固态S-nitroso-N-乙烯基胺的光解分解的机械分析
Partha S Sheet1, Gergely Lautner1, Mark E Meyerhoff2
1Department of Pharmaceutical Sciences, University of Michigan, Ann Arbor, MI, 48109, USA.
Nitric oxide : biology and chemistry
|November 18, 2023
概括
固态S-Nitroso-N-乙烯烯胺 (SNAP) 的光解释放氧化 (NO) 用于吸入治疗. 光的强度会影响NO的释放,而波长会影响光在固体SNAP中的透深度.
科学领域:
- 摄影化学的使用.
- 材料科学 材料科学 材料科学
- 医学疗法 医学疗法
背景情况:
- S-Nitroso-N-acetylpenicillamine (SNAP) 是一种常见的氧化 (NO) 捐赠分子.
- 固态光分解SNAP显示了吸入氧化 (iNO) 治疗的希望.
研究的目的:
- 研究固态SNAP的光化学NO释放动力学和机制.
- 检查光解效率,分解产物和分解途径.
- 确定光解过程中形成的激素的命运.
主要方法:
- 暴露于固态SNAP的窄频LED光线,波长和强度各不相同.
- 利用电子自旋共振 (ESR),核磁共振 (NMR),红外 (IR) 光谱和超高性能液态染色学-质谱学 (UPLC-MS) 来分析分解产物和激素命运.
- 使用粉末X射线衍射 (PXRD) 和扫描电子显微镜 (SEM) 来研究形态变化.
主要成果:
- 光解证实了NO和稳定的基 (RS·) 基的产生.
- 基与自身反应形成二硫化物 (RSSR) 或与氧反应形成各种硫/硫过氧基.
- 随着光强度的增加,NO的释放量增加;光透深度 (100-200微米) 取决于波长,而不是强度. 在光解过程中,SNAP失去了结晶性.
结论:
- 固态SNAP光解有效地产生NO,反应途径受到氧气的影响.
- 了解这些光化学反应对于开发用于iNO治疗的便携式光诱导NO释放装置至关重要.
相关概念视频
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
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Nitrous acid is a relatively weak and unstable acid prepared in situ by the reaction of sodium nitrite and cold, dilute hydrochloric acid. In an acidic solution, the nitrous acid undergoes protonation when it loses water to form a nitrosonium ion—an electrophile. Nitrous acid reacts with primary amines to give diazonium salts. The reaction is called diazotization of primary amines.
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2° Amines to N-Nitrosamines: Reaction with NaNO2
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Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.
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Nitriles to Carboxylic Acids: Hydrolysis
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Nitriles undergo acid-catalyzed hydrolysis or base-catalyzed hydrolysis to form a carboxylic acid. These reactions proceed via an amide intermediate.
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Rate-Determining Steps
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Relating Reaction Mechanisms
In a multistep reaction mechanism, one of the elementary steps progresses significantly slower than the others. This slowest step is called the rate-limiting step (or rate-determining step). A reaction cannot proceed faster than its slowest step, and hence, the rate-determining step limits the overall reaction rate.
The concept of rate-determining step can be understood from the analogy of a 4-lane freeway with a short-stretch of traffic-bottleneck caused due to...
In a multistep reaction mechanism, one of the elementary steps progresses significantly slower than the others. This slowest step is called the rate-limiting step (or rate-determining step). A reaction cannot proceed faster than its slowest step, and hence, the rate-determining step limits the overall reaction rate.
The concept of rate-determining step can be understood from the analogy of a 4-lane freeway with a short-stretch of traffic-bottleneck caused due to...
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Diazonium Group Substitution: –OH and –H
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Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
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