Lipids and Lipid Polymers in Higher Plants Edited by

M. Tevini and H. K. Lichtenthaler

Contributors

B. H. Davies A. H. B. Deas W Eichenberger 1. J. Goad T. W Goodwin E. Heinz F. W Hemming P. J. Holloway P. E. Kolattukudy H. K. Lichtenthaler C. Liljenberg H. K. Mangold P. Mazliak D. Siefermann-Harms P. Sitte F. Spener P. K. Stumpf M. Tevini

With 136 Figures

Springer-Verlag Berlin Heidelberg New York 1977

Prof. Dr. MANFRED TEVINI

Prof. Dr. HARTMUT K. LICHTENTHALER

Botanisches Institut II Universitat Karlsruhe KaiserstraJ3e 12, 7500 Karlsruhe Federal Republic of Germany

ISBN-13: 978-3-642-66634-6

DOl: 10.1007/978-3-642-66632-2

e-ISBN-13: 978-3-642-66632-2

Library of Congress Cataloging in Publication Data. Symposium on Lipids and Lipid Polymers in Higher Plants. University of Karlsruhe. 1976. Lipids and lipid polymers in higher plants. I. Plant lipids - Congresses. 2. Polymers and polymerization - Congresses. I. Tevini, M .• 1939-. II. Lichtenthaler, H.K., 1934-. III. Davis, Brian H. IV. Title, V. Title: Lipid polymers in higher plants. QK898.L56S93.1976.581.1 '9247. 77-5370.

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© by Springer-Verlag Berlin Heidelberg 1977. Softcover reprint of the hardcover 1 st edition 1977

The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use.

2l3l/3130-543210

Preface

This book contains a number of papers dealing with the main topics of a Symposium on "Lipids and Lipid Polymers in Higher Plants", held in July 1976 at the Botanical Institute of the University of Karlsruhe. The symposium was organized by Professors E. Heinz, H.K. Lichtenthaler, H.K. Mangold, and M. Tevini. The sponsorship by the Deutsche Forschungsgemeinschaft and the Erwin-Riesch-Stiftung is gratefully acknowledged.

The intention of the Symposium was to bring together in one place scientists working in very different fields of plant lipids, such as fatty acids, glycolipids, phospholipids, prenyllipids, sterols, and lipid polymers. The emphasis was placed on biosynthesis, distribution, function, and physiology of the various higher plant lipids and their role in biomembranes and epidermal cell walls.

By combining the major contributions in this book, we hope to give all plant scientists access to the recent developments in biochemistry and physiology of plant lipid metabolism. The editors are very grateful to the contributors, who have taken great care to present up-to-date reviews.

Karlsruhe, May 1977 M. TEVINI

H.K. LICHTENTHALER

Contents

Section 1. Function, Organization and Lipid Composition of Biomembranes

Chapter 1. Functional Organization of Biomembranes P. SITTE (With 15 Figures)

A. Introduction. . . . . B. Membrane Functions .

I. Membrane Diversity II. Membranes as Barriers

III. Lipids and Permeability . IV. Specific Transport . . . V. Membrane Flow and Membrane Families

VI. General Principles of Cellular Compartmentation C. Membrane Biogenesis. . . . . . . . . . . . . D. Intracellular Membranes and Their Compartments . . E. The Role of Lipid Self-Assembly. . . . . . . . . . F. The Molecular Architecture of Elementary Membranes G. Conventional Electron Microscopy of Biomembranes References . . . . . . . . . . . . . . . . . . . . .

Chapter 2. The Prenyllipids of the Membranes of Higher Plants T.W. GOODWIN (With 9 Figures)

A. Introduction. . . . . . . . B. Localization. . . . . . . .

I. Intracellular Distribution. II. Intraorganelle Distribution

C. Localization of Biosynthesis . I. General Pattern of Synthesis

II. Synthesis in the Chloroplast 1. Formation of Acetyl-CoA 2. Formation of Mevalonic Acid 3. Conversion of MV A into Carotenoids . 4. Formation of Mixed Terpenoids

a) General. . . b) Tocopherols. . . . . . . .

1 2 2 4 5 8 9

10 12 13 15 18 20 22

29 31 31 32 36 36 37 38 40 41 41 41 42

VIII Contents

D. Regulation of Prenyllipid Synthesis . I. Terpenes

References . . . . . . . . . . . . .

