Sulfur biological systems

It is well estabhshed that sulfur compounds as well as elemental sulfur have the tendency to form long chain molecules. All of these substances can be regarded as derivatives of the hydrogen polysulfanes (or polysulfanes) H2S . Polysulfanes form a long series of homologous chain-like molecules since the number n can assume any value. S-S and S-H bonds are frequently found in chemical and biological systems. Thus, polysulfanes have been the subject of numerous experimental and theoretical studies (for a recent review, see [15]). 

Fe-4S] + + clusters are certainly the most ubiquitous iron-sulfur centers in biological systems. They play the role of low potential redox centers in ferredoxins, membrane-bound complexes of the respiratory... 

Metal-sulfur aggregates are now known to occur in biological systems as the active sites of a significant number of metalloenzymes, and clarification of their detailed structures are currently progressing rapidly. In consideration of the results of these studies, many researchers are attempting to synthesize the direct structural models as well as the functional models of the active sites of natural enzymes that promote various important reactions in the biological systems under ambient conditions, which presumably leads in the near future to the... 

If one applies the same procedure to Figure 1.10B, an iron-sulfur cluster often used as a model for those in biological systems, the same magic number of 60 would be obtained. Cluster magic numbers would occur as 48 e for a triangular clusters, 60 e for tetrahedral, 72 e for trigonal bipyramidal, 74 e for square pyramidal, 86 e for octahedral, 90 e for trigonal prisms, and 120 e for cubic structures. 

In biological systems, H-bond donors and acceptors are predominantly nitrogen and oxygen atoms. However, the n electrons of aromatic systems can also act as acceptors, and H-bonds involving sulfur groups or metallic cofactors are also known. The presence of individual H-bonds in biomacromolecular structures is usually derived from the spatial arrangement of the donor and acceptor groups once the structure of a molecule has been solved by diffractive or NMR techniques. More detailed information about H-bonds... 

Bimolecular surface reactions reactants adsorption, 29 111-112 with single reactant, 29 108-109 1,1 -Binaphthyl, dehydrocyclization, 28 318 Binary oxides, 32 119 Binding energy, 32 160-162 chemisorbed sulfur, 37 281 hydrogen, sulfur effect, 37 295-296 shift, Pd, 37 62-64 ZnO/SiOj, 37 21-22 Binor-S, see Norbomadiene Biological systems, hydrogen in, activation of, 11 301... 

For biological systems such as ferredoxins, problems arise when counting electrons by the valence electron method. This system assumes six Fe-Fe bonds within the tetrahedral iron-sulfur clusters, but Fe-Fe bond distances within biological iron-sulfur clusters, as found by X-ray crystallography, often... 

The present volume comprises 17 chapters, written by 27 authors from 11 countries, and deals with theoretical aspects and structural chemistry of peroxy compounds, with their thermochemistry, O NMR spectra and analysis, extensively with synthesis of cyclic peroxides and with the uses of peroxides in synthesis, and with peroxides in biological systems. Heterocyclic peroxides, containing silicon, germanium, sulfur and phosphorus, as well as transition metal peroxides are treated in several chapters. Special chapters deal with allylic peroxides, advances in the chemistry of dioxiranes and dioxetanes, and chemiluminescence of peroxide and with polar effects of their decomposition. A chapter on anti-malarial and anti-tumor peroxides, a hot topic in recent research of peroxides, closes the book. 

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