Facile Synthesis of Well-Defined Hydrophilic Methacrylic Macromonomers Using ATRP and Click Chemistry

Topham, Paul D.; Sandon, Nicolas; Read, Elizabeth S.; Madsen, Jeppe; Ryan, Anthony J.; Armes, Steven P.

doi:10.1021/ma8019656

Cited by 82 publications

(66 citation statements)

References 66 publications

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“…[20] The key components of the nanosystem comprise PEG, tumor acidity-activated charge-reversal layer, and ROS-sensitive CPT prodrug segments, which was determined by 1 H NMR spectroscopy and gel-permeation chromatography (GPC) (Figure 1A,B). Typically, PEGP(AADA)CPTMA was synthesized via ATRP copolymerization and stepwise chemical grafting reactions.…”

Section: Synthesis and Characterization Of Micellesmentioning

confidence: 99%

A pH/ROS Cascade‐Responsive Charge‐Reversal Nanosystem with Self‐Amplified Drug Release for Synergistic Oxidation‐Chemotherapy

et al. 2018

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Poor cell uptake of drugs is one of the major challenges for anticancer therapy. Moreover, the inability to release adequate drug at tumor sites and inherent multidrug resistance (MDR) may further limit the therapeutic effect. Herein, a delivery nanosystem with a charge‐reversal capability and self‐amplifiable drug release pattern is constructed by encapsulating β‐lapachone in pH/ROS cascade‐responsive polymeric prodrug micelle. The surface charge of this micellar system would be converted from negative to positive for enhanced tumor cell uptake in response to the weakly acidic tumor microenvironment. Subsequently, the cascade‐responsive micellar system could be dissociated in a reactive oxygen species (ROS)‐rich intracellular environment, resulting in cytoplasmic release of β‐lapachone and camptothecin (CPT). Furthermore, the released β‐lapachone is capable of producing ROS under the catalysis of nicotinamide adenine dinucleotide (NAD)(P)H:quinone oxidoreductase‐1 (NQO1), which induces the self‐amplifiable disassembly of the micelles and drug release to consume adenosine triphosphate (ATP) and downregulate P‐glycoprotein (P‐gp), eventually overcoming MDR. Moreover, the excessive ROS produced from β‐lapachone could synergize with CPT and further propagate tumor cell apoptosis. The studies in vitro and in vivo consistently demonstrate that the combination of the pH‐responsive charge‐reversal, upregulation of tumoral ROS level, and self‐amplifying ROS‐responsive drug release achieves potent antitumor efficacy via the synergistic oxidation‐chemotherapy.

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Section: Synthesis and Characterization Of Micellesmentioning

confidence: 99%

A pH/ROS Cascade‐Responsive Charge‐Reversal Nanosystem with Self‐Amplified Drug Release for Synergistic Oxidation‐Chemotherapy

et al. 2018

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“…This equilibrium can be manipulated through choice of operating conditions (temperature and monomer concentration) to purposely generate macromonomer products, which are versatile intermediates extensively used as well-defined building blocks for various macromolecular architectures, e.g., comb [66], star [67], and hyperbranched [68][69][70][71]. Several methods have been described for making macromonomers including anionic polymerization [72], group transfer polymerization [73], addition fragmentation chain transfer [74], living radical polymerization [75,76], and catalytic chain transfer to alkyl cobalt complexes [77][78][79][80][81]. Many of these routes are difficult to carry out and involve high cost at industrial scale.…”

