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This rapidly expanding field probes fascinating questions about the uses of metal ions in nature. Respiration, metabolism, photosynthesis, gene regulation, and nerve impulse transmission are a few of the many natural processes that require metal ions, and new systems are continually being discovered. The use of unnatural metals - which have been introduced into human biology as diagnostic probes and drugs - is another active area of tremendous medical significance. This introductory text, written by two pioneering researchers, is destined to become a landmark in the field of bioinorganic chemistry through its organized unification of key topics. Accessible to undergraduates, the book provides necessary background information on coordination chemistry, biochemistry, and physical methods before delving into topics that are central to the field: What metals are chosen and how are they taken up by cells? How are the concentrations of metals controlled and utilized in cells? 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How do metals bind to and fold biomolecules? What principles govern electron transfer and substrate binding and activation reactions? How do proteins fine-tune the properties of metals for specific functions? For each topic discussed, fundamentals are identified and then clarified through selected examples. 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A similar situation occurs for ruthenium bound to amino - acid residues , as encountered in studies of protein electron - transfer reaction kinetics . The fast metal - ligand exchange rates of first - row transition - metal\u0026nbsp;..."},{"page_id":"PA66","page_number":"66","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e of tRNA have been crystallographically characterized . The lead ( II ) derivative can promote the cleavage of the sugar - phosphate backbone in yeast tRNAPhe , as indicated in Figure 3.19 ; this figure also illustrates the\u0026nbsp;..."},{"page_id":"PA70","page_number":"70","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e , cyanocobalamin ( Figure 1.6 ) , which is reduced in a two - electron reaction by FAD to form the Co ( I ) complex . This powerful nucleophile reacts with ATP to give the adenylated B - 12 coenzyme . The Co - C bond in coenzyme\u0026nbsp;..."},{"page_id":"PA89","page_number":"89","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e with DNA and 113Cd NMR spectral investigations of metallothionein . Finally , NMR methods are often quite useful for kinetic studies . The extremely high resolution and small line widths of NMR methods , in which differences in\u0026nbsp;..."},{"page_id":"PA99","page_number":"99","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e with 13C - enriched cyanide ion ( I = 1/2 ) , how might it affect the spectrum ? 3. The substitution of Co2 + for Zn2 + in metalloproteins is an example of a substitu- tion probe , greatly facilitating the characterization of the\u0026nbsp;..."},{"page_id":"PA113","page_number":"113","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e , in which only one bond is made to the nucleic acid . They then slowly close to bifunc- tional \u003cb\u003eadducts\u003c/b\u003e , where there are two platinum - nucleobase bonds . Both chemi- cal processes occur with half - lives of two or three hours\u0026nbsp;..."},{"page_id":"PA114","page_number":"114","snippet_text":"... Activated forms of cisplatin Tumor cell DNA cisplatin - DNA \u003cb\u003eadducts\u003c/b\u003e Figure 5.7 Administration and in vivo chemistry of the anticancer drug cisplatin . nent postulated to react with platinum anticancer drugs is ascorbic 114."},{"page_id":"PA141","page_number":"141","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e with DNA ( Sections 7.3 and 8.3 ) . These ad- ducts are harmful , but more so to tumor than to normal tissue , leading to beneficial effects at the organismal level . By contrast , the corresponding palla- dium ( II ) compound\u0026nbsp;..."},{"page_id":"PA150","page_number":"150","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e , Hg ( SR ) 2 , produced by exchange of endogenous thiols such as glutathione for the cysteinate ligands of the enzyme . This complex , in turn , is a substrate for mercuric - ion reductase , a dimeric enzyme having a subunit\u0026nbsp;..."