Chapter 3. Glyco- and Phospholipids of Biomembranes in Higher Plants P. MAZLIAK (With 12 Figures)

44 44 45

A. Introduction ............. 48 B. Lipid Composition of Plant Biomembranes 48

I. Plasmalemma 48 II. Mitochondria . . . . . . . . 50

III. Chloroplasts . . . . . . . . 52 IV. Glyoxysomes and Peroxisomes 53 V. Microsomes. . . . . . . . . 53

VI. Nuclei . . . . . . . . . . . 55 VII. Comparisons Between Different Membranes. 56

C. Biosynthesis of Membrane Lipids. . . . . . . . 59 D. Lipid Exchanges Between Cell Organelles. . . . 62 E. Role of the Lipid Environment in the Activities of Membrane-Bound

Enzymes . 67 F. Conclusions 70 References . . 71

Section 2. Physiology and Biochemistry of Fatty Acids and Glycerides

Chapter 4. Lipid Biosynthesis in Developing Seeds P.K. STUMPF (With 2 Figures)

A. Introduction. . . . . . . B. General Considerations . . . . . . C. The Role of the Leaf Compartment . D. The Developing Soybean Seed. . .

I. General Considerations . . . . II. Comparison of Capacities of Developing Tissues to Incorporate

14C-Acetate into Long-Chain Fatty Acids . . . . . . . . . III. Localization of Enzymes Involved in Fatty Acid Biosynthesis

E. Conclusions References . . . . . . . . . . . . . . . . . . . . . . . . . .

Chapter 5. The Cyclopentenyl Fatty Acids H.K. MANGOLD and F. SPENER (With 10 Figures)

A. Introduction. . . . . . . . . . . . . B. Chemistry of Cyc10pentenyl Fatty Acids

75 76 77 77 77

79 82 82 83

85 86

Contents

I. Isolation, Characterization, Synthesis II. Fatty Acids in Flacourtiaceae .

1. Methods of Analysis . . . . . . 2. Preparative Methods . . . . . . 3. Compositional and Structural Studies 4. New Cyclopentenyl Fatty Acids . .

C. Biochemistry of Cyclopentenyl Fatty Acids I. Biosynthesis . . . . . . . . . . .

1. Aleprolic Acid as Precursor . . . 2. Cyclopentenylglycine as Precursor.

II. Metabolism. D. Conclusions References . . . .

Chapter 6. Enzymatic Reactions in Galactolipid Biosynthesis E. HEINZ (With 3 Figures)

A. Introduction. . . . . . . . . . . B. Acyl-CoA and Acyl-ACP Thioesters C. sn-Glycerol 3-Phosphate. . . . . D. UDP-Galactose ....... . E. Acylation of Glycerol Phosphate . F. Diglycerides . . . . . . . . . . G. Galactosyltransferases. . . . . . H. Fatty Acid Specificities in Galactolipids . I. Radioactive Labeling of Galactolipids in vivo References . . . . . . . . . . . . . . . . .

Chapter 7. Light, Function and Lipids During Plastid Development M. TEVINI (With 8 Figures)

A. .Introduction. . . . . . . . . . . . . . . B. Light and Plastid Structure During Greening.

I. General Remarks. . . II. The Prolamellar Body .

III. Thylakoid Formation. IV. Light Regulation.

C. Light and Lipids . . . . . I. General Remarks. . .

II. Lipids in Plastids and Plastid Fractions . III. Formation of Glycerolipids During Development . IV. Formation of Fatty Acid . . . . . . . . . V. Light Regulation of Glycerolipid Metabolism

D. Light and Function. . I. General Remarks. . . . . . . . . . . . .

IX

86 89 89 89 90 93 94 94 95 97 97 98 99

102 102 103 104 105 106 107 109 112 115

121 122 122 122 123 126 126 126 127 129 132 134 135 135

x

II. Chlorophylls. . . . . III. Photosynthetic Activity IV. Light Regulation .

E. Final Remarks . References . . . . . . .

Section 3. Physiology and Biochemistry of Plant Steroids

Chapter 8. The Biosynthesis of Plant Sterols L.J. GOAD (With 12 Figures)

A. Introduction. . . . . . B. Structure and Distribution. . . . . C. Squalene Formation and Cyclisation D. Sterol Side-Chain Formation. . . . E. Ring Structure Modification in Phytosterol Formation F. Conclusions References . . . . . . . . . . . . . . . . . . . . .