Section: Macromonomer Propagationmentioning

confidence: 99%

Free‐Radical Acrylic Polymerization Kinetics at Elevated Temperatures

Wang

Hutchinson

2010

Chem Eng & Technol

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Free-radical acrylic homo-and copolymerization kinetics are reviewed, focusing on secondary reactions that impact the polymerization rate and polymer molecular weight (MW) under industrially-relevant synthesis conditions. Dependent on the monomer type (acrylate, methacrylate, styrene), mechanisms that must be considered include chain-end depropagation, monomer self-initiation, formation and reaction of midchain radicals, and incorporation of macromonomers formed by b-scission of midchain radicals. The relative importance of these reactions varies with temperature and, for copolymerization, monomer composition. A comprehensive treatment of these complexities has been completed for polymerizations conducted up to 180°C, but further work is required to extend the applicability of the model to even higher temperatures. IntroductionThe production of low-density polyethylene and associated copolymers at 200-300°C and high pressure is perhaps the bestknown example of high-temperature free-radical polymerization (FRP). However, an increasing number of acrylic resins, produced from a mixture of monomers selected from the methacrylate, acrylate, and styrene families, are also manufactured under higher temperature conditions (>120°C) in homogeneous solution. Low-molecular-weight acrylic resins are the base polymer components for many automotive coatings due to their excellent resistance to chemicals, solvents, ultraviolet light, and abrasion, as well as their exterior durability after crosslinking on the surface of the vehicle [1]. High-temperature conditions are used to produce a variety of other materials for coatings, adhesives, and paints [2]. These conditions are chosen to increase production rates and to decrease (or eliminate) the solvent employed in the formulation while maintaining reasonable solution viscosity [2][3][4].While commercially advantageous, the high polymerization temperatures greatly promote the occurrence of secondary reactions that have a strong impact on polymerization rate and polymer MW, such as monomer self-initiation, chain depropagation, and the formation and subsequent reaction of midchain radicals and unsaturated polymer chains (macromonomers). These reactions occur in addition to the well-known and well-understood set of basic FRP mechanisms consisting of initiation, propagation, termination, and chain transfer [5,6]. This article provides an overview and summarizes recent experimental and modeling efforts by our group and other researchers to improve the understanding of these mechanisms. As most high-temperature acrylic polymerization processes involve multiple monomers, the complexities of including these reactions in copolymerization will also be addressed. An accurate treatment of high-temperature FRP kinetics is a critical component of larger-scale process models used to predict the influence of the operating conditions on reaction rate and polymer properties, guide the selection and optimization of standard operating conditions for existing and new polymer grades, and guide process ...

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“…Typically, the graft polymers can be realized by 'grafting from' , [26,27] 'grafting onto' , [28][29][30] macromonomer method, [31] and self-assembly method. [32,33] However, each method has its own advantages and limitations.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of a novel amphiphilic poly (ethylene glycol)–poly (ε-caprolactone) graft copolymers

Zhang

Tong

Wu³

et al. 2016

Designed Monomers and Polymers

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A series of amphiphilic graft copolymers PEO-g-PCL with different poly (ε-caprolactone) (PCL) molecular weight were successfully synthesized by a combination of anionic ring-opening polymerization (AROP) and coordination-insertion ring-opening polymerization. The linear PEO was produced by AROP of ethylene oxide (EO) and ethoxyethyl glycidyl ether initiated by 2-(2-methoxyethoxy) ethoxide potassium, and the hydroxyl groups on the backbone were deprotected after hydrolysis. The ring-opening polymerization of CL was initiated using the linear poly (ethylene oxide) (PEO) with hydroxyl group on repeated monomer as macroinitiator and Sn(Oct) 2 as catalyst, then amphiphilic graft copolymers PEO-g-PCL were obtained. By changing the ratio of monomer and macroinitiator, a series of PEO-g-PCL with well-defined structure, molecular weight control, and narrow molecular weight distribution were prepared. The expected intermediates and final products were confirmed by 1 H NMR and GPC analyzes. In addition, these amphiphilic graft copolymers could form spherical aggregates in aqueous solution by self-assemble, which were characterized by transmission electron microscopy, and the critical micelle concentration values of graft copolymers PEO-g-PCL were also examined in this article.

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Facile Synthesis of Well-Defined Hydrophilic Methacrylic Macromonomers Using ATRP and Click Chemistry

Cited by 82 publications

References 66 publications

A pH/ROS Cascade‐Responsive Charge‐Reversal Nanosystem with Self‐Amplified Drug Release for Synergistic Oxidation‐Chemotherapy

A pH/ROS Cascade‐Responsive Charge‐Reversal Nanosystem with Self‐Amplified Drug Release for Synergistic Oxidation‐Chemotherapy

Free‐Radical Acrylic Polymerization Kinetics at Elevated Temperatures

Synthesis and characterization of a novel amphiphilic poly (ethylene glycol)–poly (ε-caprolactone) graft copolymers

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