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Gold nanoclusters with a wide range of fluorescence characteristics generated in situ in polymer thin films: potential gas sensing application†
Dalton Transactions ( IF 3.5 ) Pub Date : 2017-11-14 00:00:00 , DOI: 10.1039/c7dt02805a
U. Divya Madhuri 1, 2, 3, 4 , T. P. Radhakrishnan 1, 2, 3, 4
Affiliation  

Fabrication of gold nanoclusters (GNCs) with tunable fluorescence characteristics inside polymer thin films is attractive from the device application perspective. In this study, GNCs are generated in situ in poly(methyl methacrylate) films exploiting their weak reducing capability with no additional reducing agent, and by short and mild thermal annealing; the chemistry involved is probed through control experiments. The nanoclusters formed with ∼0.5 weight percent of gold are very stable and show appreciable fluorescence emission with a small Stokes shift (∼40 nm); interestingly, blending polystyrene enhances the fluorescence. The Au10 clusters formed in situ are characterized by using mass spectrometry, microscopy and computational modeling. Composite thin films fabricated with a gold content of ∼9 weight percent showed an unusually distinct absorption peak and enhanced fluorescence emission. Gradual coalescence of the nanoclusters in these films could be arrested by incorporating thiourea; the mechanistic aspects of the thiourea interaction are probed. The resulting films showed strong, stable and visible red emission, with very large Stokes shift (∼320 nm) and quantum yield (∼30%), attributable to ligand effects and nanocluster aggregation in the film. The study presents a novel and facile route to the in situ generation of GNCs in polymer thin films, exhibiting fluorescence emission with variable energy, intensity and Stokes shift. Preliminary experiments show that Au10 cluster embedded thin films can be used for the detection of POCl3, an important precursor for nerve agents.

中文翻译:

在聚合物薄膜中就地 产生的具有广泛荧光特性的金纳米团簇:潜在的气体传感应用

从设备应用的角度来看,在聚合物薄膜内部具有可调荧光特性的金纳米簇(GNC)的制造是有吸引力的。在这项研究中,GNC是在聚甲基丙烯酸甲酯薄膜中原位生成的利用了它们的弱还原能力,无需额外的还原剂,并且进行了短暂而温和的热退火;通过控制实验来探究所涉及的化学物质。由〜0.5重量%的金形成的纳米团簇非常稳定,并显示出可见的荧光发射,并具有小的斯托克斯位移(〜40 nm);有趣的是,共混聚苯乙烯可以增强荧光。原位形成的Au 10团簇通过质谱,显微镜和计算模型进行表征。金含量约为9%(重量)的复合薄膜显示出异常明显的吸收峰和增强的荧光发射。这些膜中纳米团簇的逐渐聚结可以通过掺入硫脲来阻止。硫脲相互作用的机制方面进行了探讨。所得的膜显示出强,稳定和可见的红色发射,具有很大的斯托克斯位移(〜320 nm)和量子产率(〜30%),这归因于膜中的配体效应和纳米团簇聚集。这项研究提出了一种新颖简便的路线到原位聚合物薄膜中生成的GNC,显示出具有可变能量,强度和斯托克斯位移的荧光发射。初步实验表明,Au 10团簇嵌入的薄膜可用于检测POCl 3,POCl 3是神经药的重要前体。
更新日期:2017-11-14
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