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Myeloperoxidase (MPO), a heme-peroxidase secreted by activated neutrophils, utilizes H2O2 and physiological level of chloride as substrates to make hypochlorous acid (HOCl). HOCl is a potent chlorinating agent serving as an antimicrobial reagent, but also causes oxidative damage of host tissue at the site of inflammation.Lysine residues in proteins are susceptible to oxidation by HOCl. Previous in vitro studies suggest 2-aminoadipic acid (2-AAA) and lysine nitrile (LysCN) may be products of protein bound lysine residues following exposure to MPO generated HOCl. However the mechanism of the reaction is poorly understood and the products of MPO catalyzed oxidation of protein bound lysine residues in vivo have not yet been examined. The present study has developed and validated an assay for 2-AAA and LysCN quantification in vivo by LC-MS/MS technique. We first demonstrated protein bound 2-AAA and LysCN are enriched in human atherosclerotic lesions with the tissue content of protein bound 2-AAA level much higher than LysCN. Then we explored the reaction mechanism by using Na-acetyl-lysine (Ac-Lys) as the target of HOCl. Two stable end products were made. At lower levels of HOCl, Na-acetyl-2-AAA was the major product through monochloramine intermediates. At higher levels of HOCl, Na-acetyl-LysCN was the major product through dichloramine intermediates. Similarly, protein bound 2-AAA was the major product formed at lower HOCl to protein target ratios and LysCN was the major product formed at higher oxidant to target ratios. Formation of both protein bound 2-AAA and LysCN require each component of the complete MPO/H2O2/Cl- system. Protein bound 2-AAA and LysCN were formed by activated neutrophils in a process that was dependent on PMA activation and inhibited by catalase and methionine. In vivo studies using an acute inflammation mouse model with C57BL/6J wild type and MPO-KO mice showed that 2-AAA was the major product of lysine oxidation by MPO in vivo, and is MPO-dependent. Collectively, these results show 2-AAA and LysCN are terminal post-translation modifications of lysine generated by MPO. Under physiological conditions, 2-AAA is the major product. MPO is a catalytic source of 2-AAA formation in vivo.
This book describes the methods of analysis and determination of oxidants and oxidative stress in biological systems. Reviews and protocols on select methods of analysis of ROS, RNS, oxygen, redox status, and oxidative stress in biological systems are described in detail. It is an essential resource for both novices and experts in the field of oxidant and oxidative stress biology.
One of the major biomedical triumphs of the post-World War II era was the defmitive demonstration that hypercholesterolemia is a key causative factor in atherosclerosis; that hypercholesterolemia can be effectively treated; and that treatment significantly reduces not only coronary disease mortality but also all cause mortality. Treatment to lower plasma levels of cholesterol - primarily low density lipoprotein (LDL) cholesterol - is now accepted as best medical practice and both physicians and patients are being educated to take aggressive measures to lower LDL. We can confidently look forward to important decreases in the toll of coronary artery disease over the coming decades. However, there is still uncertainty as to the exact mechanisms by which elevated plasma cholesterol and LDL levels initiate and favor the progression of lesions. There is general consensus that one of the earliest responses to hypercholesterolemia is the adhesion of monocytes to aortic endothelial cells followed by their penetration into the subendothelial space, where they differentiate into macrophages. These cells, and also medial smooth muscle cells that have migrated into the subendothelial space, then become loaded with mUltiple, large droplets of cholesterol esters . . . the hallmark of the earliest visible atherosclerotic lesion, the so-called fatty streak. This lesion is the precursor of the more advanced lesions, both in animal models and in humans. Thus the centrality of hypercholesterolemia cannot be overstated. Still, the atherogenic process is complex and evolves over a long period of time.
The Peroxidases in Chemistry and Biology series provides up-to-date information on a wide range of developments in the field of Peroxidases, methods and applications. This is Volume 1 originally published in 1990.
