Water-Soluble Polymers. 81. Direct Synthesis of Hydrophilic Styrenic-Based Homopolymers and Block Copolymers in Aqueous Solution via RAFT

Mitsukami, Yoshiro; Donovan, Michael S.; Lowe, Andrew B.; McCormick, Charles L.

doi:10.1021/ma0018087

Cited by 701 publications

(658 citation statements)

References 33 publications

(32 reference statements)

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“…pCMV-Luc (Lot: PF461-090623) was amplified by The Plasmid Factory (Bielefeld, Germany). Beetle Luciferin and heparin sodium salt were bought from Sigma-Aldrich Laborchemikalien GmbH (Seelze, Germany 4-Cyanopentanoic acid dithiobenzoate (CPT), used as chain transfer agent (CTA), was synthesized as described in the literature [29]. The synthesis of pDMAEMA, which was used as a macroCTA, was performed similarly to the method of Scales et al [28].…”

Section: Methodsmentioning

confidence: 99%

Low Molecular Weight pDMAEMA-block-pHEMA Block-Copolymers Synthesized via RAFT-Polymerization: Potential Non-Viral Gene Delivery Agents?

et al. 2011

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Abstract:The aim of this study was to investigate non-viral pDNA carriers based on diblock-copolymers consisting of poly(2-(dimethyl amino)ethyl methacrylate) (pDMAEMA) and poly(2-hydroxyethyl methacrylate) (pHEMA). Specifically the block-lengths and molecular weights were varied to determine the minimal requirements for transfection. Such vectors should allow better transfection at acceptable toxicity levels and the entire diblock-copolymer should be suitable for renal clearance. For this purpose, a library of linear poly(2-(dimethyl amino)ethyl methacrylate-block-poly(2-hydroxyl methacrylate) (pDMAEMA-block-pHEMA) copolymers was synthesized via RAFT (reversible additionfragmentation chain transfer) polymerization in a molecular weight (Mw) range of 17-35.7 kDa and analyzed using 1 H and 13 C NMR (nuclear magnetic resonance), ATR (attenuated total reflectance), GPC (gel permeation chromatography) and DSC (differential scanning calorimetry). Copolymers possessing short pDMAEMA-polycation chains were 1.4-9.7 times less toxic in vitro than polyethylenimine (PEI) 25 kDa, and complexed DNA into polyplexes of 100-170 nm, favorable for cellular uptake. The DNA-binding affinity and polyplex stability against competing polyanions was comparable with OPEN ACCESSPolymers 2011, 3 694 PEI 25 kDa. The zeta-potential of polyplexes of pDMAEMA-grafted copolymers remained positive (+15-30 mV). In comparison with earlier reported low molecular weight homo pDMAEMA vectors, these diblock-copolymers showed enhanced transfection efficacy under in vitro conditions due to their lower cytotoxicity, efficient cellular uptake and DNA packaging. The homo pDMAEMA 115 (18.3 kDa) self-assembled with DNA into small positively charged polyplexes, but was not able to transfect cells. The grafting of 6 and 57 repeating units of pHEMA (0.8 and 7.4 kDa) to pDMAEMA 115 increased the transfection efficacy significantly, implying a crucial impact of pHEMA on vector-cell interactions. The intracellular trafficking, in vivo transfection efficacy and kinetics of low molecular weight pDMAEMA-block-pHEMA are subject of ongoing studies.

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Section: Methodsmentioning

confidence: 99%

Low Molecular Weight pDMAEMA-block-pHEMA Block-Copolymers Synthesized via RAFT-Polymerization: Potential Non-Viral Gene Delivery Agents?

et al. 2011

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“…[95] Other examples of doubly hydrophilic block copolymers have been reported by McCormick and coworkers. [244][245][246][247] In RAFT polymerization, the order of constructing the blocks of a block copolymer can be very important. [44,77] The [38,77] 20 S 20300 S-b-DMA 43000 1.24 [38,77] 12 DMAEMA 63600 B DMAEMA-b-S 103900 B 1.28 12 EO 750 EO-b-S C 7800 1.07 [38,77] A For abbreviations see footnote A to Table 2 propagating radical for the first formed block must be a good homolytic leaving group with respect to that of the second block.…”

Section: Diblock Copolymersmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process

Moad¹,

Rizzardo²,

Thang³

2005

Aust. J. Chem.

2,128

1,894

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This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC( S)SR] by a mechanism of reversible addition-fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.

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“…N,N-Diethyl acrylamide (DEA) was dried over 4 Å molecular sieves and purified by distillation under reduced pressure. 4-Cyanopentanoic acid dithiobenzoate (CPD) was synthesized according to the method reported by McCormick and co-workers [10]. Pyrene was purified by recrystallization from methanol.…”

Section: Methodsmentioning

confidence: 99%

Thermo-Responsive and Biocompatible Diblock Copolymers Prepared via Reversible Addition-Fragmentation Chain Transfer (RAFT) Radical Polymerization

et al. 2014

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Poly(2-(methacryloyloxy)ethyl phosphorylcholine)-b-poly(N,N-diethyl acrylamide) (PMPC m -PDEA n ) was synthesized via reversible addition-fragmentation chain transfer (RAFT) controlled radical polymerization. Below, the critical aggregation temperature (CAT) the diblock copolymer dissolved in water as a unimer with a hydrodynamic radius (R h ) of ca. 5 nm. Above the CAT the diblock copolymers formed polymer micelles composed of a PDEA core and biocompatible PMPC shells, due to hydrophobic self-aggregation of the thermo-responsive PDEA block. A fluorescence probe study showed that small hydrophobic small guest molecules could be incorporated into the core of the polymer micelle above the CAT. The incorporated guest molecules were released from the core into the bulk aqueous phase when the temperature decreased to values below the CAT because of micelle dissociation.

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Water-Soluble Polymers. 81. Direct Synthesis of Hydrophilic Styrenic-Based Homopolymers and Block Copolymers in Aqueous Solution via RAFT

Cited by 701 publications

References 33 publications

Low Molecular Weight pDMAEMA-block-pHEMA Block-Copolymers Synthesized via RAFT-Polymerization: Potential Non-Viral Gene Delivery Agents?

Low Molecular Weight pDMAEMA-block-pHEMA Block-Copolymers Synthesized via RAFT-Polymerization: Potential Non-Viral Gene Delivery Agents?

Living Radical Polymerization by the RAFT Process

Thermo-Responsive and Biocompatible Diblock Copolymers Prepared via Reversible Addition-Fragmentation Chain Transfer (RAFT) Radical Polymerization

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