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Natural biochemical processes are routinely being discovered in living cells that involve RNA. Some of these processes, such as RNA interference, are now being exploited for biotechnology and medicinal applications. DNA has also proven in recent years to be more than a passive storehouse of information. For example, non-B-form DNA structures formed by G-rich DNA have been shown to participate in the regulation of gene expression, a discovery that presents new possibilities for drug targets in the genome. The current quest to understand how nucleic acid functions at the most fundamental level requires that we have a detailed understanding of nucleic acid-metal ion interactions. Because RNA and DNA are polyanions the structure and biological function of these biopolymers depends strongly on their association with metal ions. While this intimate connection between metal ions and nucleic function has been appreciated for decades, the noncovalent and dynamic nature of these interactions has continually presented challenges to the development of accurate and quantitative descriptions. Over the past few years the development of solution state spectroscopic techniques and the achievement of high resolution X-ray crystal structures have provided tremendous insights into the nature of nucleic acid-metal ion interactions, including direct evidence for their importance in determining nucleic acid structure, from the dictation of folding pathways followed by large RNA molecules to the subtle modulation of DNA groove widths. This new book provides a comprehensive review of the experimental studies that define our current understanding of nucleic acid-metal ion interactions with a particular emphasis being placed on experimental biophysical studies. However, the book is not merely a current review of the literature, as original material and fresh perspectives on published results are also presented. Particularly noteworthy topics include: -The chapter by Williams and fellow workers which reviews information provided by x-ray crystal structures and discusses what this information has revealed about the unique nature of Mg2+ interactions with RNA phosphate groups. The authors provide fresh insights, based upon structural comparisons, for how these interactions govern the local folding pathways of RNA. By dedicating separate chapters to the participation of metal ions in the kinetics and thermodynamics of RNA folding, this volume provides a more in depth treatise of both areas than is typically possible for reviews in which these two related, but distinct, topics are combined -Polyelectrolyte models of nucleic acids have proven to be extremely valuable for understanding the sequestering counterions in a so-called diffuse cloud around polymeric DNA. J. Michael Schurr provides a comprehensive review of polyanion models. Despite the success of polyelectrolyte models in describing some physical properties of nucleic acids, this topic is not always sufficiently understood by many researchers to make use of these models and this chapter serves as a valuable and up to date introduction to this topic. -The chapter by Pizarro and Sadler on metal ion-nucleic acid interactions in disease and medicine is complemented by a chapter by Lippert on coordinative bond formation between metal ions and nucleic acid bases. Together, these two chapters provide an overview of transition metal ion interactions with nucleic acids that illustrates the promise and peril that is associated with direct metal ion coordination to nucleic acid bases in living cells. The book is sufficiently detailed to serve as a reference source for researchers active in the field of nucleic acids biophysics and molecular biology. In addition, chapter authors have added introductory material and enough background material in each chapter so that the book can also can serve as an entry point for students and researchers that have not previously worked in the field which will make the book of lasting value and more accessible by a wider audience.
The development of agents capable of cleaving RNA and DNA has attracted considerable attention from researchers in the last few years, because of the immediate and very important applications they can find in the emerging fields of biotechnology and pharmacology. There are essentially two classes of these agents - nucleases that occur naturally inside cells and synthetically produced artificial nucleases. The first class includes protein enzyme nucle ases and catalytic RNA structured ribozymes that perform cleavage of the phosphodiester bonds in nucleic acids according to a hydrolytic pathway in the course of different biochemical processes in the cell. A different pathway is used by some antibiotics which cleave DNA via redox-based mechanisms resulting in oxidative damage of nucleotide units and breakage of the DNA backbone. The above molecules are indispensable tools for manipulating nucleic acids and processing RNA; DNA-cleaving antibiotics and cytotoxic ribonucleases have demonstrated utility as chemotherapeutic agents. The second class, artificial nucleases, are rationally designed to imitate the active centers of natural enzymes by simple structures possessing minimal sets of the most important characteristics that are essential for catalysis. A dif ferent approach, in vitro selection, was also used to create artificial RNA and DNA enzymes capable of cleaving RNA. Being less efficient and specific as compared to the natural enzymes, the primitive mimics are smaller and robust and can function in a broad range of conditions.
