Tuning the Sign and Magnitude of Complexation-Induced pKa Shifts in Cucurbit[7]uril Host-Guest Complexes by Molecular Engineering

IF 2.3 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Israel Journal of Chemistry Pub Date : 2024-01-09 DOI:10.1002/ijch.202300143
Alberto Trevisan, Ana S. D. Ferreira, Philippe Marrec, A. Jorge Parola, Nuno Basílio
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Abstract

Cucurbiturils are popular macrocyclic receptors that bind complementary guest molecules with high affinity in aqueous environments. They are recognized for their ability to selectively bind positively charged guest molecules, including ionizable ammonium cations which frequently display much higher affinity than their neutral counterparts. This selectivity for the protonated species is translated into an increase in the basicity of encapsulated guests (i. e. into complexation-induced positive pKa shifts). However, despite being very rare, negative pKa shifts can be observed for specific guests. Following a previous work from our group reporting slightly negative pKa shifts for flavylium and chalcone dyes featuring N-diethylamino substituents (ΔpKa=− 0.2), herein we report a systematic study on the complexation of N-dialkylaminochalcones with CB7. The results show that the pKa shifts of these host-guest complexes can be rationally tuned by the nature of the N-dialkylamino groups and as well by target substitutions on the skeleton of the dye, allowing the design of a CB7 1 : 1 host-guest complex with a ΔpKa=− 0.6.

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通过分子工程学调整葫芦[7]脲主-客复合物中络合诱导的 pKa 变化的符号和幅度
葫芦素是一种常用的大环受体,能在水环境中以高亲和力结合互补客体分子。它们被公认为能够选择性地结合带正电荷的客体分子,包括可电离的铵阳离子,后者的亲和力通常远高于中性分子。这种对质子化物种的选择性转化为包裹客体碱性的增加(即络合引起的正 pKa 变化)。不过,尽管非常罕见,但也能观察到特定客体的负 pKa 变化。继我们研究小组之前的一项工作报告了具有 N-二乙基氨基取代基(ΔpKa=- 0.2)的黄酮和查尔酮染料的 pKa 值发生轻微负偏移之后,我们在此报告了一项关于 N-二烷基氨基查尔酮与 CB7 复配的系统研究。研究结果表明,可以通过 N-二烷基氨基基团的性质以及染料骨架上的目标取代来合理调整这些主-客复合物的 pKa 值,从而设计出 CB7 1 :1 的主-客复合物,其 ΔpKa=- 0.6。
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来源期刊
Israel Journal of Chemistry
Israel Journal of Chemistry 化学-化学综合
CiteScore
6.20
自引率
0.00%
发文量
62
审稿时长
6-12 weeks
期刊介绍: The fledgling State of Israel began to publish its scientific activity in 1951 under the general heading of Bulletin of the Research Council of Israel, which quickly split into sections to accommodate various fields in the growing academic community. In 1963, the Bulletin ceased publication and independent journals were born, with Section A becoming the new Israel Journal of Chemistry. The Israel Journal of Chemistry is the official journal of the Israel Chemical Society. Effective from Volume 50 (2010) it is published by Wiley-VCH. The Israel Journal of Chemistry is an international and peer-reviewed publication forum for Special Issues on timely research topics in all fields of chemistry: from biochemistry through organic and inorganic chemistry to polymer, physical and theoretical chemistry, including all interdisciplinary topics. Each topical issue is edited by one or several Guest Editors and primarily contains invited Review articles. Communications and Full Papers may be published occasionally, if they fit with the quality standards of the journal. The publication language is English and the journal is published twelve times a year.
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Cover Picture: (Isr. J. Chem. 8-9/2024) Special Issue on RNA-Based Catalysts that Revolutionized the Discovery of Bioactive Peptides Hexagonal and Trigonal Quasiperiodic Tilings Breaking the Degeneracy of Sense Codons – How Far Can We Go? Cover Picture: (Isr. J. Chem. 6-7/2024)
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