Evaluation of multivalent dendrimers based on melamine: kinetics of thiol-disulfide exchange depends on the structure of the dendrimer.

Evaluation of multivalent dendrimers based on melamine: kinetics of thiol-disulfide exchange depends on the structure of the dendrimer.
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DOI:
10.1021/ja0210906
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发表时间:
2003-04
影响因子:
15
通讯作者:
W. Zhang;S. Tichy;L. M. Pérez;G. Maria;P. Lindahl;E. Simanek
W. Zhang;S. Tichy;L. M. Pérez;G. Maria;P. Lindahl;E. Simanek
中科院分区:
化学1区
文献类型:
--
作者:
W. Zhang;S. Tichy;L. M. Pérez;G. Maria;P. Lindahl;E. Simanek

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由二硫苏糖醇介导的丹磺酰基的硫醇-二硫键交换的速率取决于树枝状聚合物的结构。通常,交换速率随着树枝状聚合物的尺寸增加而降低。树枝状大分子与二硫化物连接附近的核心进行交换比树枝状大分子与二硫化物附近的外围更慢。交换是丹磺酰基连接的二硫化物和二硫苏糖醇之间的双分子(非合作)过程。没有观察到分子内大环化(合作)交换的证据。质谱法用于跟踪两个树枝状聚合物中的交换,提供关于该过程的定性和定量信息。数学模型表明,树枝状聚合物的所有二硫化物的交换速率是相似的,但随着交换反应的进行而增加。
The rate of thiol-disulfide exchange of dansyl groups mediated by dithiothreitol depends on the structure of the dendrimer. In general, the rate of exchange decreases as the size of the dendrimer increases. Dendrimers with disulfides attached near the core undergo exchange more slowly than dendrimers with disulfides near the periphery. Exchange is a bimolecular (noncooperative) process between dansyl-linked disulfides and dithiothreitol. No evidence for intramolecular macrocylization (cooperative) exchange is observed. Mass spectrometry is used to follow exchange in two dendrimers, providing qualitative and quantitative information about this process. Mathematical models suggest that the rates for exchange for all disulfides of a dendrimer are similar, but increase as the exchange reaction progresses.