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Self-assembled Transition Metal Coordination Frameworks of ...

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Chapter 6 _ _ __ 7<br />

the latter have larger size. The coordination number <strong>of</strong> Zn(II) complexes with<br />

semicarbazones and thiosemicarbazones (lower homologues) ranges from four to<br />

seven while that <strong>of</strong> Cd(I1) complexes ranges from four to eight [24].<br />

Zinc is an essential element, necessary for sustaining all forms <strong>of</strong> life. It is<br />

estimated that 3000 <strong>of</strong> the hundreds <strong>of</strong> thousands <strong>of</strong> proteins in the human body<br />

contain zinc prosthetic groups. In addition, there are over a dozen types <strong>of</strong> cells in the<br />

human body that secrete zinc ions, and the roles <strong>of</strong> these secreted zinc signals in<br />

medicine and health are now being actively studied [25]. Despite its critical<br />

importance in maintaining such basic functions as proliferation and cell growth, little<br />

is known about how zinc is acquired, stored, and utilized by the cell. Recent<br />

pioneering studies have started to uncover the mysteries <strong>of</strong> subcellular distribution and<br />

to some extend on the proteins that maintain it. Many zinc complexes serve as models<br />

<strong>of</strong> biologically active zinc systems [25]. In biological chemistry, zinc serves as an<br />

electrophilic catalyst; that is, it stabilizes negative charges encountered during an<br />

enzyme-catalyzed reaction. Thus, protein-zinc recognition and discrimination requires<br />

proper chemical composition and proper stereochemistry <strong>of</strong> the metal-ligand<br />

environment. The fact that zinc is not subject to any ligand field stabilization effects<br />

and the change from an octahedral to a tetrahedral ligand field is not energetically<br />

disfavored for Zn(II) also have to be considered in biological studies. Zinc(H) ion has<br />

been found to be <strong>of</strong> catalytic importance in enzymatic reactions [26]. The<br />

enhancement <strong>of</strong> antitumor activity <strong>of</strong> some thiosemicarbazones in the presence <strong>of</strong><br />

zinc(II) ions has been reported [27]. Some zinc complexes <strong>of</strong> thiosemicarbazones<br />

have been shown to be active as anti-tumor agents, are as cytotoxic as cisplatin and<br />

are also effective against cisplatin resistant cell lines [28]. Recently, the in vitro<br />

antiproliferative activity <strong>of</strong> Zn(II) thiosemicarbazones against the cells <strong>of</strong> MCF-7 and<br />

T24 human cancer cell lines have been reported [29]. Although, zinc is an important<br />

element in biological systems, cadmium, similar to zinc chemically in many ways,<br />

apparently does not substitute or "stand in" for it. The toxicity <strong>of</strong> cadmium is<br />

230

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