thermoresponsive PEG-b-P(MEO₂MA-co-EEO₂MA-co-coumarin). (c) In vitro drug release profile recorded for DOX-loaded micelles at varying GSH levels. (d) MTT-based cytotoxicity assay against HeLa cells after coincubating with free DOX or DOX-loaded micelles. (e) Confocal microscopy images recorded for A549 cells after coincubation at 37 °C with DOX-loaded micelles for 1, 6, and 12 h. Late endosomes and lysosomes were stained with LysoTracker Green (green channel). The red and blue channel fluorescence emissions are from DOX and unquenched coumarin moieties, respectively.(432) Reprinted with permission from ref 432. Copyright 2015 American Chemical Society. Figure 30. PEG-b-PADAm vesicles (B) with and (A) without CO₂. (C) Release of RB as a model dye under different conditions. Onset of a new gas stimulus is indicated by the black arrows.(435) Reprinted with permission from ref 435. Copyright 2011 John Wiley and Sons. Boronic acid-based monomers also typically display pH-responsive properties. Figure 31. Schematic illustration of the “AND” logic gate using pH and redox state as combined input stimuli.(457) Adapted with permission from ref 457. Copyright 2011 John Wiley and Sons. Figure 32. Illustration of the design concepts of a triply sensitive diblock copolymer.(460) Reprinted with permission from ref 460. Copyright 2009 American Chemical Society. Figure 33. Schematic illustration of the approach used to synthesize shell cross-linked reverse micelles and subsequent surface-initiated chain extension.(462) Reprinted with permission from ref 462. Copyright 2008 American Chemical Society. Polymer also contains a reducible disulfide linkage for redox responsiveness. Figure 34. Two categories of star polymers: (A) regular star polymers, and (B) miktoarm star polymers.(486) Adapted from ref 486. Copyright 2015 Elsevier. Figure 35. Three general methods to prepare star polymers.(492) Adapted with permission from ref 492. Copyright 2012 American Chemical Society. ^aReproduced with permission from ref 552. Copyright 2015 The Royal Society of Chemistry. ^aReproduced with permission from ref 552. Copyright 2015 The Royal Society of Chemistry. Figure 36. Schematic illustration of bioreducible star polymers and images of enhanced GFP expression mediated by star polymer with disulfide linkages and star polymer without disulfide linkage in HepG2 cells.(531) Reprinted with permission from ref 531. Copyright 2014 American Chemical Society. Figure 37. Schematic illustration of supramolecular pseudocomb conjugates composed of multiple star polymers tied tunably to a linear polymer for gene delivery.(588) Reprinted with permission from ref 588. Copyright 2013 American Chemical Society. Figure 38. Schematic illustration of unimolecular nanogel star polymer-incorporated fluorophore and siRNA.(591) Adapted with permission from ref 591. Copyright 2011 John Wiley and Sons. Figure 39. A schematic showing internalization of anti-Bcl-2 siRNA loaded “smart” particles by adsorptive endocytosis.(592) Reprinted with permission from ref 592. Copyright 2013 American Chemical Society. Figure 40. Schematic illustration of the codelivery of DOX and p53 plasmid and the potential route for intravenous administration of drug/DNA-loaded star polymers for the synergistic tumor suppression.(593) Reprinted with permission from ref 593. Copyright 2015 Elsevier. Figure 41. Schematic representation of the codelivery of DOX and microRNA-21 by star-branched amphiphilic micelles and the mechanism for enhancement of chemosensitivity of glioma cells.(594) Reprinted with permission from ref 594. Copyright 2013 Elsevier. Figure 42. Schematic illustration of dendrimer-like star polymers prepared by ATRP as ¹⁹F MRI contrast agents.(543) Reprinted with permission from ref 543. Copyright 2010 John Wiley and Sons. Figure 43. (A) Illustration of micellar nanoparticles of β-CD-based star polymers for integrated cancer cell-targeted drug delivery and MR imaging contrast enhancement. (B) MRI recorded for rats at different time: (a) preinjection and (b) 5, (c) 10, (d) 15, (e) 20, (f) 25, (g) 30, (h) 35, (i) 40, (j) 45, (k) 50, and (l) 60 min after intravenous injection of micellar nanoparticle.