Prenylation and methylation reaction in al biosynthesis is localized in the

envelope membranes of the chloroplasts, while PQ-9 biosynthesis takes place in

the envelope membranes and also in the thylakoid membranes. The sequence in a-T

biosynthesis in spinach is (see also Figure 1): Homogentisate + Phytyl-PP —> Me-6-PQH?—> 2,3-Me2PQH?—>γ J ->a T ; for the PQ-9 biosynthesis it is: Homogentisate

+ Solanesyf-PP4-> Me-6-SQH2—> PQH2

Mazliak, P.

Schultz, Gernot

Soll, Jürgen

English

Open Access LMU

BIOGENESIS AND FUNCTION OF PLANT LIPIDS Proceedings of the Symposium on Recent Advances in the Biogenesis and Function of Plant Lipids held in Paris, June 4-7, 1980. Editors P. Mazliak P. Benveniste C. Costes and R. Douce 1980 ELSEVIER/NORTH-HOLLAND BIOMEDICAL PRESS A M S T E R D A M · NEW YORK · OXFORD © 1980 Elsevier/North-Hol land B iomedica l Press A l l r ights reserved. No part o f this publ icat ion may be reproduced, stored in a retrieval system, or transmitted, in any fo rm or by any means, electronic, mechanical , photocopying, recording or otherwise, w i thout the pr ior permission o f the copyr ight owner. I S B N for this vo lume: 0-444-80273-8 I S B N for the series: 0-444-80081 -6 Published by: Elsevier/North-Hol land Biomedical Press 335 Jan van Galenstraat, P.O. Box 211 Amsterdam, The Netherlands Sole distributors for the USA and Canada: Elsevier Nor th Ho l land Inc. 52 Vanderbi l t Avenue N e w Y o r k , N .Y . 10017 L i b r a r y of Congress Cataloging in Publication Data Symposium on Recent Advances in the Biogenesis and Function of Plant Lipids, Paris, 1980. Biogenesis and function of plant l i p i d s . (Developments in plant "biology ; v. 6) Bibliography: p. Includes index, 1 . Plant lipids—Congresses. I . Mazliak, P. I I . T i t l e . I I I . Series. QK898.L56S96 1980 5 8 l . l 9 f 2 U 7 80-20135 ISBN O-W-80273-8 Printed in The Netherlands i x CONTENTS Dedication V Preface V I I LIPID METABOLISM IN CHLOROPLASTS AND LEAVES Oleic acid, the central substrate P.K. Stumpf, D.N. Kuhn, D.J. Murphy, M.R. Pollard, T. McKeon and J. MacCarthy 3 The role of chloroplasts in leaf l i p i d metabolism and poly-unsaturated f a t t y acid synthesis G. Roughan and R. Slack 11 Use of mesophyll protoplasts to study l i p i d metabolism i n c e l l organelles R. Haas and E. Heinz 19 The s t r u c t u r a l organization of chloroplast l i p i d s in vivo and in model systems: Some aspects C. Liljenberg 29 Lysogalactolipids as intermediates i n g a l a c t o l i p i d synthesis in chloroplasts K.-P. Heise and A. Sauer 39 Galactolipid formation i n chloroplast envelopes. A discussion on differences between experiments in vivo and in vitro J.F.G.M. Wintermans, A. van Besouw, G. Bögemann and J, Aerts 49 Studies on the biosynthesis of sulfoquinovosyl diacylglycerol i n higher plants J.B. Mudd, R. Dezacks and J. Smith 57 Long chain acyl-coenzyme A thioesters as substrates i n g l y c e r o l i p i d biosynthesis of chloroplasts M. Bertrams and E. Heinz 67 Synthesis of long-chain acyl-CoA i n chloroplast envelope membranes J. Joyard and P.K. Stumpf 73 Cooperation between chloroplasts and the e x t r a - p l a s t i d i a l compartment fo r the biosynthesis of leaf l i p i d s A. Tremolieres, J.-P. Dubacq, D. Drapier and P. Mazliak 77 Phospholipid exchange proteins from photosynthetic tissues M. Julienne, D. Douady, J.-P. Dubacq, A. Tremolieres, D. Drapier, Μ. Grosbois, P. Mazliak and J.-C. Kader 81 Changes i n l i p i d composition and synthesis and i n chloroplast structure observed in greening barley leaves A.O. Davies, A.T. James, R. Jeffcoat and J.L, Harwood 85 χ A hypothetic r o l e f o r phosphatidyl glycerol and 3-trarcs-hexadecenoic acid i n the l i g h t reactions of the photosynthetic process J.-C. Duval, J.-P. Dubacq and A."Tremolieres 91 Trans-3-hexadecenoic acid and grana stacking T. Guillot-Salomon, A. Tremolieres, C. Tuquet and J.-P. Dubacq 95 L i p i d changes i n plastids isolated from a l f a l f a seedlings grown under sa l t - s t r e s s F. Harzallah-Skhiri, T. Guillot-Salomon and M. Signol 99 Influence of growth temperature on acyl l i p i d s of leaves D. J. Chapman and J. Barber 103 Fatty acid synthesis i n isolated chromoplasts and chromoplast homogenates. ACP sti m u l a t i o n , substrate u t i l i s a t i o n , and cerulenin i n h i b i t i o n B. Liedvogel and H. Kleinig 107 P a r t i a l p u r i f i c a t i o n and properties of a soluble f a t t y acid synthetase from o l i v e leaves L.M. Daza, M. Garrido and J.P. Donaire 111 Function and d i s t r i b u t i o n of phospholipids i n spinach thylakoid membranes as revealed by phospholipase A 2 treatment A. Rawyler and P.