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手性有机金属（2,2':6',2″-三联吡啶）甲基铂（II）配合物与聚（L-谷氨酸）超分子手性自组装过程的动力学研究。

A Kinetic Investigation of the Supramolecular Chiral Self-Assembling Process of Cationic Organometallic (2,2':6',2″-terpyridine)methylplatinum(II) Complexes with Poly(L-glutamic Acid).

机构信息

Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, University of Messina, V.le F. Stagno D'Alcontres, 31, 98166 Messina, Italy.

CNR-ISMN Istituto per lo Studio dei Materiali Nanostrutturati c/o Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, University of Messina, V.le F. Stagno D'Alcontres, 31, 98166 Messina, Italy.

出版信息

Int J Mol Sci. 2024 Jan 18;25(2):1176. doi: 10.3390/ijms25021176.

DOI:10.3390/ijms25021176
PMID:38256248
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10816852/
Abstract

The cationic platinum(II) organometallic complex [Pt(terpy)Me] (terpy = 2,2':6',2″-terpyridine) at mild acidic pH interacts with poly(L-glutamic acid) (L-PGA) in its α-helix conformation, affording chiral supramolecular adducts. Their kinetics of formation have been investigated in detail as a function of the concentrations of both reagents and changing pH, ionic strength, the length of the polymeric scaffold and temperature. After a very fast early stage, the kinetic traces have been analyzed as three consecutive steps, suggesting a mechanism based on the electrostatic fast formation of a not-organized aggregate that subsequently evolves through different rearrangements to form the eventual supramolecular adduct. A model for this species has been proposed based on (i) the attractive electrostatic interaction of the cationic platinum(II) complexes and the polyelectrolyte and (ii) the π-stacking interactions acting among the [Pt(terpy)Me] units.

摘要

在温和的酸性 pH 值下，带正电荷的铂 (II) 有机金属配合物 [Pt(terpy)Me]（terpy = 2,2':6',2″-三联吡啶）与聚 L-谷氨酸 (L-PGA) 在其 α-螺旋构象中相互作用，形成手性超分子加合物。作为对两种试剂浓度以及 pH 值、离子强度、聚合物支架长度和温度变化的函数，详细研究了它们的形成动力学。在非常快速的早期阶段之后，动力学轨迹被分析为三个连续的步骤，表明该机制基于带正电荷的铂 (II) 配合物与聚电解质之间的静电快速形成未组织的聚集体，随后通过不同的重排进一步演化形成最终的超分子加合物。基于以下两点提出了这种物质的模型：(i) 阳离子铂 (II) 配合物和聚电解质之间的吸引静电相互作用，以及 (ii) [Pt(terpy)Me] 单元之间的π-堆积相互作用。

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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/791f/10816852/975768405945/ijms-25-01176-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/791f/10816852/21d0e174eac3/ijms-25-01176-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/791f/10816852/742fb760589a/ijms-25-01176-g009.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/791f/10816852/7563473950d5/ijms-25-01176-sch002.jpg
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