Automated ARGET ATRP Accelerates Catalyst Optimization for the Synthesis of Thiol-Functionalized Polymers.
Automated ARGET ATRP Accelerates Catalyst Optimization for the Synthesis of Thiol-Functionalized Polymers.
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DOI：
10.1021/ma3000219
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发表时间：
2012-02-14
期刊：
影响因子：
5.5
通讯作者：
Anderson DG
中科院分区：
文献类型：
--
作者：
Siegwart DJ;Leiendecker M;Langer R;Anderson DG
ATRP合成聚合物的传统方法是产量相对较低，需要在惰性气氛中反复优化条件。自动化、高通量可控自由基聚合被开发出来，以加速催化剂优化和生产二硫功能化聚合物，而不需要惰性气体。利用ARGET ATRP，快速确定了8种不同单体的聚合条件，包括第一个ARGET甲基丙烯酸二乙氨基乙酯和二乙二醇甲基醚甲基丙烯酸酯。以二(2-羟乙基)二硫代双(2-溴-2-甲基丙酸)酯为引发剂，三(2-吡啶甲基)胺为配体，2-乙基己酸亚锡为还原剂，合成了丙烯酸丁酯、低聚(乙二醇甲基)甲基丙烯酸酯300和475、甲基丙烯酸二甲氨基乙酯、苯乙烯和甲基丙烯酸甲酯。针对每个单体分别对催化剂和还原剂的浓度进行了优化，并利用优化后的条件系统地合成了高分子库。在二硫苏糖醇的作用下，二硫键功能化的链可以裂解成两条硫醇末端的链，这可能对合成聚合物生物偶联物有一定的应用价值。最后，我们证明了这些新的条件完美地转化为传统的间歇聚合。我们相信，这里开发的方法可能会被证明是普遍有用的，以加速各种化学反应和聚合的系统优化。
Conventional synthesis of polymers by ATRP is relatively low throughput, involving iterative optimization of conditions in an inert atmosphere. Automated, high-throughput controlled radical polymerization was developed to accelerate catalyst optimization and production of disulfide-functionalized polymers without the need of an inert gas. Using ARGET ATRP, polymerization conditions were rapidly identified for eight different monomers, including the first ARGET ATRP of 2-(diethylamino)ethyl methacrylate and di(ethylene glycol) methyl ether methacrylate. In addition, butyl acrylate, oligo(ethylene glycol) methacrylate 300 and 475, 2-(dimethylamino)ethyl methacrylate, styrene, and methyl methacrylate were polymerized using bis(2-hydroxyethyl) disulfide bis(2-bromo-2-methylpropionate) as the initiator, tris(2-pyridylmethyl)amine as the ligand, and tin(II) 2-ethylhexanoate as the reducing agent. The catalyst and reducing agent concentration was optimized specifically for each monomer, and then a library of polymers was synthesized systematically using the optimized conditions. The disulfide-functionalized chains could be cleaved to two thiol-terminated chains upon exposure to dithiothreitol, which may have utility for the synthesis of polymer bioconjugates. Finally, we demonstrated that these new conditions translated perfectly to conventional batch polymerization. We believe the methods developed here may prove generally useful to accelerate the systematic optimization of a variety of chemical reactions and polymerizations.
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影响因子：
4.6
作者：
Hoogenboom, R;Fijten, MWM;Schubert, US
通讯作者：
Schubert, US
影响因子：
15
作者：
Brocchini, S;James, K;Kohn, J
通讯作者：
Kohn, J
影响因子：
--
作者：
Fiten, MWM;Paulus, RM;Schubert, US
通讯作者：
Schubert, US
影响因子：
15
作者：
Oh, JK;Tang, CB;Matyjaszewski, K
通讯作者：
Matyjaszewski, K
DOI：
10.1073/pnas.0602675103
发表时间：
2006-10-17
影响因子：
11.1
作者：
Matyjaszewski, Krzysztof;Jakubowski, Wojciech;Tsarevsky, Nicolay V.
通讯作者：
Tsarevsky, Nicolay V.