Dimitriev Oleg, Slominskii Yuri, Giancaspro Mariangela, Rizzi Federica, Depalo Nicoletta, Fanizza Elisabetta, Yoshida Tsukasa
V. Lashkaryov Institute of Semiconductor Physics NAS of Ukraine, pr. Nauki 41, 03028 Kyiv, Ukraine.
Graduate School of Organic Materials Science, Yamagata University, Jonan 4-3-16, Yonezawa 992-8510, Japan.
Nanomaterials (Basel). 2023 Jan 27;13(3):510. doi: 10.3390/nano13030510.
Functionalization of colloidal nanoparticles with organic dyes, which absorb photons in complementary spectral ranges, brings a synergistic effect for harvesting additional light energy. Here, we show functionalization of near-infrared (NIR) plasmonic nanoparticles (NPs) of bare and amino-group functionalized mesoporous silica-coated copper sulphide (CuS@MSS and CuS@MSS-NH) with specific tricarbocyanine NIR dye possessing sulfonate end groups. The role of specific surface chemistry in dye assembling on the surface of NPs is demonstrated, depending on the organic polar liquids or water used as a dispersant solvent. It is shown that dye binding to the NP surfaces occurs with different efficiency, but mostly in the monomer form in polar organic solvents. Conversely, the aqueous medium leads to different scenarios according to the NP surface chemistry. Predominant formation of the disordered dye monomers occurs on the bare surface of mesoporous silica shell (MSS), whereas the amino-group functionalized MSS accepts dye predominantly in the form of dimers. It is found that the dye-NP interaction overcomes the dye-dye interaction, leading to disruption of dye J-aggregates in the presence of the NPs. The different organization of the dye molecules on the surface of silica-coated copper sulphide NPs provides tuning of their specific functional properties, such as hot-band absorption and photoluminescence.
用在互补光谱范围内吸收光子的有机染料对胶体纳米颗粒进行功能化，可为收集额外的光能带来协同效应。在此，我们展示了用具有磺酸酯端基的特定三碳菁近红外染料对裸露的和氨基功能化的介孔二氧化硅包覆硫化铜近红外（NIR）等离子体纳米颗粒（CuS@MSS和CuS@MSS-NH）进行功能化。根据用作分散溶剂的有机极性液体或水，证明了特定表面化学在染料在纳米颗粒表面组装中的作用。结果表明，染料与纳米颗粒表面的结合效率不同，但在极性有机溶剂中大多以单体形式存在。相反，水性介质根据纳米颗粒的表面化学导致不同的情况。无序染料单体主要在介孔二氧化硅壳（MSS）的裸露表面形成，而氨基功能化的MSS主要以二聚体形式接受染料。研究发现，染料与纳米颗粒的相互作用克服了染料与染料之间的相互作用，导致在纳米颗粒存在的情况下染料J-聚集体的破坏。二氧化硅包覆硫化铜纳米颗粒表面染料分子的不同组织方式可调节其特定功能特性，如热带吸收和光致发光。
