Carotenoids

Agnieszka Kaczor is a postgraduate researcher in the Faculty of Chemistry at Jagiellonian University in Krakow, Poland. Her scientific interests concentrate on the application of vibrational spectroscopy and multitechnique imaging to study biological samples. Recently, she has focused on studying changes in cells and tissues upon pathology development with the help of Raman and AFM imaging as well as the application of Raman optical activity to investigate bioactive compounds. Malgorzata Baranska is a professor in the Faculty of Chemistry at Jagiellonian University in Krakow, Poland. She focuses on research of plant and medical bioactive compounds by means of spectroscopic methods, particularly modern Raman techniques (i.e., Raman imaging and Raman optical activity). The new direction of her research is related to lifestyle diseases, their development and methods of curing. This research in various in vitro, ex vivo and in vivo animal models is conducted partly in the Jagiellonian Centre for Experimental Therapeutics (JCET).

List of Contributors xi

1 Carotenoids: Overview of Nomenclature, Structures, Occurrence, and Functions 1
Agnieszka Kaczor, Malgorzata Baranska, and Krzysztof Czamara

1.1 Introduction 1

1.2 Nomenclature and structures 2

1.3 Occurrence and functions 7

1.3.1 Functions in plants 7

1.3.2 Antioxidants in humans 8

1.3.3 Role in visual and cognitive function 8

1.3.4 Carotenoids in human skin 8

1.3.5 Signaling function 9

1.3.6 Industrial applications 9

1.3.7 Carotenoids of specified properties 9

References 10

Part I Therapy 15

2 The Role of Antioxidants in Prevention of Premature Skin Aging 17
Jürgen Lademann, Maxim Evgen’evich Darvin, Fanny Knorr, Sascha Jung, Leonhard Zastrow, and Martina Claudia Meinke

2.1 Introduction 17

2.2 State of the art 17

2.2.1 Solar radiation and skin aging 17

2.2.2 Carotenoids and the antioxidants of the human skin 18

2.2.3 Factors influencing the antioxidant status of the skin 20

2.2.4 Antioxidants and sun protection 21

2.2.5 Antioxidants and skin aging 22

2.2.6 Investigations into the antioxidant status of high school students 22

2.2.7 Accumulation of antioxidants in human skin by systemic and topical application 23

2.2.8 Ethnic influences on the antioxidant status 24

2.2.9 The antioxidant status in pregnant women and neonates 25

2.3 Summary 26

Conclusions 26

References 27

3 Antitumor Activity of Dietary Carotenoids, and Prospects for Applications in Therapy: Carotenoids and Cancer by Raman Imaging 31
Halina Abramczyk and Jakub Surmacki

3.1 Results 33

3.2 Conclusions 38

3.3 Perspectives 38

References 39

4 Photoprotection and Radiation Protection by Dietary Carotenoids 43
Fritz Boehm, Ruth Edge, Terence George Truscott, and Christian Witt

