Enhancement of photoinduced reactive oxygen species generation in open-cage fullerenes†

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Cristina Castanyer, Çetin Çelik, Albert Artigas, Anna Roglans, Anna Pla-Quintana, Anton J. Stasyuk, Yoko Yamakoshi and Miquel Solà
{"title":"Enhancement of photoinduced reactive oxygen species generation in open-cage fullerenes†","authors":"Cristina Castanyer, Çetin Çelik, Albert Artigas, Anna Roglans, Anna Pla-Quintana, Anton J. Stasyuk, Yoko Yamakoshi and Miquel Solà","doi":"10.1039/D4SC05428H","DOIUrl":null,"url":null,"abstract":"<p >Photodynamic therapy is an important tool in modern medicine due to its effectiveness, safety, and the ability to provide targeted treatment for a range of diseases. Photodynamic therapy utilizes photosensitizers to generate reactive oxygen species (ROS). Fullerenes can be used as photosensitizers to produce ROS in high quantum yields. Open-cage fullerenes are a subclass of fullerenes characterized by a partially open structure, with one or more openings or apertures. The promising electrochemical properties of open-cage fullerenes motivated us to investigate their use for DNA-cleavage and ROS generation under visible light irradiation through type I electron transfer and type II energy transfer reactions. Our results show that open-cage C<small><sub>60</sub></small> fullerenes are more efficient for photoinduced cleavage of DNA and ROS generation <em>via</em> both the type I electron transfer and type II energy transfer pathways than pristine C<small><sub>60</sub></small> or a C<small><sub>60</sub></small> pyrrolidine derivative without open-cage. The greater efficiency of ROS generation by open-cage C<small><sub>60</sub></small> fullerene in type I and type II reactions can be attributed to the increased rate of the initial intersystem crossing process, resulting from larger total reorganization energies, as indicated by computationally calculated relative rates using the Marcus equation, and the lower reduction potential of the open-cage derivative <strong>3</strong>, as determined by CV, which facilitates a more efficient generation of the corresponding radical anion (C<small><sub>60</sub></small>˙<small><sup>−</sup></small>).</p>","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" 6","pages":" 2673-2681"},"PeriodicalIF":7.6000,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/sc/d4sc05428h?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/sc/d4sc05428h","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

Abstract

Photodynamic therapy is an important tool in modern medicine due to its effectiveness, safety, and the ability to provide targeted treatment for a range of diseases. Photodynamic therapy utilizes photosensitizers to generate reactive oxygen species (ROS). Fullerenes can be used as photosensitizers to produce ROS in high quantum yields. Open-cage fullerenes are a subclass of fullerenes characterized by a partially open structure, with one or more openings or apertures. The promising electrochemical properties of open-cage fullerenes motivated us to investigate their use for DNA-cleavage and ROS generation under visible light irradiation through type I electron transfer and type II energy transfer reactions. Our results show that open-cage C60 fullerenes are more efficient for photoinduced cleavage of DNA and ROS generation via both the type I electron transfer and type II energy transfer pathways than pristine C60 or a C60 pyrrolidine derivative without open-cage. The greater efficiency of ROS generation by open-cage C60 fullerene in type I and type II reactions can be attributed to the increased rate of the initial intersystem crossing process, resulting from larger total reorganization energies, as indicated by computationally calculated relative rates using the Marcus equation, and the lower reduction potential of the open-cage derivative 3, as determined by CV, which facilitates a more efficient generation of the corresponding radical anion (C60˙).

Abstract Image

开放式笼型富勒烯光诱导活性氧生成的增强
光动力疗法因其有效性、安全性和为一系列疾病提供靶向治疗的能力而成为现代医学的重要工具。光动力疗法利用光敏剂产生活性氧(ROS)。富勒烯可以作为光敏剂以高量子产率产生活性氧。开笼型富勒烯是富勒烯的一个亚类,其特征是部分开放的结构,具有一个或多个开口或孔径。由于开笼富勒烯具有良好的电化学性能,我们研究了其在可见光照射下通过I型电子转移和II型能量转移反应进行dna切割和ROS生成的应用。我们的研究结果表明,通过I型电子转移和II型能量转移途径,开笼C60富勒烯比原始C60或没有开笼的C60吡咯烷衍生物更有效地光诱导DNA切割和ROS生成。在I型和II型反应中,开笼C60富勒烯生成ROS的效率更高,可归因于初始系统间交叉(ISC)过程的速率增加,这是由Marcus方程计算出的相对速率所导致的,总重组能更大,而开笼衍生物3的还原电位更低,由CV确定,这有利于更有效地生成相应的自由基阴离子(C60•-)。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
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