-A. Siegenthaler 117 Characterization and meaning of chloroplast lipoxygenase a c t i v i t i e s R. Douillard 121 Galactolipid biosynthesis i n Euglena gracilis E. Blee and R. Schantz 127 Phosphatidyl glycerol biosynthesis i n Euglena gracilis A. Chammai and R, Schantz 131 Discovery of a new glyceroglycolipid i n blue-green algae and i t s role i n g a l a c t o l i p i d biosynthesis G. B. Feige, Ε. Heinz, Κ. Wrage, Ν. Cochems and Ε. Ponzelar 135 LIPID METABOLISM IN N0N-PH0T0SYNTHETIC TISSUES Fatty acid synthesis J.L. Harwood 143 Phospholipid l o c a l i z a t i o n in biol o g i c a l membranes J.A.F. Op den Kamp, Τ. Kauerz and G. van Meer 153 Phospholipid exchange protein from higher plants M. Yamada, T. Tanaka and J . - I . Ohnishi 161 L i p i d metabolism as a factor i n environmental adaptation P.J.C. Kuiper 169 Biogenesis of l i p i d s i n oilseed plants L.-Ä. Appelqvist 177 x i The biochemistry of l i p i d s i n cereal crops T. G a l l i a r d and P.J. Barnes 191 Lip i d composition of sycamore c e l l s c u l t i v a t e d at various temperatures M. Gawer, F. Trapy, J. Guern and P. Mazliak 199 Oxygen and temperature e f f e c t s on the f a t t y acid composition of sycamore c e l l s {Acer pseudoplatanus L.) F. Rebeille, R. Bligny and R, Douce 203 Desaturation of f a t t y acids in l i p i d s i n response to the growth temperature i n the blue-green alga, Anabaena variabilis Ν. Sato and N. Murata 207 Subcellular l o c a l i s a t i o n of f a t t y acid synthetases i n c e l l cultures of higher plants F. Spener 211 Biosynthesis of parinaric acid (9,11,13,15-octadecatetraenoic acid) M. Nöda, Κ. Ohga, Y. Nakagawa and K. Ichihara 215 A comparison of the polypeptide and phospholipid composition of o i l body and microsomal preparations from safflower and linseed cotyledons R. Slack and G. Roughan 219 Lipid metabolism i n developing wheat seeds D.N. Stokes, T. G a l l i a r d and J.L. Harwood 223 α-ketodicarboxylic acids i n lipogenic substrates i n Flacourtiaceae I . Tober "and F. Spener 227 Root phospholipid composition as a f a c t o r of the d i f f e r e n t i a l C a - s e n s i t i v i t y of plants M. Rossignol and C. Grignon 231 Calcium binding, phosphatidic acid formation and f a t t y acid breakdown i n plant mitochondria J. Dupont and C. Lance 235 The a v a i l a b i l i t y of palmitoyl-CoA influences the a c t i v i t y of palmitoy!-CoA hydrolase in carrot homogenate P. Baardseth and E. Sünde 239 Effect of sodium chloride and calcium s u l f a t e on the l i p i d composition of sunflower leaves (Helianthus annuus L,) L.Bettaieb, M. Gharsalli and A. Cherif 243 Relationships between temperature, microviscosity and desaturases a c t i v i t i e s i n the microsomal membranes of two fungi with d i f f e r e n t behaviour L. Chavant, C. Montant and C. Wolf 249 Scopulariopsis brevicaulis (Bainier) : Study of the l i p i d content i n r e l a t i o n to growth J.-L. F o n v i e i l l e and M. Sancholle 253 •Fatty acid biosynthesis i n c e l l free preparations of Anabaena cylindrica Z.T. A T A r a j i and T.J. Walton 259 x i i The e f f e c t of biotrophic fungal i n f e c t i o n on the l i p i d metabolism of green plants D.M. Lösel WAX METABOLISM Light promotes synthesis of the very long f a t t y acid acyl chains in maize wax P. von Wettstein-Knowles, P. Avato and J, D. Mikkelsen Alkanes and alkenes i n the ep i c u t i c u l a r waxes from Cistus plants P.-G. Gülz Stearoyl-CoA metabolism i n the microsomes from leek epidermal c e l l s Thioesterase, acyltransferase and elongase a c t i v i t i e s T. Abdul-Karim, R. Lessire and C. Cassagne Synthesis of l i p i d s by epidermal and mesophyll protoplasts isolated from barley leaf sheaths J.D. Mikkelsen Long chain f a t t y acid a c t i v a t i o n : Relations with very long chain f a t t y acids biosynthesis R. Lessire and C. Cassagne PIGMENTS Prenyl qui nones i n plant leaves H.K. Lichtenthaler Current concept of organization of chlorophyll biosynthesis A.A. Shlyk Carotenoid biosynthesis in plants J.W. Porter, S.L. Spurgeon and D. Pan The role of carotenoids i n chloroplasts of higher plants D. Siefermann-Harms Biosynthesis of α-tocopherol and plastoquinone-9 i n spinach chloroplasts J. Soil and G. Schultz Carotenoid biosynthesis i n Scenedesmus obliquus (Chiorophyta): Experiments with deuterium oxide G. B r i t t o n and A.P. Mundy The influence of k i n e t i n on the chlorophyll biosynthesis i n radish cotyledons C. Buschmann Properties of membrane-bound 3-hydroxy-3-methylglutaryl-coenzyme A reductase (EC 1.1.1.34) from radish seedlings and some aspects of i t s regulation T.J. Bach, Η.K. Lichtenthaler and J. Retey Carotenoid biosynthesis: Biogenesis of capsanthin and capsorubin in pepper f r u i t s (Capsicum annuum) B. Camara and R. Moneger Level of chlorophyll b and the l i g h t harvesting chlorophyll-protein complex i n Raphanus