银纳米簇二维组装体合成、发光与抑菌性能

doi:10.3969/j.issn.2097-2806.2025.10.002

摘要/Abstract

摘要：

二维片状结构的银纳米簇配合物组装体在发光、催化以及抑菌等方面具有很好的应用前景。在室温下利用D-青霉胺作为稳定剂采用“一锅法”制备了银纳米簇配合物组装体，并利用红外光谱、X-射线光电子能谱、核磁波谱、元素分析、高分辨质谱以及热重分析对其进行了详细表征。透射电镜、冷冻选区电子衍射、原子力显微镜以及粉末X-射线衍射分析表明银纳米簇组装体是由银纳米簇组装形成的六方片状结构，单片厚度约8.3 nm。这种超薄结构的银纳米簇组装体H[Ag₅（DPA） ₆]表现出很强的绿色发光，绝对发光量子产率高达10.6%，在540 nm的发光寿命约为14.5 µs，因此组装体的发光起源于三重态的配体到金属-金属的电荷转移跃迁（³LMMCT）。进一步研究发现，片状结构的银纳米簇组装体只有当D-青霉胺和硝酸银的摩尔比超过2时才会形成，说明在这种条件下形成的纳米簇H[Ag₅（DPA） ₆]可以在Ag（I） …Ag（I）相互作用和氢键作用下进行取向连接形成六方结构的组装体。此外，这种片状结构的银纳米簇组装体通过改变细菌细胞膜的通透性表现出很好的抑菌性能，在化妆品中具有很好的应用前景。本研究不仅为超薄二维组装体的构筑、发光和抑菌性能研究提供了一个很好的模型，还可为其它二维材料的设计和构筑提供有价值的参考。

关键词: 银纳米簇组装, 自组装, 超薄结构, 发光, 抑菌性能

Abstract:

Ag （I）-S complex assemblies of two-dimensional （2D） sheet structure have good application prospects in luminescence, catalysis, and bacteriostatic performance. D-penicillamine is used as a capping agent to prepare Ag （I） -S complex assembly by “one-pot” method at room temperature, which is in detail characterized by ATR-FTIR spectrum, X-ray photoelectron spectrum, NMR spectrum, elemental analysis, high-resolution mass spectrum, and thermogravimetric analysis. Transmission electron microscope, cryogenic-selected area electron diffraction, atomic force microscope, and powder X-ray diffraction analyses indicate that Ag （I） -S complex assembly is a type of novel sheet structure comprised of Ag nanoclusters, in which the single sheet merely possesses a thickness of around 8.3 nm. The 2D Ag （I） -S nanocluster assembly H [Ag₅（DPA） ₆] shows intense green emission, and its absolute luminescent quantum yield is found to be as high as 10.6%, the photoluminescent lifetime at 540 nm is around 14.5 µs, and thus the assembly luminescence is believed to arise from triplet ligand-to-metal-metal charge transfer transition （³LMMCT）. The Ag （I） nanocluster assembly of sheet structure can be formed only when the molar ratio of D-penicillamine and silver nitrate is larger than 2, which suggests that in this case Ag nanoclusters H [Ag₅（DPA） ₆] can undergo oriented attachment with each other into close-packed sheet supramolecular assembly through Ag （I） …Ag （I） interactions and inter-ligand hydrogen bonds. In addition, the Ag （I） -S assembly shows good bacteriostatic performance, which functions through the destroying of cellular membrane permeability, and has great application potentials in cosmetics area. Our work not only provides a good model for the construction of ultrathin 2D assembly and the investigation of luminescent and bacteriostatic behaviors but also offers significant guidance and reference for the design and construction of other 2D materials.

Key words: Ag （I） nanocluster assembly, self-assemble, ultrathin sheet structure, luminescence, bacteriostatic performance

中图分类号:

TQ658

孔令灿,韩毅. 银纳米簇二维组装体合成、发光与抑菌性能[J]. 日用化学工业（中英文）, 2025, 55(10): 1236-1244.

Lingcan Kong,Yi Han. Synthesis, luminescence, and bacteriostatic performance of Ag（I） nanocluster 2D assembly[J]. China Surfactant Detergent & Cosmetics, 2025, 55(10): 1236-1244.

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2θ/ （°）	d_obs/?	d_cal/?	（hkl）	error/%
7.03	12.56	12.60	（002）	0.32
9.73	9.08	9.09	（100）/（010）	0.11
11.85	7.46	7.38	（102）	-1.07
14.10	6.28	6.30	（004）	0.32
17.04	5.20	5.25	（110）	0.96
18.28	4.85	4.85	（111）	0.01
19.53	4.54	4.55	（200）	0.22
25.76	3.45	3.44	（210）	-0.29
29.30	3.04	3.03	（300）	-0.33
30.40	2.94	2.95	（302）	0.34
33.87	2.64	2.62	（220）	-0.76
35.60	2.52	2.52	（310）	0.01
42.97	2.10	2.09	（320）	-0.48

	MIC/ （μg/mL）	IC₅₀/ （μg/mL）	literature
GO-IONP-Ag	32	No data	[26]
Multiple Ag NPs	20~180	No data	[27]
DPA-ACA	10	2.5	This work