Graphene Oxide/Zinc Phthalocyanine Selective Singlet Oxygen Visible-Light Nanosensor for Raman-Inactive Compounds.

IF 10.7 2区 材料科学 Q1 CHEMISTRY, PHYSICAL
Alexandra I Zvyagina, Olga A Shiryaeva, Evgenia Yu Afonyushkina, Olesya O Kapitanova, Alexey A Averin, Ilya D Kormschikov, Alexander G Martynov, Yulia G Gorbunova, Irina A Veselova, Maria A Kalinina
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Abstract

A novel phthalocyanine-based hybrid nanofilm is for the first time successfully applied as an oxidative platform for surface enhanced Raman spectroscopy (SERS) sensing to fine-resolve Raman-inactive compounds. The hybrid is formed by self-assembly of zinc(II) 2,3,9,10,16,17,23,24-Octa[(3',5'-dicarboxy)-phenoxy]phthalocyaninate (ZnPc*) with the solid-supported monolayer of graphene oxide (GO) mediated by zinc acetate metal cluster. Atomic force microscopy, UV-vis and fluorescence spectroscopies confirm that this simple coordination motive in combination with molecular structure of ZnPc* prevents contact quenching of the light-excited triplet state through aromatic stacking with GO particles. Fluorescence probing with Sensor Green and terephthalic acid as specific indicators of active oxygen intermediates shows that the hybrid nanofilm initiates selective singlet oxygen generation under visible light. Direct one-electron oxidation of tetramethylbenzidine (TMB) (1.0×10-7 m) on the hybrid surface in the presence of 100 nm silver nanoparticles as plasmonic hot-spots under 450-640-nm light irradiation yields well-resolved resonance Raman spectrum of the oxidized form TMB+1. Using these hybrid nanofilms as visible light platforms for redox reaction of target analytes without additional oxidizing agents, the range of Raman-detectable compounds can be significantly expanded through a rapid ultrasensitive SERS screening of substances currently considered Raman-inactive.

用于拉曼非活性化合物的氧化石墨烯/酞菁锌选择性单线态氧可见光纳米传感器。
一种新型酞菁基杂化纳米膜首次成功地作为表面增强拉曼光谱(SERS)传感的氧化平台,用于精细分辨拉曼非活性化合物。该杂化物是由锌(II) 2,3,9,10,16,17,23,24-八[(3',5'-二羧基)-苯氧基]酞菁酸锌(ZnPc*)与醋酸锌金属团簇介导的氧化石墨烯(GO)固体支撑单层自组装而成的。原子力显微镜、紫外可见光谱和荧光光谱证实,这种简单的配位动机与ZnPc*的分子结构相结合,可以防止光激发三重态通过芳香层与氧化石墨烯颗粒的接触猝灭。以Sensor Green和对苯二甲酸作为活性氧中间体特异性指标的荧光探测表明,杂化纳米膜在可见光下选择性地产生单线态氧。在450-640 nm光照射下,在100 nm银纳米粒子作为等离子体热点存在下,四甲基联苯胺(1.0×10-7 m)在杂化表面上的直接单电子氧化得到了氧化态TMB+1的高分辨共振拉曼光谱。使用这些杂化纳米膜作为目标分析物氧化还原反应的可见光平台,无需额外的氧化剂,通过快速超灵敏的SERS筛选目前认为拉曼不活性的物质,可以显著扩大拉曼可检测化合物的范围。
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来源期刊
Small Methods
Small Methods Materials Science-General Materials Science
CiteScore
17.40
自引率
1.60%
发文量
347
期刊介绍: Small Methods is a multidisciplinary journal that publishes groundbreaking research on methods relevant to nano- and microscale research. It welcomes contributions from the fields of materials science, biomedical science, chemistry, and physics, showcasing the latest advancements in experimental techniques. With a notable 2022 Impact Factor of 12.4 (Journal Citation Reports, Clarivate Analytics, 2023), Small Methods is recognized for its significant impact on the scientific community. The online ISSN for Small Methods is 2366-9608.
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