Chapter 9. Steryl Glycosides and Acylated Steryl Glycosides W. EICHENBERGER (With 4 Figures)

A. Introduction. . . . . . . B. Structure and Distribution. C. Biosynthesis . . .

I. Glycosylation . . . . II. Acylation . . . . . .

III. Intracellular Localization D. Metabolism . . . E. Possible Functions F. Conclusions References . . . . .

Section 4. Physiology and Biochemistry of Prenyllipids

Chapter 10. The Biosynthesis and Biological Significance of Prenols and Their Phosphorylated Derivatives F.W. HEMMING (With 10 Figures)

A. Biosynthesis . I. General.

Contents

136 137 138 139 140

146 146 150 155 161 164 164

169 169 171 172 172 176 177 177 178 179

183 183

Contents XI

II. a. Formation of Isopentenyl Pyrophosphate from Acetyl-CoA 183 II. b. Subcellular Distribution of the Pathway from Acetyl-CoA

to Isopentenyl Pyrophosphate . . . . 184 III. a. Monoterpenes-Formation . . . . 185 III. b. Different Pools of Soluble Precursors . 186 IV. Sesquiterpenes-Formation 186 V. Diterpenes-Formation . . . . . . . . 187

VI. Polyterpenes-Formation . . . . . . . 188 VII. Stereochemistry of the Substituted Double Bond in Polyprenols 189

1. General . . . . . . . . . . . . . . . . . . .. 189 2. Stereochemistry of the IX-Isoprene Residue of Mono- and

Sesquiterpenes . . . . . . . . 189 VIII. Phosphorylation of Prenols . . . . 191

IX. Control of the Rate of Biosynthesis . 191 1. General. . . . . . . . . . . . 191 2. Compartmentation of Early Steps 192 3. Key Enzymes? 192 4. Hormonal . . . . . . . . . . 192 5. Light Effects . . . . . . . . . 192 6. Compartmentation of Polyisoprenoid Biosynthesis 193

B. Function of Isoprenoid Alcohols and Their Phosphates 193 I. A Precursor Role. . . . 193

II. A Role in Glycosylation. 194 References . . . . . . . . . . 195

Chapter 11. Carotenoids in Higher Plants B.H. DAVIES (With 9 Figures)

A. Nomenclature . . . . . 199 B. Distribution . . . . . . 200

I. Photosynthetic Tissues 200 II. Fruits. . . . 200

III. Flowers. . . 201 IV. Other Tissues 201

C. Formation. . . . 202 I. Early Steps . 203

II. Formation of 15-Cis-Phytoene . 203 III. Carotene Desaturation . 205 IV. Carotene Cyclization . . . . . 207 V. Xanthophyll Formation. . . . 209

VI. Factors Affecting Carotenoid Formation. 211 D. Function . . . . . . . . . . . . . . . . 211 E. Appendix . . . . . . . . . . . . . . . . 213

Trivial and Semi-systematic Names and Structures of Some Higher Plant Carotenoids 213

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213

XII

Chapter 12. The Xanthophyll Cycle in Higher Plants D. SIEFERMANN-HARMs (With 11 Figures)

A. Introduction. . . . . . . . . . . . . . . . . B. General Characteristics of the Xanthophyll Cycle. C. The De-epoxidation Pathway . . . .

I. The Cosubstrates of De-epoxidation II. The De-epoxidase . . . . . . .

D. The Epoxidation Pathway. . . . . I. The Cosubstrates of Epoxidation

II. The Epoxidase . . . . . . . . E. A Transmembrane Model of the Xanthophyll Cycle F. The Control of the Xanthophyll Cycle by Light . . G. Hypothesis on the Function of the Xanthophyll Cycle References . . . . . . . . . .. . . . . . . . . . . .

Chapter 13. Regulation of Prenylquinone Synthesis in Higher Plants H.K. LrcHTENTHALER (With 15 Figures)

Contents

218 218 219 219 220 221 221 223 224 224 227 229

A. Introduction. . . . . . . . . . 231 B. Function of Prenylquinones . . . ·235 C. Biosynthesis of Prenylquinones . 236 D. Site of Synthesis of Prenylquinones and Chromanols in the Plant Cell 237 E. Regulation of Light-induced Prenylquinone Synthesis by

Phytochrome Pfr . . . . . . . . . . . . . . . . . . . . . . . . 240 F. Regulation of Lipoquinone Synthesis by Blue and Red Light . . .. 243 G. Influence of Phytohormones on Lipoquinone Metabolism and

Photosynthetic Activity . . . . . . . . . . . . . . . . . . . . . 245 H. Formation of Excess Prenylquinones . . . . . . . . . . . . . . . 247 I. Stimulation of Prenylquinone Synthesis by Supplying Additional

Aromatic Compounds. . . . . . . . . . . . . . 249 J. Turnover of Prenylquinones . . . . . . . . . . . . 250 K. Regulation of Prenylquinone Synthesis by Herbicides . 251 1. Formation of Prenylquinones in Plant Tissue Cultures. 253 M. Conclusions 255 References . . . . . . . . . . . . . . . . . . . . . 256

Chapter 14. Chlorophyll Formation: The Phytylation Step C. LrLJENBERG (With 5 Figures)

A. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . 259 B. Biosynthetic Pathways for the Different Protochlorophyll Forms to

Chlorophyll a . . . . . . . . . . . . . . . . . . . . . . . . . 259

Contents XIII

C. The Occurrence of the Two Forms of Protochlorophyll Pigments in Dark-grown Plants and Their Photoreduction . . . . . . . " 262

D. The Esterification of Chlorophyll ide a . . . . . . . . . . .. 263 E. Light-induced Changes in the Rate of the Esterification Reaction 265 F. Biosynthesis of Esterifying Prenols . . . . . . . . . . . . .. 266 G. The Pools of Free Phytol and Phytol Bound as Acyl Esters During

Greening 266 References. . . . . . . . . . . . . . . . . . . . . . . . . . . . 268

Section 5. Lipid Polymers in Higher Plants

Chapter 15. Biosynthesis and Degradation of Lipid Polymers P.E. KOLATTUKUDY (With 10 Figures)

A. Introduction. . . . . . . . . . . . . . . . . 271 B. Biosynthesis of Cutin . . . . . . . . . . . . . 271

I. Biosynthesis of the C 16 Family of Cutin Acids 272 1. In vivo Studies . . . . . . . . . . . . 272 2. Enzymatic Synthesis of the C 16 Family of Cutin Acids 273

a) (V-Hydroxylation . . . . . . . . . . 273 b) In-Chain Hydroxylation . . . . . . . . 274

II. Biosynthesis of the C 1S Family of Cutin Acids. 276 1. In vivo Experiments . . . . . . . . . . . 276 2. Enzymatic Synthesis of the C 1S Family of Cutin Acids 277

a) Epoxidation . . . . . . . . 277 b) Epoxide Hydration . . . . . 278

III. Synthesis of Cutin from Monomers . 279 C. Biosynthesis of Suberin . . . . . . . . 281

I. Experiments with Tissue Slices. . . 281 II. Experiments with Cell-Free Preparations. 283

D. Degradation of Lipid Polymers. . . 285 I. Degradation by Plants . . . . . . . . 285

II. Degradation by Microorganisms . . . . 285 I. Isolation and Characterization of Cutinases 285 2. Characterization of Cutinases as Glycoproteins 287

III. Degradation by Animals 288 E. Conclusions 289 References . . . . . . . . . . 290

Chapter 16. The Intermolecular Structure of Some Plant Cutins A.H.B. DEAS and PJ. HOLLOWAY (With 1 Figure) 293

References . . . . . 298

Subject Index. . . . . . . . . . . . . . . . . . . . . . . . . . . 301

List of Contributors

DAVIES, B.H., Department of Biochemistry, University College of Wales, Penglais Aberystwyth, Wales, Great Britain

DEAS, A.H.B., Long Ashton Research Station, University of Bristol, Bristol, Great Britain

EICHENBERGER, W., Institut fUr Biochemie der Universitat Bern, Bern, Switzer­land

GOAD, L.J., Department of Biochemistry, University of Liverpool, Liverpool, Great Britain

GOODWIN, T.W., Department of Biochemistry, University of Liverpool, Liverpool, Great Britain

HEINZ, E., Botanisches Institut der Universitat Kaln, Kaln, Federal Republic of Germany

HEMMING, F.W., Department of Biochemistry, University Hospital and Medical School, Nottingham, Great Britain

HOLLOWAY, P.J., Long Ashton Research Station, University of Bristol, Bristol, Great Britain

KOLATTUKUDY, P.E., Department of Agricultural Chemistry, Washington State University, Pullman, Washington, U.S.A.

LICHTENTHALER, H.K., Botanisches Institut II der Universitat Karlsruhe, Karls­ruhe, Federal Republic of Germany

LILJENBERG, C, University of Gateborg, Botanical Institute, Department of Plant Physiology, Gateborg, Sweden

MANGOLD, H.K., Institut fUr Biochemie und Technologie, H.P. Kaufmann­Institut, Munster, Federal Republic of Germany

MAZLIAK, P., Universite de Paris, Laboratoire de Physiologie cellulaire, Paris, France

SIEFERMANN-HARMS, D., Biologisches Institut der Universitat Tubingen, Tubin­gen, Federal Republic of Germany

SITTE, P., Institut fUr Biologie II, Lehrstuhl fUr Zellbiologie, Universitat Freiburg, Freiburg, Federal Republic of Germany

SPENER, F., Institut fUr Biochemie der Universitat Munster, Munster, Federal Republic of Germany

STUMPF, P.K., Department of Biochemistry and Biophysics, University of California, Davis, U.S.A.

TEVINI, M., Botanisches Institut II der Universitat Karlsruhe, Karlsruhe, Federal Republic of Germany