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普朗尼克 F127 微环境对 S-亚硝基谷胱甘肽光化学一氧化氮释放的影响。

Influence of Pluronic F127 microenvironments on the photochemical nitric oxide release from S-nitrosoglutathione.

机构信息

Institute of Chemistry, University of Campinas, UNICAMP, CP 6154, 13083-970, Campinas, SP, Brazil.

Brasilian Synchroton Light Laboratory, LNLS, CP 6192, 13083-970, Campinas, SP, Brazil.

出版信息

J Colloid Interface Sci. 2019 May 15;544:217-229. doi: 10.1016/j.jcis.2019.02.087. Epub 2019 Feb 26.

Abstract

Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) (F127) hydrogels have been used to deliver nitric oxide (NO) topically in biomedical applications. Here, the effect of F127 microenvironments on the photochemical NO release from S-nitrosoglutathione (GSNO) was investigated in F127 solutions 7.6 wt% 15 wt% and 22.5 wt% at 15 °C and 37 °C. Small-angle X-ray Scattering (SAXS) and Differential Scanning Calorimetry (DSC) measurements, along with proton Nuclear Magnetic Resonance (H NMR) spectral shifts and T relaxation data at six different concentration-temperature conditions, allowed identifying F127 microphases characterized by: a sol phase of unimers; micelles in non-defined periodic order, and a gel phase of cubic packed micelles. Kinetic measurements showed that GSNO photodecompositon proceeds faster in micellized F127 where GSNO is segregated to the intermicellar microenvironment. Real time kinetic monitoring of NO release and T relaxation profiles showed that NO is preferentially partitioned into the hydrophobic PPO cores of the F127 micelles, with the consequent decrease in its rate of release to the gas phase. These results show that F127 microphases affect both the kinetics of GSNO photodecomposition and the rate of NO escape and can be used to modulate the photochemical NO delivery from F127/GSNO solutions.

摘要

聚(环氧乙烷)-聚(环氧丙烷)-聚(环氧乙烷)(PEO-PPO-PEO)(F127)水凝胶已被用于在生物医学应用中局部递送一氧化氮(NO)。在这里,研究了 F127 微环境对 S-亚硝基谷胱甘肽(GSNO)光化学 NO 释放的影响,实验在 15°C 和 37°C 下,F127 浓度为 7.6 wt%、15 wt%和 22.5 wt%的溶液中进行。小角 X 射线散射(SAXS)和差示扫描量热法(DSC)测量,以及质子核磁共振(H NMR)谱移和六个不同浓度-温度条件下的 T 弛豫数据,允许识别出具有以下特征的 F127 微相:单体的溶相;非定域周期性排列的胶束,以及立方堆积胶束的凝胶相。动力学测量表明,GSNO 在胶束化的 F127 中光分解速度更快,其中 GSNO 被隔离到胶束间的微环境中。NO 释放的实时动力学监测和 T 弛豫曲线表明,NO 优先分配到 F127 胶束的疏水性 PPO 核中,从而降低了其向气相的释放速率。这些结果表明,F127 微相既影响 GSNO 光分解的动力学,又影响 NO 逸出的速率,可以用于调节 F127/GSNO 溶液的光化学 NO 输送。

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