S-nitrosothiol-terminated Pluronic F127: Influence of microstructure on nitric oxide release
S-nitrosothiol-terminated Pluronic F127: Influence of microstructure on nitric oxide release
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DOI：
10.1016/j.jcis.2020.05.049
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发表时间：
2020-09-15
影响因子：
9.9
通讯作者：
de Oliveira, Marcelo G.
中科院分区：
文献类型：
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作者：
Picheth, Guilherme F.;da Silva, Laura C. E.;de Oliveira, Marcelo G.
假设：已描述了含有溶解的 S-亚硝基硫醇或 N-二醇二氮烯鎓 (NONOate) 基团的释放一氧化氮 (NO) 的 Pluronic F127 水凝胶 (F127)。这些水凝胶的 NO 充电通常受到其稳定性低或胶束堆积破坏的限制。 S-亚硝基硫醇封端的 F127 可能会成为生物医学应用中允许以不同速率传递 NO 的新策略。 实验：F127 的末端羟基被酯化并还原生成 F127-巯基丙酸酯 (HS-F127-SH)，随后进行 S-亚硝化生成 S-亚硝基硫醇封端的 F127 (ONS-F127-SNO)。使用微差扫描量热法、H-1核磁共振自旋-自旋弛豫(T-2)、温度依赖性小角X射线散射和低温透射电子显微镜来确定胶束堆积结构，同时使用实时化学发光NO检测和紫外-可见分光光度法来评估NO释放动力学。结果：HS-F127-SH胶束化和凝胶化过程与天然F127类似，然而，胶束的短程有序性降低。 ONS-F127-SNO 水凝胶通过优先胶束内 SNO 二聚反应释放 NO。增加 ONS-F127-SNO 浓度可降低 SNO 二聚速率，并提高 NO 释放到气相的总体速率，为定制 F127 水凝胶 NO 输送开辟了新的可能性。 (C) 2020 Elsevier Inc. 保留所有权利。
Hypothesis: Nitric oxide (NO)-releasing Pluronic F127 hydrogels (F127) containing dissolved S-nitrosothiols or pendant N-diazeniumdiolate (NONOate) groups have been described. The NO charging of these hydrogels is usually limited by their low stability or disruption of the micellar packing. S-nitrosothiol-terminated F127 may emerge as a new strategy for allowing NO delivery at different rates in biomedical applications.Experiments: Terminal hydroxyl groups of F127 were esterified and reduced to produce F127-mercaptopropionate (HS-F127-SH), which was subsequently S-nitrosated to generate S-nitrosothiolterminated F127 (ONS-F127-SNO). Micro-differential scanning calorimetry, H-1 NMR spin-spin relaxation (T-2), temperature-dependent small-angle X-ray scattering, and cryo-transmission electron microscopy, were used to determine the micellar packing structure, while real-time chemiluminescence NO detection and UV-Vis spectrophotometry were used to evaluate the kinetics of NO release.Findings: HS-F127-SH micellization and gelation processes were analogous to native F127, however, with a decreased short-range ordering of the micelles. ONS-F127-SNO hydrogels released NO thorough a preferentially intramicellar SNO dimerization reaction. Increasing ONS-F127-SNO concentration reduces the rate of SNO dimerization and increases the overall rate of NO release to the gas phase, opening up new possibilities for tailoring NO delivery from F127-based hydrogels. (C) 2020 Elsevier Inc. All rights reserved.