RESUMEN
Tuning metal-support interaction has been considered as an effective approach to modulate the electronic structure and catalytic activity of supported metal catalysts. At the atomic level, the understanding of the structure-activity relationship still remains obscure in heterogeneous catalysis, such as the conversion of water (alkaline) or hydronium ions (acid) to hydrogen (hydrogen evolution reaction, HER). Here, we reveal that the fine control over the oxidation states of single-atom Pt catalysts through electronic metal-support interaction significantly modulates the catalytic activities in either acidic or alkaline HER. Combined with detailed spectroscopic and electrochemical characterizations, the structure-activity relationship is established by correlating the acidic/alkaline HER activity with the average oxidation state of single-atom Pt and the Pt-H/Pt-OH interaction. This study sheds light on the atomic-level mechanistic understanding of acidic and alkaline HER, and further provides guidelines for the rational design of high-performance single-atom catalysts.
RESUMEN
A method is described for the determination of ascorbic acid (AA) in complex biological fluids. It based on maganese(II)-doped zinc/germanium oxide nanoparticles (Mn@ZnGe NPs) with appealing time-resolved phosphorescence (TRP). TRP can provide a background-free reporter signal in analytical methods. The absorption of AA overlaps the excitation band of Mn@ZnGe NPs at 254 nm. This reduces the intensity of fluorescence via an inner filter effect (IFE) with increasing concentration of AA. Typical experimental conditions include an emission peak at 536 nm, a delay time of 50 µs and a counting time of 2 ms. This method can detect AA in a range of 5-500 µM with a 0.13 µM limit of detection. If AA is oxidized by the enzyme AA oxidase (AAOx), dehydroascorbic acid will be formed which doesn't absorb at 254 nm. Hence, the IFE cannot occur and fluorescence is not reduced. The strategy can be used to quantify AAOx in the activity range of 1-4 U·mL-1. By using a handheld UV lamp and a smart phone with a color-scanning feature, the feasibility for visual detection and real-time/onsite quantitative scanometric monitoring of AA and AAOx is demonstrated. Graphical abstract Schematic presentation of a fluorometric method for determination of ascorbic acid (AA) and ascorbic oxidase and a scanometric visual assay. It based on the use of maganese(II)-doped zinc/germanium oxide nanoparticles (Mn@ZnGe NPs) with appealing time-resolved phosphorescence (TRP) and the inner-filter effect (IFE) between AA and Mn@ZnGe NPs.
Asunto(s)
Ascorbato Oxidasa/análisis , Ácido Ascórbico/análisis , Colorantes Fluorescentes/química , Nanopartículas del Metal/química , Animales , Ácido Ascórbico/sangre , Ácido Ascórbico/orina , Pruebas de Enzimas/instrumentación , Pruebas de Enzimas/métodos , Germanio/química , Límite de Detección , Masculino , Manganeso/química , Ratas , Teléfono Inteligente , Espectrometría de Fluorescencia/instrumentación , Espectrometría de Fluorescencia/métodos , Zinc/químicaRESUMEN
Tb3+-doped carbon dots (Tb3+@CDs) were prepared in a facile hydrothermal method by using ammonium citrate as carbon source and Tb3+ as dopant. A 15-bp GT-rich single-strand DNA (ssDNA) was introduced to sensitize Tb3+ via the antenna effect for generating two fluorescence signals (CDs and Tb3+), forming a conjugate of Tb3+@CDs/ssDNA. The ratiometric fluorescence of Tb3+@CDs/ssDNA could be reversibly regulated by Ag+ and Cys, in which the fluorescence peak at 546â¯nm of Tb3+ could be switched to "On" or "Off" as the signal indicator while the fluorescence peak at 444â¯nm of CDs remained constant as the build-in reference. The proposed Ag+/Cys-mediated reversible fluorescence changes in Tb3+@CDs/ssDNA was also proven for the design of a self-calibrating ratiometric fluorescence logic system. By integrated with the specific reaction between H2O2 and Cys, Tb3+@CDs/ssDNA was applied for ratiometric fluorescence detection of H2O2. More importantly, the sensing strategy could be further successfully extended to the monitoring of H2O2-produced oxidase-related reactions, such as GOx-biocatalyzed oxidation of glucose (the limit of detection: 0.06⯵M) and was well applied in rat serum compared to commercial kits. This work unveiled a novel ratiometric fluorescent design, which is cost-effective, simple to prepare and easy-to-use without chemical modification or fluorescence labeling.
Asunto(s)
Técnicas Biosensibles/métodos , Carbono/química , ADN de Cadena Simple/química , Nanopartículas/química , Oxidorreductasas/metabolismo , Terbio/química , Animales , Secuencia de Bases , Biocatálisis , Glucemia/análisis , Calibración , Cisteína/química , Cistina/química , ADN de Cadena Simple/genética , Peróxido de Hidrógeno/química , Masculino , Modelos Moleculares , Conformación Molecular , RatasRESUMEN
A novel and facile ratiometric fluorescence method for evaluating Cu2+ has been developed based on coumarin-labeled single-stranded DNA (C-ssDNA) coupled with the Cu2+-induced oxidation of o-phenylenediamine (OPD). By combining the microdialysis technique, the ratiometric fluorescence method has also been successfully exploited to monitor the cerebral Cu2+ in the rat brain, promising new opportunities for studying the cerebral Cu2+-associated physiological and pathological events.