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用于汞(2+)离子传感、细胞成像和抗菌应用的抗生素标记金纳米颗粒及蓝色发光金8量子簇的成核与生长研究。

Study of the nucleation and growth of antibiotic labeled Au NPs and blue luminescent Au8 quantum clusters for Hg(2+) ion sensing, cellular imaging and antibacterial applications.

作者信息

Khandelwal Puneet, Singh Dheeraj K, Sadhu Subha, Poddar Pankaj

机构信息

Physical & Material Chemistry Division, CSIR-National Chemical Laboratory, Pune-411008, India.

出版信息

Nanoscale. 2015 Dec 21;7(47):19985-20002. doi: 10.1039/c5nr05619e. Epub 2015 Nov 13.

Abstract

Herein, we report a detailed experimental study supported by DFT calculations to understand the mechanism behind the synthesis of cefradine (CFD--an antibiotic) labeled gold nanoparticles (Au NPs) by employing CFD as both a mild reducing and capping agent. The analysis of the effect of growth conditions reveals that a higher concentration of HAuCl4 results in the formation of an increasing fraction of anisotropic structures, higher temperature leads to the formation of quasi-spherical particles instead of anisotropic ones, and larger pH leads to the formation of much smaller particles. The cyclic voltammetry (CV) results show that when the pH of the reaction medium increases from 4 to 6, the reduction potential of CFD increases which leads to the synthesis of nanoparticles (in a pH 4 reaction) to quantum clusters (in a pH 6 reaction). The MALDI-TOF mass spectrometry results of supernatant of the pH 6 reaction indicate the formation of [Au8(CFD)2S6] QCs which show fluorescence at ca. 432 nm with a Stokes shift of ca. 95 nm. The blue luminescence from Au8 QCs was applied for sensing of Hg(2+) ions on the basis of an aggregation-induced fluorescence quenching mechanism and offers good selectivity and a high sensitivity with a limit of detection ca. 2 nM which is lower than the detection requirement of 10 nM by the U.S. EPA and 30 nM by WHO for drinking water. We have also applied the sensing probe to detect Hg(2+) ions in bacterial samples. Further, we have investigated the antibacterial property of as-synthesized Au NPs using MIC, growth curve and cell survival assay. The results show that Au NPs could reduce the cell survival very efficiently rather than the cell growth in comparison to the antibiotic itself. The scanning electron microscopy study shows the degradation and blebbing of the bacterial cell wall upon exposure with Au NPs which was further supported by fluorescence microscopy results. These Au NPs did not show reactive oxygen species generation. We believe that the bacterial cytotoxicity is due to the direct contact of the Au NPs with bacterial cells.

摘要

在此,我们报告一项由密度泛函理论(DFT)计算支持的详细实验研究,以了解通过使用头孢拉定(CFD,一种抗生素)作为温和还原剂和封端剂来合成头孢拉定标记的金纳米颗粒(Au NPs)背后的机制。对生长条件影响的分析表明,较高浓度的四氯合金酸(HAuCl4)会导致各向异性结构的比例增加,较高温度会导致形成准球形颗粒而非各向异性颗粒,而较大的pH值会导致形成小得多的颗粒。循环伏安法(CV)结果表明,当反应介质的pH值从4增加到6时,CFD的还原电位增加,这导致纳米颗粒(在pH值为4的反应中)合成转变为量子簇(在pH值为6的反应中)。pH值为6的反应上清液的基质辅助激光解吸电离飞行时间质谱(MALDI - TOF)结果表明形成了[Au8(CFD)2S6]量子簇,其在约432 nm处显示荧光,斯托克斯位移约为95 nm。基于聚集诱导荧光猝灭机制,Au8量子簇的蓝色发光被用于检测Hg(2+)离子,具有良好的选择性和高灵敏度,检测限约为2 nM,低于美国环境保护局(EPA)对饮用水10 nM的检测要求以及世界卫生组织(WHO)30 nM的检测要求。我们还将该传感探针应用于检测细菌样品中的Hg(2+)离子。此外,我们使用最低抑菌浓度(MIC)、生长曲线和细胞存活试验研究了合成的Au NPs的抗菌性能。结果表明,与抗生素本身相比,Au NPs能非常有效地降低细胞存活率而非细胞生长。扫描电子显微镜研究显示,与Au NPs接触后细菌细胞壁会降解和起泡,荧光显微镜结果进一步证实了这一点。这些Au NPs未显示产生活性氧。我们认为细菌的细胞毒性是由于Au NPs与细菌细胞的直接接触。

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