4.1 Introduction 43

4.2 Carotenoids and singlet oxygen 44

4.2.1 Organic solvents 44

4.2.2 Cell models 46

4.2.3 Cells 47

4.3 Radicals 48

4.3.1 Radical cations 48

4.3.2 Carotenoid–radical adducts 49

4.3.3 Neutral radicals 50

4.3.4 Radical anions 51

4.3.5 The interaction of CARs with the superoxide radical and its protonated conjugated acid 51

4.4 Future prospects and challenges 53

4.5 Conclusion 53

Acknowledgments 54

References 54

5 Macular Carotenoids: Human Health Aspects 59
Aruna Gorusupudi and Paul S. Bernstein

5.1 Introduction 59

5.2 Macular pigment distribution 60

5.3 Human health aspects 61

5.4 Age]related macular degeneration (AMD) 61

5.5 Macular carotenoid absorption 63

5.6 Stereochemistry and metabolism of macular carotenoids 65

5.7 Measurement of macular carotenoids 67

5.8 Conclusions and perspectives 68

References 68

Part II Spectroscopy 75

6 Vibrational Spectroscopy as a Tool to Investigate Carotenoids 77
Jan Cz. Dobrowolski

6.1 Introduction 77

6.2 Vibrations of carotenoids 77

6.2.1 Geometry 78

6.2.2 Geometrical cis]trans isomerism 78

6.2.3 Syn]periplanar (s]cis) or anti]periplanar (s]trans) conformations 79

6.2.4 π]electron delocalization 79

6.2.5 The nature, shape, and energy of the electronic ground and excited states 79

6.2.6 Electron affinity, ionization, reduction, and oxidation potentials 80

6.2.7 The nature and shape of molecular vibrations and vibrational coupling patterns 80

6.2.8 The role of methyl groups attached to the polyene chain and the end groups 81

6.3 Recent applications of vibrational spectroscopy to study natural carotenoids 81

6.3.1 Bacteria lichens and algae 83

6.3.2 Corals and pearls 87

6.3.3 Art and archeology 90

6.4 Perspectives 91

Acknowledgments 92

References 92

7 Structural Studies of Carotenoids in Plants, Animals, and Food Products 103
Takashi Maoka

7.1 Introduction 103

7.2 Extraction and pre]preparation of carotenoids 103

7.3 Chromatography and separation of carotenoids 105

7.3.1 Column chromatography and thin]layer chromatography 105

7.3.2 High]performance liquid chromatography 105

7.4 Quantification of carotenoids 106

7.5 Identification and structural elucidation of carotenoids 106

7.5.1 Chemical dramatization 107

7.5.2 UV]Vis, IR, and Raman spectrometry 107

7.5.3 Mass spectrometry 108

7.5.4 NMR spectrometry 111

7.6 Determination of absolute configuration of carotenoids 120

7.6.1 Circular dichroism (CD) spectroscopy 120

7.6.2 NMR spectrometry using the modified Mosher method 122

7.6.3 Synthetic approach 123

7.6.4 X]ray crystallography 124

7.6.5 Examples of structural determination of natural carotenoids 124

7.7 Conclusion (future prospects and challenges) 126

Acknowledgments 126

References 127

8 In Situ Studies of Carotenoids in Plants and Animals 131
Malgorzata Baranska, Jan Cz. Dobrowolski, and Grzegorz Zajac

8.1 Introduction 131

8.2 Plants 131

8.3 Animals 134

8.4 Humans 137

8.4.1 Skin 137

8.4.2 Macular pigment 139

8.4.3 Carotenoids in single human cells 140

8.5 Perspectives 142

Acknowledgments 143

References 143

9 Carotenoids in Pigment–Protein Complexes: Relation between Carotenoid Structure and Function 147
Wieslaw I. Gruszecki

9.1 Biological functions of carotenoids 147

9.2 Carotenoids in pigment–protein complexes 149

9.3 Final remarks 154

9.4 Perspectives 155

Acknowledgments 155

References 155

Part III Technology 159

10 Carotenoid Biosynthesis and Regulation in Plants 161
Rafal Baranski and Christopher I. Cazzonelli

10.1 Biosynthetic pathways 161

10.1.1 Occurrence in nature 161

10.1.2 Cellular localization and compartmentalization 162

10.1.3 Pathways to generate isoprenoid precursors for carotenoid biosynthesis 163

10.1.4 The main pathway toward carotenoid biosynthesis 165

10.1.5 Specialty branches of the pathway 169

10.2 Regulation of carotenoid biosynthesis 170

10.2.1 Cross]talk between and within the carotenoid and MEP pathways 171

10.2.2 Environmental and developmental control 171

10.2.3 Regulation by epigenetic and posttranscriptional mechanisms 172

10.2.4 Carotenoids in plastid biogenesis, differentiation, and control 173

10.2.5 Enzyme localization and metabolon compartmentalization 174

10.2.6 Carotenoid degradation and production of signaling metabolites 175

10.3 Biofortification and health perspectives 178

Acknowledgments 179

References 179

11 Carotenoid Bioavailability from the Food Matrix: Toward Efficient Extraction Procedures 191
Hartwig Schulz

11.1 Introduction 191

11.2 Occurrence of carotenoids in food materials 193

11.3 Bioavailability and bioefficiency of carotenoids 194

11.4 Extraction of carotenoids from various food matrices 197

11.5 Conclusions 210

11.6 Perspectives 211

References 211

12 Carotenoid Production by Bacteria, Microalgae, and Fungi 217
Ralf Martin Schweiggert and Reinhold Carle

12.1 Introduction 217

12.2 Microbial biosynthesis of carotenoids 218

12.3 Carotenoid]rich microorganisms 223

12.3.1 Microalgae 223

12.3.2 Yeasts and filamentous fungi 225

12.3.3 Bacteria 226

12.4 Selected examples of biotechnological carotenoid production 228

12.4.1 Production of β]carotene 228

12.4.2 Production of astaxanthin 230

12.4.3 Production of lycopene 232

12.4.4 Production of lutein and zeaxanthin 233

12.5 Perspectives and conclusions 234

References 235

13 Impact of Stress Factors on Carotenoid Composition, Structures, and Bioavailability in Microbial Sources 241
Agnieszka Kaczor and Marta Z. Pacia

13.1 Introduction 241

13.2 Light 242

13.3 Temperature 246

13.4 Carbon and nitrogen sources 249

13.5 Aerobic versus anaerobic conditions 250

13.6 Inorganic and organic salts 250

13.7 Other chemical agents 253

13.8 pH 253

13.9 Multiple stress factors 254

13.10 Perspectives and conclusions 254

Acknowledgments 255

References 255

14 Syntheses with Carotenoids 261
Hans]Richard Sliwka and Vassilia Partali

14.1 Introduction 261

14.2 Reaction with double bonds 263

14.2.1 Hydrogenation 263

14.2.2 Halogenation 263

14.2.3 Oxidation 263

14.2.4 Electron transfer from and to carotenoids 264

14.2.5 Iron carbonyl 264

14.2.6 Nitration 265

14.2.7 In]chain modification 265

14.3 Transformation of substituents 265

14.3.1 −C=O → −C=C− 265

14.3.2 −CH=O → CH=S 267

14.3.3 −C=O → −C=S 268

14.3.4 −C=O → −C−OH 268

14.3.5 Inversion of −OH 269

14.3.6 −OH → −F, −Cl, −Br, and −I 269

14.3.7 −OH → −SR, −SCN, −SH, −N2, −NH2, and −SeR 269

14.3.8 −OH → −OR 270

14.3.9 −OH → glycosides 271

14.3.10 Reactions with carotenoid epoxides 271

14.3.11 Reactions with halogen carotenoids 271

14.3.12 Metal complexes with carotenols, carotenals, and carotenones 272

14.4 Preparative derivatization 272

14.5 Syntheses with carotenoid acids and carotenols 272

14.5.1 −COOH → −COCl 273

14.5.2 −COOH → COO− M+ 273

14.5.3 −COOH → COOR 273

14.5.4 −COOR → −COOH 277

14.5.5 −COOH → −CONH2 279

14.5.6 −COOH → −CO−O−OC− (carotenoid anhydrides) 279

14.6 Carotenoid reactions with Au 280

14.7 Valuation and conclusion 281

Acknowledgments 282

References 283

Index 291