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Green-light ATRP that tolerates open air

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

Source

Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

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

doi.org/10.1039/d2sc04210jRead the full paper ↗56 citationscc by

What they did

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*.

What they found

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).

The limits

What it doesn't show

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.

Key terms

ATRP
Atom transfer radical polymerization: Cu-catalyzed reversible activation of C–X chain ends.
Photoredox catalyst
Here eosin Y, which absorbs green light and exchanges electrons with the copper ATRP cycle.
Dispersity (Đ)
Mw/Mn; values near 1.1–1.2 mean a narrow polymer size distribution.
Oxidative quenching
Excited 3EY* donates an electron to Cu(II), generating Cu(I) activator.
Oxygen tolerance
Polymerization still controlled in open vials despite O2 quenching radicals and Cu(I).

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Copper is required in this dual system to:

Common questions

Why add copper if eosin Y already starts radicals?

Copper enforces the ATRP equilibrium so chains stay dormant most of the time and Đ stays low.

Why green light instead of UV?

UV can damage biomolecules; eosin Y absorbs near 520 nm.

Can you stir in air?

Yes—up to 1000 rpm still gave Đ < 1.18.

Which quenching path is favored?

Oxidative quenching of 3EY* by Cu(II) (ΔGet ≈ −0.92 eV), not reductive quenching by TPMA.

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