Principles, Basic Roles and Applications, SL Neidleman, J Geigert

Tags: future directions, chemical diversity, chemical description, J. Geigert Ellis Horwood, FEBS LETTERS, chapter outlines, Biohalogenation Principles, Chichester, Applications, marine animals, thyroid peroxidase, reaction mechanisms, enzymes, molecular targets, industrial chemicals, medical significance, monograph, chemical pathways, reductive dehalogenation, haloperoxidase, reversibility, oxidation-reduction, precise knowledge, substrate range, industrial aspects
Content: Volume 208, number 1
November 1986
tional research accurately enough. Most, however,
are progress reports of specific research rather
than state-of-the-art reviews although sections by
M.E. Farago (metal ions and Plants), R.J.
Shamberger (Selenium Metabolism in Man and
Animals) and R.J.P. Williams (The Inorganic
Chemistry of Biominerals) are among the excep-
tions. The main emphasis is in the structural and
mechanistic studies of metallo-proteins
bioinorganic complexes and the examination of
models of metal-ion containing binding sites.
The book should certainly be carefully scruti-
nized by all those using the current basic spec-
troscopic techniques whether Mossbauer, EPR,
NMR or EXAFS, and notably by those interested
in the possibility of optical detection of
paramagnetic resonance by magnetic circular
dichroism (paper by Thomson, Barrett, Peterson
and Greenwood). Iron, iron-sulphur and copper
environments receive most attention but there are also a number of studies of nickel-containing proteins. There are only 3 reports on MO and a similar number on nucleic acid-metal interactions, the latter including a disappointingly brief paper by the Eichhorn group on their influence on genetic information transfer. While presented as an interdisciplinary survey the conference reports will be of much greater value to the chemist and less relevant to those mainly interested in environmental or clinical applications, despite the presence of an examination by Cross, Read, Smith and Williams of `Plutonium Speciation from Disposal Vault to Man', a survey by Kolchuk on `Clinical Disorders of Zinc Metabolism' and a good review `Gold Drugs' by Berners-Price and Sadler. J. Mason
Principles, Basic Roles and Applications by S.L. Neidleman and J. Geigert
Ellis Horwood; Chichester, 1986 203 pages. f25.00
This monograph on biohalogenation is organised
into a brief introduction (chapter l), 7 main
chapters, a short concluding chapter on future
for biological
bibliography and an index.
Chapter 2 gives a chemical description of halo-
metabolites and their sources. One immediately
has an impression of the scope of this area by the
chemical diversity of halometabolites, and by
deduction, the range of enzymes that elaborate
these compounds. The sources of these metabolites
are then amply documented by extensive lists and
structures and detailed consideration is given to the
role of bacteria, fungi, algae, higher plants and
in the production
Chapter 3 is concerned with an excellent descrip-
tion of the halogenating enzymes (haloperox-
idases) and sub-classifies them as iodo-, bromo-
and chloroperoxidases, and describes the reaction
types which each of the enzymes catalyse. A useful
section in this chapter outlines step-by-step pro-
tocols for the isolation and purification of
eosinophil peroxidase, bac-
toperoxidase, thyroid peroxidase and a listing of
commercially available enzyme preparations. This
latter section is coupled with detailed methodology
on several assay systems currently used to detect
and monitor enzyme activity. The chapter con-
cludes with a compendium of in vitro haloperox-
idase reactions, focussing on the reasons why these
Volume 208, number 1
November 1986
enzymes do not exhibit the classical enzymatic pro-
perties of reversibility, high product selectivity and
narrow substrate range.
Chapter 4 consists of a more detailed discussion
of the enzymology of the haloperoxidases by
highlighting current knowledge, but also em-
phasises the lack of precise knowledge of active site
geometry, haem ligand coordination and the con-
troversial nature of the halogenating intermediate.
Consideration is given to the basic haem chemistry
of the haloperoxidase prosthetic group and the role
of this protoporphyrin in catalysing the heterolytic
cleavage of Hz02 and in the regulation of the
potential. The authors also
consider the role of the glycoprotein component in
determining enzyme reactivity and stabilisation of
the reactive halogenating intermediate.
This chapter continues with the basic protein
biochemistry of the haloperoxidases including
documentation of molecular mass, amino acid
contents and sequence, carbohydrate content,
subunits and known isoenzymes. This section is
augmented with a review of the optimal pH,
substrate binding sites, reaction rate constants and
concludes with reaction mechanisms. For the reac-
tion mechanisms, emphasis is placed on the 5
oxidation-reduction states that are known for these
enzymes, concluding with a discussion of the possi-
ble halogenating intermediate.
Chapter 5 is addressed to the role of enzymes
and halometabolites in both (1) key elements in the
biochemical synthesis of metabolites and (2) as a
means of elaborating compounds with enhanced
and desirable biological activities. Chapter 6 con-
siders the role of halogenating enzymes in mam-
malian defence mechanisms as viewed from
cellular, biochemical and molecular targets and
concludes with a brief discussion of the medical
significance of haloperoxidase activity.
Chapter 7 outlines some of the commercial ap-
plications of the haloperoxidases with emphasis on
process technology and biotechnology, particular-
ly on how to overcome suicide inactivation of the
enzymes and therefore to prolong their active life
as a biocatalyst. It must be emphasised that these
enzymes have not found widespread use in in-
dustry at present, and the authors outline potential
uses in the areas of (1) haloperoxidase-driven
catalysis in the production of industrial chemicals,
(2) medical application in bacterial chemotherapy
(release of hypohalous acid), (3) in pollution con-
trol as a biocide to overcome slime growth, (4)
removing industrial contaminants
and (5) as
analytical diagnostics.
Chapter 8 is concerned with the process of
removing halogens from organic compounds
with an emphasis on en-
vironmental pollutants including halogenated
solvents, gasoline additives, fumigants and
pesticides. This chapter highlights the ability of
microorganisms to dehalogenate these chemicals,
albeit slowly, as reflected in the long (sometimes
years) biological persistence in the ecosphere. The
majority of the chapter deals with a detailed
description of the chemistry of enzymatic degrada-
tion of halo-compounds
including reductive
dehalogenation, dehydrohalogenation,
and oxidative
displacement. This chapter concludes with the ap-
plication of Genetic Engineering techniques in
developing plasmids encoding the degrading
I was fascinated by this book in that it covered
all of the aspects one would expect (and hope) to
find in a monograph of this nature. The extent of
coverage is impressive and gives detailed discussion
of the chemical, biochemical and industrial aspects
of haloperoxidases. I particularly like the inclusion
of the chapter on dehalogenation as it gave a well-
rounded shape to the book.
The authors have developed a crisp, clear style
of writing that gets right to the heart of the matter
without the need for pages of extraneous material.
The monograph is amply illustrated, particularly
the chemical pathways. Because this is an authored
monograph (as opposed to an edited, multi-author
work), there is continuity of style, with little
overlap in the subject matter between chapters.
There is an extensive bibliography at the end of the
book containing 412 references, many of which
refer to recent work up to 1985. As the authors
point out, the last review of this subject appeared
in 1976 and this monograph is therefore timely in
its publication. My only minor criticism is that the
index is rather sparse. However, this should not
detract from the fact that Biohalogenation is well
worth purchasing and will serve both as a primer
to this ubiquitous area of science and as a superb
overview of the subject.
G. Gordon Gibson

SL Neidleman, J Geigert

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