Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives

Matyjaszewski, Krzysztof

doi:10.1021/ma3001719

Cited by 2,384 publications

(2,086 citation statements)

References 338 publications

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“…Cationic nanogels were prepared by activators generated by electron transfer atom transfer radical polymerization [5,35,36,[45][46][47][48][49]64] in inverse miniemulsion by copolymerizing quaternized dimethyl aminoethylmethacrylate, oligo(ethylene oxide) methacrylate (M n = 300), and a water-soluble disulfide methacrylate crosslinker with a poly(ethylene glycol 2-bromoisobutyrate) initiator and a copper bromide tris(2-[dimethylamino]ethyl)amine catalyst system dissolved in water. The inverse miniemulsion was prepared by ultrasonication of the aqueous phase in a cyclohexane Span80 solution.…”

Section: Nanogel Synthesismentioning

confidence: 99%

Cationic Nanogel-mediated Runx2 and Osterix siRNA Delivery Decreases Mineralization in MC3T3 Cells

Shrivats

Hsu

Averick

et al. 2015

Clinical Orthopaedics &Amp; Related Research

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Background Heterotopic ossification (HO) may occur after musculoskeletal trauma, traumatic brain injury, and total joint arthroplasty. As such, HO is a compelling clinical concern in both military and civilian medicine. A possible etiology of HO involves dysregulated signals in the bone morphogenetic protein osteogenic cascade. Contemporary treatment options for HO (ie, nonsteroidal antiinflammatory drugs and radiation therapy) have adverse effects associated with their use and are not biologically engineered to abrogate the molecular mechanisms that govern osteogenic differentiation. Questions/purposes We hypothesized that (1) nanogelmediated short interfering RNA (siRNA) delivery against Runt-related transcription factor 2 (Runx2) and osterix (Osx) genes will decrease messenger RNA expression; (2) inhibit activity of the osteogenic marker alkaline phosphatase (ALP); and (3) inhibit hydroxyapatite (HA) deposition in osteoblast cell cultures. Methods Nanogel nanostructured polymers delivered siRNA in 48-hour treatment cycles against master osteogenic regulators, Runx2 and Osx, in murine calvarial preosteoblasts (MC3T3-E1.4) stimulated for osteogenic differentiation by recombinant human bone morphogenetic protein (rhBMP-2). The efficacy of RNA interference (RNAi) therapeutics was determined by quantitation of messenger RNA knockdown (by quantitative reverse transcription-polymerase chain reaction), downstream protein knockdown (determined ALP enzymatic activity assay), and HA deposition (determined by OsteoImage TM assay). Results Gene expression assays demonstrated that nanogelbased RNAi treatments at 1:1 and 5:1 nanogel:short interfering RNA weight ratios reduced Runx2 expression by 48.59% ± 19.53% (p \ 0.001) and 43.22% ± 18.01% (both p \ 0.001). The same 1:1 and 5:1 treatments against both Runx2 and Osx reduced expression of Osx by 51.65% ± 10.85% and 47.65% ± 9.80% (both p \ 0.001). Moreover, repeated 48-hour RNAi treatment cycles against Runx2 and Osx rhBMP-2 administration reduced ALP activity after 4 and 7 days. ALP reductions after 4 days in culture by nanogel 5:1 and 10:1 RNAi treatments were 32.4% ± 12.0% and 33.6% ± 13.8% (both p \ 0.001). After 7 days in culture, nanogel 1:1 and 5:1 RNAi treatments produced 35.9% ± 14.0% and 47.7% ± 3.2% reductions in ALP activity. Osteoblast mineralization data after 21 days suggested that Two of the authors (ARS, EH) contributed equally.

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Section: Nanogel Synthesismentioning

confidence: 99%

Cationic Nanogel-mediated Runx2 and Osterix siRNA Delivery Decreases Mineralization in MC3T3 Cells

Shrivats

Hsu

Averick

et al. 2015

Clinical Orthopaedics &Amp; Related Research

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“…To select the appropriate initiator, good knowledge of the reactivity of different alkyl halides towards initiation is important in order to maintain good control over the polymerization process and the polymer end groups, the latter example being especially important for the efficient synthesis of block copolymers. 1,[9][10][11] The selection of a suitable catalyst is also of importance as different reactivities could lead to vastly different rates of polymerization (kp), thus compromising overall control of the polymerization. 1,12 In addition the activity as well as the concentration of ligand plays an important role in the success of a polymerization with ligands ranging from very high (e.g.…”