This volume is the newest release in the authoritative series of quantitative estimates of nutrient intakes to be used for planning and assessing diets for healthy people. Dietary Reference Intakes (DRIs) is the newest framework for an expanded approach developed by U.S. and Canadian scientists. This book discusses in detail the role of vitamin C, vitamin E, selenium, and the carotenoids in human physiology and health. For each nutrient the committee presents what is known about how it functions in the human body, which factors may affect how it works, and how the nutrient may be related to chronic disease. Dietary Reference Intakes provides reference intakes, such as Recommended Dietary Allowances (RDAs), for use in planning nutritionally adequate diets for different groups based on age and gender, along with a new reference intake, the Tolerable Upper Intake Level (UL), designed to assist an individual in knowing how much is "too much" of a nutrient.
The use of antioxidants in sports is controversial due to existing evidence that they both support and hinder athletic performance. Antioxidants in Sport Nutrition covers antioxidant use in the athlete ́s basic nutrition and discusses the controversies surrounding the usefulness of antioxidant supplementation. The book also stresses how antioxidants may affect immunity, health, and exercise performance. The book contains scientifically based chapters explaining the basic mechanisms of exercise-induced oxidative damage. Also covered are methodological approaches to assess the effectiveness of antioxidant treatment. Biomarkers are discussed as a method to estimate the bioefficacy of dietary/supplemental antioxidants in sports. This book is useful for sport nutrition scientists, physicians, exercise physiologists, product developers, sport practitioners, coaches, top athletes, and recreational athletes. In it, they will find objective information and practical guidance.
Methodology and applications of redox proteomics The relatively new and rapidly changing field of redox proteomics has the potential to revolutionize how we diagnose disease, assess risks, determine prognoses, and target therapeutic strategies for people with inflammatory and aging-associated diseases. This collection brings together, in one comprehensive volume, a broad array of information and insights into normal and altered physiology, molecular mechanisms of disease states, and new applications of the rapidly evolving techniques of proteomics. Written by some of the finest investigators in this area, Redox Proteomics: From Protein Modifications to Cellular Dysfunction and Diseases examines the key topics of redox proteomics and redox control of cellular function, including: * The role of oxidized proteins in various disorders * Pioneering studies on the development of redox proteomics * Analytical methodologies for identification and structural characterization of proteins affected by oxidative/nitrosative modifications * The response and regulation of protein oxidation in different cell types * The pathological implications of protein oxidation for conditions, including asthma, cardiovascular disease, diabetes, preeclampsia, and Alzheimer's disease Distinguished by its in-depth discussions, balanced methodological approach, and emphasis on medical applications and diagnosis development, Redox Proteomics is a rich resource for all professionals with an interest in proteomics, cellular physiology and its alterations in disease states, and related fields.
Coronary heart disease (CHD) is the leading cause of death worldwide. Cardioprotection refers to the prevention of CHD and the clinical improvement in patients suffering from cardiovascular problems.
Our understanding of the quantitative aspects of free radical chemistry and the involvement of radicals in such areas as biology, medicine, the environment, etc., has developed spectacularly over recent years, yet the various topics are commonly discussed separately, in specific meetings and specialised publications. Free Radicals in Biology and Environment draws together two important areas of free radical chemistry, using as a bridge the fundamental physical chemistry of free radicals (spectroscopic detection of free radicals, evaluation of absolute rate constants, elucidation of mechanisms of free radical reactions and catalysis, photochemical and radiation processes, etc.). The most relevant topics covered are the EPR detection of radicals in biochemical systems and in pollutant formation and degradation, oxidation processes in biology and in the troposphere, radiation and induced damage, and atmospheric pollutants arising from incomplete combustion. Also covered are the chemistry and biochemistry of nitric oxide and peroxynitrite, the chemistry and biochemistry of DNA radicals, the role of radicals in myeloperoxidase, lignineperoxidase, radicals and cardiovascular injury, radiation and the fragmentation of cells and tissues.