Blue LED light-activated RAFT polymerization of PEG acrylate with high chain-end fidelity for efficient PEGylation,Polymer Chemistry

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Blue LED light-activated RAFT polymerization of PEG acrylate with high chain-end fidelity for efficient PEGylation
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-07-22 , DOI: 10.1039/d0py00838a
Alicia Rasines Mazo _{1,

2,

3,

4,

5} , Thi Nga Tran _{6,

7,

8,

9} , Wenhao Zhang _{6,

7,

8,

9} , Yuwen Meng _{6,

7,

8,

9} , Amin Reyhani _{1,

2,

3,

4,

5} , Sagrario Pascual _{6,

7,

8,

9} , Laurent Fontaine _{6,

7,

8,

9} , Greg G. Qiao _{1,

2,

3,

4,

5} , Sandie Piogé _{6,

7,

8,

9}

Affiliation

A challenge in PEGylation strategies is the site-specific conjugation of peptides, proteins, and antibodies onto a “clickable” well-defined PEG architecture whilst retaining the therapeutic potency of the parent molecule. Here, we investigated several activation processes of reversible addition–fragmentation chain transfer (RAFT) polymerization to prepare well-defined brush poly(poly(ethylene glycol) methyl ether acrylate) (PPEGA) with a long backbone of up to DP = 50 and a high fraction of living chains at near-total conversions and therefore potential applicability in PEGylation. The thermal and UV light activation methods used in the RAFT polymerization of PEGA in DMF showed the loss of control at high conversions (>70%), explained by the presence of chain transfer reactions. However, the use of the light irradiation (blue LED light) activation process with low energy intake for the RAFT polymerization of PEGA in DMF showed an unprecedented control (Đ ≤ 1.2). Blue LED light RAFT could be carried out without an exogenous initiator at room temperature, at various initial monomer concentrations at near-total conversions (ρ > 93%). The PEGylation potential of PPEGA obtained by blue LED light-initiated RAFT polymerization was highlighted by extensions of PPEGA at α- and ω-chain ends.

中文翻译：

具有高链端保真度的PEG丙烯酸酯的蓝色LED光激活的RAFT聚合，可实现有效的PEG化

PEG化策略的挑战是将肽，蛋白质和抗体在“可点击的”定义明确的PEG结构上进行位点特异性缀合，同时保留母体分子的治疗效力。在这里，我们研究了可逆加成-断裂链转移（RAFT）聚合反应的几个活化过程，以制备定义明确的毛刷聚（聚（乙二醇）甲基醚丙烯酸酯）（PPEGA），其主链最长可达DP = 50，且几乎全部转化时，生命链的比例很高，因此在PEG化中具有潜在的适用性。在DMF中PEGA的RAFT聚合中使用的热活化方法和UV光活化方法显示，在高转化率（> 70％）时失去了控制，这可以通过链转移反应来解释。然而，Đ≤1.2）。可以在室温下以不同的初始单体浓度在接近总转化率（ρ > 93％）的情况下在不使用外源引发剂的情况下进行蓝色LED灯RAFT 。通过蓝色LED光引发的RAFT聚合获得的PPEGA的PEG化潜力通过PPEGA在α链和ω链末端的延伸突出显示。

更新日期：2020-08-18

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