},{"page_id":"PA151","page_number":"151","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e . Mercury - atom release and binding of the next Hg ( II ) with accompanying carbon - sulfur bond cleavage completes the cycle . It should be noted that , once mercury atoms are pro- duced , they simply diffuse through the cell\u0026nbsp;..."},{"page_id":"PA177","page_number":"177","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e , and zinc release was monitored by the visible absorbance of the zinc - dye complex . Modification of approximately 24 cysteine residues resulted in the release of the six zinc ions from the holoenzyme . This process. 177."},{"page_id":"PA178","page_number":"178","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e with excess thiol produced apo - regulatory subunits that would reassociate with the cata- lytic subunit only when zinc was added . These experiments strongly sug- gested the presence of the zinc - cysteinate complexes in the\u0026nbsp;..."},{"page_id":"PA198","page_number":"198","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e forms . The major species are intrastrand cross - links of the kind cis- [ Pt ( NH3 ) 2 { d ( GpG ) } ] and cis- [ Pt ( NH3 ) 2 { d ( ApG ) } ] , which to- gether account for up to 90 percent of the bound platinum . The ability\u0026nbsp;..."},{"page_id":"PA199","page_number":"199","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e of d ( pGpG ) . positions of platinum on the DNA bases have been elucidated by NMR spectroscopic and ... \u003cb\u003eadducts\u003c/b\u003e are embedded . The purine rings are completely destacked as a result of platination and have dihedral angles\u0026nbsp;..."},{"page_id":"PA200","page_number":"200","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e were oligomerized ( Figure 7.19 ) . Molecules of 88 , 110 , and 132 bp lengths , corresponding to ... \u003cb\u003eadducts\u003c/b\u003e of cisplatin . The existence of such factors was proved by the gel - mobility - shift assay , outlined in\u0026nbsp;..."},{"page_id":"PA201","page_number":"201","snippet_text":"... \u003cb\u003eAdduct\u003c/b\u003e Unwinding Bend 2.1 angle angle cis - GTG 1.9 cis - GG 13 ° 32-34 ° cis - AG 13 ° 32-34 ° Rt cis - GTG 23 ° 32-34 ° 1.7 1.5 1.3 19 20 21 22 23 24 Figure 7.19 Interplatinum distance ( bp ) Scheme illustrating the method used to\u0026nbsp;..."},{"page_id":"PA204","page_number":"204","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e . By using site specifically modified DNA molecules , researchers demonstrated that the recognition mo- tif was afforded by the cis- [ Pt ( NH3 ) 2 { d ( GPG ) } ] or cis- [ Pt ( NH3 ) 2 { d ( ApG ) } ] intrastrand cross - links\u0026nbsp;..."},{"page_id":"PA210","page_number":"210","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e have also been characterized by their ability to bind to cruciform structures that occur in double - stranded DNA having palindromic sequences . Comment on the implications of this observation for the likely structures of these\u0026nbsp;..."},{"page_id":"PA221","page_number":"221","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e . This high degree of regiospecificity , which far exceeds the frequency of nearest neighbor pairs of purine nucleosides , appears to be dictated by both thermodynamic and kinetic factors . Theoretical studies of the electro\u0026nbsp;..."},{"page_id":"PA222","page_number":"222","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e . Kinetic analysis revealed the half - life for closure of the monofunctional to bifunctional \u003cb\u003eadducts\u003c/b\u003e to be two hours . This value is characteristic of the time required for hydrolysis of chloride ligands from Pt ( II )\u0026nbsp;..."},{"page_id":"PA223","page_number":"223","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e , while that at ~ -2450 8 corresponds to bifunctional \u003cb\u003eadducts\u003c/b\u003e on the nitrogen donor atoms of the DNA bases adenine and guanine . ( Adapted from D. P. Bancroft et al . , Journal of the American Chemical Society 112 , 6860-6871\u0026nbsp;..."