Current topics in bioenergetics Vol. 4

421 Pages·1971·23.525 MB·English

by  C P Lee, D Rao Sanadi

Advisory Board
B. CHANCE
J. GERGELY
R. D. KEYNES
L. P. VERNON
Contributors to This Volume
HERRICK BALTSCHEFFSKY
MARGARETA BALTSCHEFFSKY
S. ROY CAPLAN
RICHARD A. DILLEY
CYRIL L. MOORE
G. K. RADDA
J. MURDOCH RITCHIE
J. C. SKOU
V. P. SKULACHEV
ANDERS THORE
Advisory Board
B. CHANCE
J. GERGELY
R. D. KEYNES
L. P. VERNON
Contributors to This Volume
HERRICK BALTSCHEFFSKY
MARGARETA BALTSCHEFFSKY
S. ROY CAPLAN
RICHARD A. DILLEY
CYRIL L. MOORE
G. K. RADDA
J. MURDOCH RITCHIE
J. C. SKOU
V. P. SKULACHEV
ANDERS THORE
Current Topics in Bioenergetics
Edited by D. RAO SANADI
Boston Biomedical Research Institute
Boston, Massachusetts
VOLUME 4
1971
ACADEMIC PRESS NEW YORK AND LONDON
COPYRIGHT © 1971, BY ACADEMIC PRESS, INC.
ALL RIGHTS RESERVED
NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORM,
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PRINTED IN THE UNITED STATES OF AMERICA
List of Contributors
Numbers in parentheses indicate the pages on which the authors' contributions begin.
HERRICK BALTSCHEFFSKY (273), Bioenergetics Group, Department of
Plant Physiology and Department of Biochemistry, University of
Stockholm, Stockholm, Sweden
MARGARETA BALTSCHEFFSKY (273), Bioenergetics Group, Depart
ment of Plant Physiology and Department of Biochemistry, Uni
versity of Stockholm, Stockholm, Sweden
S. ROY CAPLAN (1), Biophysical Laboratory, Harvard Medical School,
Boston, Massachusetts
RICHARD A. DILLEY (237), C. F. Kettering Research Laboratory,
Yellow Springs, Ohio
CYRIL L. MOORE (191), Albert Einstein College of Medicine, Bronx,
New York
G. K. RADDA (81), Department of Biochemistry, University of Oxford,
Oxford, England
J. MURDOCH RITCHIE (327), Department of Pharmacology, Yale Uni
versity School of Medicine, New Haven, Connecticut
J. C. SKOU (357), Institute of Physiology, University of Aarhus,
Aarhus, Denmark
V. P. SKULACHEV (127), Department of Bioenergetics, Laboratory of
Bioorganic Chemistry, Moscow State University, Moscow
ANDERS THORE (273), Research Institute of National Defense,
Sundbyberg, Sweden
IX
Preface
Bioenergetics has been an active area of research for the last two
decades and the literature has become enormous. Recent contro­
versies on mechanisms have led to development of new techniques
and outlook with a resulting increase in the publications. In spite of
this, progress in understanding the molecular basis for energy trans-
duction in membranous systems is still slow.
The articles on nonequilibrium thermodynamics and fluorescent
probes deal with relatively unexplored areas and should stimulate
further research. The article by Skulachev includes work that is not as
readily available outside the U.S.S.R. The two articles on ion trans­
port in mitochondria and chloroplasts are complementary and provide
an opportunity for comparing the two systems. Also related are the
articles on electrogenic ion pumping and monovalent-cation-de-
dendent ATPase; both are concerned with ion transport at the cell
level. Bacterial photosynthesis has been discussed for the first time
in this series.
D. RAO SANADI
May, 1971
XI
Contents of Previous Volumes
Volume I
Kinetics and Intermediates of the Oxygen Evolution Step in
Photosynthesis
Bessel Kok and George M. Cheniae
Fluorescence Yield in Photo synthetic Systems and Its Relation to
Electron Transport
Warren L. Butler
Uncoupling and Energy Transfer Inhibition in Photophosphorylation
Norman Good, Seikichi Izawa, and Geoffrey Hind
The Chemistry of Bioluminescence
/. W. Hastings
Structure and Function of the Contractile Protein Myosin
A. Stracher and P. Dreizen
Energized Calcium Transport and Relaxing Factors
Annemarie Weber
Ion Transport to Mitochondria
E. J. Harris, J. D. Judah, and K. Ahmed
AUTHOR INDEX —SUBJECT INDEX
Volume 2
Mechanism of Photoinduced Electron Transport in Isolated
Chloroplasts
Mordhay Avron
The Energized Movement of Ions and Water by Chloroplasts
Lester Packer and Antony R. Crofts
Energy-Linked Reactions of Plant Mitochondria
/. B. Hanson and T. K. Hodges
180 and Related Exchanges in Enzymic Formation and Utilization of
Nucleoside Triphosphates
P. D. Boyer
Xlll
xiv CONTENTS OF PREVIOUS VOLUMES
On the Role of Ubiquinone
A. Kröger and M. Klingenberg
Energy-Linked Reactions in Chemoautotrophic Organisms
Lutz A. Kiesow
Respiration and Adenosine Triphosphate Synthesis in Nuclei
Thomas E. Conover
The Oscillation of Insect Flight Muscle
R. T. Tregear
Contractile Mechanisms in Cilia and Flagella
Michael Holwill
Genesis of the Cochlear Endolymphatic Potential
Brian M. Johnstone
AUTHOR INDEX-SUBJECT INDEX
Volume 3
