Pozhidaeva Nina, Cormier Marie-Eve, Chaudhari Anita, Woolley G Andrew
Department of Chemistry, University of Toronto, 80 Saint George Street, Toronto M5S 3H6, Canada.
Bioconjug Chem. 2004 Nov-Dec;15(6):1297-303. doi: 10.1021/bc049855h.
Cross-linking reagents based on an azobenzene core can be used to reversibly photoregulate secondary structure when introduced as intramolecular bridges in peptides and proteins. Photoisomerization of the azobenzene core in the trans to cis direction is triggered by photon absorption but isomerization from cis to trans occurs thermally as well as photochemically. The rate of the thermal process effectively determines the half-life of the cis form as well as the extent to which the trans form can be recovered. We designed and characterized a series of methanethiosulfonate (MTS)-bearing thiol-reactive azo-benzene-based cross-linkers. These cross-linkers are shown to permit photoregulation of helix content in a test peptide with half-lives for the cis conformation ranging from 11 s to 43 h at 25 degrees C. The cross-linkers described here thus broaden the range of reagents available for reversible photocontrol of peptide and protein conformation.
基于偶氮苯核心的交联试剂在作为肽和蛋白质中的分子内桥引入时，可用于可逆地光调节二级结构。偶氮苯核心从反式到顺式方向的光异构化由光子吸收触发，但从顺式到反式的异构化既可以热方式发生，也可以光化学方式发生。热过程的速率有效地决定了顺式形式的半衰期以及反式形式能够恢复的程度。我们设计并表征了一系列带有甲硫基磺酸盐（MTS）的、对硫醇具有反应性的基于偶氮苯的交联剂。这些交联剂被证明能够在25摄氏度下对测试肽中的螺旋含量进行光调节，顺式构象的半衰期范围为11秒至43小时。因此，本文所述的交联剂拓宽了可用于可逆光控制肽和蛋白质构象的试剂范围。
