Table 1. PET-RAFT Polymerization of a variety of monomers using Chl a as biocatalyst and 4.8 W red LED lamp as a light source (λ_max = 635 nm).

#	Exp. Cond. a [M] : [RAFT agent] : [Chl a]	Monomer	RAFT agent	[Chl a]/[M] (ppm)	Time (h)	α b (%)	M n,th. c (g mol–1)	M n,GPC d (g mol–1)	M w/Mn
1	200 : 1 : 8 × 10–4	MA	BTPA	4	5	76	13 300	10 800	1.06
2	200 : 0 : 8 × 10–4	MA	—	4	10	6	—	—	—
3	200 : 1 : 8 × 10–4	MMA	CPADB	4	4	24	5100	6570	1.10
4	200 : 1 : 8 × 10–4	MMA	CPADB	4	20	50	10 300	14 650	1.14
5	200 : 1 : 8 × 10–4	MMA	CPADB	4	36	94	19 100	20 300	1.13
6	200 : 1 : 2 × 10–3	MMA	CPADB	10	25	94	19 100	20 420	1.16
7	200 : 1 : 5 × 10–3	MMA	CPADB	25	25	71	14 500	16 700	1.13
8	200 : 1 : 5 × 10–3	MMA	CPADB	25	15	50	10 300	12 360	1.15
9	200 : 1 : 5 × 10–3	MMA	CPADB	25	10	29	6100	8400	1.12
10	200 : 0 : 8 × 10–4	MMA	—	4	20	0	—	—	—
11	200 : 1 : 8 × 10–4	NIPAAm	BTPA	4	4	47	10 900	13 970	1.08
12	200 : 1 : 8 × 10–4	HPMA	CPADB	4	12	53	15 600	9800 (15 900) i	1.05
13	200 : 1 : 8 × 10–4	HEMA	CPADB	4	6	77	20 330	22 700	1.09
14	200 : 1 : 8 × 10–4	PFPA	BTPA	4	6	55	26 180	22 300	1.08
15	200 : 1 : 8 × 10–4	GMA	CPADB	4	12	53	15 330	16 300	1.12
16	200 : 1 : 8 × 10–4	DMAEMA	CPADB	4	14	20	6300	9600	1.18
17	200 : 1 : 0	DMAEMA	CPADB	0	10	0	—	—	—
18	200 : 1 : 8 × 10–4	MA	BSTP	4	3	41	7340	7920	1.20
19	370 : 1 : 8 × 10–4	MMA	CDB	4	12	33	12 500	15 550	1.27
20	200 : 1 : 8 × 10–4	MMA	CPD	4	12	60	12 240	13 700	1.17
21	200 : 1 : 8 × 10–4	MMA	CDTPA	4	14	79	16 200	12 800	1.17
22 f	200 : 1 : 8 × 10–4	MA	BTPA	4	8	53	9400	11 500	1.07
23 g	200 : 1 : 8 × 10–4	MA	BTPA	4	20	44	7800	8700	1.06
24 j	200 : 1 : 8 × 10–4	MMA-stat-MAA e	CPADB	4	9	ND h	ND h	25 000	1.19

^aThe polymerizations were performed in the absence of oxygen at room temperature in dimethylsulfoxide (DMSO) using 4.8 W red LED lamp as a light source (λ_max = 635 nm).

^bMonomer conversion was determined by using ¹H NMR spectroscopy.

^cTheoretical molecular weight was calculated using the following equation: M_n,th = [M]_o/[RAFT] × MW^M × α + MW^RAFT, where [M]_o, [RAFT]_o, MW^M, α, and MW^RAFT correspond to initial monomer concentration, initial RAFT concentration, molar mass of monomer, conversion determined by ¹H NMR, and molar mass of RAFT agent.

^dMolecular weight and polydispersity were determined by GPC analysis (DMAc as eluent) based on polystyrene standards.

^e[MMA]₀ : [MAA]₀ : [RAFT] : [Chl a] = 100 : 100 : 1 : 8 × 10^–4.

^fThe reaction was carried out in N,N-dimethylformamide (DMF) under red LED light irradiation.

^gThe reaction was carried out in acetonitrile (MeCN) under red LED light irradiation.

^hNot determined.

ⁱMolecular weight determined by ¹H NMR.

^jMethylation was carried out with trimethylsilyldiazomethane prior to GPC analysis (DMAc eluent) based on polystyrene standards.