A Scrutiny of Mitchell's Chemiosmotic Hypothesis of Respiratory
Chain and Photosynthetic Phosphorylation
G. D. Greville
Electron Transfer and Energy Conservation
Robert J. P. Williams
Translocators in Bimolecular Lipid Membranes: Their Role in
Dissipative and Conservative Bioenergy Transductions
Paul Mueller and Donald O. Rudin
Energy Relationships and the Active Transport of Ions
Peter C. Caldwell
Energy Utilization and Oxidative Recovery Metabolism in Skeletal
Muscle
Frans F.Jöbsis
The Mechanism of the Visual Process
Sjoerd L. Routing
Energy Transduction in Algal Phototaxis
Gordon Tollin
AUTHOR INDEX-SUBJECT INDEX
Nonequilibrium Thermodynamics and
Its Application to Bioenergetics
S. ROY CAPLAN
Biophysical Laboratory,
Harvard Medical School,
Boston, Massachusetts
I. Introduction 2
II. Coupled Phenomena . . 3
A. Dissipation by Irreversible Processes 3
B. Relationships between "Flows" and "Forces":
The Phenomenological Equations 8
C. Chemical Reactions 10
D. Transport Phenomena 17
E. Coupling between Reactions and Flows 28
III. Energy Conversion —General Considerations 35
A. Degree of Coupling 35
B. Energy Expenditure without Performance of Work. . . 38
C. Effectiveness of Energy Utilization 39
D. The "High-Energy Bond" and Related Questions . .. 42
IV. Active Transport 45
A. Standard Approaches 45
B. The Composite Observable System 47
C. Experimental Characterization 49
D. Evaluation of the Affinity 51
E. The "Stoichiometric Ratio" 52
F. Energetics of Active Transport 53
G. Mode of Action of Substances That Influence Transport. 55
V. Oxidative Phosphorylation 56
A. Standard Approaches . 56
B. Nonequilibrium Thermodynamic Analysis 58
C. Chemical Hypothesis 59
D. Chemoiosmotic Hypothesis 60
E. Coupling and Stoichiometry 61
VI. Muscular Contraction 63
A. Standard Approaches 63
B. Nonequilibrium Thermodynamic Analysis 67
C. Regulation of Energy Conversion 68
D. Relationship of the Phenomenological Coefficients to
Molecular Parameters 73
VII. Conclusions 74
References 75
List of Symbols 77
1
2 S. ROY CAPLAN
I. Introduction
In recent years nonequilibrium thermodynamics, or the thermo­
dynamics of irreversible processes, has been increasingly invoked
as a tool for the macroscopic description of biological energetics (Prig-
ogine, 1961; Katchalsky and Curran, 1965). As Prigogine (1961) has
pointed out, classical thermodynamics is seriously limited for this
purpose. Its method is based on equilibrium states and the concept of
reversible processes (i.e., hypothetical ideal processes that occur
without disturbing equilibrium), whereas the phenomena studied in
biology are irreversible and take place away from equilibrium. To
treat such phenomena has required a major extension of the thermo-
dynamic method. The object in writing this chapter was not to review
these developments so much as to introduce them to biologists and
biochemists, especially those who might be totally unfamiliar with
the subject. Inevitably a rather personal view, not entirely free of
prejudice, has emerged. No attempt is made here to present the argu­
ments rigorously; on the other hand, an effort is made to acquaint the
reader with the modus operandi, the language, and the scope of the
new approach —especially those aspects of it that relate to problems
of energy conversion.
The power of thermodynamics, broadly speaking, lies in its ability
to predict correlations among observations in the absence of detailed
knowledge of the structure of the system: it establishes a framework
within which patterns of behavior can be organized and tested for
self-consistency. Nonequilibrium thermodynamics extends and com­
plements the classical method by the explicit introduction of time. It
enables one to formulate a description of real processes, rather than
idealizations that happen in well-defined equilibrium states, and the
correlations it provides are between kinetic parameters. As will be
seen, the most tractable processes are those that occur when the sys­
tem is in a "steady state." However, under stationary conditions the
state parameters of the system give no information about the processes
occurring; to study these processes it is necessary to look at their
effects on the surroundings, and indeed this is the essence of the ap­
proach. The resulting analysis immediately determines the number
and nature of the degrees of freedom involved. This indicates to the
experimenter how many (and what) constraints are required to define
a steady state of his system, in addition to predicting correlations be­
tween such states. Likewise the theoretician is provided with a
scaffolding around which models can be constructed conforming to
the proper thermodynamic restrictions.