(528) Reprinted with permission from ref 528. Copyright 2011 Elsevier. Figure 44. Schematic illustration of star copolymers dually acting as pDNA delivery vectors and MR imaging contrast agents.(595) Reproduced with permission from ref 595. Copyright 2014 The Royal Society of Chemistry. Figure 45. (A) Structures of star polymers prepared via ATRP. (B) Schematic illustration of antifouling activity of (i) star polymers coated with poly(sulfone) (PSf) ultrafiltration membranes, and (ii) linear polymers coated with (PSf) ultrafiltration membranes.(598) Reproduced with permission from ref 598. Copyright 2012 The Royal Society of Chemistry. Figure 46. Schematic illustration of the synthesis of cationic nanogels using AGET ATRP in inverse miniemulsion for the delivery of siRNA and pDNA.(633) Reprinted with permission from ref 633. Copyright 2012 American Chemical Society. ^aReprinted with permission from ref 656. Copyright 2012 American Chemical Society. ^aReprinted with permission from ref 656. Copyright 2012 American Chemical Society. ^aReproduced with permission from ref 666. Copyright 2011 The Royal Society of Chemistry. ^aReproduced with permission from ref 666. Copyright 2011 The Royal Society of Chemistry. Figure 47. Poly(2-hydroxyethyl methacrylate) PHEMA bottlebrushes (a) are modified to yield either PBiBEM (b) or PCL (b′). Subsequently, side chains are grafted via ATRP to from either epoxy-functionalized POEGMA (c) or epoxy-functionalized PCL-b-POEGMA core–shell CPBs (c′). (A)–(E) show the library of synthesized bottlebrushes with different lengths.(679) Reprinted with permission from ref 679. Copyright 2015 American Chemical Society. Figure 48. DOX release kinetics from bottlebrush and linear copolymers.(683) Reprinted with permission from ref 683. Copyright 2009 American Chemical Society. ^aReprinted with permission from ref 691. Copyright 2011 American Chemical Society. ^aReprinted with permission from ref 691. Copyright 2011 American Chemical Society. ^aReprinted with permission from ref 713. Copyright 2013 Macmillan Publishers Ltd. ^aReprinted with permission from ref 713. Copyright 2013 Macmillan Publishers Ltd. ^aReproduced with permission from ref 730. Copyright 2015 The Royal Society of Chemistry. ^aReproduced with permission from ref 730. Copyright 2015 The Royal Society of Chemistry. ^aUpon activation by Cu(I) and addition of a unimer unit, active species can propagate to form either branched or linear structure depending on the relative reactivity between two reactive sites (A** or B**).(739) Reprinted with permission from ref 739. Copyright 2015 American Chemical Society. ^aUpon activation by Cu(I) and addition of a unimer unit, active species can propagate to form either branched or linear structure depending on the relative reactivity between two reactive sites (A** or B**).(739) Reprinted with permission from ref 739. Copyright 2015 American Chemical Society. ^a(A) Schematic illustration for the synthesis of amphiphilic hyperbranched fluoropolymers 4a, 4b, and 4c and the subsequent self-assembly into unimolecular micelles 5a, 5b, and 5c. ¹⁹F MRI phantom images (1024 scans, 13 h) of (B) micelles 5a, (C) micelles 5b, and (D) micelles 5c.(748) Reprinted with permission from ref 748. Copyright 2008 American Chemical Society. ^a(A) Schematic illustration for the synthesis of amphiphilic hyperbranched fluoropolymers 4a, 4b, and 4c and the subsequent self-assembly into unimolecular micelles 5a, 5b, and 5c. ¹⁹F MRI phantom images (1024 scans, 13 h) of (B) micelles 5a, (C) micelles 5b, and (D) micelles 5c.(748) Reprinted with permission from ref 748. Copyright 2008 American Chemical Society. ^aReproduced with permission from ref 809. Copyright 2012 American Chemical Society. ^aReproduced with permission from ref 809. Copyright 2012 American Chemical Society. Figure 49. Site-specific protein–polymer conjugation through the use of organic arsenicals.(797) Reproduced with permission from ref 797. Copyright 2015 American Chemical Society. Figure 50. “Grafting from” streptavidin.(784) Reproduced with permission from ref 784. Copyright 2005 American Chemical Society. Figure 51. BSA-maleimide macroinitiator used to copolymerize OEGMA and fluorescent monomers.(771) Reproduced with permission from ref 771. Copyright 2006 American Chemical Society. Figure 52. AGET ATRP for polymerization under biologically relevant conditions.