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DMF 保护的金纳米簇的稳定性:光化学、分散和热性质。

Stability of the DMF-protected Au nanoclusters: photochemical, dispersion, and thermal properties.

机构信息

Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering, Kansai University, 3-3-35 Yamate-cho, Suita-shi, Osaka 564-8680, Japan.

出版信息

Langmuir. 2010 Apr 20;26(8):5926-33. doi: 10.1021/la9038842.

Abstract

We have reported the synthesis of dimethylformamide (DMF)-protected gold nanoclusters using a surfactant-free DMF reduction method. DMF-protected gold nanoclusters (Au NCs) are obtained without the formation of gold nanoparticles and bulk metals as byproducts using a hot injection process for the homogeneous reduction. The as-prepared DMF-protected Au NCs were a mixture of various-sized Au NCs with a cluster number of less than 20 including at least Au(8) and Au(13). The photoluminescence emission from Au(8) and Au(13) was confirmed in the photoluminescence spectra. The Au NCs are stabilized with DMF molecules through the interaction of amide groups of DMF with Au NCs. DMF-protected Au NCs in solution were found to have high thermal stability, high dispersion stability in various solvents, and high photochemical stability. The DMF-protected Au NCs dispersed well for at least a month in various solvents such as water, acid (pH 2), alkali (pH 12) and 0.5 M NaCl aqueous solution, and methanol without further surface modification. The thermal stability of DMF-protected Au NCs was approximately 150 degrees C, which was comparable to that of thiolate-protected Au NCs. The photobleaching of Au NCs in water gradually occurred under UV light irradiation (356 nm, 1.3 mW/cm(2)) because of the photoinduced oxidation of Au NCs. After 8 h irradiation, the fluorescence intensity slowly decreased to approximately 50% of the maximum and to approximately 20% after 96 h under the present condition, compared to the photobleaching of CdSe semiconductor quantum dots. We also found that the fluorescence intensity remained to be about 30% of the maximum even in the presence of concentrated 30% H(2)O(2). These findings demonstrate that the photobleaching process under the UV irradiation is effectively suppressed for DMF-protected Au NCs.

摘要

我们已经报道了使用无表面活性剂的二甲基甲酰胺(DMF)还原法合成二甲基甲酰胺(DMF)保护的金纳米团簇。DMF 保护的金纳米团簇(Au NCs)是通过均相还原的热注射过程获得的,没有形成金纳米粒子和块状金属作为副产物。所制备的 DMF 保护的 Au NCs 是各种尺寸的 Au NCs 的混合物,其簇数小于 20,包括至少 Au(8)和 Au(13)。在荧光光谱中证实了 Au(8)和 Au(13)的荧光发射。Au NCs 通过 DMF 分子与 Au NCs 的酰胺基团的相互作用稳定在 DMF 分子中。在溶液中的 DMF 保护的 Au NCs 具有高的热稳定性、在各种溶剂中的高分散稳定性和高的光化学稳定性。DMF 保护的 Au NCs 在未经进一步表面修饰的情况下,在各种溶剂如水中、酸(pH 2)、碱(pH 12)和 0.5 M NaCl 水溶液以及甲醇中至少能稳定分散一个月。DMF 保护的 Au NCs 的热稳定性约为 150°C,与硫醇保护的 Au NCs 相当。由于 Au NCs 的光诱导氧化,在 UV 光(356nm,1.3mW/cm²)照射下,Au NCs 在水中的光漂白逐渐发生。在 8 小时照射后,荧光强度缓慢降低至最大的约 50%,在 96 小时后,在目前的条件下,降低至最大的约 20%,与 CdSe 半导体量子点的光漂白相比。我们还发现,即使在存在浓 30%H₂O₂的情况下,荧光强度仍保持在最大荧光强度的约 30%左右。这些发现表明,在 UV 照射下,DMF 保护的 Au NCs 的光漂白过程得到有效抑制。

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