Bioanorganische Chemie pp 248-270 | Cite as
Zink: Enzymatische Katalyse von Aufbau- und Abbau-Reaktionen sowie strukturelle und genregulatorische Funktionen
Überblick
Nach dem Element Eisen ist Zink mit ca. 2 g pro 70 kg Körpergewicht das zweithäufigste 3d-Metall im menschlichen Organismus, eine bedeutende Rolle spielt es auch für viele andere Lebewesen (Bertini et al.; Prince; Williams; Vahrenkamp; Vallee, Auld; Prasad). Das Element kommt unter physiologischen Bedingungen nur zweifach ionisiert vor; aufgrund der abgeschlossenen d-Schale (d10-Konfiguration) ist Zn2+ in Komplexverbindungen diamagnetisch und farblos. Entfällt dadurch einerseits die Möglichkeit von leichter elektronischer Anregung am Metall selbst, so findet sich andererseits Zink(II) biologisch nie von (farbigen) Tetrapyrrol-Liganden koordiniert, obwohl synthetische Komplexe dieses Typs sehr stabil sind. Zink-enthaltende Proteine konnten folglich erst mit verbesserten analytischen Methoden seit etwa 1930 eindeutig nachgewiesen werden; inzwischen sind schon über 300 Vertreter bekannt (vgl. Tab. 12.1). Unter diesen befinden sich zahlreiche essentielle Enzyme, die den Aufbau (Synthetasen, Polymerasen, Ligasen, Transferasen) oder den Abbau (Hydrolasen) von Proteinen, Nukleinsäuren, Lipid-Molekülen, Porphyrin-Vorstufen und anderen wichtigen bioorganischen Verbindungen katalysieren. Weitere Funktionen betreffen das Fixieren bestimmter, die Reaktionsgeschwindigkeit und/oder die Stereoselektivität beeinflussender Konformationen von Proteinen in Oxidoreduktasen sowie die strukturelle Stabilisierung von Insulin, von Hormon/Rezeptor-Komplexen oder auch von Transkriptions-regulierenden Faktoren für die Übertragung genetischer Information. Es ist daher nicht verwunderlich, daß Zinkmangel zu gravierenden pathologischen Erscheinungen führt (Bryce-Smith) und daß die schwereren Homologen Cadmium und Quecksilber nicht zuletzt durch Verdrängen des Zn2+ aus seinen Enzymen toxisch wirken (s. Kap. 17.3 und 17.5).
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