越多越不同渐进式β-巯基诱导卟啉聚合切换单线态氧光敏作用

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Mengliang Zhu, Hang Zhang, Yuhang Yao, Mingpu Wen, Guangliu Ran, Yi Yu, Ruijing Zhang, Xing-Jie Liang, Jing Zhang, Wenkai Zhang and Jun-Long Zhang
{"title":"越多越不同渐进式β-巯基诱导卟啉聚合切换单线态氧光敏作用","authors":"Mengliang Zhu, Hang Zhang, Yuhang Yao, Mingpu Wen, Guangliu Ran, Yi Yu, Ruijing Zhang, Xing-Jie Liang, Jing Zhang, Wenkai Zhang and Jun-Long Zhang","doi":"10.1039/D4SC03642E","DOIUrl":null,"url":null,"abstract":"<p >Incorporating sulfur atoms into photosensitizers (PSs) has been well-established to populate triplet states and increase singlet oxygen (<small><sup>1</sup></small>O<small><sub>2</sub></small>) production when exposed to light. In this work, we found that progressive thiolation of porphyrin β-periphery does promote intersystem crossing (ISC) between triplets and singlets, as seen in the excited state dynamics in dichloromethane or PS nanoparticles in water. However, in the latter case, more sulfur substitution deactivates <small><sup>1</sup></small>O<small><sub>2</sub></small> photosensitization, in contrast to the expected trend observed in dichloromethane. This observation was further supported by photocytotoxicity studies, where <small><sup>1</sup></small>O<small><sub>2</sub></small> photosensitization was switched off in living cells and multicellular spheroids despite being switched on in <em>in vivo</em> mice models. To understand the inconsistency, we performed molecular dynamics simulation and time-dependent density functional theory calculations to investigate possible aggregation and related excited states. We found that the extent of thiolation could regulate molecular packing inside nanoparticles, which gradually lowers the energy levels of triplet states even lower than that of <small><sup>1</sup></small>O<small><sub>2</sub></small> and, in turn, alters their energy dissipation pathways. Therefore, this study provides new insights into the design of metal-free PSs and sheds light on the excited state dynamics in aqueous media beyond the molecular level.</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 34","pages":" 13841-13852"},"PeriodicalIF":7.6000,"publicationDate":"2024-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/sc/d4sc03642e?page=search","citationCount":"0","resultStr":"{\"title\":\"More is different: progressive β-thiolation induced-porphyrin aggregation switches singlet oxygen photosensitization†\",\"authors\":\"Mengliang Zhu, Hang Zhang, Yuhang Yao, Mingpu Wen, Guangliu Ran, Yi Yu, Ruijing Zhang, Xing-Jie Liang, Jing Zhang, Wenkai Zhang and Jun-Long Zhang\",\"doi\":\"10.1039/D4SC03642E\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Incorporating sulfur atoms into photosensitizers (PSs) has been well-established to populate triplet states and increase singlet oxygen (<small><sup>1</sup></small>O<small><sub>2</sub></small>) production when exposed to light. In this work, we found that progressive thiolation of porphyrin β-periphery does promote intersystem crossing (ISC) between triplets and singlets, as seen in the excited state dynamics in dichloromethane or PS nanoparticles in water. However, in the latter case, more sulfur substitution deactivates <small><sup>1</sup></small>O<small><sub>2</sub></small> photosensitization, in contrast to the expected trend observed in dichloromethane. This observation was further supported by photocytotoxicity studies, where <small><sup>1</sup></small>O<small><sub>2</sub></small> photosensitization was switched off in living cells and multicellular spheroids despite being switched on in <em>in vivo</em> mice models. To understand the inconsistency, we performed molecular dynamics simulation and time-dependent density functional theory calculations to investigate possible aggregation and related excited states. We found that the extent of thiolation could regulate molecular packing inside nanoparticles, which gradually lowers the energy levels of triplet states even lower than that of <small><sup>1</sup></small>O<small><sub>2</sub></small> and, in turn, alters their energy dissipation pathways. Therefore, this study provides new insights into the design of metal-free PSs and sheds light on the excited state dynamics in aqueous media beyond the molecular level.</p>\",\"PeriodicalId\":9909,\"journal\":{\"name\":\"Chemical Science\",\"volume\":\" 34\",\"pages\":\" 13841-13852\"},\"PeriodicalIF\":7.6000,\"publicationDate\":\"2024-07-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2024/sc/d4sc03642e?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Science\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2024/sc/d4sc03642e\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/sc/d4sc03642e","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

摘要

在光敏剂(PSs)中加入硫原子可在光照下填充三重态并增加单线态氧(1O2)的产生,这一点已得到证实。在这项工作中,我们发现,从二氯甲烷或 PS 纳米粒子在水中的激发态动力学中可以看出,卟啉 β-外围的渐进硫醇化确实促进了三重态和单重态之间的系统间交叉(ISC)。然而,在后一种情况下,更多的硫取代会使 1O2 光敏失活,这与在二氯甲烷中观察到的预期趋势相反。光细胞毒性研究进一步证实了这一观察结果,在活细胞和多细胞球体内,1O2 的光敏作用被关闭,而在活体小鼠模型中,1O2 的光敏作用却被开启。为了理解这种不一致,我们进行了分子动力学模拟和随时间变化的密度泛函理论计算,以研究可能的聚集和相关激发态。我们发现硫醇化的程度可以调节纳米粒子内部的分子堆积,从而逐渐降低三重态的能级,甚至低于 1O2 的能级,进而改变其能量耗散途径。因此,这项研究为无金属 PS 的设计提供了新的见解,并从分子水平揭示了水介质中的激发态动力学。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

More is different: progressive β-thiolation induced-porphyrin aggregation switches singlet oxygen photosensitization†

More is different: progressive β-thiolation induced-porphyrin aggregation switches singlet oxygen photosensitization†

Incorporating sulfur atoms into photosensitizers (PSs) has been well-established to populate triplet states and increase singlet oxygen (1O2) production when exposed to light. In this work, we found that progressive thiolation of porphyrin β-periphery does promote intersystem crossing (ISC) between triplets and singlets, as seen in the excited state dynamics in dichloromethane or PS nanoparticles in water. However, in the latter case, more sulfur substitution deactivates 1O2 photosensitization, in contrast to the expected trend observed in dichloromethane. This observation was further supported by photocytotoxicity studies, where 1O2 photosensitization was switched off in living cells and multicellular spheroids despite being switched on in in vivo mice models. To understand the inconsistency, we performed molecular dynamics simulation and time-dependent density functional theory calculations to investigate possible aggregation and related excited states. We found that the extent of thiolation could regulate molecular packing inside nanoparticles, which gradually lowers the energy levels of triplet states even lower than that of 1O2 and, in turn, alters their energy dissipation pathways. Therefore, this study provides new insights into the design of metal-free PSs and sheds light on the excited state dynamics in aqueous media beyond the molecular level.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信