NITROXIDES – THEORY, EXPERIMENT AND APPLICATIONS Edited by Alexander I. Kokorin Nitroxides – Theory, Experiment and Applications http://dx.doi.org/10.5772/2887 Edited by Alexander I. Kokorin Contributors Lawrence J. Berliner, Günter Grampp, Kenneth Rasmussen, Andrey Kh. Vorobiev, Natalia A. Chumakova, Alexander I. Kokorin, Boris Dzikovski, Jack Freed, Rui Tamura, Yoshiaki Uchida, Katsuaki Suzuki, Elena Kovaleva, Leonid Molochnikov, Toshihide Yamasaki, Fumiya Mito, Yuta Matsuoka, Mayumi Yamato, Ken-ichi Yamada, Eugene M. Pliss, Ivan V. Tikhonov, Alexander I. Rusakov, Yaroslav Tkachev, Vladimir Timofeev, Valery V. Khramtsov, Stefan Hauck, Yvonne Lorat, Fabian Leinisch, Christian Kopp, Jessica Abrossinow, Wolfgang E. Trommer, Lev Weiner, Vasily D. Sen', Alexei A. Terentiev, Nina P. Konovalova, Anatoly Filippov, Elena Chernikova, Vladimir Golubev, Ganna Gryn’ova, Ching Yeh Lin, Michelle L. Coote Published by InTech Janeza Trdine 9, 51000 Rijeka, Croatia Copyright © 2012 InTech All chapters are Open Access distributed under the Creative Commons Attribution 3.0 license, which allows users to download, copy and build upon published articles even for commercial purposes, as long as the author and publisher are properly credited, which ensures maximum dissemination and a wider impact of our publications. After this work has been published by InTech, authors have the right to republish it, in whole or part, in any publication of which they are the author, and to make other personal use of the work. Any republication, referencing or personal use of the work must explicitly identify the original source. Notice Statements and opinions expressed in the chapters are these of the individual contributors and not necessarily those of the editors or publisher. No responsibility is accepted for the accuracy of information contained in the published chapters. The publisher assumes no responsibility for any damage or injury to persons or property arising out of the use of any materials, instructions, methods or ideas contained in the book. Publishing Process Manager Ana Nikolic Typesetting InTech Prepress, Novi Sad Cover InTech Design Team First published September, 2012 Printed in Croatia A free online edition of this book is available at www.intechopen.com Additional hard copies can be obtained from orders@intechopen.com Nitroxides – Theory, Experiment and Applications, Edited by Alexander I. Kokorin p. cm. ISBN 978-953-51-0722-4 Contents Preface IX Section 1 Theory 1 Chapter 1 History of the Use of Nitroxides (Aminoxyl Radicals) in Biochemistry: Past, Present and Future of Spin Label and Probe Method 3 Lawrence J. Berliner Chapter 2 ESR Spectroscopy of Nitroxides: Kinetics and Dynamics of Exchange Reactions 25 Günter Grampp and Kenneth Rasmussen Chapter 3 Simulation of Rigid-Limit and Slow-Motion EPR Spectra for Extraction of Quantitative Dynamic and Orientational Information 57 Andrey Kh. Vorobiev and Natalia A. Chumakova Chapter 4 Forty Years of the d 1 /d Parameter 113 Alexander I. Kokorin Section 2 Experiment 165 Chapter 5 Spin Labels in the Gel Phase and Frozen Lipid Bilayers: Do They Truly Manifest a Polarity Gradient? 167 Boris Dzikovski and Jack Freed Chapter 6 Magnetic and Electric Properties of Organic Nitroxide Radical Liquid Crystals and Ionic Liquids 191 Rui Tamura, Yoshiaki Uchida and Katsuaki Suzuki Chapter 7 pH-Sensitive Nitroxide Radicals for Studying Inorganic and Organo-Inorganic Materials and Systems 211 Elena Kovaleva and Leonid Molochnikov VI Contents Chapter 8 Synthesis and Utilization of α-Substituted Nitroxides 247 Toshihide Yamasaki, Fumiya Mito, Yuta Matsuoka, Mayumi Yamato and Ken-ichi Yamada Chapter 9 Kinetics and Mechanism of Reactions of Aliphatic Stable Nitroxide Radicals in Chemical and Biological Chain Processes 263 Eugene M. Pliss, Ivan V. Tikhonov and Alexander I. Rusakov Chapter 10 Uniform EPR Spectra Analysis of Spin-Labeled Macromolecules by Temperature and Viscosity Dependences 285 Yaroslav Tkachev and Vladimir Timofeev Section 3 Applications 315 Chapter 11 In vivo Spectroscopy and Imaging of Nitroxide Probes 317 Valery V. Khramtsov Chapter 12 Fluorescent Nitrones for the Study of ROS Formation with Subcellular Resolution 347 Stefan Hauck, Yvonne Lorat, Fabian Leinisch, Christian Kopp, Jessica Abrossinow and Wolfgang E. Trommer Chapter 13 Quantitative Determination of Thiol Status of Proteins and Cells by Nitroxyl Biradical . RS-SR . 369 Lev Weiner Chapter 14 Platinum Complexes with Bioactive Nitroxyl Radicals: Synthesis and Antitumor Properties 385 Vasily D. Sen', Alexei A. Terentiev and Nina P. Konovalova Chapter 15 Use of Spin Trap Technique for Kinetic Investigation of Elementary Steps of RAFT-Polymerization 407 Anatoly Filippov, Elena Chernikova, Vladimir Golubev, Ganna Gryn’ova, Ching Yeh Lin and Michelle L. Coote Preface After opening a new class of chemical reactions in 1964, reactions in which unpaired electrons of stable radicals were not involved, nitroxide (aminoxyl) radicals became one of the most interesting and rapidly developing area of modern physical chemistry with their application to biophysics, molecular biology, polymer sciences and medicine. Further development of this field depends on new pathways in the nitroxide chemistry, modern methods in EPR spectroscopy and revealing new perspective practical approaches. This book contains reviews of the authors actively working in three main areas of chemical physics: theoretical approaches, novel experimental results, and practical applications. The first chapter, written by Prof. Lawrence J. Berliner who started his work in this area just from its very beginning, describes the history of the spin label technique. Unfortunately, he did not practically pay attention to numerous publications of Soviet and Russian scientists, whose impact to the field was really great. This will be fixed in the next edition of the book. The following 14 chapters analyze in detail the modern state and some perspectives of various usages of nitroxide radicals. The book, recommended by the Governing Council of N. Semenov International Center of Chemical Physics, Moscow, will be useful to many scientists: chemists, physical chemists, biophysicists, biologists, physicians and other experts in a variety of disciplines in which spin labels and probes are used, as well as to students and PhD students. It may be also suitable for teaching, and help promote the progress in natural sciences. Any comments, remarks and advices from the readers will be appreciated for the next edition. Prof. Dr. Alexander I. Kokorin Department of Kinetics and Catalysis, N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russian Federation . NITROXIDES – THEORY, EXPERIMENT AND APPLICATIONS Edited by Alexander I. Kokorin Nitroxides – Theory, Experiment and Applications http://dx.doi.org/10.5772/2887. Additional hard copies can be obtained from orders@intechopen.com Nitroxides – Theory, Experiment and Applications, Edited by Alexander I. Kokorin p. cm. ISBN 978-953-51-0722-4 . R 2 C=N–O·. Its use is strongly discouraged. In the Sigma/Aldrich catalog, the spin probe TEMPO is listed as 2,2,6,6- tetramethylpiperidine 1-oxyl. Nitroxides – Theory, Experiment and Applications