An ultrafast investigation is carried out on synthetic eumelanin suspended either in water or in DMSO-methanol. Upon photoexcitation by visible femtosecond pulses, the transient absorption (TA) dynamics of the suspensions are probed in a broad visible spectral range, showing clear nonlinearities. The latter arise from pump-probe interactions that induce the inverse Raman scattering (IRS) effect. We show how eumelanin TA dynamics are modified in proximity of the solvent Stokes and anti-Stokes scattering peaks, demonstrating that IRS affects the sign of TA but not the relaxation times. We compare the results obtained in both suspensions, unveiling the role of the surrounding environment. Eventually, the intrinsic response of synthetic eumelanin to ultrafast photoexcitation is evaluated.
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http://dx.doi.org/10.1364/BOE.6.004000 | DOI Listing |
Nanoscale
January 2025
Key Laboratory of 3D Micro/Nano Fabrication and Characterization of Zhejiang Province, School of Engineering, Westlake University, 18 Shilongshan Road, Hangzhou 310024, Zhejiang Province, China.
Lowering the population inversion threshold is key to leveraging quantum dots (QDs) for nanoscale lasing and laser miniaturization. However, optical realization of population inversion in QDs has an inherent limitation: the number of excited electrons per QD is bound by the absorbed photons. Here we show that one can break this population limit and realize near-zero threshold inversion plasmonic doping.
View Article and Find Full Text PDFChemSusChem
January 2025
Universita degli Studi di Ferrara, Dipartimento di Scienze Chimiche e Farmaceutiche, Via Borsari 46, 44121, Ferrara, ITALY.
Direct photochemical conversion of CO2 into a single carbon-based product currently represents one of the major issues in the catalysis of the CO2 reduction reaction (CO2RR). In this work, we demonstrate that the combination of an organic photosensitizer with a heptacoordinated iron(II) complex allows to attain a noble-metal-free photochemical system capable of efficient and selective conversion of CO2 into CO upon light irradiation in the presence of N,N-diisopropylethylamine (DIPEA) and 2,2,2-trifluoroethanol (TFE) as the electron and proton donor, respectively, with unprecedented performances (ΦCO up to 36%, TONCO > 1000, selectivity > 99%). As shown by transient absorption spectroscopy studies, this can be achieved thanks to the fast rates associated with the electron transfer from the photogenerated reduced dye to the catalyst, which protect the dye from parallel degradation pathways ensuring its stability along the photochemical reaction.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
East China Normal University, Department of Chemistry, 3663 N. Zhongshan Road, 200062, Shanghai, CHINA.
Aiming at the construction of novel platforms with excellent performances in both circularly polarized photoluminescence (CP-PL) and electrochemiluminescence (CP-ECL), a new family of pyrenophanes with rigidly locked pyrene dimers and varied bridges has been designed and synthesized. Attributed to densely packed pyrene excimers, the resultant pyrenophanes revealed tunable bridge-dependent emission behaviors, as investigated by femtosecond time-resolved transient absorption spectroscopy. More importantly, all these planar chiral pyrenophanes display strong CP-PL with large dissymmetry factor (gPL) values up to 0.
View Article and Find Full Text PDFSmall
January 2025
Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, 68 Jincheng Street, Wuhan, Hubei, 430078, P. R. China.
Hydrogen peroxide (HO) production through photocatalytic O reduction reaction (ORR) is a mild and cost-efficient alternative to the anthraquinone oxidation strategy. Of note, singlet state oxygen (O) plays a crucial role in ORR. Herein, a hollow TiO@TpPa (TOTP) S-scheme heterojunction by the Schiff base reactions involving 1,3,5-triformylphloroglucinol (Tp) and paraphenylenediamine (Pa) for efficient photocatalytic HO production in deionized water has been developed.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States.
Given their molecular properties and electronic structure, graphyne and graphdiyne are promising materials with numerous applications in different fields of material science. Dehydrobenzoannules (DBAs) are candidates that can serve as building blocks for synthesizing and designing new 2D carbon allotropes; however, only a few graphynes have been produced on a practical scale. Herein, we present our investigation of three DBAs, which serve as a model to understand the relationship between the structure and property, contributing to 2D carbon allotropes' rational design and synthetic effort.
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