High Resolution EPR: Applications to Metalloenzymes and Metals in Medicine (Biological Magnetic Resonance, 28)

**__High Resolution EPR: Applications to Metalloenzymes and Metals in Medicine__** **Prof. Graeme Hanson, University of Queensland and Prof. Lawrence Berliner, University of Denver** Metalloproteins are involved in a variety of biologically important processes, including metal ion and oxygen transport, biosynthesis, electron transfer, biodegradation, drug metabolism, proteolysis and peptide hydrolysis, environmental oxygen, sulphur, and nitrogen cycles, and disease states. High-resolution EPR spectroscopy is crucial in determining the geometric and electronic structural characterization of the redox cofactors in metalloenzymes, which is essential for understanding their reactivity in complex biological systems. This volume, Part I of a two-volume set, covers high-resolution EPR methods, computer simulation, density functional theory, and their application to iron proteins, nickel, and copper enzymes and metals in medicine. The following chapters, written by experts in their fields, include: Advanced Pulse EPR Methods for the Characterization of Metalloproteins: Jeffrey Harmer, George Mitrikas, and Arthur Schweiger Probing Structural and Electronic Parameters in Randomly Oriented Metalloproteins by Orientation-Selective ENDOR Spectroscopy: Reinhard Kappl, Gerhard Bracic, and Jürgen Hüttermann Molecular Sophe: An Integrated Approach to the Structural Characterization of Metalloproteins: The Next Generation of Computer Simulation Software: Graeme Hanson, Christopher Noble, and Simon Benson Spin-Hamiltonian Parameters from First Principle Calculations: Theory and Application: Frank Neese EPR of Mononuclear Non-Heme Iron Proteins: Betty Gaffney Binuclear Non-Heme Iron Enzymes: Nataša Mitic, Gerhard Schenk, and Graeme Hanson Probing the Structure–Function Relationship of Heme Proteins Using Multifrequency Pulse EPR Techniques: Sabine Van Doorslaer EPR Studies of the Chemical Dynamics of NO and Hemoglobin Interactions: Benjamin Luchsinger, Eric Walter, Lisa Lee, Jonathan Stamler, and David Singel EPR Investigation of [NiFe] Hydrogenases: Maurice van Gastel and Wolfgang Lubitz Unique Spectroscopic Features and Electronic Structures of Copper Proteins: Relation to Reactivity: Jungjoo Yoon and Edward Solomon Insulin-Enhancing Vanadium Pharmaceuticals: The Role of Electron Paramagnetic Resonance Methods in the Evaluation of Antidiabetic Potential: Barry Liboiron Chromium in Cancer and Dietary Supplements: Aviva Levina, Rachel Codd, and Peter Lay High-Frequency EPR and ENDOR Characterization of MRI Contrast Agents: Arnold Raitsimring, Andrei Astashkin, and Peter Caravan Metalloproteins comprise approximately 30% of all known proteins, and are involved in a variety of biologically important processes, including oxygen transport, biosynthesis, electron transfer, biodegradation, drug metabolism, proteolysis, and hydrolysis of amides and esters, environmental sulfur and nitrogen cycles, and disease mechanisms. EPR spectroscopy has an important role in not only the geometric structural characterization of the redox cofactors in metalloproteins but also their electronic structure, as this is crucial for their reactivity. The advent of x-ray crystallographic snapshots of the active site redox cofactors in metalloenzymes in conjunction with high-resolution EPR spectroscopy has provided detailed structural insights into their catalytic mechanisms. This volume was conceived in 2005 at the Rocky Mountain Conference on Analytical Chemistry (EPR Symposium) to highlight the importance of high-resolution EPR spectroscopy to the structural (geometric and electronic) characterization of redox active cofactors in metalloproteins. We have been fortunate to have enlisted internationally recognized experts in this joint venture to provide the scientific community with an overview of high-resolution EPR and its application to metals in biology. This volume, High-Resolution EPR: Applications to Metalloenzymes and Metals in Medicine, covers high-resolution EPR methods, iron proteins, nickel and copper enzymes, and metals in medicine. An eloquent synopsis of each chapter is provided by John Pilbrow in the Introduction. A second volume, Metals in Biology: Applications of High-Resolution EPR to Metalloenzymes, will appear later this year covering the complement of other metalloproteins. One of the pioneers in the development of pulsed EPR and its application to metalloproteins was Arthur Schweiger, whose contribution we include in this volume. Unfortunately, he passed away suddenly during the preparation of this volume. The editors and coauthors are extremely honored to dedicate this volume to the memory of Arthur Schweiger in recognition of his technical advances and insights into pulsed EPR and its application to metalloproteins. Arthur was extremely humble and treated everyone with equal respect. He was a gifted educator with an ability to explain complex phenomena in terms of simple intuitive pictures, had a delightful personality, and continues to be sadly missed by the community. It is an honor for the editors to facilitate the dissemination of these excellent contributions to the scientific community. Suggestions for future volumes are always appreciated. Front Matter....Pages i-xxii Introduction....Pages 1-10 Front Matter....Pages 11-11 Advanced Pulse EPR Methods for the Characterization of Metalloproteins....Pages 13-61 Probing Structural and Electronic Parameters in Randomly Oriented Metalloproteins by Orientation-Selective ENDOR Spectroscopy....Pages 63-103 Molecular Sophe: An Integrated Approach to the Structural Characterization of Metalloproteins: The Next Generation of Computer Simulation Software....Pages 105-173 Spin-Hamiltonian Parameters from First Principle Calculations: Theory and Application....Pages 175-229 Front Matter....Pages 231-231 EPR of Mononuclear Non-Heme Iron Proteins....Pages 233-268 Binuclear Non-Heme Iron Enzymes....Pages 269-395 Probing the Structure–Function Relationship of Heme Proteins Using Multifrequency Pulse EPR Techniques....Pages 397-417 EPR Studies of the Chemical Dynamics of NO and Hemoglobin Interactions....Pages 419-438 Front Matter....Pages 439-439 EPR Investigation of [NiFe] Hydrogenases....Pages 441-470 Unique Spectroscopic Features and Electronic Structures of Copper Proteins: Relation to Reactivity....Pages 471-504 Front Matter....Pages 505-505 Insulin-Enhancing Vanadium Pharmaceuticals: The Role of Electron Paramagnetic Resonance Methods in the Evaluation of Antidiabetic Potential....Pages 507-549 Chromium in Cancer and Dietary Supplements....Pages 551-579 High-Frequency EPR and ENDOR Characterization of MRI Contrast Agents....Pages 581-621 Back Matter....Pages 1-43 cover-large.JPG 1 front-matter.pdf 2 fulltext.pdf 24 fulltext_001.pdf 73 fulltext_002.pdf 114 fulltext_003.pdf 183 fulltext_004.pdf 238 fulltext_005.pdf 248 fulltext_006.pdf 284 fulltext_007.pdf 411 fulltext_008.pdf 432 fulltext_009.pdf 452 fulltext_010.pdf 482 fulltext_011.pdf 516 fulltext_012.pdf 559 fulltext_013.pdf 588 back-matter.pdf 629