(772) Reproduced with permission from ref 772. Copyright 2012 American Chemical Society. Figure 53. ATRP performed from an apoferritin nanocage.(820) Adapted from ref 820. Copyright 2007 Royal Society of Chemistry. Figure 54. Functionalization of bacteriophage Qβ VLP with ATRP initiator.(832) Reprinted with permission from ref 832. Copyright 2011 American Chemical Society. Figure 55. Synthesizing polymer network for small molecule loading within the internal cavity of P22 capsid.(836) Reprinted with permission from ref 836. Copyright 2012 Macmillan Publisher Ltd.: Nature Chemistry. Figure 56. Genetically encoding an ATRP initiator for polymer growth.(776) Reproduced with permission from ref 776. Copyright 2010 American Chemical Society. Figure 57. Modulating the size of star polymer through DNA hybridization.(589) Reproduced with permission from ref 589. Copyright 2011 American Chemical Society. Figure 58. Conjugation of polymers to DNA strands before self-assembly into DNA tetrahedron.(864) Reproduced with permission from ref 864. Copyright 2011 American Chemical Society. Figure 59. DNA detection through ATRP polymerization.(865) Reproduced with permission from ref 865. Copyright 2005 American Chemical Society. Figure 60. Solid-phase incorporation of ATRP initiator.(868) Reproduced with permission from ref 868. Copyright 2014 John Wiley and Sons. Figure 61. Autotransfection by siRNA through polymer escorts.(878) Reproduced with permission from ref 878. Copyright 2013 American Chemical Society. ^aAdapted from ref 898. Copyright 2011 Elsevier. ^aAdapted from ref 898. Copyright 2011 Elsevier. Figure 62. Inhibition of gp120 binding to DC-SIGN through the use of glycopolymers with mannose pendant groups. Reproduced with permission from ref 933. Copyright 2014 American Chemical Society. Figure 63. Conjugation of glycopolymers with pyridyl disulfide end-functionalized with N-acetyl-d-glucosamine (GlcNAc) side chains to siRNA and gold surface.(801) Reproduced with permission from ref 801. Copyright 2009 American Chemical Society. Figure 64. Structures of some polysaccharides. Figure 65. Structure of diblock and graft copolymers obtained by copper-mediated polymerization using polysaccharide. Polyion complex micelle between chitosan and PEG-b-PAMPS. ^aAdapted from ref 954. Copyright 2008 American Chemical Society. ^aAdapted from ref 954. Copyright 2008 American Chemical Society. Figure 66. Drug release diagrams of the copolymers. Reprinted with permission from ref 960. Copyright 2014 Springer. ^aAdapted from ref 984. Copyright 2010 American Chemical Society. ^aAdapted from ref 984. Copyright 2010 American Chemical Society. Figure 67. Schematic representation of pH-induced formation of single micelles and of the multiple micellar aggregation process. Adapted with permission from ref 977. Copyright 2009 American Chemical Society. ^aAdapted from ref 1000. Copyright 2013 Elsevier. ^aAdapted from ref 1000. Copyright 2013 Elsevier. ^aAdapted from ref 1006. Copyright 2012 CRC Press. ^aAdapted from ref 1006. Copyright 2012 CRC Press. ^aAdapted from ref 1008. Copyright 2014 Royal Society of Chemistry. ^aAdapted from ref 1008. Copyright 2014 Royal Society of Chemistry. ^aAdapted from ref 1027. Copyright 2000 American Chemical Society. ^aAdapted from ref 1027. Copyright 2000 American Chemical Society. ^aAdapted from ref 1052. Copyright 2009 American Chemical Society. ^aAdapted from ref 1052. Copyright 2009 American Chemical Society. ^aAdapted from ref 1066. Copyright 2014 Wiley. ^aAdapted from ref 1066. Copyright 2014 Wiley. Figure 68. Schematic illustration of methods for the immobilization/formation of polymer brushes via the “grafting to” and “grafting from” methods, respectively.(1074) Reproduced with permission from ref 1074. Copyright 2014 The Royal Society of Chemistry. Figure 69. Illustration of the effect of surface curvature on polymer brush conformation. For flat surfaces, chain conformation is determined by the density of polymer brushes. D denotes distance between tethered chain, and R_G denotes the polymeric radius of gyration. For a curved surface, chain conformation is affected mainly by the surface curvature.