seedlings grown at d i f f e r e n t l i g h t quanta fluence rates U. Prenzel, H.K. Lichtenthaler and D. Meier Circular dichroism studies of the spontaneous organization of xantophyll compounds in water-alcohol solutions. Correlations with the role played by the polyene substances i n the s t r u c t u r a l organization of bio l o g i c a l systems J. Lematre, B. Maudinas and C. Ernst Light influence on zeaxanthin epoxidation i n h i b i t i o n of S-ethyl di p r o p y l t h i ocarbamate R.E. Wilkinson L i p i d s , pigments, light-harvesting chlorophyll protein complex and structure of a virescent mutant of maize E. Selstam STEROLS AND TERPENES Function as an evolutionary determinant of biosynthesis W.R. Nes The use of mutants and azasterols in studies of yeast sterol biosynthesis A.C. Oehlschlager, H.D, Pierce, J r . , A.M. Pierce, R,H. Angus, E. Quantin-Martenot, A.M. Unrau and R, Srinivasan Biosynthesis of sterol conjugates i n plants Z.A. Wojciechowski A monolayer study of l i p i d : Protein interactions i n the chloroplast membrane D.G. Bishop and J.R. Kenrick 14 Incorporation of C-labeled C0 2 ) phosphoglycerate, phosphoenoi-pyruvate, pyruvate, acetate and mevalonate i n t o terpenoids and a c y l l i p i d s of isolated i n t a c t spinach chloroplasts K.H. Grumbach Site of synthesis of geranylgeraniol derivatives i n i n t a c t spinach chloroplasts M.A. Block, J. Joyard and R. Douce Latency of uridine diphosphate glucose-sterol-ß-D-glucoysl-transferase and uridine diphosphatase i n p u r i f i e d membrane fra c t i o n s from maize coleoptiles M. M'Voula-TsieVi, P. Benveniste, E. Martenot and M.-A. Hartmann-Bouillon xiv Biosynthesis and c e l l u l a r l o c a l i s a t i o n of terpene hydrocarbons i n maritime pine C. Bernard-Dagan, M. Gleizes, G. Pauly, J.P. Carde and A. Marpeau 437 Membrane systems involved i n synthesis and transport of monoterpene hydrocarbons i n pine leaves J.-P. Carde, C. Bernard-Dagan and M. Gleizes 441 Presence of s t e r y l glycosides and amyrin glycosides i n a blue-green alga: Nostoo commune and a red aT-ga: Porphyridium sp, R. Duperon, P. Doireau, A. Verger and P. Duperon 445 Author index 449 © 1980 Elsevier/North-Holland Biomedical Press Biogenesis and Function o f Plant Lipids P. Mazliak, P. Benveniste r C . Costes and R. Douce, editors 341 BIOSYNTHESIS OF ^ -TOCOPHEROL AND PLAST0QUIN0NE-9 IN SPINACH CHLOROPLASTS JÜRGEN SOLL AND GERNOT SCHULTZ I n s t i t u t für Tierernährung, Arbeitsgruppe für Phytochemie und Fut t e r m i t t e l kün-de, Tierärztliche Hochschule, D - 3000 Hannover 1 (FRG) ABSTRACT Prenylation and methylation reaction i n al biosynthesis i s localized in the envelope membranes of the chloroplasts, while PQ-9 biosynthesis takes place i n the envelope membranes and also i n the thylakoid membranes. The sequence i n a-T biosynthesis in spinach i s (see also Figure 1): Homogentisate + Phytyl-PP — Me-6-PQH ?—»~ 2,3-Me2PQH?—• γ J - ^ a T ; f o r the PQ-9 biosynthesis i t i s : Homo­gentisate + Solanesyf-PP 4-*- Me-6-SQH2—- PQH2> RESULTS The two major prenyl qui nones of the chloroplast are aT and PQ-9. The aroma­t i c moiety of both derives from homogentisate*; the prenyl sidechain originates from a polyprenyl-PP (C\>Q i n the case of a l , C 5^ i n that of PQ-9). Homogenti­sate i s formed by an i n t r a p l a s t i d i c occurring shikimate pathway 2' 3. α-Tocopherol biosynthesis The only s i t e of al biosynthesis i n spinach chloroplasts are the envelope 4 5 membranes ' . Phytyl-PP derives by reduction from GGPP which i s synthesized by a recombinated system of chloroplast envelope or thylakoid membranes with, s t r o ­ma (soluble f r a c t i o n ) 6 . Homogentisate i s solely prenylated with phytyl-PP to 5 form Me-6-PQH9 . There i s no stimulation by other chloroplast f r a c t i o n s l i k e 5 stroma or thylakoid membranes . The prenyl transferase in spinach shows a strong s p e c i f i t y f o r phytyl-PP (26 pmol/h. mg p r o t e i n ) ; GGPP is inactive in t h i s ς system ! From the possible po s i t i o n isomers only Me-6-PQH9 but not Me-5- or 5 L Me-3-PQH9 are formed . A kinase which forms phytyl-PP from phytol + ATP i s 5 localized in the stroma . The following two methylation steps with SAM as methyl-group donor to form Abbreviations: GGPP - geranylgeranyl-PP; Me-6-GGQH? - 2-methyl-6-geranylgeranyl* q u i n o l ; M.e-6-PQH2 and isomers - 2-methyl-6-phytylqui no! and 5- and 3-phytyl-isomers; 2,3-MeJQH2 - 2,3-dimethyl-5-phytylquinol; Me~PQH? - t r i m e t h y l p h y t y l -q u i n o l ; Me-6-SQfL - 2-methyl-6-solanesylquinol; PQ-9 - pla5toquinone-9; PQH? -plastoquinol-9; SAM - S-adenosylmethionine; aT, y l , hi - a ,y , δ-tocopherol; V^3 " y t o c o t ^ ' e n o l . 