Spectral studies of protonated and anionic forms of porphyrins with an asymmetric substitution system

IF 2.3 4区 化学 Q2 Agricultural and Biological Sciences Journal of Inclusion Phenomena and Macrocyclic Chemistry Pub Date : 2022-01-21 DOI:10.1007/s10847-022-01131-8
Yulia B. Ivanova, Svetlana G. Pukhovskaya, Alexey V. Lyubimtsev, Anna O. Plotnikova, Sergei A. Syrbu
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引用次数: 2

Abstract

The directed synthesis of asymmetrically substituted porphyrins—tetraphenylporphyrine derivatives containing amino acid residues as a functional group, which can be used as “anchor” groups, for incorporation into the structure of a protein molecule, was carried out. The obtained compounds were characterized by a number of spectral methods confirming their structure and purity. Their base and acid ionization constants in the AN–HClO4 and DMSO–potassium cryptate (KOH[222])—systems were measured by spectrophotometric titration. It was found that the asymmetric substitution architecture contributed to the stabilization of the protonated forms of porphyrins. This allowed, for the first time, to extract and spectrally characterize the mono- and doubly-protonated forms (H3P+ and H4P2+) of each ligands in the AN–HClO4 system. The analysis of the spectral changes of the monoamino derivative led to identify three stages of the protonation, which first involves the nitrogen atom of the periphery substituent (pKb = 13.26) and then the central nitrogen atoms of the macrocycle (pKb1 = 11.50; pKb2 = 9.65; pKb1,2 = 21.15). The relative stability of the first intermediate is assumed to be caused by charge delocalization. The electron-donor nature of the solvent in the DMSO–KOH [222] system led to the leveling of the ionization constants for the first and second stages, which allowed us to determine only the total values for the porphyrins studied. The successive stages of acid–base interactions were analyzed in the article.

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不对称取代系统中质子化和阴离子形式卟啉的光谱研究
定向合成了以氨基酸残基为官能团的不对称取代卟啉-四苯基卟啉衍生物,该衍生物可以作为“锚”基团,结合到蛋白质分子结构中。用多种光谱方法对所得化合物进行了表征,证实了它们的结构和纯度。用分光光度滴定法测定了它们在AN-HClO4和dmso -隐酸钾(KOH[222])体系中的碱和酸电离常数。发现不对称取代结构有助于卟啉质子化形式的稳定。这使得首次提取和光谱表征了AN-HClO4体系中每个配体的单质子形式和双质子形式(H3P+和H4P2+)。通过对单氨基衍生物的光谱变化分析,确定了质子化的三个阶段,首先是外围取代基的氮原子(pKb = 13.26),然后是大环的中心氮原子(pKb1 = 11.50;pKb2 = 9.65;pKb1,2 = 21.15)。假设第一中间体的相对稳定性是由电荷离域引起的。DMSO-KOH[222]体系中溶剂的电子给体性质导致第一和第二阶段的电离常数趋于平衡,这使我们能够仅确定所研究的卟啉的总价值。本文分析了酸碱相互作用的各个阶段。图形抽象
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来源期刊
CiteScore
3.30
自引率
8.70%
发文量
0
审稿时长
3-8 weeks
期刊介绍: The Journal of Inclusion Phenomena and Macrocyclic Chemistry is the premier interdisciplinary publication reporting on original research into all aspects of host-guest systems. Examples of specific areas of interest are: the preparation and characterization of new hosts and new host-guest systems, especially those involving macrocyclic ligands; crystallographic, spectroscopic, thermodynamic and theoretical studies; applications in chromatography and inclusion polymerization; enzyme modelling; molecular recognition and catalysis by inclusion compounds; intercalates in biological and non-biological systems, cyclodextrin complexes and their applications in the agriculture, flavoring, food and pharmaceutical industries; synthesis, characterization and applications of zeolites. The journal publishes primarily reports of original research and preliminary communications, provided the latter represent a significant advance in the understanding of inclusion science. Critical reviews dealing with recent advances in the field are a periodic feature of the journal.
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