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Oxidation and Antioxidants in Organic Chemistry and Biochemistry. By Evgeny T. Denisov and Igor B. Afanas'ev

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Angewandte
Books
Chemie
Oxidation and Antioxidants in
Organic Chemistry and
Biochemistry
By Evgeny T. Denisov and Igor B.
Afanas’ev. CRC
Press, Andover
2005. 1024 pp.,
hardcover
$ 199.95.—ISBN
0-8247-5356-9
This book (1024 pages!) is a sort of
encyclopedia on the oxidation of
organic and biological compounds by
molecular oxygen in the liquid phase.
The volume is divided into three parts.
The first two have been written by
Evgeny T. Denisov, an eminent scientist
of the Russian Academy of Sciences,
whose expertise on the kinetics of freeradical liquid-phase reactions is almost
unequaled, and the third one is written
by Igor B. Afanas+ev, one of the leading
experts on the reactivity of the superoxide ion and of other biologically
significant free radicals. Part I is dedicated to the chemistry and kinetics of
the oxidation of organic compounds by
O2, and Part II to the chemistry of
antioxidants and the mechanisms by
which they inhibit the autoxidation of
hydrocarbons and other derivatives.
Part III deals with oxidative processes
in biology, both physiological and pathological.
The treatise begins by describing the
earlier hypotheses about the mechanism
of hydrocarbon oxidation that were
proposed in the middle of the 19th
century, which led, after the discovery
of free radicals as active intermediates
Angew. Chem. Int. Ed. 2006, 45, 4715 – 4716
(1900), to the formulation of the radical
chain reaction theory of the oxidation of
organic compounds. All the elementary
steps of this reaction are examined in
detail, by considering both the thermodynamic and kinetic aspects, as well as
the possible competing reactions. The
whole of Chapter 3 is devoted to the
chemistry of radical initiators: thermal
initiators (peroxides and azo compounds), which decompose with dissociation of one bond or with simultaneous dissociation of two or more bonds
(concerted fragmentation), photoinitiators, radiolytic initiators, and addition of
chemically active gases (ozone, nitrogen
dioxide, halogens). Chapters 4 and 5
deal with the oxidation of hydrocarbons
at relatively high temperatures in the
absence of initiating additives, and the
co-oxidation of hydrocarbons with oxygenated species. A short section is also
dedicated to the catalysis of hydrocarbon oxidation by nitroxyl radicals.
Chapter 6 contains the discussion of
a very effective instrument for the
analysis of radical reactions, namely
the parabolic model or IPM (intersecting parabolas model). This was developed by Denisov in 1990, and allows one
to predict (starting from empirical
parameters) activation energies, rate
constants, and the geometry of the
transition state (a CD containing the
program accompanies the book). Several examples of applications to reactions occurring during hydrocarbon oxidation are reported, with a careful
evaluation of the factors that determine
the reactivity (exothermicity, triplet
repulsion, etc.), accompanied by many
tables of useful data.
In the following chapters (7–9), the
oxidation of specific classes of compounds, such as alcohols and ethers,
aldehydes and ketones, amines, amides
and esters, is examined by considering,
for each class, peculiarities in the mechanism of reaction (polar factors, solvent
effects, etc.). Chapter 10 deals with the
technologically important subject of the
homogeneous catalysis of hydrocarbon
oxidation by molecular oxygen, catalyzed by transition-metal ions, acids, and
bases. Two short chapters (11 and 12)
deal briefly with oxidation in microheterogeneous systems and with sulfoxidation of hydrocarbons. Part I ends with
Chapter 13, which discusses the oxida-
tion of polymers, a very important
process leading to the degradation of
polymeric materials.