342 aJ from Me-6-PQH2 are also only due to the envelope membranes : ( t h a t i s : Me-6-PQH2-^L 2,3-Me2PQH2 — VJ ^L^aJ). Again no stimulation occurs by combining envelope membranes with stroma protein. In marked contrast to the prenylation enzyme, the methyl transferase e x h i b i t s a preference f o r Me-6-GGQHU 4 8 (2 nmol/h. mg protein) i n comparison to Me-6-PQH2 (0,7 nmol/h. mg protein ) ' . In spinach, however only products of the pathway with phytyl-PP as substrate are found. The c y c l i z a t i o n of the prenylquinol to the corresponding chromanol ( i n t h i s case: 2,3-Me9PQhL—*~yT) which is a prerequisite f o r the second methylation 7 8 step takes place only i n i n t a c t chloroplasts ' but not in isolated envelope membranes. This might be due to lack of cofactors i n the medium used. I t i s 4 9 also probable that the procedure to prepare envelope membranes ' markedly effects the enzymes involved in the c y c l i z a t i o n reaction. Tyr-Shikimate pathway -p-Hydroxyphenylpyruvate (HPP) OH Homogentisate CH2-COOH Prenyl-PP-synthesis env ι%ι Geranylgeranyl-PP (GGPP) s t r ATP Phytyl-PP-KM Phytol Solanesyl-PP "Ί^^erw t h y l Me-6-Phytylquinol (Me-6-PQH2) J SAM env 2,3-Me 9-Phytylquinol ^(2,3-Me2PQH2) J C y c l i z a t i o n y-Tocopherol (yT) SAM env • Me-6-Solanesylqui nol (Me-6-SQH2) SAM env t h y l PIastoquinol-9 (PQH2) s£r Stroma env Envelope t h y l Thylakoids α-Tocopherol (al) Fig. 1. Biosynthesis of al and PQ-9 i n spinach chloroplasts. 343 P1astoquinone-9 biosynthesis PQ-9 biosynthesis, both prenylation and methylation i s not only performed by the envelope membranes (1,2 pmol/h. mg protein and 10 pmol/h. mg protein) but also at low rates by the thylakoid membranes (0,ol3 pmol/h. mg protein and 5 0,35 pmol/h. mg protein) . However, i f one takes i n t o account the rate of thy­lakoid protein to that of envelope protein per mg chlorophyll the yi e l d s in t o t a l are not as d i f f e r e n t as they are calculated on the basis of protein i t s e l f . The sequence of reactions involved in the PQ-9 biosynthesis i s s i m i l a r to a l . Solanesyl-PP (C^^) serves as prenyl compound in the prenylation reaction to form Me-6-SQH2 with homogentisate. In the following steps Me-6-SQH2 is methylated with SAM to y i e l d PQ-9. In e i t h e r case, al and PQ-9 biosynthesis, the quinol stage of the precursor is involved in the methylation reaction and not quinone stage 7. CONCLUSIONS Prenylquinones synthesized in chloroplasts operate in d i f f e r e n t ways in the photosynthetic mechanism. Whereas PQ-9 acts in the photosynthetic electron transport, α Τ inactivates energetisized oxygen species formed by l i g h t (by sca­venging radicals and/or quenching of *0 2 ^ » ^ 2 . Both it Τ and PQ-9, are formed by enzyme systems of l i p o p h i l i c membranes of the chloroplast being in d i r e c t contact to more hydrophilic areas of the stroma. The steps of the synthesis, both prenylation and methylation of the quinols, are conceivable as e l e c t r o p h i l i c s u b s t i t u t i o n of aromatics, the mechanism i s not yet clear. In fewer cases, tocopherols and tocotrienols in plants occur also in l a t i c i -13 fers and o i l seeds but compartmentation of synthesis in comparison to chloro­plast remains of future i n t e r e s t . ACKNOWLEDGEMENTS Financial support by the Deutsche Forschungsgemeinschaft and the Centre Na­ti o n a l de l a Recherche Sci e n t i f i q u e (ERA 847 to Prof. Dr. R. Douce, Biologie Vegetale, CENG and USM-G, Grenoble, France) are g r e a t f u l l y acknowledged. We thank Dr. D.R. T h r e l f a l l (University of H u l l , U.K.) f o r making his manuscript available to us p r i o r to publication. 344 REFERENCES 1. T h r e l f a l l , D.R. (1971) Vitam. Horm., 29, 153-200. 2. Bickel, Η., Palme, L. and Schultz, 6. (1978) Phytochemistry, 17, 119-124. 3. Löffelhardt, W. and Kind!, H. (1979) FEBS Lette r s , 104, 332-334. 4. S o l l , J., Douce, R. and Schultz, G. (1980) FEBS Letters, 112, 243-246. 5. S o i l , J., Kemmerling, M. and Schultz, G. (1980) Arch. Biochem. Biophys., submitted f o r publication. 6. Block, M. and Douce, R. (1980) Biochim Biophys. Acta, in press. 7. S o l l , J. and Schultz, G. (1980) Phytochemistry, 19, 215-218. 8. S o l l , J. and Schultz, G. (1979) Biochem. Biophys. Res. Commun., 91, 715-720. 9. Douce, R. and Joyard, J. (1979) Adv. Bot. Res., 7, 1-116. 10. Hutson, K.G. and T h r e l f a l l , D.R. (1980) Biochim. Biophys. Acta, submitted f o r publication. 11. Foote, C.S., Clough, R.L. and Yee, B.G. (1978) Tocopherol, Oxygen and Bio-membranes (de Duve, C, and Hayaishi, 0., eds.), El sevier/North-Hol land, Amsterdam, pp. 13-21. 12. Yamauchi, R. and Matsushita, S. (1979) Agric. B i o l . Chem., 43, 2157-2161. 13. Peake, I.R., Audley, B.G. and Pennock, J.F. (1970) Biochem. J., 119, 58p. 

