The assumption that all biological catalysts are either proteins or ribozymes leads to an outstanding enigma of biogenesis-how to determine the synthetic pathways to the monomers for the efficient formation of catalytic macromolecules in the absence of any such macromolecules. The last 60 years have witnessed chemists developing an understanding of organocatalysis and ligand field theory, both of which give demonstrable low-molecular-weight catalysts. We assume that transition-metal-ligand complexes are likely to have occurred in the deep ocean trenches by the combination of naturally occurring oceanic metals and ligands synthesized from the emergent CO(2), H(2), NH(3), H(2)S, and H(3)PO(4). We are now in a position to investigate experimentally the metal-ligand complexes, their catalytic function, and the reaction networks that could have played a role in the development of metabolism and life itself.
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http://dx.doi.org/10.1086/BBLv219n1p1 | DOI Listing |
J Chem Inf Model
January 2025
Schrödinger Incorporated, Cambridge, Massachusetts 02142, United States.
Biomed Rep
March 2025
Department of Rheumatology and Immunology, People's Hospital of Longhua, Shenzhen, Guangdong 518109, P.R. China.
Systemic lupus erythematosus (SLE) is a chronic autoimmune disease with a complex etiology primarily linked to abnormalities in B lymphocytes within the human body, resulting in the production of numerous pathogenic autoantibodies. Telitacicept is a relatively novel humanized, recombinant transmembrane activator, calcium modulator and cyclophilin ligand interactor fused with the Fc portion (TACI-Fc). It works by competitively inhibiting the TACI site, neutralizing the activity of B-cell lymphocyte stimulator and A proliferation-inducing ligand.
View Article and Find Full Text PDFCatal Sci Technol
January 2025
Department of Chemistry and Chemical Biology, Stevens Institute of Technology 1 Castle Point Terrace Hoboken NJ 07030 USA
Engineered heme proteins possess excellent biocatalytic carbene N-H insertion abilities for sustainable synthesis, and most of them have His as the Fe axial ligand. However, information on the basic reaction mechanisms is limited, and ground states of heme carbenes involved in the prior computational mechanistic studies are under debate. A comprehensive quantum chemical reaction pathway study was performed for the heme model with a His analogue as the axial ligand and carbene from the widely used precursor ethyl diazoacetate with aniline as the substrate.
View Article and Find Full Text PDFCommun Chem
January 2025
Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo, Hokkaido, 060-8628, Japan.
Photoinduced metal-to-ligand (or ligand-to-metal) charge-transfer (CT) states in metal complexes have been extensively studied toward the development of luminescent materials. However, previous studies have mainly focused on CT transitions between d- and π-orbitals. Herein, we report the demonstration of CT emission from 4f- to π-orbitals using a trivalent europium (Eu(III)) complex, supported by both experimental and theoretical analyses.
View Article and Find Full Text PDFBrain
January 2025
Athinoula A. Martinos Center for Biomedical Imaging, Department of Radiology, Massachusetts General Hospital, Harvard Medical School, Boston, MA 02129, USA.
Although the pathophysiology of migraine involves a complex ensemble of peripheral and central nervous system changes that remain incompletely understood, the activation and sensitization of the trigeminovascular system is believed to play a major role. However, non-invasive, in vivo neuroimaging studies investigating the underlying neural mechanisms of trigeminal system abnormalities in human migraine patients are limited. Here, we studied 60 patients with migraine (55 females, mean age ± SD: 36.
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