The Biogeochemical Cycles of Elements and the Evolution of Life. Biogeochemistry of Dihydrogen. Dioxygen over Geological Time. The Nitrogen Cycle: Its Biology. The Biological Cycle of Sulfur. Biological Cycling of Phosphorus. Iron, Phytoplankton Growth, and the Carbon Cycle, The Biogeochemistry and Fate of Mercury in the Environment. The Biogeochemistry of Cadmium. Biogeochemistry and Cycling of Lead
The acidity constants for (N3)H of the uridine-type ligands (U) 5-fluorouridine, 5-chloro-2′-deoxyuridine, uridine, and thymidine (2′-deoxy-5-methyluridine) and the stability constants of the M(U–H) + complexes for M 2+ = Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Cd 2+ , and Pb 2+ were measured (potentiometric pH titrations; aqueous solution; 25°C; I = 0.1 M, NaNO 3 ). Plots of \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \setlength{\oddsidemargin}{-69pt} \begin{document} \begin{equation*}{\mathrm{log}}K_{{\mathrm{M}}({\mathrm{U}}-{\mathrm{H}})}^{{\mathrm{M}}}\end{equation*}\end{document} vs. \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \setlength{\oddsidemargin}{-69pt} \begin{document} \begin{equation*}{\mathrm{p}}K_{{\mathrm{U}}}^{{\mathrm{H}}}\end{equation*}\end{document} result in straight lines that are compared with previous plots for simple pyridine-type and o -amino(methyl)pyridine-type ligands as well as with the stabilities of the corresponding M(cytidine) 2+ complexes. The results indicate monodentate coordination to (N3) – in M(U–H) + for Co 2+ and Ni 2+ . For the M(U–H) + species of Cd 2+ , Zn 2+ , or Cu 2+ , increased stabilities imply that semichelates form, i.e., M 2+ is (N3) – -bound and coordinated water molecules form hydrogen bonds to (C2)O and (C4)O; these “double” semichelates are in equilibrium with “single” semichelates involving either (C2)O or (C4)O and possibly also with four-membered chelates for which M 2+ is innersphere-coordinated to (N3) – and a carbonyl oxygen. For the alkaline earth ions, semichelates dominate with the M 2+ outersphere bound to (N3) – and innersphere to one of the carbonyl oxygens. Mn(U–H) + is with its properties between those of Cd 2+ (which probably also hold for Pb 2+ ) and the alkaline earth ions. In nucleic acids, M 2+ –C(O) interactions are expected, if support is provided by other primary binding sites. (N3)H may possibly be acidified via carbonyl-coordinated M 2+ to become a proton donor in the physiological pH range, at which direct (N3) – binding of M 2+ also seems possible.