Excited-state mixed valence (ESMV) occurs in the 1,2-diphenyl-1,2-diisopropyl hydrazine radical cation, a molecule in which the ground state has a symmetrical charge distribution localized primarily on the hydrazine, but the phenyl to hydrazine charge-transfer excited state has two interchangeably equivalent phenyl groups that have different formal oxidation states. Electronic absorption and resonance Raman spectra are presented. The neighboring orbital model is employed to interpret the absorption spectrum and coupling. Resonance Raman spectroscopy is used to determine the excited-state distortions. The frequencies of the enhanced modes from the resonance Raman spectra are used together with the time-dependent theory of spectroscopy to fit the two observed absorption bands that have resolved vibronic structure. The origins of the vibronic structure and relationships with the neighboring orbital model are discussed.
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http://dx.doi.org/10.1021/ja0609093 | DOI Listing |
ACS Appl Mater Interfaces
January 2025
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China.
Alkaline phosphatase (ALP) is a biomarker for many diseases, and monitoring its activity level is important for disease diagnosis and treatment. In this study, we used the microdroplet technology combined with an laser-induced polymerization method to prepare the Ag nanoparticle (AgNP) doped hydrogel microbeads (HMBs) with adjustable pore sizes that allow small molecules to enter while blocking large molecules. The AgNPs embedded in the hydrogel microspheres can provide SERS activity, improving the SERS signal of small molecules that diffuse to the AgNPs.
View Article and Find Full Text PDFSmall
January 2025
Department of Clinical Laboratory, Sir Run Run Shaw Hospital, Zhejiang University School of Medicine, Hangzhou, 310016, China.
DNA methylation is an epigenetic mechanism that regulates gene expression and is implicated in diseases such as cancer and atherosclerosis. However, traditional clinical methods for detecting DNA methylation often lack sensitivity and specificity, making early diagnosis challenging. Nanomaterials offer a solution with their unique properties, enabling highly sensitive photochemical and electrochemical detection techniques.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry and Dodd Walls Centre, University of Otago, Dunedin 9016, New Zealand.
Three triphenylamine-Indane donor-acceptor dyes with different functional groups on the acceptor were studied to investigate how substitution would affect the optical properties. The dyes studied were IndCN, containing two malononitrile groups; InO, with two ketone groups; and InOCN, which features mixed functional groups. A combination of Raman spectroscopy, UV-vis absorption and emission spectroscopy, and density functional theory (DFT) calculations were employed for characterization.
View Article and Find Full Text PDFIn this study, we investigated in detail the regulation mechanism of electron transfer under laser-induced breakdown (LIB) on weak O-D stimulated Raman scattering (SRS) in DMSO-DO solutions. Significantly, the Raman activity of O-D vibrations was greatly enhanced by two orders of magnitude due to electron transfer in DMSO molecules. Density functional theory (DFT) calculations showed that the O-D Raman activity was significantly enhanced in the DMSO-DO dimer compared to the DO dimer.
View Article and Find Full Text PDFChem Sci
January 2025
Department of Chemistry, Rice University Houston Texas 77005 USA
We recently demonstrated molecular plasmons in cyanine dyes for the conversion of photon energy into mechanical energy through a whole-molecule coherent vibronic-driven-action. Here we present a model, a molecular plasmon analogue of molecular orbital theory and of plasmon hybridization in metal nanostructures. This model describes that molecular plasmons can be obtained from the combination or hybridization of elementary molecular fragments, resulting in molecules with hybridized plasmon resonances in the electromagnetic spectrum.
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