Kinetic Insights into Hydrogen Sulfide Delivery from Caged-Carbonyl Sulfide Isomeric Donor Platforms.
Kinetic Insights into Hydrogen Sulfide Delivery from Caged-Carbonyl Sulfide Isomeric Donor Platforms.
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DOI：
10.1021/jacs.7b09527
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发表时间：
2017-11-15
影响因子：
15
通讯作者：
Pluth MD
中科院分区：
文献类型：
--
作者：
Zhao Y;Henthorn HA;Pluth MD
硫化氢（H2S）是一种重要的生物小气体分子，对多种生理和病理过程具有良好的保护作用。为了研究H2S在生物学中的扩展作用，研究人员经常使用H2S供体来模拟酶促H2S合成或在特定情况下提供增加的H2S水平。由于需要新的广泛且易于修改的H2S捐赠平台，我们在这里报告了一系列异构体笼型羰基硫化物（COS）化合物的制备和H2S释放动力学，包括硫代氨基甲酸酯、硫代碳酸酯和二硫代碳酸酯，所有这些化合物释放的COS都能被普遍存在的碳酸酐酶迅速转化为H2S。每个供体都被设计为在过氧化氢（H2O2）激活触发器后释放COS/H2S。除了提供广泛的新的H2O2响应基元外，我们还展示了H2O2剂量依赖于每个供体核心的COS/H2S释放，建立了释放谱可以通过结构修饰来修改，并比较了异构体核心结构的COS/H2S释放速率和效率。为了支持我们的实验研究，我们还提供了从每个平台释放COS/H2S的势能面的计算见解。此外，我们还报道了对二硫代氨基甲酸酯核的初步研究，该核在h2o2介导的激活下直接释放H2S。总的来说，从这些研究中获得的关于COS/H2S释放的见解为扩展响应性COS/H2S供体系统的新兴领域奠定了基础。
Hydrogen sulfide (H2S) is a biologically-important small gaseous molecule that exhibits promising protective effects against a variety of physiological and pathological processes. To investigate the expanding roles of H2S in biology, researchers often use H2S donors to mimic enzymatic H2S synthesis or to provide increased H2S levels under specific circumstances. Aligned with the need for new broad and easily-modifiable platforms for H2S donation, we report here the preparation and H2S release kinetics from a series of isomeric caged-carbonyl sulfide (COS) compounds, including thiocarbamates, thiocarbonates, and dithiocarbonates, all of which release COS that is quickly converted to H2S by the ubiquitous enzyme carbonic anhydrase. Each donor is designed to release COS/H2S after the activation of a trigger by activation by hydrogen peroxide (H2O2). In addition to providing a broad palette of new, H2O2-responsive donor motifs, we also demonstrate the H2O2 dose-dependent COS/H2S release from each donor core, establish that release profiles can be modified by structural modifications, and compare COS/H2S release rates and efficiencies from isomeric core structures. Supporting our experimental investigations, we also provide computational insights into the potential energy surfaces for COS/H2S release from each platform. In addition, we also report initial investigations into dithiocarbamate cores, which release H2S directly upon H2O2-mediated activation. As a whole, the insights on COS/H2S release gained from these investigations provide a foundation for the expansion of the emerging area of responsive COS/H2S donors systems.
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DOI：
10.1039/p29830000437
发表时间：
1983-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2
影响因子：
--
作者：
HILL, SV;THEA, S;WILLIAMS, A
通讯作者：
WILLIAMS, A
影响因子：
4.4
作者：
Kesselmeier, J;Teusch, N;Kuhn, U
通讯作者：
Kuhn, U
DOI：
10.1080/00022470.1975.10470199
发表时间：
1975-01-01
期刊：
JOURNAL OF THE AIR POLLUTION CONTROL ASSOCIATION
影响因子：
--
作者：
HANST, PL;SPILLER, LL;MILLER, MF
通讯作者：
MILLER, MF
影响因子：
5.2
作者：
Devarie-Baez, Nelmi O.;Bagdon, Powell E.;Peng, Bo;Zhao, Yu;Park, Chung-Min;Xian, Ming
通讯作者：
Xian, Ming
影响因子：
5.2
作者：
Chauhan, Preeti;Bora, Prerona;Chakrapani, Harinath
通讯作者：
Chakrapani, Harinath