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基于聚(二乙基乙烯基膦酸酯)包覆金纳米粒子的热响应和光响应智能纳米材料

Thermo- and Photoresponsive Smart Nanomaterial Based on Poly(diethyl vinyl phosphonate)-Capped Gold Nanoparticles.

作者信息

Buonerba Antonio, Lapenta Rosita, Della Monica Francesco, Piacentini Roberto, Baldino Lucia, Scognamiglio Maria Rosa, Speranza Vito, Milione Stefano, Capacchione Carmine, Rieger Bernhard, Grassi Alfonso

机构信息

Department of Chemistry and Biology "Adolfo Zambelli", University of Salerno, via Giovanni Paolo II, 84084 Fisciano, Italy.

CIRCC-Consorzio Interuniversitario per le Reattività Chimiche e la Catalisi, Villa La Rocca, via Celso Ulpiani 27, 70126 Bari, Italy.

出版信息

Nanomaterials (Basel). 2024 Oct 1;14(19):1589. doi: 10.3390/nano14191589.

Abstract

A new nanodevice based on gold nanoparticles (AuNPs) capped with poly(diethylvinylphosphonate) (PDEVP) has been synthesized, showing interesting photophysical and thermoresponsive properties. The synthesis involves a properly designed Yttriocene catalyst coordinating the vinyl-lutidine (VL) initiator active in diethyl vinyl phosphonate polymerization. The unsaturated PDEVP chain ending was thioacetylated, deacetylated, and reacted with tetrachloroauric acid and sodium borohydride to form PDEVP-VL-capped AuNPs. The NMR, UV-Vis, and ESI-MS characterization of the metal nanoparticles confirmed the formation of the synthetic intermediates and the expected colloidal systems. AuNPs of subnanometric size were determined by WAXD and UV-Vis analysis. UV-Vis and fluorescence analysis confirmed the effective anchoring of the thiolated PDEVP to AuNPs. The formation of 50-200 nm globular structures was assessed by SEM and AFM microscopy in solid state and confirmed by DLS in aqueous dispersion. Hydrodynamic radius studies showed colloidal contraction with temperature, demonstrating thermoresponsive behavior. These properties suggest potential biomedical applications for the photoablation of malignant cells or controlled drug delivery induced by light or heat for the novel PDEVP-capped AuNP systems.

摘要

一种基于聚(二乙基乙烯基膦酸酯)(PDEVP)包覆的金纳米颗粒(AuNP)的新型纳米器件已被合成,展现出有趣的光物理和热响应特性。该合成过程涉及一种经过合理设计的钇茂催化剂,它能配位在二乙基乙烯基膦酸酯聚合反应中具有活性的乙烯基吡啶(VL)引发剂。不饱和的PDEVP链端经过硫代乙酰化、脱乙酰化处理,并与氯金酸和硼氢化钠反应,形成PDEVP-VL包覆的AuNP。金属纳米颗粒的核磁共振(NMR)、紫外可见光谱(UV-Vis)和电喷雾质谱(ESI-MS)表征证实了合成中间体和预期胶体体系的形成。通过广角X射线衍射(WAXD)和紫外可见光谱分析确定了亚纳米尺寸的AuNP。紫外可见光谱和荧光分析证实了硫醇化的PDEVP有效地锚定在AuNP上。通过扫描电子显微镜(SEM)和原子力显微镜(AFM)在固态下评估了50 - 200 nm球状结构的形成,并通过动态光散射(DLS)在水分散体中得到了证实。流体动力学半径研究表明胶体随温度收缩,证明了其热响应行为。这些特性表明新型PDEVP包覆的AuNP系统在恶性细胞光消融或光热诱导的可控药物递送方面具有潜在的生物医学应用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f58a/11478069/fa48a493faad/nanomaterials-14-01589-g001.jpg

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