Carotenoids Volume 4: Natural Functions Edited by G.Britton S.Liaaen-Jensen H.Pfander CH.O Birkhauser
Contents List of Contributors Preface......... xxiv Acknowledgements Editors'Notes xxvi Abbreviations xxviii Chapter 1:Special Molecules,Special Properties George Britton,Synnove Liaaen-Jensen and Hanspeter Pfander A Introduction B.Structure,Properties and Function 2 1.Three-dimensional shape 2 2.The conjugated double-bond system 3.Molecular interactions C.Functions of Carotenoids D.Metabolites and Breakdown Products 6 E.Conclusions 6 Chapter 2:Structure and Chirality Synnove Liaaen-Jensen A.Introduction > B.Three-dimensional Carotenoid Structures 1 C.Methods for Structure Determination.... 9 References 14 Chapter 3:E/Z Isomers and Isomerization Synnove Liaaen-Jensen and Bjart Frode Lutnces A.Introduction 15 B.E/Z Isomers 1 1.Geometrical isomerism:Definition and nomenclature 15 2.Structural examples of common Z isomers 19
v Contents List of Contributors ……………………………………………………..…… xviii Preface …………………………………………………………...…………… xxiv Acknowledgements …………………………………………………………... xxv Editors’ Notes ………………………………………………………………… xxvi Abbreviations ………………………………………………………………… xxviii Chapter 1: Special Molecules, Special Properties George Britton, Synnøve Liaaen-Jensen and Hanspeter Pfander A. Introduction ………………………………………………………………… 1 B. Structure, Properties and Function ……………………………………….. 2 1. Three-dimensional shape ……………………………………………….. 2 2. The conjugated double-bond system ……………………………………. 3 3. Molecular interactions ………………………………….……………….. 4 C. Functions of Carotenoids …………………………………………………... 5 D. Metabolites and Breakdown Products ……………………………………. 6 E. Conclusions …………………………………………………………………. 6 Chapter 2: Structure and Chirality Synnøve Liaaen-Jensen A. Introduction ………………………………………………………………… 7 B. Three-dimensional Carotenoid Structures ……………………………….. 7 C. Methods for Structure Determination ……………………………………. 9 References ……………………………………………………………………… 14 Chapter 3: E/Z Isomers and Isomerization Synnøve Liaaen-Jensen and Bjart Frode Lutnæs A. Introduction ………………………………………………………………… 15 B. E/Z Isomers …………………………………………………………………. 15 1. Geometrical isomerism: Definition and nomenclature …………………. 15 2. Structural examples of common Z isomers ……………………………... 19
3.Physical properties 9 a）Chromatography b)Solubility 20 4.Spectrosc0py… 20 a)UV/Vis spectroscopy 20 b)NMR spectroscopy 21 c)IR and resonance Raman spectroscopy 22 d)Mass spectrometry 22 e)Circular dichroism...... 22 5.Total synthesis 22 C.E/z Isomerization.................. 1.Thermodynamic and kinetic aspects 23 a)Thermodynamic equilibrium 23 b)Reversibility test. 23 c)Kinetically controlled isomerization 24 2.Photochemical isomerization catalysed by iodine 26 a)Conditions for E/Z isomerization 26 b)Conditions for simultaneous E/Z and allenic R/S isomerization...... 3 c)Mechanistic aspects 27 3.Photochemical isomerization catalysed by diphenyl diselenide. 29 a)Conditions 29 b)Thermodynamic equilibrium 29 c)Mechanistic aspects 30 4.Avoiding unwanted E/Zisomerization 31 5.Isolation artefacts. 31 a)Precautions for avoiding E/Z isomerization 31 b)Proof of natural occurrence of cis isomers ....... 31 D.Biological Implications of Carotenoid Z Isomers.... 31 1.Biosynthesis 31 2.Photosynthesis 32 3.Transport,accumulation,and E/Zisomerization in biological tissues a）Human serum....4.. b)Salmonid fishes 33 4.Metabolic conversions 5.Antioxidant properties 34 6.Formation during food and feed processing 4 7.Conclusion… 34 References 34