(1071) Adapted from ref 1071. Copyright 2014 American Chemical Society. Surface grafting via monomer reactive group. Figure 70. Prussian blue staining of murine peritoneal macrophages after incubation with nanoparticles for 24 h: (A) long POEGMA-functionalized IONPs, and (B) short POEGMA-functionalized IONPs. (C) Resovist: Iron concentration used for the experiment was 30 μg Fe/mL. (D) MRI of long POEGMA-functionalized IONPs in water at various concentrations generated on a T₂-weighted spin–echo sequence with an echo time of 80 ms and pulse repetition time of 4000 ms at 4.7 T. (E,F) In vivo T₂-weighted magnetic resonance image of long POEGMA-functionalized IONPs at a single dose of 200 μmol Fe/kg body weight.(1088) Reprinted with permission from ref 1088. Copyright 2013 American Chemical Society. Figure 71. (A) Schematic representation of the synthesis of FA-functionalized IONPs, [email protected](GMA-co-OEGMA)-FA utilizing SI-ATRP and azide–alkyne click chemistry. (B) In vitro cell viabilitites of 3T3 fibroblast, macrophages, and KB cells against different concentrations of FA-functionalized IONPs after incubation for 24 h. (C) Intracellular uptake of FA-functionalized IONPs by 3T3 fibroblast, macrophages, and KB cells at different incubation times.(1084) Reprinted with permission from ref 1084. Copyright 2012 American Chemical Society. Figure 72. Normalized extinction coefficients of AuNPs with different shapes and dimensions: (A) gold nanospheres with different diameters, (B) gold nanorods with different aspect ratios (diameter × length), (C) gold nanoshells with different shell thicknesses, and (D) gold nanocages with different gold content.(1112) Reproduced with permission from ref 1112. Copyright 2014 The Royal Society of Chemistry. *Surface grafting via monomer reactive group. Figure 73. Gold nanocages covered by smart polymers for controlled release of therapeutic agents with NIR light. (A) Cross-sectional illustration of mechanism. Upon laser irradiation, converted heat triggers the polymer collapse and subsequent release of loaded therapeutic agents. (B) TEM image of PNIPAAm-co-PAAm-functionalized gold nanocages showing the hollow structure. (C) ATRP of NIPAAm and AAm monomers employing a disulfide initiator in the presence of CuBr/PMDETA. (D) Absorption spectra of alizarin-PEG released from the gold nanocages by exposure to a pulsed NIR laser at a power density of 10 mW/cm² for 1, 2, 4, 8, and 16 min.(1117) Reprinted with permission from ref 1117. Copyright 2009 Macmillan Publisher Ltd.: Nature Materials. ^aReprinted with permission from ref 1122. Copyright 2012 American Chemical Society. ^aReprinted with permission from ref 1122. Copyright 2012 American Chemical Society. Figure 74. (A) SERS spectra of SKBR-3 cells treated with HER2-targeted vesicles (black line) and nontargeted vesicles (purple line), MCF-7 cells treated with HER2-targeted vesicles (red line), and SKBR-3 control cells (blue line) after 30 min incubation. (B) Cell viability results of HER2-targeted pH-sensitive vesicles with (green bar) and without (blue bar) DOX, nontargeted pH-sensitive vesicles with DOX (purple bar), HER2-targeted pH-insensitive vesicles with DOX (red bar), and free DOX (wine bar) obtained from cultured SKBR-3 cells (black bar: control SKBR-3 cells). Dark field (C,G,K), fluorescence (E,I,M), and the overlaid images (D,F,H,J,L,N) of SKBR-3 cells labeled with DOX loaded pH-sensitive plasmonic vesicles after 30 min incubation (C–F) and postincubation images of cell at 60 min (G–J) and 90 min (K–N). DOX has red fluorescence, and the cell nuclei were counterstained with Hoechst 3342 exhibiting blue fluorescence.(1122) Reprinted with permission from ref 1122. Copyright 2012 American Chemical Society. ^aReproduced with permission from ref 1128. Copyright 2015 The Royal Society of Chemistry. ^aReproduced with permission from ref 1128. Copyright 2015 The Royal Society of Chemistry. Me₆TATD = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. ^a(A) Schematic representation of the synthesis of POEGMA-functionalized silica particles. (B) Amount of hybrid particles remaining in the blood 1 h after intravenous injection as a function of the hydrodynamic diameter of POEGMA-functionalized silica particles; filled circles represent data of silica particles with fixed