更多是不同的:渐进的β-thiolation诱导的氨酸聚合开关单片氧光敏化
Mengliang Zhu1,2, Hang Zhang1, Yuhang Yao1
1Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University Beijing 100871 P. R. China zhangjunlong@pku.edu.cn.
Chemical science
|August 12, 2024
概括
将硫添加到光敏感剂 (PSs) 中通常会增加单片氧 (O2) 生产. 然而,这项研究表明,纳米颗粒中的提化增加意外地在水性环境中禁用了O2生成.
科学领域:
- 摄影化学的使用.
- 材料科学 材料科学 材料科学
- 生物物理学的生物物理.
背景情况:
- 在光敏化剂 (PSs) 中的硫结合增强了三重状态的人口和单一氧 (O2) 生成.
- 氨酸结构的硫化是一种已知的调节光物理性质的策略.
研究的目的:
- 为了研究渐进型硫化对光物理性质和氨酸基PSs在不同环境中的产生的影响.
- 阐明在有机溶剂与水性介质中的光敏化1O2观察到的差异的潜在机制.
- 了解纳米颗粒中的分子包装如何影响激发状态动力学和能量消散途径.
主要方法:
- 研究了水中的二甲和PS纳米粒子中的兴奋状态动态.
- 在活细胞和多细胞球体,以及活体小鼠模型中进行了光细胞毒性研究.
- 采用分子动力学模拟和时间依赖密度函数理论 (TD-DFT) 计算.
主要成果:
- 在二甲中,渐进的硫化促进了系统间交叉 (ISC).
- 增加的硫替代使水性PS纳米颗粒中的光敏感性失活,这与预期相反.
- 在体内观察到光敏化,但不是在活细胞或球状体中.
- 化调节了纳米颗粒中的分子包装,降低了三重状态能量水平到1O2以下,并改变了能量消散.
结论:
- 在PS纳米颗粒中的硫化程度极大地影响了它们在水性介质中的聚合状态和兴奋状态动态.
- 分子包装和改变的能量消散途径,而不是仅仅是ISC,决定了基于纳米粒子的PSS中的O2生产.
- 这项工作为设计特定应用的可调节光物理性质的无金属PS提供了关键的见解,特别是在水环境中.
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