Catalytic Formation of Disulfide Bonds in Peptides by Molecularly Imprinted Microgels at Oil/Water Interfaces
Catalytic Formation of Disulfide Bonds in Peptides by Molecularly Imprinted Microgels at Oil/Water Interfaces
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DOI：
10.1021/acsami.6b10131
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发表时间：
2016-11-09
影响因子：
9.5
通讯作者：
Sellergren, Borje
中科院分区：
文献类型：
--
作者：
Shen, Xiantao;Huang, Chuixiu;Sellergren, Borje
本文描述了分子印迹聚合物（MIP）微凝胶（MG）稳定皮克林乳液（PEs）的制备和研究，因为它们能够催化多肽在O/W界面上形成二硫键。通过沉淀聚合和程序化引发剂变化策略合成了MIP MGs。通过DLS分析、SEM测量和光学显微镜分析对MIP mggs进行了表征。干、湿MIP颗粒的水动力直径分别为100 nm和280 nm。模板再结合实验表明，在饱和状态下，与非印迹参考聚合物（NIP） mg （10 mg g(-1)）相比，MIP mg结合的模板量（24 mg g(-1)）增加了两倍。以MIP mg为稳定剂，在不同氧化剂的作用下，对油相和水相进行乳化，制备了催化氧化体系。在环化过程中，巯基前体和氧化试剂的分离非选择性地减少了副产物的形成，而MIP mggs上的印迹空腔选择性地促进了肽的分子内环化。当使用I-2作为氧化剂时，MIP-PE-I-2体系的产物收率为50%，与非印迹聚合物NIP-PE-I-2体系（26%）相比，提高了近2倍。我们相信，本研究提出的界面催化系统可以通过提高生产效率同时抑制副产物的形成，为合成肽化学提供显著的好处。
This work describes the preparation and investigation of molecularly imprinted polymer (MIP) microgel (MG) stabilized Pickering emulsions (PEs) for their ability to catalyze the formation of disulfide bonds in peptides at the O/W interface. The MIP MGs were synthesized via precipitation polymerization and a programmed initiator change strategy. The MIP MGs were characterized using DLS analysis, SEM measurement, and optical microscopy analysis. The dry and wet MIP MGs showed a hydrodynamic diameter of 100 and 280 nm, respectively. A template rebinding experiment showed that the MIP MGs bound over two times more template (24 mg g(-1)) compared to the uptake displayed by a nonimprinted reference polymer (NIP) MG (10 mg g(-1)) at saturation. Using the MIP MGs as stabilizers, catalytic oxidation systems were prepared by emulsifying the oil phase and water phase in the presence of different oxidizing agents. During the cyclization, the isolation of the thiol precursors and the oxidizing reagents nonselectively decreased the formation of the byproducts, while the imprinted cavities on the MIP MGs selectively promoted the intramolecular cyclization of peptides. When I-2 was used as the oxidizing agent, the MIP-PE-I-2 system showed a product yield of 50%, corresponding to a nearly 2-fold increase compared to that of the nonimprinted polymer NIP-PE-I-2 system (26%). We believe the interfacial catalysis system presented in this work may offer significant benefits in synthetic peptide chemistry by raising productivity while suppressing the formation of byproducts.