core of 130 nm and different POEGMA chain length, while open circles represent data for silica particles with different silica core size and nearly similar length of POEGMA chain. (C) Biodistribution of POEGMA-functionalized silica particles 24 h after intravenous injection through the tail vein of healthy and tumor-bearing mice. Black and red bars represent 15 nm silica cores with 67 000 number-average molecular weight POEGMA brushes in healthy and tumor bearing mice, respectively. The green and blue bars represent data for 290 nm silica cores with 113 000 number-average molecular weight POEGMA brushes in healthy and tumor-bearing mice, respectively. (D) Optical fluorescence images of identical tumor-bearing mice taken at 0, 6, and 24 h post injection. Images were obtained with an exposure time of 1 s using Cy5.5 filter sets.(1143) Adapted from ref 1143. Copyright 2012 American Chemical Society. ^a(A) Schematic representation of the synthesis of POEGMA-functionalized silica particles. (B) Amount of hybrid particles remaining in the blood 1 h after intravenous injection as a function of the hydrodynamic diameter of POEGMA-functionalized silica particles; filled circles represent data of silica particles with fixed core of 130 nm and different POEGMA chain length, while open circles represent data for silica particles with different silica core size and nearly similar length of POEGMA chain. (C) Biodistribution of POEGMA-functionalized silica particles 24 h after intravenous injection through the tail vein of healthy and tumor-bearing mice. Black and red bars represent 15 nm silica cores with 67 000 number-average molecular weight POEGMA brushes in healthy and tumor bearing mice, respectively. The green and blue bars represent data for 290 nm silica cores with 113 000 number-average molecular weight POEGMA brushes in healthy and tumor-bearing mice, respectively. (D) Optical fluorescence images of identical tumor-bearing mice taken at 0, 6, and 24 h post injection. Images were obtained with an exposure time of 1 s using Cy5.5 filter sets.(1143) Adapted from ref 1143. Copyright 2012 American Chemical Society. ^aReprinted with permission from ref 1135. Copyright 2009 American Chemical Society. ^aReprinted with permission from ref 1135. Copyright 2009 American Chemical Society. Surface grafting via monomer reactive group. Surface grafting via π–π stacking. Figure 75. Upconversion luminescence (UCL) images of HCCHM3 cells incubated with (a) 10, (b) 15, and (c) 20 μg/mL Con A-functionalized upconversion nanoparticles for 1 h, and (d) CL cells incubated with 40 μg/mL Con A-functionalized UCNPs for 1 h. Excitation wavelengths for upconversion/hoechest 33342 were 980 nm/740 nm, and emission was collected at 500–550 nm/425–475 nm. In vivo imaging of nude mice inoculated with HCCHM3 cells after injection with (e) Con A-functionalized UCNPs, and (f) PPEGMA-functionalized UCNPs. Images were obtained under 980 nm excitation wavelength at 0 h, 3 h, and 3 days after the injection.(1156) Reprinted with permission from ref 1156. Copyright 2014 American Chemical Society. Figure 76. Cu(0)-mediated polymerization catalyzed by a copper plate. (a) Reaction scheme; (b) thickness of PMMA brush versus time; and (c) picture of experimental setup.(1178) Reproduced with permission from ref 1178. Copyright 2015 The Royal Society of Chemistry. Figure 77. (A) OEGMA monomers and catechol initiator for SI-ATRP from a Ti surface. (B) Typical fluorescence images showing 3T3 cell attachment on POEGMA-functionalized Ti surfaces at selected time of long-term cell adhesion assay (scale bar for bare Ti surface represents 100 μm, and all images have the same scale).(1201) Reprinted with permission from ref 1201. Copyright 2006 American Chemical Society. ^aAdapted with permission from ref 1204. Copyright 2011 American Chemical Society. ^aAdapted with permission from ref 1204. Copyright 2011 American Chemical Society. ^aReprinted with permission from ref 1037. Copyright 2004 American Chemical Society. ^aReprinted with permission from ref 1037. Copyright 2004 American Chemical Society. Figure 78. Determination of the cell kill capacity dependence on surface charge density. (A) Samples of a glass surface with high density of cationic charges (8 × 10¹⁵ charge/cm²) loaded with increasing concentrations (challenges) of E. coli. (B) Mosaic of live/dead staining of E. coli cells made from 500 images of a glass slide cosynthesized with silicon wafer slide. The positive charge/cm² (×10¹⁵) was measured by fluorescein staining and superimposed over the image (areas in green showed attached live cells, areas in yellow showed both live and dead cells, and areas in red showed dead cells).