Biochim Biophys. Acta,

Biosynthesis of α-Tocopherol and Plastoquinone-9 in spinach chloroplasts

Universität München: Elektronischen Publikationen

BIOGENESIS AND FUNCTION OF PLANT 
LIPIDS 
Proceedings of the Symposium on Recent Advances in the Biogenesis and 
Function of Plant Lipids held in Paris, June 4-7, 1980. 
Editors 
P. Mazliak 
P. Benveniste 
C. Costes 
and 
R. Douce 
1980 
ELSEVIER/NORTH-HOLLAND BIOMEDICAL PRESS 
A M S T E R D A M · NEW YORK · OXFORD 
© 1980 Elsevier/North-Hol land B iomedica l Press 
A l l r ights reserved. No part o f this publ icat ion may be reproduced, stored in a retrieval system, or transmitted, 
in any fo rm or by any means, electronic, mechanical , photocopying, recording or otherwise, w i thout the pr ior 
permission o f the copyr ight owner. 
I S B N for this vo lume: 0-444-80273-8 
I S B N for the series: 0-444-80081 -6 
Published by: 
Elsevier/North-Hol land Biomedical Press 
335 Jan van Galenstraat, P.O. Box 211 
Amsterdam, The Netherlands 
Sole distributors for the USA and Canada: 
Elsevier Nor th Ho l land Inc. 
52 Vanderbi l t Avenue 
N e w Y o r k , N .Y . 10017 
L i b r a r y of Congress Cataloging in Publication Data 
Symposium on Recent Advances in the Biogenesis and 
Function of Plant Lipids, Paris, 1980. 
Biogenesis and function of plant l i p i d s . 
(Developments in plant "biology ; v. 6) 
Bibliography: p. 
Includes index, 
1 . Plant lipids—Congresses. I . Mazliak, P. 
I I . T i t l e . I I I . Series. 
QK898.L56S96 1980 5 8 l . l 9 f 2 U 7 80-20135 
ISBN O-W-80273-8 
Printed in The Netherlands 
i x 
CONTENTS 
Dedication V 
Preface V I I 
LIPID METABOLISM IN CHLOROPLASTS AND LEAVES 
Oleic acid, the central substrate 
P.K. Stumpf, D.N. Kuhn, D.J. Murphy, M.R. Pollard, 
T. McKeon and J. MacCarthy 3 
The role of chloroplasts in leaf l i p i d metabolism and poly-
unsaturated f a t t y acid synthesis 
G. Roughan and R. Slack 11 
Use of mesophyll protoplasts to study l i p i d metabolism i n c e l l 
organelles 
R. Haas and E. Heinz 19 
The s t r u c t u r a l organization of chloroplast l i p i d s in vivo and 
in model systems: Some aspects 
C. Liljenberg 29 
Lysogalactolipids as intermediates i n g a l a c t o l i p i d synthesis 
in chloroplasts 
K.-P. Heise and A. Sauer 39 
Galactolipid formation i n chloroplast envelopes. A discussion on 
differences between experiments in vivo and in vitro 
J.F.G.M. Wintermans, A. van Besouw, G. Bögemann and J, Aerts 49 
Studies on the biosynthesis of sulfoquinovosyl diacylglycerol i n 
higher plants 
J.B. Mudd, R. Dezacks and J. Smith 57 
Long chain acyl-coenzyme A thioesters as substrates i n g l y c e r o l i p i d 
biosynthesis of chloroplasts 
M. Bertrams and E. Heinz 67 
Synthesis of long-chain acyl-CoA i n chloroplast envelope membranes 
J. Joyard and P.K. Stumpf 73 
Cooperation between chloroplasts and the e x t r a - p l a s t i d i a l compartment 
fo r the biosynthesis of leaf l i p i d s 
A. Tremolieres, J.-P. Dubacq, D. Drapier and P. Mazliak 77 
Phospholipid exchange proteins from photosynthetic tissues 
M. Julienne, D. Douady, J.-P. Dubacq, A. Tremolieres, 
D. Drapier, Μ. Grosbois, P. Mazliak and J.-C. Kader 81 
Changes i n l i p i d composition and synthesis and i n chloroplast structure 
observed in greening barley leaves 
A.O. Davies, A.T. James, R. Jeffcoat and J.L, Harwood 85 
χ 
A hypothetic r o l e f o r phosphatidyl glycerol and 3-trarcs-hexadecenoic 
acid i n the l i g h t reactions of the photosynthetic process 
J.-C. Duval, J.-P. Dubacq and A."Tremolieres 91 
Trans-3-hexadecenoic acid and grana stacking 
T. Guillot-Salomon, A. Tremolieres, C. Tuquet and J.-P. Dubacq 95 
L i p i d changes i n plastids isolated from a l f a l f a seedlings grown 
under sa l t - s t r e s s 
F. Harzallah-Skhiri, T. Guillot-Salomon and M. Signol 99 
Influence of growth temperature on acyl l i p i d s of leaves 
D. J. Chapman and J. Barber 103 
Fatty acid synthesis i n isolated chromoplasts and chromoplast 
homogenates. ACP sti m u l a t i o n , substrate u t i l i s a t i o n , and 
cerulenin i n h i b i t i o n 
B. Liedvogel and H. Kleinig 107 
P a r t i a l p u r i f i c a t i o n and properties of a soluble f a t t y acid 
synthetase from o l i v e leaves 
L.M. Daza, M. Garrido and J.P. Donaire 111 
Function and d i s t r i b u t i o n of phospholipids i n spinach thylakoid 
membranes as revealed by phospholipase A 2 treatment 
A. Rawyler and P.-A. Siegenthaler 117 
Characterization and meaning of chloroplast lipoxygenase a c t i v i t i e s 
R. Douillard 121 
Galactolipid biosynthesis i n Euglena gracilis 
E. Blee and R. Schantz 127 
Phosphatidyl glycerol biosynthesis i n Euglena gracilis 
A. Chammai and R, Schantz 131 
Discovery of a new glyceroglycolipid i n blue-green algae and 
i t s role i n g a l a c t o l i p i d biosynthesis 