Part II, devoted to the chemistry of
antioxidants, begins in Chapter 14 by
describing the first applications of antioxidants and explaining their classification. The theory of the inhibition of
autoxidation is then outlined, and the
various mechanisms of inhibition are
described. Chapter 15 deals with chainbreaking antioxidants (phenols and aromatic amines), and the structural and
environmental factors that determine
their reactivity are analyzed. Chapter 16
discusses the cyclic chain termination
mechanism for inhibiting the oxidation
of alcohols and amines, where the cyclic
regeneration of the inhibitor may give
rise to stoichiometric factors as large as
100 or more. Chapter 17 describes
hydroperoxide-decomposing
antioxidants, with an emphasis on organophosphorus derivatives and sulfur-containing
compounds. Synergism of antioxidant
action is the subject of Chapter 18;
mixtures consisting of two chain-breaking antioxidants (CBAs), of a CBA and
a peroxide decomposer, and of two
CBAs, of which one is a peroxyl-radical
scavenger and the other is an alkylradical scavenger, are examined. However, the important case of a mixture of
a phenol and a polyphenol is completely
ignored. Chapters 19 and 20 provide
short discussions of oxidation in polymeric matrices and the heterogeneous
inhibition of oxidation.
Part III of the book deals with the
biological consequences of free-radicalmediated processes, such as lipid peroxidation, oxidative degradation of proteins and DNA, and cell damage. First,
Chapters 21 and 22 discuss the properties of biologically relevant radical species (superoxide ion, hydroxyl radical,
peroxyl radicals, nitric oxide, peroxynitrite, “free” iron), and describe how they
are generated enzymatically. The production of free radicals by mitochondria
and microsomes, and the mechanistic
implications of such processes, are discussed in Chapters 23 and 24, respectively. The following chapters (25 and
26) deal with the most intensively studied oxidative processes in biological
systems: lipid peroxidation, both nonenzymatic and enzymatic. Since most of
the studies on lipid peroxidation have
% 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4715
Books
been carried out in vitro, the question of
the transferability of the results to in
vivo systems is discussed. Attention is
also paid to the oxidation of low-density
lipoproteins (LDL), because of the dual
role that a-tocopherol has in this case,
namely, antioxidant and prooxidant.
The oxidation of proteins is further
developed in Chapter 27, while Chapter
28 is dedicated to the mechanism of
free-radical-induced damage and repair
of DNA.
The nature and properties of antioxidants of biological importance are
described in Chapter 29. Radical scavengers (phenolic compounds, ascorbic
acid, dihydrolipoic acid, glutathione,
ubihydroquinones, uric acid, etc.) and
chelators of transition-metal ions are
considered, while antioxidant enzymes
(SOD, catalase, etc.) are treated in
Chapter 30. The two final chapters (31
and 32) discuss the possible role of free
4716
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radicals in many pathologies (cardiovascular disorders, cancer, diabetes, inflammation, arthritis, etc.), and the experimental methods for detecting reactive
oxygen and nitrogen species (superoxide ion, hydroxyl radical, nitric oxide,
peroxynitrite).
This book presents a comprehensive
panorama of the chemistry of oxidation
of organic compounds by atmospheric
oxygen, and of the properties of antioxidants, both in chemistry and in biology. The kinetics and thermodynamics
of the various processes are discussed in
great detail, and a large compilation of
physicochemical data that are needed to
predict the relative importance of the
possible reaction paths is presented in
the numerous tables. The inclusion of a
CD containing a program by which
enthalpies of reaction, activation energies, and rate constants can be calculated makes this task even easier.
% 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
The text is generally up-to-date. It is
only in a few topics that some recent
advances have been overlooked (e.g.,
synergism between antioxidants, pyridinols and pyrimidinol antioxidants,
hydrogen-bonding effects). The literature coverage is exhaustive, and contains many citations from Russian scientific journals that are not usually
easily accessible in western countries.
The number of typing errors, wrong
formulas, and incorrect citations is tolerable. In conclusion, the book is recommend to every chemist and biochemist working in the field of oxidation and
antioxidants.
Gianfranco Pedulli
Dipt. di Chimica Organica
Universit5 di Bologna (Italy)
DOI: 10.1002/anie.200585361
Angew. Chem. Int. Ed. 2006, 45, 4715 – 4716
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