(1227) Reprinted with permission from ref 1227. Copyright 2007 Elsevier. ^aAdapted with permission from ref 1241. Copyright 2011 Elsevier. ^aAdapted with permission from ref 1241. Copyright 2011 Elsevier. ^aReproduced with permission from ref 1251. Copyright 2014 The Royal Society of Chemistry. ^aReproduced with permission from ref 1251. Copyright 2014 The Royal Society of Chemistry. Figure 79. Interactions between E. coli and the hybrid surfaces at different temperatures.(1251) Reproduced with permission from ref 1251. Copyright 2014 The Royal Society of Chemistry. Figure 80. Top: Representation of POEGMA-co-PMEO₂MA coating at 37 °C (a) and 25 °C (b), and the corresponding cell response. Bottom: Phase-contrast microscopy images of L929 mouse fibroblasts on POEGMA-co-PMEO₂MA-modified gold substrates after 44 h of incubation at 37 °C (left) and 30 min after cooling the sample to 25 °C (right). The surface presented was prepared using the macroinitiator “grafting-from” approach. Scale bars correspond to 100 mm.(1257) Reprinted with permission from ref 1257. Copyright 2008 John Wiley and Sons. Figure 81. (A) Bacterial infection on biomaterial: (i) attachment of cells, (ii) formation of biofilm, and (iii) detachment of bacterial cells. (B) pH-responsive, drug release polymer bilayer system, composed of an inner layer of tobramycin (yellow)-loaded PAA brushes (red) and an outer layer of chitosan (blue), which provides biocompatibility and hemocompatibility.(1259) Reprinted with permission from ref 1259. Copyright 2015 American Chemical Society. ^aReprinted with permission from ref 529. Copyright 2011 Elsevier. ^aReprinted with permission from ref 529. Copyright 2011 Elsevier. ^a(A) Protein immobilization by EDAC/NHS coupling, (B) protein immobilization through avidin–biotin interactions, and (C) immobilization of biotin using BSA as linkages.(1266) Note: EDC = EDAC. Reprinted with permission from ref 1266. Copyright 2007 American Chemical Society. ^a(A) Protein immobilization by EDAC/NHS coupling, (B) protein immobilization through avidin–biotin interactions, and (C) immobilization of biotin using BSA as linkages.(1266) Note: EDC = EDAC. Reprinted with permission from ref 1266. Copyright 2007 American Chemical Society. Figure 82. Process for the patterning of PEG and PAA brushes on silicon surface.(1266) Reprinted with permission from ref 1266. Copyright 2007 American Chemical Society. The authors declare no competing financial interest. We thank UNSW for funding and the referees for their help in improving this Review. C.B. acknowledges the Australian Research Council (ARC) for his Future Fellowship (FT120090). 2-vinylpyridine 4-vinylpyridine (4-vinylphenyl)boronic acid 5-fluorouracil acrylic acid acrylamide (N-amidino)dodecyl acrylamide 2-aminoethyl methacrylate N-acryloyl glucosamine alternating magnetic field 1-allyl-3-methylimidazolium chloride antimicrobacterial peptides acrylonitrile N-(3-aminopropyl) methacrylamide 3-aminopropyltrimethoxysilane atom transfer nitroxide radical coupling atom transfer radical coupling gold nanoparticles azobenzene-based methacrylate 3-azidopropyl methacrylate N,N-bis(acryloyl) cystamine barnacle cement blocking from α-bromoisobutyric acid 2-bromoisobutyric anhydride bromoisobutyryl bromide 2-(bromoisobutyryl)ethyl methacrylate 5,6-benzo-2-methylene-1,3-dioxepane benzophenone bis(2-bromopropionyl)-ethane 2,2′-bipyridine bovine serum albumin fluorescein isothiocyanate-labeled bovine serum albumin blocking to cellulose acetate chloroacetylated cellulose (3-acryloylamino-propyl)-(2-carboxy-ethyl)-dimethylammonium catalase from bovine liver carboxybetaine methacrylate (3-methacryloylamino-propyl)-(2-carboxy-ethyl)-dimethyl-ammonium carboxy betaine 3-methacryloylamino-propyl)-(2-carbxy-ethyl)-dimethylammonium core cross-linked cyclodextrin cellulose