“Green” Atom Transfer Radical Polymerization:  From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials

Tsarevsky, Nicolay V.; Matyjaszewski, Krzysztof

doi:10.1021/cr050947p

Cited by 1,229 publications

(895 citation statements)

References 465 publications

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“…PEG- b -PR copolymers were synthesized by atom transfer radical polymerization (ATRP) following procedures previously reported 36 . PEG- b -PDPA is used as an example to illustrate the procedure.…”

Section: Methodsmentioning

confidence: 99%

A STING-activating nanovaccine for cancer immunotherapy

et al. 2017

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Generation of tumor-specific T cells is critically important for cancer immunotherapy1,2. A major challenge in achieving a robust T cell response is the spatio-temporal orchestration of antigen cross-presentation in antigen presenting cells (APCs) with innate stimulation. Here we report a minimalist nanovaccine by a simple physical mixture of an antigen with a synthetic polymeric nanoparticle, PC7A NP, which generated a strong cytotoxic T cell response with low systemic cytokine expression. Mechanistically, PC7A NP achieved efficient cytosolic delivery of tumor antigens to APCs in draining lymph nodes leading to increased surface presentation while simultaneously activating type I interferon-stimulated genes. This effect was dependent on STING but not Toll-like receptor or MAVS pathway. Nanovaccine produced potent tumor growth inhibition in melanoma, colon cancer, and human papilloma virus-E6/E7 tumor models. Combination of PC7A nanovaccine with an anti-PD-1 antibody showed great synergy with 100% survival over 60 days in a TC-1 tumor model. Rechallenging of these tumor-free animals with TC-1 cells led to complete inhibition of tumor growth, suggesting generation of long-term antitumor memory. The STING-activating nanovaccine offers a simple, safe and robust strategy in boosting anti-tumor immunity for cancer immunotherapy.

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Section: Methodsmentioning

confidence: 99%

A STING-activating nanovaccine for cancer immunotherapy

et al. 2017

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“…Dense PAA brushes are have successfully been used for protein separation using electrostatic interaction as well as for covalent binding of both positively and negatively charged biomolecules. 42 46,47 After intensive washing to remove all free PtBA chains, the samples were analyzed to confirm the success of the surface polymerization. Figure X shows a typical FTIR spectrum of a cut monolithic sample after tBA polymerization exhibiting characteristic PtBA bands such as the ester carbonyl at 1728 cm -1 and methyl bending at1367 cm -1 .…”

Section: Grafting Of Polymer From Atrp Functional Polyhipesmentioning

confidence: 99%

Protein Immobilization onto Poly(acrylic acid) Functional Macroporous PolyHIPE Obtained by Surface-Initiated ARGET ATRP

et al. 2012

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Amino-functional macroporous monoliths from polymerized high internal phase emulsion (polyHIPE) were surface modified with initiators for atom transfer radical polymerization (ATRP). The ATRP initiator groups on the polyHIPE surface were successfully used to initiate activator regeneration by electron transfer (ARGET) ATRP of (meth)acrylic monomers, such as methyl methacrylate (MMA) or tert-butyl acrylate (tBA) resulting in a dense coating of polymers on the polyHIPE surface. Addition of sacrificial initiator permitted control of the amount of polymer grafted onto the monolith surface. Subsequent removal of the tertbutyl protecting groups yielded highly functional polyHIPE-g-poly(acrylic acid). The versatility to use the high density of carboxylic acid groups for secondary reactions was demonstrated by the successful conjugation of enhanced green fluorescent protein (eGFP) and coral derived red fluorescent protein (DsRed) using EDC/sulfo-NHS chemistry, on the polymer 3D-scaffold surface. The materials and methodologies presented here are simple and robust, thus, opening new possibilities for the bioconjugation of highly porous polyHIPE for bioseparation applications.

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“…[1][2][3][4] Some synthetic routes have been exploited to synthesize amphiphilic block copolymers, including living anionic polymerization, 5-7 cationic polymerization, [8][9][10] and the controlled/ ''living'' radical polymerization and so forth. [11][12][13] Among these methods reported, living radical polymerization (LRP), which exemplifies stable free radical polymerization (SFRP), 14,15 atom transfer radical polymerization (ATRP), [16][17][18] and reversible addition-fragmentation transfer polymerization (RAFT), [19][20][21] has become preferred to others lying in its accurate control of molecular weight, polydispersity, and chain-end functionality. The combination of fundamentally different synthetic techniques, however, proved to be more suitable to the synthesis of block copolymers, which has motivated more researchers to synthesize various block copolymers by this strategy.…”

Section: Introductionmentioning

confidence: 99%

“…As known to date, ATRP has been successfully employed to the synthesis of many macromolecules with predetermined architectures. [16][17][18] Chemoenzymatic method, which combines eROP with ATRP, provides a new strategy to synthesize amphiphilic block copolymers with controlled molecular weight, well-tailored architecture and precisely adjustable functionality owing to its integration of advantages of both polymerization techniques. 36,37 Since Andreas Heise et al first reported the chemoenzymatic synthesis of AB-type diblock copolymer PCL-b-PSt via the combination of eROP of CL and ATRP of St, 38 more researchers have attempted to employ chemoenzyme-catalyzed routes to construct block copolymers.…”

Section: Introductionmentioning

confidence: 99%

Chemoenzymatic Synthesis of H-shaped Amphiphilic Pentablock Copolymer and Its Self-assembly Behavior

Chen¹,

Li²,

Li³

et al. 2013

Polymer Korea

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H-shaped amphiphilic pentablock copolymers (PSt) 2 -b-PCL-b-PEO-b-PCL-b-(PSt) 2 was synthesized via chemoenzymatic method by combining enzyme-catalyzed ring-opening polymerization (eROP) of ε-caprolactone (ε-CL) and atom transfer radical polymerization (ATRP) of styrene. By this process, we obtained copolymers with controlled molecular weight and low polydispersity. The structure and composition of the obtained copolymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and infrared spectroscopy analysis (IR). The crystallization behavior of the copolymers was analyzed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The crystallization behavior of the H-shaped block copolymers demonstrated a PCL dominate crystallization. The self-assembly behavior of the copolymers was investigated in aqueous media. The hydrodynamic diameters of the copolymer micelles in aqueous solution were measured by dynamic light scattering (DLS). The morphology of the copolymer micelles was observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The hydrodynamic diameters of spherical micelles declined gradually with the increase of the hydrophobic chain lengths of the copolymers. The critical micelle concentration (CMC) values were determined from fluorescence emission, and it was found that the CMCs decreased with an increase of PSt hydrophobic block lengths.

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“Green” Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials

Cited by 1,229 publications

References 465 publications

A STING-activating nanovaccine for cancer immunotherapy

A STING-activating nanovaccine for cancer immunotherapy

Protein Immobilization onto Poly(acrylic acid) Functional Macroporous PolyHIPE Obtained by Surface-Initiated ARGET ATRP

Chemoenzymatic Synthesis of H-shaped Amphiphilic Pentablock Copolymer and Its Self-assembly Behavior

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