G. B. Feige, Ε. Heinz, Κ. Wrage, Ν. Cochems and Ε. Ponzelar 135 
LIPID METABOLISM IN N0N-PH0T0SYNTHETIC TISSUES 
Fatty acid synthesis 
J.L. Harwood 143 
Phospholipid l o c a l i z a t i o n in biol o g i c a l membranes 
J.A.F. Op den Kamp, Τ. Kauerz and G. van Meer 153 
Phospholipid exchange protein from higher plants 
M. Yamada, T. Tanaka and J . - I . Ohnishi 161 
L i p i d metabolism as a factor i n environmental adaptation 
P.J.C. Kuiper 169 
Biogenesis of l i p i d s i n oilseed plants 
L.-Ä. Appelqvist 177 
x i 
The biochemistry of l i p i d s i n cereal crops 
T. G a l l i a r d and P.J. Barnes 191 
Lip i d composition of sycamore c e l l s c u l t i v a t e d at various temperatures 
M. Gawer, F. Trapy, J. Guern and P. Mazliak 199 
Oxygen and temperature e f f e c t s on the f a t t y acid composition of 
sycamore c e l l s {Acer pseudoplatanus L.) 
F. Rebeille, R. Bligny and R, Douce 203 
Desaturation of f a t t y acids in l i p i d s i n response to the growth 
temperature i n the blue-green alga, Anabaena variabilis 
Ν. Sato and N. Murata 207 
Subcellular l o c a l i s a t i o n of f a t t y acid synthetases i n c e l l cultures 
of higher plants 
F. Spener 211 
Biosynthesis of parinaric acid (9,11,13,15-octadecatetraenoic acid) 
M. Nöda, Κ. Ohga, Y. Nakagawa and K. Ichihara 215 
A comparison of the polypeptide and phospholipid composition of 
o i l body and microsomal preparations from safflower and linseed 
cotyledons 
R. Slack and G. Roughan 219 
Lipid metabolism i n developing wheat seeds 
D.N. Stokes, T. G a l l i a r d and J.L. Harwood 223 
α-ketodicarboxylic acids i n lipogenic substrates i n Flacourtiaceae 
I . Tober "and F. Spener 227 
Root phospholipid composition as a f a c t o r of the d i f f e r e n t i a l 
C a - s e n s i t i v i t y of plants 
M. Rossignol and C. Grignon 231 
Calcium binding, phosphatidic acid formation and f a t t y acid breakdown 
i n plant mitochondria 
J. Dupont and C. Lance 235 
The a v a i l a b i l i t y of palmitoyl-CoA influences the a c t i v i t y of 
palmitoy!-CoA hydrolase in carrot homogenate 
P. Baardseth and E. Sünde 239 
Effect of sodium chloride and calcium s u l f a t e on the l i p i d composition 
of sunflower leaves (Helianthus annuus L,) 
L.Bettaieb, M. Gharsalli and A. Cherif 243 
Relationships between temperature, microviscosity and desaturases 
a c t i v i t i e s i n the microsomal membranes of two fungi with 
d i f f e r e n t behaviour 
L. Chavant, C. Montant and C. Wolf 249 
Scopulariopsis brevicaulis (Bainier) : Study of the l i p i d content 
i n r e l a t i o n to growth 
J.-L. F o n v i e i l l e and M. Sancholle 253 
•Fatty acid biosynthesis i n c e l l free preparations of Anabaena cylindrica 
Z.T. A T A r a j i and T.J. Walton 259 
x i i 
The e f f e c t of biotrophic fungal i n f e c t i o n on the l i p i d metabolism 
of green plants 
D.M. Lösel 
WAX METABOLISM 
Light promotes synthesis of the very long f a t t y acid acyl chains 
in maize wax 
P. von Wettstein-Knowles, P. Avato and J, D. Mikkelsen 
Alkanes and alkenes i n the ep i c u t i c u l a r waxes from Cistus plants 
P.-G. Gülz 
Stearoyl-CoA metabolism i n the microsomes from leek epidermal c e l l s 
Thioesterase, acyltransferase and elongase a c t i v i t i e s 
T. Abdul-Karim, R. Lessire and C. Cassagne 
Synthesis of l i p i d s by epidermal and mesophyll protoplasts 
isolated from barley leaf sheaths 
J.D. Mikkelsen 
Long chain f a t t y acid a c t i v a t i o n : Relations with very long chain 
f a t t y acids biosynthesis 
R. Lessire and C. Cassagne 
PIGMENTS 
Prenyl qui nones i n plant leaves 
H.K. Lichtenthaler 
Current concept of organization of chlorophyll biosynthesis 
A.A. Shlyk 
Carotenoid biosynthesis in plants 
J.W. Porter, S.L. Spurgeon and D. Pan 
The role of carotenoids i n chloroplasts of higher plants 
D. Siefermann-Harms 
Biosynthesis of α-tocopherol and plastoquinone-9 i n spinach 
chloroplasts 
J. Soil and G. Schultz 
Carotenoid biosynthesis i n Scenedesmus obliquus (Chiorophyta): 
Experiments with deuterium oxide 
G. B r i t t o n and A.P. Mundy 
The influence of k i n e t i n on the chlorophyll biosynthesis i n 
radish cotyledons 
C. Buschmann 
Properties of membrane-bound 3-hydroxy-3-methylglutaryl-coenzyme A 
reductase (EC 1.1.1.34) from radish seedlings and some aspects 
of i t s regulation 
T.J. Bach, Η.K. Lichtenthaler and J. Retey 
Carotenoid biosynthesis: Biogenesis of capsanthin and capsorubin 
in pepper f r u i t s (Capsicum annuum) 
B. Camara and R. Moneger 
Level of chlorophyll b and the l i g h t harvesting chlorophyll-protein 
complex i n Raphanus seedlings grown at d i f f e r e n t l i g h t quanta 
fluence rates 
U. Prenzel, H.K. Lichtenthaler and D. Meier 
Circular dichroism studies of the spontaneous organization of 
xantophyll compounds in water-alcohol solutions. Correlations 
