Tuttle Robert R, Daly Ryann E, Rithner Christopher D, Reynolds Melissa M
ACS Appl Mater Interfaces. 2021 Nov 10;13(44):52006-52013. doi: 10.1021/acsami.1c08917. Epub 2021 Jul 19.
Herein, we establish a method to quantitatively monitor a metal-organic framework (MOF)-catalyzed, biomedically relevant reaction directly in blood plasma, specifically, the generation of nitric oxide (NO) from the endogenous substrate -nitrosoglutathione (GSNO) catalyzed by H[(CuCl)-(BTTri)] (CuBTTri). The reaction monitoring method uses UV-vis and H NMR spectroscopies along with a nitric oxide analyzer (NOA) to yield the reaction stoichiometry and catalytic rate for GSNO to NO conversion catalyzed by CuBTTri in blood plasma. The results show 100% loss of GSNO within 16 h and production of 1 equiv. of glutathione disulfide (GSSG) per 2 equiv. of GSNO. Only 78 ± 10% recovery of NO(g) was observed, indicating that blood plasma can scavenge the generated NO before it can escape the reaction vessel. Significantly, to best apply and understand reaction systems with biomedical importance, such as NO release catalyzed by CuBTTri, methods to study the reaction directly in biological solvents must be developed.
在此，我们建立了一种方法，可直接在血浆中定量监测金属有机框架（MOF）催化的、与生物医学相关的反应，具体而言，是由H[(CuCl)-(BTTri)]（CuBTTri）催化内源性底物亚硝基谷胱甘肽（GSNO）生成一氧化氮（NO）的反应。该反应监测方法利用紫外可见光谱和核磁共振氢谱以及一氧化氮分析仪（NOA），得出CuBTTri在血浆中催化GSNO转化为NO的反应化学计量比和催化速率。结果显示，16小时内GSNO完全消耗，每2当量的GSNO生成1当量的谷胱甘肽二硫化物（GSSG）。仅观察到78±10%的NO(g)回收率，这表明血浆能够在生成的NO逸出反应容器之前将其清除。重要的是，为了更好地应用和理解具有生物医学重要性的反应体系，如CuBTTri催化的NO释放，必须开发在生物溶剂中直接研究该反应的方法。
