Substrate-initiated synthesis of cell-penetrating poly(disulfide)s.
Substrate-initiated synthesis of cell-penetrating poly(disulfide)s.
复制标题
DOI：
10.1021/ja311961k
复制
发表时间：
2013-02-13
影响因子：
15
通讯作者：
Matile S
中科院分区：
文献类型：
--
作者：
Bang EK;Gasparini G;Molinard G;Roux A;Sakai N;Matile S
从表面引发聚合的经验教训适用于生长细胞穿透聚（二硫化物）的自由选择的基板上直接。细胞摄取后的还原性解聚应释放天然底物并使毒性最小化。在硫醇化底物的存在下，含有来自天冬酰胺或优选地硫辛酸的应变二硫化物和胍阳离子的繁殖体在室温下在pH 7下在小于5分钟内转化成聚（二硫化物）。底物引发的阳离子聚（二硫化物）的聚合和它们与二硫苏糖醇的解聚导致荧光囊泡中转运活性的出现和消失。相同的过程进一步通过凝胶渗透色谱法和荧光共振能量转移来表征。
Lessons from surface-initiated polymerization are applied to grow cell-penetrating poly(disulfide)s directly on substrates of free choice. Reductive depolymerization after cellular uptake should then release the native substrates and minimize toxicity. In the presence of thiolated substrates, propagators containing a strained disulfide from asparagusic or, preferably, lipoic acid and a guanidinium cation polymerize into poly(disulfide)s in less than 5 min at room temperature at pH 7. Substrate-initiated polymerization of cationic poly(disulfide)s and their depolymerization with dithiothreitol causes the appearance and disappearance of transport activity in fluorogenic vesicles. The same process is further characterized by gel-permeation chromatography and fluorescence resonance energy transfer.