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Photochemistry

Green-light ATRP that tolerates open air

Szczepaniak G, Jeong J, Kapil K, et al. · Chemical science · 2022

Open access · cc by · source: Europe PMC

Eosin Y plus a copper ATRP catalyst polymerizes OEOMA under green light in open vials, giving low dispersity even at 1000 rpm stirring.

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Green-light ATRP that tolerates open air

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EY without Cu reached 89% conversion but Đ of 4.30

O-ATRP catalyzed with the EY/TPMA (without CuBr 2 ) enabled rapid polymerization, reaching 89% monomer conversion within 30 min (entry 2, ), but size exclusion chromatography (SEC) analysis showed that the polymer had a high dispersity ( Đ ) of 4.30.

EY plus CuBr2 gave 88% conversion and Đ = 1.19

when EYH 2 was used in combination with CuBr 2 and excess TPMA ligand, high monomer conversion (88%) and well-controlled polymerization ( Đ = 1.19) were achieved (entry 3, ).
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Key findings

Without EY, no conversion. EY without copper gave 89% conversion but Đ = 4.30. EY + Cu gave ~88% conversion and Đ = 1.19. Stirring up to 1000 rpm still kept Đ < 1.18. Even 7.5 μM EY (25 ppm) gave 80% conversion and Đ = 1.16. Oxidative quenching of 3EY* by Cu(II) is downhill (ΔGet = −0.92 eV).

Methodology

They ran photo-ATRP of OEOMA500 in PBS/DMSO open vials with eosin Y (EYH2), CuBr2, and TPMA under green light. Controls omitted EY or copper. Kinetics, SEC, Stern–Volmer quenching, and ΔGet estimates compared oxidative vs reductive quenching of 3EY*.

Limitations

Oxygen tolerance is demonstrated for this aqueous OEOMA system; hydrophobic monomers in DMSO are only briefly extended. Protein/DNA hybrids are claimed but cytocompatibility is comparative, not a full toxicology study.

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