Aqueous metal-catalyzed living radical polymerization: highly active water-assisted catalysis

Ouchi, Makoto; Yoda, Hiroaki; Terashima, Takaya; Sawamoto, Mitsuo

doi:10.1038/pj.2011.59

Cited by 24 publications

(27 citation statements)

References 28 publications

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“…Because our polymerization is driven by EET flux to a metal catalyst, we predicted that other metals besides Cu would show appreciable polymerization activity under both anaerobic and aerobic conditions. Indeed, metal catalysts comprised of Fe 19 , 20 , Co 21 , 22 , Ni 23 , 24 , and Ru 25 have all been reported to exhibit ATRP-like activity. Although alternative metal catalysts are generally less active than Cu, they are potentially advantageous due to their lower toxicity.…”

Section: Resultsmentioning

confidence: 99%

Aerobic radical polymerization mediated by microbial metabolism

et al. 2020

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Performing radical polymerizations under ambient conditions is a significant challenge because molecular oxygen is an effective radical quencher. Here we show that the facultative electrogen Shewanella oneidensis can control metal-catalyzed living radical polymerizations under apparent aerobic conditions by first consuming dissolved oxygen via aerobic respiration, then directing extracellular electron flux to a metal catalyst. In both open and closed containers, S. oneidensis enabled living radical polymerizations without requiring the pre-removal of oxygen. Polymerization activity was closely tied to S. oneidensis anaerobic metabolism through specific extracellular electron transfer (EET) proteins and was effective for a variety of monomers using low (ppm) concentrations of metal catalysts. Finally, polymerizations survived repeated challenges of oxygen exposure and could be initiated using lyophilized or spent (recycled) cells. Overall, our results demonstrate how the unique ability of S. oneidensis to use both oxygen and metals as respiratory electron acceptors can be leveraged to address salient challenges in polymer synthesis.

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Section: Resultsmentioning

confidence: 99%

Aerobic radical polymerization mediated by microbial metabolism

et al. 2020

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“…The accelerated half-reaction via the hydrogen bonding interaction of H 2 O…H 2 O may be termed as H 2 O-assisted hydrolysis, which is similar to Lewis-base catalysis in SiO 2 ALD through the OH…N hydrogen bond [ 14 , 23 , 24 ]. As a matter of fact, there are H 2 O-assisted reactions in nature, such as hydrolysis or solvolysis [ 25 - 28 ], tautomerization or proton transfer [ 29 - 34 ], decomposition [ 35 - 37 ], and catalysis [ 38 , 39 ]. H 2 O-assisted hydrolysis and solvolysis facilitate the exchange and dissociation of Cl ligand in HfO 2 ALD using HfCl 4 and H 2 O [ 40 ].…”

Section: Resultsmentioning

confidence: 99%

Stepwise mechanism and H2O-assisted hydrolysis in atomic layer deposition of SiO2 without a catalyst

et al. 2015

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Atomic layer deposition (ALD) is a powerful deposition technique for constructing uniform, conformal, and ultrathin films in microelectronics, photovoltaics, catalysis, energy storage, and conversion. The possible pathways for silicon dioxide (SiO2) ALD using silicon tetrachloride (SiCl4) and water (H2O) without a catalyst have been investigated by means of density functional theory calculations. The results show that the SiCl4 half-reaction is a rate-determining step of SiO2 ALD. It may proceed through a stepwise pathway, first forming a Si-O bond and then breaking Si-Cl/O-H bonds and forming a H-Cl bond. The H2O half-reaction may undergo hydrolysis and condensation processes, which are similar to conventional SiO2 chemical vapor deposition (CVD). In the H2O half-reaction, there are massive H2O molecules adsorbed on the surface, which can result in H2O-assisted hydrolysis of the Cl-terminated surface and accelerate the H2O half-reaction. These findings may be used to improve methods for the preparation of SiO2 ALD and H2O-based ALD of other oxides, such as Al2O3, TiO2, ZrO2, and HfO2.

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“…[PPh 2 (C 6 H 4 OH): Aldrich, purity >98%] 36 were used as received, and [RuCp*(µ 3 -Cl)] 4 was synthesized according to the published procedure. 37 These ruthenium complexes and a ligand were handled in a glove box under moisture-and oxygen-free argon (H 2 O < 1 ppm; O 2 < 1 ppm).…”

Section: Methodsmentioning

confidence: 99%

Single-chain crosslinked star polymers via intramolecular crosslinking of self-folding amphiphilic copolymers in water

Terashima

Sugita

Sawamoto

2015

Polym J

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Single-chain crosslinked star polymers with hydrophilic multiple short arms and a hydrophobic core were created as novel microgel star polymers of single polymer chains. The synthetic process involves the intramolecular crosslinking of self-folding amphiphilic random copolymers in water. For this, amphiphilic random copolymers bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic olefin pendants were synthesized by ruthenium-catalyzed living radical copolymerization of PEG methyl ether methacrylate, dodecyl methacrylate, and hydroxyl-functionalized methacrylates, and the in-situ or post esterification of the hydroxyl pendants of the resulting copolymers with methacryloyl chloride. The olefin-bearing copolymers with 20-40 mol% hydrophobic units efficiently self-folded with hydrophobic interaction in water and were crosslinked intramolecularly using a free radical initiator or a ruthenium catalyst to selectively provide single-chain crosslinked star polymers, while a counterpart with 50 mol% hydrophobic units induced bimolecular aggregation in water to give double-chain crosslinked star polymers. Primary structure of the star polymers can be precisely controlled with random copolymer precursors. Owing to PEG arm units, the star polymers further showed thermosensitive solubility in water.

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Aqueous metal-catalyzed living radical polymerization: highly active water-assisted catalysis

Cited by 24 publications

References 28 publications

Aerobic radical polymerization mediated by microbial metabolism

Aerobic radical polymerization mediated by microbial metabolism

Stepwise mechanism and H2O-assisted hydrolysis in atomic layer deposition of SiO2 without a catalyst

Single-chain crosslinked star polymers via intramolecular crosslinking of self-folding amphiphilic copolymers in water

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