with the role played by the polyene substances i n the s t r u c t u r a l 
organization of bio l o g i c a l systems 
J. Lematre, B. Maudinas and C. Ernst 
Light influence on zeaxanthin epoxidation i n h i b i t i o n of S-ethyl 
di p r o p y l t h i ocarbamate 
R.E. Wilkinson 
L i p i d s , pigments, light-harvesting chlorophyll protein complex and 
structure of a virescent mutant of maize 
E. Selstam 
STEROLS AND TERPENES 
Function as an evolutionary determinant of biosynthesis 
W.R. Nes 
The use of mutants and azasterols in studies of yeast sterol 
biosynthesis 
A.C. Oehlschlager, H.D, Pierce, J r . , A.M. Pierce, R,H. Angus, 
E. Quantin-Martenot, A.M. Unrau and R, Srinivasan 
Biosynthesis of sterol conjugates i n plants 
Z.A. Wojciechowski 
A monolayer study of l i p i d : Protein interactions i n the chloroplast 
membrane 
D.G. Bishop and J.R. Kenrick 
14 
Incorporation of C-labeled C0 2 ) phosphoglycerate, phosphoenoi-
pyruvate, pyruvate, acetate and mevalonate i n t o terpenoids 
and a c y l l i p i d s of isolated i n t a c t spinach chloroplasts 
K.H. Grumbach 
Site of synthesis of geranylgeraniol derivatives i n i n t a c t spinach 
chloroplasts 
M.A. Block, J. Joyard and R. Douce 
Latency of uridine diphosphate glucose-sterol-ß-D-glucoysl-transferase 
and uridine diphosphatase i n p u r i f i e d membrane fra c t i o n s from maize 
coleoptiles 
M. M'Voula-TsieVi, P. Benveniste, E. Martenot and 
M.-A. Hartmann-Bouillon 
xiv 
Biosynthesis and c e l l u l a r l o c a l i s a t i o n of terpene hydrocarbons i n 
maritime pine 
C. Bernard-Dagan, M. Gleizes, G. Pauly, J.P. Carde and A. Marpeau 437 
Membrane systems involved i n synthesis and transport of monoterpene 
hydrocarbons i n pine leaves 
J.-P. Carde, C. Bernard-Dagan and M. Gleizes 441 
Presence of s t e r y l glycosides and amyrin glycosides i n a blue-green 
alga: Nostoo commune and a red aT-ga: Porphyridium sp, 
R. Duperon, P. Doireau, A. Verger and P. Duperon 445 
Author index 449 
© 1980 Elsevier/North-Holland Biomedical Press 
Biogenesis and Function o f Plant Lipids 
P. Mazliak, P. Benveniste r C . Costes and R. Douce, editors 341 
BIOSYNTHESIS OF ̂ -TOCOPHEROL AND PLAST0QUIN0NE-9 IN SPINACH CHLOROPLASTS 
JÜRGEN SOLL AND GERNOT SCHULTZ 
I n s t i t u t für Tierernährung, Arbeitsgruppe für Phytochemie und Fut t e r m i t t e l kün-
de, Tierärztliche Hochschule, D - 3000 Hannover 1 (FRG) 
ABSTRACT 
Prenylation and methylation reaction i n al biosynthesis i s localized in the 
envelope membranes of the chloroplasts, while PQ-9 biosynthesis takes place i n 
the envelope membranes and also i n the thylakoid membranes. The sequence i n a-T 
biosynthesis in spinach i s (see also Figure 1): Homogentisate + Phytyl-PP — 
Me-6-PQH ?—»~ 2,3-Me2PQH?—• γ J - ^ a T ; f o r the PQ-9 biosynthesis i t i s : Homo­
gentisate + Solanesyf-PP 4-*- Me-6-SQH2—- PQH2> 
RESULTS 
The two major prenyl qui nones of the chloroplast are aT and PQ-9. The aroma­
t i c moiety of both derives from homogentisate*; the prenyl sidechain originates 
from a polyprenyl-PP (C\>Q i n the case of a l , C 5̂ i n that of PQ-9). Homogenti­
sate i s formed by an i n t r a p l a s t i d i c occurring shikimate pathway 2' 3. 
α-Tocopherol biosynthesis 
The only s i t e of al biosynthesis i n spinach chloroplasts are the envelope 
4 5 
membranes ' . Phytyl-PP derives by reduction from GGPP which i s synthesized by 
a recombinated system of chloroplast envelope or thylakoid membranes with, s t r o ­
ma (soluble f r a c t i o n ) 6 . Homogentisate i s solely prenylated with phytyl-PP to 
5 
form Me-6-PQH9 . There i s no stimulation by other chloroplast f r a c t i o n s l i k e 
5 
stroma or thylakoid membranes . The prenyl transferase in spinach shows a strong 
s p e c i f i t y f o r phytyl-PP (26 pmol/h. mg p r o t e i n ) ; GGPP is inactive in t h i s 
ς 
system ! From the possible po s i t i o n isomers only Me-6-PQH9 but not Me-5- or 
5 L 
Me-3-PQH9 are formed . A kinase which forms phytyl-PP from phytol + ATP i s 
5 
localized in the stroma . 
The following two methylation steps with SAM as methyl-group donor to form 
Abbreviations: GGPP - geranylgeranyl-PP; Me-6-GGQH? - 2-methyl-6-geranylgeranyl* 
q u i n o l ; M.e-6-PQH2 and isomers - 2-methyl-6-phytylqui no! and 5- and 3-phytyl-
isomers; 2,3-MeJQH2 - 2,3-dimethyl-5-phytylquinol; Me~PQH? - t r i m e t h y l p h y t y l -
q u i n o l ; Me-6-SQfL - 2-methyl-6-solanesylquinol; PQ-9 - pla5toquinone-9; PQH? -
plastoquinol-9; SAM - S-adenosylmethionine; aT, y l , hi - a ,y , δ-tocopherol; 
V^3 " y t o c o t ^ ' e n o l . 
342 
aJ from Me-6-PQH2 are also only due to the envelope membranes : ( t h a t i s : 
Me-6-PQH2-^L 2,3-Me2PQH2 — VJ ^L^aJ). Again no stimulation occurs by 
combining envelope membranes with stroma protein. In marked contrast to the 
prenylation enzyme, the methyl transferase e x h i b i t s a preference f o r Me-6-GGQHU 
