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
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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].

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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。
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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.
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