Investigation of azobenzene-functionalized (2-phenylpyridine)Pt(II) complexes as switchable luminescent probes for amyloid fibrils

IF 2.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Polyhedron Pub Date : 2025-03-01 Epub Date: 2025-01-08 DOI:10.1016/j.poly.2025.117394

Zhuoheng Li, F. Christopher Pigge

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Abstract

Two new cyclometalated platinum(II) acetylacetone (acac) complexes have been prepared and characterized. Each complex features a 2-phenylpyridine (ppy) cyclometalating ligand substituted with a peripheral photoswitchable azobenzene group. Azobenzene trans to cis photoisomerization and thermally-induced cis to trans back-isomerization were examined using UV–visible and ¹H NMR spectroscopy. Solutions of both complexes were found to be non-luminescent when irradiated at 410 nm in various solvents of differing polarity. A turn-on emission response was observed, however, when the complex possessing a ppy ligand functionalized with an azobenzene unit via an amide linkage was treated with amyloid fibrils prepared from denaturation of hen egg-white lysozyme (HEWL). The emission response is ascribed to steric inhibition of azobenzene photoisomerization upon interaction of the complex with hydrophobic surfaces of HEWL fibrils. X-ray crystal structures of four new Pt(II) complexes are reported as well.

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偶氮苯功能化（2-苯基吡啶）Pt（II）配合物作为淀粉样原纤维可切换发光探针的研究

制备了两种新的环金属化铂（II）乙酰丙酮（acac）配合物，并对其进行了表征。每个配合物的特征是一个2-苯基吡啶（ppy）环金属化配体被一个外围可光切换的偶氮苯基取代。利用紫外可见光谱和核磁共振氢谱研究了偶氮苯的反式到顺式光异构化和热诱导顺式到反式反异构化。在不同极性的溶剂中辐照410 nm时，两种配合物的溶液都不发光。然而，当通过酰胺链与偶氮苯单元功能化的具有ppy配体的复合物用由蛋清溶菌酶（HEWL）变性制备的淀粉样原纤维处理时，观察到开启发射响应。发射响应归因于偶氮苯与hhl原纤维疏水表面相互作用时的立体抑制。本文还报道了四种新型Pt（II）配合物的x射线晶体结构。

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.