4 8 
(2 nmol/h. mg protein) i n comparison to Me-6-PQH2 (0,7 nmol/h. mg protein ) ' . 
In spinach, however only products of the pathway with phytyl-PP as substrate 
are found. 
The c y c l i z a t i o n of the prenylquinol to the corresponding chromanol ( i n t h i s 
case: 2,3-Me9PQhL—*~yT) which is a prerequisite f o r the second methylation 
7 8 
step takes place only i n i n t a c t chloroplasts ' but not in isolated envelope 
membranes. This might be due to lack of cofactors i n the medium used. I t i s 
4 9 
also probable that the procedure to prepare envelope membranes ' markedly 
effects the enzymes involved in the c y c l i z a t i o n reaction. 
Tyr-
Shikimate pathway 
-p-Hydroxyphenylpyruvate 
(HPP) 
OH Homogentisate 
CH2-COOH 
Prenyl-PP-synthesis 
env ι%ι 
Geranylgeranyl-PP 
(GGPP) 
s t r 
ATP Phytyl-PP-
KM 
Phytol Solanesyl-PP 
"Ί^^erw t h y l 
Me-6-Phytylquinol 
(Me-6-PQH2) J SAM env 
2,3-Me 9-Phytylquinol 
^(2,3-Me2PQH2) 
J C y c l i z a t i o n 
y-Tocopherol (yT) 
SAM env 
• 
Me-6-Solanesylqui nol 
(Me-6-SQH2) 
SAM env t h y l 
PIastoquinol-9 
(PQH2) 
s£r Stroma 
env Envelope 
t h y l Thylakoids 
α-Tocopherol (al) 
Fig. 1. Biosynthesis of al and PQ-9 i n spinach chloroplasts. 
343 
P1astoquinone-9 biosynthesis 
PQ-9 biosynthesis, both prenylation and methylation i s not only performed by 
the envelope membranes (1,2 pmol/h. mg protein and 10 pmol/h. mg protein) but 
also at low rates by the thylakoid membranes (0,ol3 pmol/h. mg protein and 
5 
0,35 pmol/h. mg protein) . However, i f one takes i n t o account the rate of thy­
lakoid protein to that of envelope protein per mg chlorophyll the yi e l d s in 
t o t a l are not as d i f f e r e n t as they are calculated on the basis of protein i t s e l f . 
The sequence of reactions involved in the PQ-9 biosynthesis i s s i m i l a r to a l . 
Solanesyl-PP (C^^) serves as prenyl compound in the prenylation reaction to form 
Me-6-SQH2 with homogentisate. In the following steps Me-6-SQH2 is methylated 
with SAM to y i e l d PQ-9. In e i t h e r case, al and PQ-9 biosynthesis, the quinol 
stage of the precursor is involved in the methylation reaction and not quinone 
stage 7. 
CONCLUSIONS 
Prenylquinones synthesized in chloroplasts operate in d i f f e r e n t ways in the 
photosynthetic mechanism. Whereas PQ-9 acts in the photosynthetic electron 
transport, α Τ inactivates energetisized oxygen species formed by l i g h t (by sca­
venging radicals and/or quenching of *0 2 ^ » ^ 2 . 
Both it Τ and PQ-9, are formed by enzyme systems of l i p o p h i l i c membranes of the 
chloroplast being in d i r e c t contact to more hydrophilic areas of the stroma. The 
steps of the synthesis, both prenylation and methylation of the quinols, are 
conceivable as e l e c t r o p h i l i c s u b s t i t u t i o n of aromatics, the mechanism i s not yet 
clear. 
In fewer cases, tocopherols and tocotrienols in plants occur also in l a t i c i -
13 
fers and o i l seeds but compartmentation of synthesis in comparison to chloro­
plast remains of future i n t e r e s t . 
ACKNOWLEDGEMENTS 
Financial support by the Deutsche Forschungsgemeinschaft and the Centre Na­
ti o n a l de l a Recherche Sci e n t i f i q u e (ERA 847 to Prof. Dr. R. Douce, Biologie 
Vegetale, CENG and USM-G, Grenoble, France) are g r e a t f u l l y acknowledged. We 
thank Dr. D.R. T h r e l f a l l (University of H u l l , U.K.) f o r making his manuscript 
available to us p r i o r to publication. 
344 
REFERENCES 
1. T h r e l f a l l , D.R. (1971) Vitam. Horm., 29, 153-200. 
2. Bickel, Η., Palme, L. and Schultz, 6. (1978) Phytochemistry, 17, 119-124. 
3. Löffelhardt, W. and Kind!, H. (1979) FEBS Lette r s , 104, 332-334. 
4. S o l l , J., Douce, R. and Schultz, G. (1980) FEBS Letters, 112, 243-246. 
5. S o i l , J., Kemmerling, M. and Schultz, G. (1980) Arch. Biochem. Biophys., 
submitted f o r publication. 
6. Block, M. and Douce, R. (1980) Biochim Biophys. Acta, in press. 
7. S o l l , J. and Schultz, G. (1980) Phytochemistry, 19, 215-218. 
8. S o l l , J. and Schultz, G. (1979) Biochem. Biophys. Res. Commun., 91, 
715-720. 
9. Douce, R. and Joyard, J. (1979) Adv. Bot. Res., 7, 1-116. 
10. Hutson, K.G. and T h r e l f a l l , D.R. (1980) Biochim. Biophys. Acta, submitted 
f o r publication. 
11. Foote, C.S., Clough, R.L. and Yee, B.G. (1978) Tocopherol, Oxygen and Bio-
membranes (de Duve, C, and Hayaishi, 0., eds.), El sevier/North-Hol land, 
Amsterdam, pp. 13-21. 
12. Yamauchi, R. and Matsushita, S. (1979) Agric. B i o l . Chem., 43, 2157-2161. 
13. Peake, I.R., Audley, B.G. and Pennock, J.F. (1970) Biochem. J., 119, 58p. 


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Biosynthesis of α-Tocopherol and Plastoquinone-9 in spinach chloroplasts

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