vi 3. Physical properties ……………………………………………………… 19 a) Chromatography ……………………………………………………. 19 b) Solubility …………………………………………………………… 20 4. Spectroscopy …………………………………………………………….. 20 a) UV/Vis spectroscopy ……………………………………………….. 20 b) NMR spectroscopy …………………………………………………. 21 c) IR and resonance Raman spectroscopy …………………………….. 22 d) Mass spectrometry …………………………………………………. 22 e) Circular dichroism …………………………………………………... 22 5. Total synthesis ………………………………………………………….. 22 C. E/Z Isomerization …………………………………………………………... 22 1. Thermodynamic and kinetic aspects ……………………………………. 23 a) Thermodynamic equilibrium ……………………………………….. 23 b) Reversibility test ……………………………………………………. 23 c) Kinetically controlled isomerization ……………………………….. 24 2. Photochemical isomerization catalysed by iodine ……………………… 26 a) Conditions for E/Z isomerization …………………………………… 26 b) Conditions for simultaneous E/Z and allenic R/S isomerization …… 27 c) Mechanistic aspects ………………………………………………… 27 3. Photochemical isomerization catalysed by diphenyl diselenide ……….. 29 a) Conditions …………………………………………………………... 29 b) Thermodynamic equilibrium ……………………………………….. 29 c) Mechanistic aspects ………………………………………………… 30 4. Avoiding unwanted E/Z isomerization …………………………………. 31 5. Isolation artefacts ……………………………………………………….. 31 a) Precautions for avoiding E/Z isomerization ………………………… 31 b) Proof of natural occurrence of cis isomers …………………………. 31 D. Biological Implications of Carotenoid Z Isomers ………………………… 31 1. Biosynthesis …………………………………………………………….. 31 2. Photosynthesis …………………………………………………………... 32 3. Transport, accumulation, and E/Z isomerization in biological tissues ….. 32 a) Human serum ……………………………………………………….. 32 b) Salmonid fishes ……………………………………………………... 33 4. Metabolic conversions ………………………………………………….. 33 5. Antioxidant properties ………………………………………………….. 34 6. Formation during food and feed processing ……………………………. 34 7. Conclusion ……………………………………………………………… 34 References ……………………………………………………………………... 34
vi Chapter 4:Three-dimensional Structures of Carotenoids by X-ray Crystallography Madeleine Helliwell A.Survey of Previously Reported Carotenoid Crystal Struetures.37 B.New Experimental Methods …41 1.Methods for crystallization of free carotenoids 2.Data collection ....... C.New Determinations of Crystal Structures 43 1.Astaxanthin and related xanthophylls 43 2 Carotenes 49 D.Conclusions 51 References Chapter 5:Aggregation and Interface Behaviour of Carotenoids Sonja Kohn,Henrike Kolbe,Michael Korger,Christian Kopsel,Bernhard Mayer,Helmut Auweter,Erik Liiddecke,Hans Bettermann and Hans-Dieter Martin A.Introduction 53 1.Molecular aggregates 2.Aggregates of carotenoids B.Aggregation in Solution 56 1.Optical and related properties a)UV/Vis spectra 56 b)Geometry of aggregate formation ““+4……+44小+4“+440+4…4小444…*4……4 58 c)Geometry of H-and J-aggregates 61 d)Chirality of aggregates 61 e)Factors that control J-or H-aggregate formation.. 6 f Excited-state dynamics 68 g）)π，r-Stacking interactions 68 h)Emission spectra 2.Light scattering 70 3 Raman spectroscopy C.Aggregation in Different Environments ……4+444……+…44…”*44+*+”…444 3 I.Surfaces and interfaces ......................................................... 73 a)‘Supermicroscopy 73 b)Electrical conductivity of model carotenoids......... 74 c)Bola-amphiphiles 76
vii Chapter 4: Three-dimensional Structures of Carotenoids by X-ray Crystallography Madeleine Helliwell A. Survey of Previously Reported Carotenoid Crystal Structures ………… 37 B. New Experimental Methods ……………………………………………….. 41 1. Methods for crystallization of free carotenoids ………………………… 41 2. Data collection …………………………………………………………. 41 C. New Determinations of Crystal Structures ………………………………. 43 1. Astaxanthin and related xanthophylls …………………………………... 43 2. Carotenes ……………………………………………………………….. 49 D. Conclusions …………………………………………………………………. 51 References ……………………………………………………………………… 51 Chapter 5: Aggregation and Interface Behaviour of Carotenoids Sonja Köhn, Henrike Kolbe, Michael Korger, Christian Köpsel, Bernhard Mayer, Helmut Auweter, Erik Lüddecke, Hans Bettermann and Hans-Dieter Martin A. Introduction ………………………………………………………………… 53 1. Molecular aggregates …………………………………………………… 53 2. Aggregates of carotenoids ……………………………………………… 54 B. Aggregation in Solution ……………………………………………………. 56 1. Optical and related properties …………………………………………... 56 a) UV/Vis spectra ……………………………………………………… 56 b) Geometry of aggregate formation …………………………………... 58 c) Geometry of H- and J-aggregates …………………………………... 61 d) Chirality of aggregates ……………………………………………… 61 e) Factors that control J- or H-aggregate formation .………………….5 66 f) Excited-state dynamics ……………………………………………… 68 g) ,-Stacking interactions …………………………………………… 68 h) Emission spectra ……………………………………………………. 70 2. Light scattering …………………………………………………………. 70 3. Raman spectroscopy ……………………………………………………. 71 C. Aggregation in Different Environments ………………………………….. 73 1. Surfaces and interfaces …………………………………………………. 73 a) ‘Supermicroscopy’ ………………………………………………….. 73 b) Electrical conductivity of model carotenoids ………………………. 74 c) Bola-amphiphiles …………………………………………………… 76