diacetate 1,1′-carbonyldiimidazole complementary DNA colony forming unit critical micelle concentration carboxymethyl cellulose concanavalin A 2-((4-methyl-2-oxo-2H-chromen-7-yl)oxy)ethyl methacrylate critical packing parameter chitosan computed tomography copper-mediated azide–alkyne cycloaddition dendritic cells dichloromethane DC-specific intercellular adhesion molecule 3-grabbing nonintegrin N,N-diethyl acrylamide (7-(diethylamino)-2-oxo-2H-chromen-4-yl)methyl methacrylate 2-(diethylamino)ethyl methacrylate dextran fluorescein isothiocyanate-labeled dextran dynamic light scattering N,N′-dimethylacrylamide dimethylacetamide 2-(dimethylamino)ethyl acrylate 2-(dimethylamino)ethyl methacrylate 4-(dimethylamino)pyridine 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane dimethylformamide dimethyl sulfoxide N,N′-dimethyl-N-(p-vinylbenzyl)-N-(3-sulfopropyl) ammonium deoxyribonucleic acid 4,4′-di-5-nonyl-2,2′-bipyridine doxorubicin 2-(diisopropylamino)ethyl methacrylate PDMAEMA functionalized dextran DNA polymer-hybrids 2,2-dimethoxy-2-phenyl acetophenone degree of polymerization bis(2-methacryloyl)oxyethyl disulfide diethylenetriaminepentaacetate divinylsulfone ethyl acrylate electrochemically mediated atom transfer radical polymerization ethyl 2-bromoisobutyrate ethyl cellulose 1-ethyl-3-(3-(dimethylamino)propyl) carbodiimide 2-(2-ethoxyethoxy)ethyl methacrylate ethylene glycol dimethacrylate enhanced green fluorescent protein 2-ethylhexyl acrylate enzyme-linked immunosorbent assay enhanced permeation and retention electrospray ionization mass spectrometry folic acid fluorescein isothiocyanate fluorescence resonance energy transfer Fourier transform infrared spectroscopy glycidyl acrylate 2-glucoamidoethyl methacrylate green fluorescent protein galactoglucomannan glass-ionomer cement N-acetylglucosamine glycidyl methacrylate GMA-modified mannosamine graphene oxide gel permeation chromatography glutathione hemoglobin Hepatitis C virus 2-hydroxyethyl acrylate 2-hydroxyethyl-2-bromo-isobutyrate hydroxyethyl cellulose human embryonic kidney hydroxyethyl methacrylate human immunodeficiency virus hexagonally packed hollow hoops hexyl methacrylate 1,1,4,7,10,10-hexamethyltriethylenetetramine hydroxypropyl cellulose PDMAEMA-functionalized HPC horseradish peroxidase herpes simplex virus human umbilical vein endothelial cells isobornyl methacrylate initiators for continuous activator regeneration ionic liquid iron oxide nanoparticles inner sphere electron transfer 2-lactobionamidoethyl methacrylate large compound micelle lower critical solution temperature light emitting diode ligand to metal charge transfer living radical polymerization laccase from Trametes versicolour methyl acrylate methacrylic acid sodium methacrylate 2-(methacryloyloxy) ethyl ferrocene-carboxylate 3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-d-glucofuranose matrix-assisted laser desorption/ionization-time of flight mass spectroscopy mannose binding lectin methyl-2-bromopropionate merocyanine 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane tris(2-dimethylaminoethyl)amine 2-methoxyethyl acrylate [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide 2-hydrazinyl-2-oxoethyl methacrylate 2-(2-methoxyethoxy)ethyl methacrylate metal to ligand charge transfer methyl methacrylate matrix metalloproteinase magnetic resonance imaging methotrexate molecular weight manganese and zinc doped ferrite ortho-nitrobenzyl acrylate nitrobenzoxadiazole 4-(2-acryloyloxyethylamino)-7-nitro-2,1,3-benzoxadiazole ortho-nitrobenzyl methacrylate n-butyl acrylate n-butyl methacrylate nanodiamonds N-hydroxysuccinimide N-isopropylacrylamide near-infrared nitroxide-mediated polymerization nuclear magnetic resonance Nile Red N-vinyl carbazole oligodeoxyribonucleotides oligo(ethylene glycol) methyl ether acrylate oligo(ethylene glycol) methyl ether methacrylate outer sphere electron transfer poly(2-vinylpyridine) poly(4-vinylpyridine) poly(acrylic acid) poly(acrylamide) poly(acrylamidophenylboronic acid) poly((N-amidino)dodecyl acrylamide) poly(N-acryloyl glucosamine) poly(acrylonitrile) poly(N-(3-aminopropyl) methacrylamide) poly(3-azidopropyl methacrylate) (5-ethyl-2-phenyl-1,3,2-dioxaborinan-5-yl)methyl methacrylate poly(2-(bromoisobutyryl)ethyl