30 years after its discovery as an antitumor agent, cisplatin represents today one of the most successful drugs in chemotherapy. This book is intended to reminisce this event, to take inventory, and to point out new lines of development in this field. Divided in 6 sections and 22 chapters, the book provides an up-to-date account on topics such as - the chemistry and biochemistry of cisplatin, - the clinical status of Pt anticancer drugs, - the impact of cisplatin on inorganic and coordination chemistry, - new developments in drug design, testing and delivery. It also includes a chapter describing the historical development of the discovery of cisplatin. The ultimate question - How does cisplatin kill a cell? - is yet to be answered, but there are now new links suggesting how Pt binding to DNA may trigger a cascade of cellular reactions that eventually result in apoptosis. p53 and a series of damage recognition proteins of the HMG-domain family appear to be involved. The book addresses the problem of mutagenicity of Pt drugs and raises the question of the possible relevance of the minor DNA adducts, e.g. of interstrand cross-links, and the possible use of trans-(NH3)2Pt(II)-modified oligonucleotides in antisense and antigene strategies. Our present understanding of reactions of cisplatin with DNA is based upon numerous model studies (from isolated model nucleobases to short DNA fragments) and application of a large body of spectroscopic and other physico-chemical techniques. Thanks to these efforts there is presently no other metal ion whose reactions with nucleic acids are better understood than Pt. In a series of chapters, basic studies on the interactions of Pt electrophiles with nucleobases, oligonucleotides, DNA, amino acids, peptides and proteins are reported, which use, among others, sophisticated NMR techniques or X-ray crystallography, to get remarkable understanding of details on such reactions. Reactivity of cisplatin, once bound to DNA and formerly believed to be inert enough to stay, is an emerging phenomenon. It has (not yet) widely been studied but is potentially extremely important. Medicinal bioinorganic chemistry - the role of metal compounds in medicine - has received an enormous boost from cisplatin, and so has bioinorganic chemistry as a whole. There is hardly a better example than cisplatin to demonstrate what bioinorganic chemistry is all about: The marriage between classic inorganic (coordination) chemistry and the other life sciences - medicine, pharmacy, biology, biochemistry. Cisplatin has left its mark also on areas that are generally considered largely inorganic. The subject of mixed-valance Pt compounds is an example: From the sleeping beauty it made its way to the headlines of scientific journals, thanks to a class of novel Pt antitumor agents, the so-called "platinum pyrimidine blues". In the aftermath diplatinum (III) compounds were recognized and studies in large numbers, and now an organometalic chemistry of these diplatinum (III) species is beginning to emerge. The final section of the book is concerned with new developments such as novel di- and trinuclear Pt(II) drugs with DNA binding properties different from those of cisplatin, with orally active Pt(IV) drugs which are presently in clinical studies, and with attempts to modify combinatorial chemistry in such a way that it may become applicable to fast screening of Pt antitumor drugs. The potential of including computational methods in solving questions of Pt-DNA interactions is critically dealt with in the concluding chapter.
The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant. The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed. Review articles for the individual volumes are invited by the volume editors. Readership: research scientists at universities or in industry, graduate students Special offer For all customers who have a standing order to the print version of Structure and Bonding, we offer free access to the electronic volumes of the Series published in the current year via SpringerLink.
Bioinorganic photochemistry is a rapidly evolving field integrating inorganic photochemistry with biological, medical and environmental sciences. The interactions of light with inorganic species in natural systems, and the applications in artificial systems of medical or environmental importance, form the basis of this challenging inter-disciplinary research area. Bioinorganic Photochemistry provides a comprehensive overview of the concepts and reactions fundamental to the field, illustrating important applications in biological, medical and environmental sciences. Topics covered include: Cosmic and environmental photochemistry Photochemistry of biologically relevant nanoassemblies Molecular aspects of photosynthesis Photoinduced electron transfer in biosystems Modern therapeutic strategies in photomedicine The book concludes with an outlook for the future of environmental protection, discussing emerging techniques in the field of pollution abatement, and the potential for bioinorganic photochemistry as a pathway to developing cheap, environmentally friendly sources of energy. Written as an authoritative guide for researchers involved in the development of bioinorganic photochemical processes, Bioinorganic Photochemistry is also accessible to scientists new to the field, and will be a key reference source for advanced courses in inorganic, and bioinorganic chemistry.
This Special Issue is one of the first for the new MDPI flagship journal Chemistry (ISSN 2624-8549) which has a broad remit for publishing original research in all areas of chemistry. The theme of this issue is Supramolecular Chemistry in the 3rd Millennium and I am sure that this topic will attract many exciting contributions. We chose this topic because it encompasses the unity of contemporary pluridisciplinary science, in which organic, inorganic, physical and theoretical chemists work together with molecular biologists and physicists to develop a systems-level understanding of molecular interactions. The description of supramolecular chemistry as 'chemistry beyond the molecule' (Jean-Marie Lehn, Nobel Lecture and Gautam R. Desiraju, Nature, 2001, 412, 397) addresses the wide variety of weak, non-covalent interactions that are the basis for the assembly of supramolecular architectures, molecular receptors and molecular recognition, programed molecular systems, dynamic combinatorial libraries, coordination networks and functional supramolecular materials. We welcome submissions from all disciplines involved in this exciting and evolving area of science.