2.Vesicles,lipid bilayers and miscellaneous environments a)Lipid membrane bilayers:phase transitions ............................. b)CD studies 79 c)Surfactant solutions d)Relationship between structure and formation of H-or J-aggregates. 82 e)Some natural examples 0 New applications… 85 3.Influence of additives 4.Natural and artificial nanosized particles containing carotenoids:non- crystalline,crystalline and crystalloidal materials... 87 a)Carotenoid aggregates and crystals in chromoplasts 87 b)Chiral assemblies… c)Primary aggregates and crystals 9 d)Nanodispersions........................................................... e)How natural and artificial assemblies may form 93 References.. Chapter 6:Carotenoid-Protein Interactions George Britton and John R.Helliwell A.Introduction:Interactions of Carotenoids with Other Molecules.......... 99 B.Carotenoid-protein Complexes in Plants and Microorganisms 100 1.Photosynthetic pigment-protein complexes 100 2.Soluble proteins 100 C.Carotenoid-protein Interactions in Animals 101 1.Blood lipoproteins 101 2.Fish muscle 102 3.Feathers 103 D.Carotenoproteins 103 1.General features 103 2.Crustacyanin.... 104 3.The X-ray structure of B-crustacyanin 106 4.The carotenoid-binding site 107 5.Carotenoid-protein interactions 108 6.Mechanism of the spectral shift 112 7.Other carotenoproteins 114 a）Asteriarubin… 114 b)Linckiacyanin 115 c)The carotenoprotein of the Westemn Rock Lobster...................... 115
viii 2. Vesicles, lipid bilayers and miscellaneous environments ………………. 77 a) Lipid membrane bilayers: phase transitions ………………………... 77 b) CD studies …………………………………………………………... 79 c) Surfactant solutions …………………………………………………. 81 d) Relationship between structure and formation of H- or J-aggregates .. 82 e) Some natural examples ……………………………………………... 83 f) New applications …………………………………………………….. 85 3. Influence of additives …………………………………………………… 86 4. Natural and artificial nanosized particles containing carotenoids: noncrystalline, crystalline and crystalloidal materials ………………………. 87 a) Carotenoid aggregates and crystals in chromoplasts ……………….. 87 b) Chiral assemblies …………………………………………………… 89 c) Primary aggregates and crystals ……………………………………. 89 d) Nanodispersions ……………………………………………………. 91 e) How natural and artificial assemblies may form . ………………….. 93 References ……………………………………………………………………… 95 Chapter 6: Carotenoid-Protein Interactions George Britton and John R. Helliwell A. Introduction: Interactions of Carotenoids with Other Molecules ………. 99 B. Carotenoid-protein Complexes in Plants and Microorganisms …………. 100 1. Photosynthetic pigment-protein complexes …………………………….. 100 2. Soluble proteins …………………………………………………………. 100 C. Carotenoid-protein Interactions in Animals ……………………………... 101 1. Blood lipoproteins ………………………………………………………. 101 2. Fish muscle ……………………………………………………………... 102 3. Feathers …………………………………………………………………. 103 D. Carotenoproteins …………………………………………………………… 103 1. General features ………………………………………………………… 103 2. Crustacyanin ……………………………………………………………. 104 3. The X-ray structure of -crustacyanin ………………………………….. 106 4. The carotenoid-binding site …………………………………………….. 107 5. Carotenoid-protein interactions ………………………………………… 108 6. Mechanism of the spectral shift ………………………………………… 112 7. Other carotenoproteins …………………………………………………. 114 a) Asteriarubin ………………………………………………………… 114 b) Linckiacyanin ………………………………………………………. 115 c) The carotenoprotein of the Western Rock Lobster …………………. 115