Complexes between 2,2′-azobis(2-methylpropionamidine) dihydrochloride (AAPH) and cucurbit[n]uril hosts modulate the yield and fate of photolytically-generated AAPH radicals†

IF 3.9 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY RSC Advances Pub Date : 2024-11-11 DOI:10.1039/D4RA07150F
Angie C. Forero-Girón, Mauricio Oyarzún, Kevin Droguett, Denis Fuentealba, Soledad Gutiérrez-Oliva, Barbara Herrera, Alejandro Toro-Labbé, Eduardo Fuentes-Lemus, Michael J. Davies, Camilo López-Alarcón and Margarita E. Aliaga
{"title":"Complexes between 2,2′-azobis(2-methylpropionamidine) dihydrochloride (AAPH) and cucurbit[n]uril hosts modulate the yield and fate of photolytically-generated AAPH radicals†","authors":"Angie C. Forero-Girón, Mauricio Oyarzún, Kevin Droguett, Denis Fuentealba, Soledad Gutiérrez-Oliva, Barbara Herrera, Alejandro Toro-Labbé, Eduardo Fuentes-Lemus, Michael J. Davies, Camilo López-Alarcón and Margarita E. Aliaga","doi":"10.1039/D4RA07150F","DOIUrl":null,"url":null,"abstract":"<p >Using theoretical and experimental tools we investigated the recognition of AAPH (2,2′-azobis(2-methylpropionamidine) dihydrochloride), a well-known water-soluble azo-compound employed as a source of peroxyl radicals, by cucurbit[6]uril (CB[6]), and cucurbit[8]uril (CB[8]). Density functional theory calculations and isothermal titration calorimetry experiments demonstrated that AAPH was not included in the cavity of CB[6], however, an exclusion complex was generated. Inclusion of AAPH in the CB[8] cavity was favored, forming stable inclusion complexes at 1 : 1 and 2 : 1 stoichiometries; AAPH@CB[8] and 2AAPH@CB[8], respectively. Radical formation upon photolytic cleavage of AAPH was examined theoretically, and by spin trapping with electron paramagnetic resonance. The radical yields detected with uncomplexed (free) AAPH and the AAPH-CB[6] (exclusion) complex were identical, whereas a marked decrease was shown for AAPH@CB[8]. Lower decreases were seen with a bimolecular (2 : 1) AAPH-CB[8] inclusion complex (2AAPH@CB[8]). This modulation was corroborated by the consumption of pyrogallol red (PGR), an oxidizable dye that does not associate with CB[6] or CB[8]. AAPH-CB[6] and 2AAPH@CB[8] did not significantly modify the initial consumption rate (Ri) of PGR, whereas AAPH@CB[8] decreased this. The oxidative consumption of free Trp, Gly–Trp and Trp–Gly by radicals derived from AAPH in the presence of CB[8] showed a dependence on the association of the targets with CB[8].</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 48","pages":" 35980-35991"},"PeriodicalIF":3.9000,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ra/d4ra07150f?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"RSC Advances","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/ra/d4ra07150f","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

Using theoretical and experimental tools we investigated the recognition of AAPH (2,2′-azobis(2-methylpropionamidine) dihydrochloride), a well-known water-soluble azo-compound employed as a source of peroxyl radicals, by cucurbit[6]uril (CB[6]), and cucurbit[8]uril (CB[8]). Density functional theory calculations and isothermal titration calorimetry experiments demonstrated that AAPH was not included in the cavity of CB[6], however, an exclusion complex was generated. Inclusion of AAPH in the CB[8] cavity was favored, forming stable inclusion complexes at 1 : 1 and 2 : 1 stoichiometries; AAPH@CB[8] and 2AAPH@CB[8], respectively. Radical formation upon photolytic cleavage of AAPH was examined theoretically, and by spin trapping with electron paramagnetic resonance. The radical yields detected with uncomplexed (free) AAPH and the AAPH-CB[6] (exclusion) complex were identical, whereas a marked decrease was shown for AAPH@CB[8]. Lower decreases were seen with a bimolecular (2 : 1) AAPH-CB[8] inclusion complex (2AAPH@CB[8]). This modulation was corroborated by the consumption of pyrogallol red (PGR), an oxidizable dye that does not associate with CB[6] or CB[8]. AAPH-CB[6] and 2AAPH@CB[8] did not significantly modify the initial consumption rate (Ri) of PGR, whereas AAPH@CB[8] decreased this. The oxidative consumption of free Trp, Gly–Trp and Trp–Gly by radicals derived from AAPH in the presence of CB[8] showed a dependence on the association of the targets with CB[8].

Abstract Image

查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
2,2′-azobis(2-methylpropionamidine) dihydrochloride (AAPH) 与葫芦[n]脲宿主之间的复合物可调节光解产生的 AAPH 自由基的产量和归宿†。
我们利用理论和实验工具研究了葫芦[6]脲(CB[6])和葫芦[8]脲(CB[8])对 AAPH(2,2′-偶氮双(2-甲基丙脒)二盐酸盐)的识别,AAPH 是一种著名的水溶性偶氮化合物,被用作过氧自由基的来源。密度泛函理论计算和等温滴定量热实验表明,CB[6]的空腔中不包含 AAPH,但会产生一种排阻复合物。在 CB[8] 的空腔中含有 AAPH 是有利的,在 1 :1 和 2 :1 的比例形成稳定的包合物;分别为 AAPH@CB[8] 和 2AAPH@CB[8]。理论上研究了 AAPH 光解裂解时形成的自由基,并利用电子顺磁共振进行了自旋捕获。未络合(游离)的 AAPH 和 AAPH-CB[6](排他性)络合物检测到的自由基产量相同,而 AAPH@CB[8] 则明显减少。双分子(2:1)AAPH-CB[8]包合物(2AAPH@CB[8])的下降幅度较小。消耗焦枯红(PGR)证实了这种调节作用,焦枯红是一种不与 CB[6] 或 CB[8] 结合的可氧化染料。AAPH-CB[6] 和 2AAPH@CB[8] 并未显著改变 PGR 的初始消耗率(Ri),而 AAPH@CB[8] 则降低了这一消耗率。在 CB[8] 存在的情况下,AAPH 产生的自由基对游离 Trp、Gly-Trp 和 Trp-Gly 的氧化消耗显示出目标与 CB[8] 的关联性。
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 去求助
来源期刊
RSC Advances
RSC Advances chemical sciences-
CiteScore
7.50
自引率
2.60%
发文量
3116
审稿时长
1.6 months
期刊介绍: An international, peer-reviewed journal covering all of the chemical sciences, including multidisciplinary and emerging areas. RSC Advances is a gold open access journal allowing researchers free access to research articles, and offering an affordable open access publishing option for authors around the world.
期刊最新文献
Combining de novo molecular design with semiempirical protein–ligand binding free energy calculation† Characterization and enhanced carbon dioxide sensing performance of spin-coated Na- and Li-doped and Co-doped cobalt oxide thin films† Regulation of oxidative stress enzymes in Candida auris by Dermaseptin: potential implications for antifungal drug discovery Design of an LiF-rich interface layer using high-concentration fluoroethylene carbonate and lithium bis(fluorosulfonyl)imide (LiFSI) to stabilize Li metal batteries A catalytic approach for the dehydrogenative upgradation of crude glycerol to lactate and hydrogen generation†
×
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
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 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 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1