The inorganic platinum complexes currently in clinical use for cancer treatment have severe side effects, and complexes with fewer side effects are required. One option is to use complexes that are inactive until they are light-activated. Theoretical chemistry can contribute to the design of these complexes, but most current theoretical methods lack explicit treatment of relativistic effects (since the target complexes often contain heavy elements). In particular, spin-orbit coupling is required for accurate predictions of the complexes' photo-physical properties. In this perspective, we summarize relativistic methods developed in recent years that can contribute to our understanding of light-induced reactivity and thereby help predict new, suitable complexes.
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http://dx.doi.org/10.1039/d2dt02233h | DOI Listing |
Chemistry
January 2025
Umeå Universitet: Umea Universitet, Department of Chemistry, Department of Chemistry, 90187, Umeå, SWEDEN.
Chemically induced dimerization/proximity (CID/CIP) systems controlled by chemical dimerizers (also known as molecular glues) provide valuable means for understanding and manipulating complex, dynamic biological systems. In this study, we present the development of versatile chemo-optogenetic systems utilizing azobenzene-based photoswitchable molecular glues (sMGs) for reversible protein dimerization controlled by visible light. These systems allow multiple cycles of light-induced dimerization, overcoming the limitations of irreversible photolysis in previous systems.
View Article and Find Full Text PDFChem Sci
December 2024
College of Materials Science and Engineering, Fuzhou University New Campus 350108 China
Atomically precise metal nanoclusters (NCs) have recently been recognized as an emerging sector of metal nanomaterials but suffer from light-induced poor stability, giving rise to the detrimental self-transformation into metal nanocrystals (NYs), losing the photosensitization effect and ultimately retarding their widespread applications in photoredox catalysis. Are metal NCs definitely superior to metal NYs in heterogeneous photocatalysis in terms of structural merits? To unlock this mystery, herein, we conceptually demonstrate how to rationally manipulate the instability of metal NCs to construct high-efficiency artificial photosystems and examine how the metal NYs self-transformed from metal NCs influence charge transfer in photoredox selective organic transformation. To our surprise, the results indicate that the Schottky-type electron-trapping ability of Au NYs surpasses the photosensitization effect of glutathione (GSH)-protected Au clusters [Au(GSH) NCs] in mediating charge separation and enhancing photoactivities towards selective photoreduction of aromatic nitro compounds to amino derivatives and photocatalytic oxidation of aromatic alcohols to aldehydes under visible light irradiation.
View Article and Find Full Text PDFNat Commun
January 2025
School of Physics and Technology, and Key Laboratory of Artificial Micro- and Nano-structures of Ministry of Education, Wuhan University, Wuhan, China.
Tin-lead perovskites provide an ideal bandgap for narrow-bandgap perovskites in all-perovskite tandem solar cells, fundamentally improving power conversion efficiency. However, light-induced degradation in ambient air is a major issue that can hinder the long-term operational stability of these devices. Understanding the specifics of what occurs during this pathway provides the direction for improving device stability.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
January 2025
Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305.
A central paradigm of nonequilibrium physics concerns the dynamics of heterogeneity and disorder, impacting processes ranging from the behavior of glasses to the emergent functionality of active matter. Understanding these complex mesoscopic systems requires probing the microscopic trajectories associated with irreversible processes, the role of fluctuations and entropy growth, and the timescales on which nonequilibrium responses are ultimately maintained. Approaches that illuminate these processes in model systems may enable a more general understanding of other heterogeneous nonequilibrium phenomena, and potentially define ultimate speed and energy cost limits for information processing technologies.
View Article and Find Full Text PDFNano Lett
January 2025
Institute for Experimental and Applied Physics, University of Regensburg, 93040 Regensburg, Germany.
Understanding and controlling the electronic properties of two-dimensional materials are crucial for their potential applications in nano- and optoelectronics. Monolayer transition metal dichalcogenides have garnered significant interest due to their strong light-matter interaction and extreme sensitivity of the band structure to the presence of photogenerated electron-hole pairs. In this study, we investigate the transient electronic structure of monolayer WS on a graphene substrate after resonant excitation of the A-exciton using time- and angle-resolved photoemission spectroscopy.
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