},{"page_id":"PA230","page_number":"230","snippet_text":"... \u003cb\u003eAdduct\u003c/b\u003e Cross - Linking the Intercalating Drug N - methyl - 2,7 - diazapyrenium . \u0026quot; Nucleic Acids Res . 18 , 3887-3891 . W. I. Sundquist , D. P. Bancroft , L. Chassot , and S. J. Lippard . 1988. “ DNA Promotes the Reaction of cis\u0026nbsp;..."},{"page_id":"PA260","page_number":"260","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e reveal several important features ( Figure 10.2 ) . The tyrosine ring displaces water molecules and resides in the hydrophobic pocket mentioned above . The glycine residue forms a bidentate chelate with zinc using both its amide\u0026nbsp;..."},{"page_id":"PA286","page_number":"286","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e of Mb and Hb , however , the X - ray data reveal a distorted structure in which the Fe - C = O angle is either bent or , more likely , tilted off the proximal histidine N - Fe bond axis to avoid steric clash with the distal\u0026nbsp;..."},{"page_id":"PA289","page_number":"289","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e could be de- oxygenated by flushing the films with N2 . The strategy of using steric factors to prohibit approach of two iron - porphyrin moieties was subsequently ap- plied in the synthesis of sterically encumbered ligands to\u0026nbsp;..."},{"page_id":"PA307","page_number":"307","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e of cytochrome P - 450 cam revealed the sub- strate to bind in a hydrophobic region of the protein , near the heme iron center , expelling all of the water molecules present in the substrate - binding pocket . Very little\u0026nbsp;..."},{"page_id":"PA315","page_number":"315","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e then undergoes a series of transformations leading to products . Some aspects of this mechanism have been experimentally probed . In particular , EXAFS studies of the corresponding enzyme from Brevibacterium fuscum have been\u0026nbsp;..."},{"page_id":"PA395","page_number":"395","snippet_text":"... \u003cb\u003eadduct\u003c/b\u003e , 260 , 261 Hydroxide , zinc bound , 263 Inhibitors , 260-262 , 266 Kinetic studies , 263 Mechanism , 263-267 Metal - substitution , 262-263 pH dependence of reaction rate , 263 Site - directed mutagenesis , 266 Structure , 259\u0026nbsp;...","page_url":"https://books.google.com.sg/books?id=zGJtXzPINAUC\u0026pg=PA395\u0026vq=adducts\u0026dq=subject:%22Science+Chemistry%22"},{"page_id":"PA397","page_number":"397","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e , 89 , 198-204 Proteins binding to , 200-204 , 205 Unwinding and bending , 198-200 , 201 , 202 Promoted reaction chemistry , 227 , 228 Sugar pucker , 58 Supercoiled , gel electrophoresis of , 207 Structure , 61-64 Torsion angles\u0026nbsp;...","page_url":"https://books.google.com.sg/books?id=zGJtXzPINAUC\u0026pg=PA397\u0026vq=adducts\u0026dq=subject:%22Science+Chemistry%22"},{"page_id":"PA399","page_number":"399","snippet_text":"... \u003cb\u003eAdduct\u003c/b\u003e with carboxypeptidase A , 260 , mRNA , 147 Model complex , 130 Ferrocene / ferricinium electrode , 98 Gold Regulation , 145-148 Ferrochelatase , 131 , 223–227 Ferromagnetic coupling , 97 Flavin , 5 , 150 , 311 Formate\u0026nbsp;...","page_url":"https://books.google.com.sg/books?id=zGJtXzPINAUC\u0026pg=PA399\u0026vq=adducts\u0026dq=subject:%22Science+Chemistry%22"},{"page_id":"PA406","page_number":"406","snippet_text":"... \u003cb\u003eadducts\u003c/b\u003e , 68 , 89 , 198–204 , 210 d ( GPG ) , d ( ApG ) intrastand cross - links , 198-204 , 221 Structure , 199 , 202 Unwinding and bending of DNA , 198-202 DNA - promoted reaction with ethidium , 227 , 228 Hydrolysis , 113 , 114 , 141\u0026nbsp;...","page_url":"https://books.google.com.sg/books?id=zGJtXzPINAUC\u0026pg=PA406\u0026vq=adducts\u0026dq=subject:%22Science+Chemistry%22"}],"search_query_escaped":"adducts"},{});</script></div></div></div><script>(function() {var href = window.location.href;if (href.indexOf('?') !== -1) {var parameters = href.split('?')[1].split('&');for (var i = 0; i < parameters.length; i++) {var param = parameters[i].split('=');if (param[0] == 'focus') {var elem = document.getElementById(param[1]);if (elem) {elem.focus();}}}}})();</script>