methacrylate) poly(benzyl l-glutamate) phosphate buffered saline poly(carboxybetaine methacrylate) poly(ε-caprolactone) poly(2-(diethylamino)ethyl acrylate) poly(2-(diethylamino)ethyl methacrylate) poly(N,N-diethyl-2-((4-vinylbenzyl)oxy)nicotinamide) poly(N,N′-dimethylacrylamide) poly(2-(dimethylamino)ethyl methacrylate) plasmid DNA poly(2-(diisopropylamino)ethyl methacrylate) poly(ethylene glycol) oligo(ethylene glycol) methacrylate poly(ethylene imine) 4-hydroxyethylphenyl methacrylate poly(triethoxysilylpropyl methacrylate) photoinduced electron transfer poly(2-glucoamidoethyl methacrylate) ethanolamine-functionalized poly(glycidyl methacrylate) poly(glycerol acrylate) poly(glycerol methacrylate) poly(glycidyl methacrylate) N-phthaloyl chitosan poly(2-hydroxyethyl acrylate) poly(2-hydroxyethyl methacrylate) N-(n-propyl)pyridylmethanimine poly(isoprene) poly(N-(3-(1H-imidazol-1-yl)propyl)acrylamide) poly(lactide) poly(2-lactobionamidoethyl methacrylate) poly(l-glutamic acid) poly(l-lysine) poly(methyl acrylate) poly(methacrylic acid) poly(3-O-methacryloyl-1,2:5,6-di-O-isopropylidene-d-glucofuranose) N,N,N′,N′,N″-pentamethyldiethylenetriamine [2(methacryloyloxy)ethyl]trimethylammonium chloride poly([2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide) poly(2-methoxy-2-oxoethyl methacrylate) poly(2-(2-methoxyethoxy)ethyl methacrylate) poly(2-methacryloyloxyethyl phosphorylcholine) poly[N-(3-(methacryloylamino)propyl)-N,N-dimethyl-N-(3-sulfopropyl)ammonium hydroxide] p-methoxyphenacyl methacrylate poly(4-(2-acryloyloxyethylamino)-7-nitro-2,1,3-benzoxadiazole) poly(ortho-nitrobenzyl methacrylate) poly(N-isopropylacrylamide) polyhedral oligomeric silsesquioxanes poly(phenylalanine) poly(poly(ethylene glycol) ethyl ether methacrylate) poly(oligo (ethylene glycol) methacrylate poly(pentafluorostyrene) poly(propylene glycol) methacrylate parts per million poly(propylene oxide) particle replication in nonwetting templates propyl(2-pyridyl)methanimine poly(styrene) poly(sulfobetaine methacrylate) poly(sulfone) poly(1′-(2-methacryloxyethyl)-3′,3′-dimethyl-6-nitro-spiro(2H-1-benzo-pyran-2,2′-indoline)) poly(3-sulfopropyl methacrylate) poly(tert-butyl acrylate) poly(tert-butyl methacrylate) poly(3-(trimethoxysilyl)propyl methacrylate) paclitaxel pullulan-based gene vector pyrene quaternary ammonium quantum dots quaternized DPD quaternized HPDs rhodamine B reversible deactivation radical polymerization reticuloendothelial system arginine-glycine-aspartic acid recombinant human growth hormone RNA interference ribonuclease A ring-opening metathesis polymerization ring-opening polymerization alkyl (pseudo) halide solketal acrylate self-assembled monolayer supplemental activators and reducing agents sulfobetaine methacrylate self-condensing vinyl polymerization scanning electron microscope surface-enhanced Raman scattering single electron transfer-degenerative transfer living radical polymerization single electron transfer-living radical polymerization surface-initiated ATRP silicon nanowire arrays small interfering ribonucleic acid surface-initiated SET-LRP solketal methacrylate spiropyran 1′-(2-methacryloxyethyl)-3′,3′-dimethyl-6-nitro-spiro(2H-1-benzo-pyran-2,2′-indoline) surface plasmon resonance simultaneous reverse and normally initiated disulfide bridges stainless steel single-stranded DNA styrene succinic anhydride single-walled carbon nanotubes longitudinal relaxation time transverse relaxation time tert-butyl acrylate tert-butyl methacrylate tris(2-carboxyethyl)phosphine triethylamine transmission electron microscope N,N,N′,N′-tetramethylethylenediamine terminator multifunctional initiator tetrahydropyran protected 2-hydroxyethyl methacrylate tetrahydropyranyl methacrylate 2-(methacryloyloxy)-N,N,N-trimethylethanaminium chloride tris((4-methoxy-3,5-dimethylpyridin-2-yl)methyl)amine trimethylsilyl 3-(trimethoxysilyl)propyl methacrylate tris[(2-pyridyl)methyl]amine tris(2-pyridylmethyl) amine 2,4,6-trimethylbenzoyl diphenylphosphine oxide tris(2-aminoethyl)amine upconversion luminescence ultraviolet ultraviolet–visible N-(p-vinylbenzyl)phthalimide vinyl benzoic acid virus-like particles This article references 1306 other publications.

更新日期：2015-11-04

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