Section: Introductionmentioning

confidence: 99%

“…methacrylates), where ligands typically have low lying π* orbitals capable of accepting electrons from the metal stabilizing Cu (I). 9 However, it should be noted that active ligands have also been reported to mediate the polymerization of methacrylates although no evidence of end group fidelity is provided. 14,15 Finally, although solvent choice certainly has a much lower impact on radical polymerizations (in terms of both rate and stereochemistry) as opposed to ionic polymerizations, the choice of the reaction medium can still significantly affect the ATRP equilibrium and relevant rate constants.…”

Section: Introductionmentioning

confidence: 99%

Universal Conditions for the Controlled Polymerization of Acrylates, Methacrylates, and Styrene via Cu(0)-RDRP

et al. 2017

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Usually atom transfer radical polymerization (ATRP) requires various parameters, such as the type of initiator, transition metal, ligand, solvent, temperature, deactivator, added salts and reducing agents, need to be optimised in order to achieve a high degree of control over molecular weight and dispersity. These components play a major role when switching monomers e.g. from acrylic to methacrylic and/or styrenic monomers during the synthesis of homo-and block copolymers as the stability and reactivity of the carbon centered propagating radical dramatically changes. This is a challenge for both "experts" and non-experts as choosing the appropriate conditions for successful polymerization can be time consuming and an arduous task. In this work we describe some universal conditions for the efficacious polymerization of acrylates, methacrylates and styrene (using an identical initiator, ligand, copper salt and solvent) based on commercially available reagents (PMDETA, IPA, Cu(0) wire). The versatility of these conditions is demonstrated by the near quantitative polymerization of these monomer families to yield well-defined materials over a range of molecular weights with low dispersities (~1.1-1.2). The control and high end group fidelity is further exemplified by in situ block copolymerization upon sequential monomer addition for the case of methacrylates and styrene furnishing higher molecular weight copolymers with minimal termination. The facile nature of these conditions, combined with readily available reagents will greatly expand the access and availability of tailored polymeric materials to all researchers.

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“…Among the 22 non-conjugated polymers, free-radical polymerization is the most widely used polymerization method, which amounts to 45.5% of all polymers synthesized due to its well-established chemistry and high functional group tolerance. 128,129 The average yields, M n and PDI of polymers generated via free-radical polymerization are 78.3%, 14.3 kDa and 2.5, respectively. The more advanced living radical polymerization such as nitroxide-mediated polymerization (NMP) allows polymers with much lower PDIs (1.2-1.4) to be synthesized.…”

Section: Conjugated Versus Non-conjugated Polymers: Materials Preparatmentioning

confidence: 99%

“…46,133 However, strongly nucleophilic organomagnesium species is inevitably present in GRIM, which severely limit the scope of monomers that can be polymerized, whereas radical polymerization is well known to have high functional group tolerance. 128,129 Interestingly, block copolymers are unpopular in PLED applications: only one non-conjugated block copolymer was reported recently 46 and conjugated block copolymer was absent. 134,135 A critical parameter of OLED materials is purity because impurities can act as charge trapping sites and quenchers during device operation.…”

Section: Conjugated Versus Non-conjugated Polymers: Materials Preparatmentioning

confidence: 99%

Recent Advances in Polymer Organic Light-Emitting Diodes (PLED) Using Non-conjugated Polymers as the Emitting Layer and Contrasting Them with Conjugated Counterparts

Wong

2017

Journal of Elec Materi

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Polymer organic light-emitting diodes (PLED) are one of the most studied subjects in flexible electronics thanks to their economical wet fabrication procedure for enhanced price advantage of the product device. In order to optimize PLED efficiency, correlating the polymer structure with the device performance is essential. An important question for the researchers in this field is whether the polymer backbone is conjugated or not as it affects the device performance. In this review, recent advances in non-conjugated polymers employed as the emitting layer in PLED devices are first discussed, followed by their contrast with the conjugated counterparts in terms of polymer synthesis, sample quality, physical properties and device performances. Such comparison between conjugated and non-conjugated polymers for PLED applications is rarely attempted, and; hence, this review shall provide a useful insight of emitting polymers employed in PLEDs.

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Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives

Cited by 2,384 publications

References 338 publications

Cationic Nanogel-mediated Runx2 and Osterix siRNA Delivery Decreases Mineralization in MC3T3 Cells

Cationic Nanogel-mediated Runx2 and Osterix siRNA Delivery Decreases Mineralization in MC3T3 Cells

Universal Conditions for the Controlled Polymerization of Acrylates, Methacrylates, and Styrene via Cu(0)-RDRP

Recent Advances in Polymer Organic Light-Emitting Diodes (PLED) Using Non-conjugated Polymers as the Emitting Layer and Contrasting Them with Conjugated Counterparts

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