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 theapplication 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 xi1 Carotenoids: Overview of Nomenclature, Structures, Occurrence, and Functions 1Agnieszka Kaczor, Malgorzata Baranska, and Krzysztof Czamara1.1 Introduction 11.2 Nomenclature and structures 21.3 Occurrence and functions 71.3.1 Functions in plants 71.3.2 Antioxidants in humans 81.3.3 Role in visual and cognitive function 81.3.4 Carotenoids in human skin 81.3.5 Signaling function 91.3.6 Industrial applications 91.3.7 Carotenoids of specified properties 9References 10Part I Therapy 152 The Role of Antioxidants in Prevention of Premature Skin Aging 17Jürgen Lademann, Maxim Evgen’evich Darvin, Fanny Knorr, Sascha Jung, Leonhard Zastrow, and Martina Claudia Meinke2.1 Introduction 172.2 State of the art 172.2.1 Solar radiation and skin aging 172.2.2 Carotenoids and the antioxidants of the human skin 182.2.3 Factors influencing the antioxidant status of the skin 202.2.4 Antioxidants and sun protection 212.2.5 Antioxidants and skin aging 222.2.6 Investigations into the antioxidant status of high school students 222.2.7 Accumulation of antioxidants in human skin by systemic and topical application 232.2.8 Ethnic influences on the antioxidant status 242.2.9 The antioxidant status in pregnant women and neonates 252.3 Summary 26Conclusions 26References 273 Antitumor Activity of Dietary Carotenoids, and Prospects for Applications in Therapy: Carotenoids and Cancer by Raman Imaging 31Halina Abramczyk and Jakub Surmacki3.1 Results 333.2 Conclusions 383.3 Perspectives 38References 394 Photoprotection and Radiation Protection by Dietary Carotenoids 43Fritz Boehm, Ruth Edge, Terence George Truscott, and Christian Witt4.1 Introduction 434.2 Carotenoids and singlet oxygen 444.2.1 Organic solvents 444.2.2 Cell models 464.2.3 Cells 474.3 Radicals 484.3.1 Radical cations 484.3.2 Carotenoid–radical adducts 494.3.3 Neutral radicals 504.3.4 Radical anions 514.3.5 The interaction of CARs with the superoxide radical and its protonated conjugated acid 514.4 Future prospects and challenges 534.5 Conclusion 53Acknowledgments 54References 545 Macular Carotenoids: Human Health Aspects 59Aruna Gorusupudi and Paul S. Bernstein5.1 Introduction 595.2 Macular pigment distribution 605.3 Human health aspects 615.4 Age]related macular degeneration (AMD) 615.5 Macular carotenoid absorption 635.6 Stereochemistry and metabolism of macular carotenoids 655.7 Measurement of macular carotenoids 675.8 Conclusions and perspectives 68References 68Part II Spectroscopy 756 Vibrational Spectroscopy as a Tool to Investigate Carotenoids 77Jan Cz. Dobrowolski6.1 Introduction 776.2 Vibrations of carotenoids 776.2.1 Geometry 786.2.2 Geometrical cis]trans isomerism 786.2.3 Syn]periplanar (s]cis) or anti]periplanar (s]trans) conformations 796.2.4 π]electron delocalization 796.2.5 The nature, shape, and energy of the electronic ground and excited states 796.2.6 Electron affinity, ionization, reduction, and oxidation potentials 806.2.7 The nature and shape of molecular vibrations and vibrational coupling patterns 806.2.8 The role of methyl groups attached to the polyene chain and the end groups 816.3 Recent applications of vibrational spectroscopy to study natural carotenoids 816.3.1 Bacteria lichens and algae 836.3.2 Corals and pearls 876.3.3 Art and archeology 906.4 Perspectives 91Acknowledgments 92References 927 Structural Studies of Carotenoids in Plants, Animals, and Food Products 103Takashi Maoka7.1 Introduction 1037.2 Extraction and pre]preparation of carotenoids 1037.3 Chromatography and separation of carotenoids 1057.3.1 Column chromatography and thin]layer chromatography 1057.3.2 High]performance liquid chromatography 1057.4 Quantification of carotenoids 1067.5 Identification and structural elucidation of carotenoids 1067.5.1 Chemical dramatization 1077.5.2 UV]Vis, IR, and Raman spectrometry 1077.5.3 Mass spectrometry 1087.5.4 NMR spectrometry 1117.6 Determination of absolute configuration of carotenoids 1207.6.1 Circular dichroism (CD) spectroscopy 1207.6.2 NMR spectrometry using the modified Mosher method 1227.6.3 Synthetic approach 1237.6.4 X]ray crystallography 1247.6.5 Examples of structural determination of natural carotenoids 1247.7 Conclusion (future prospects and challenges) 126Acknowledgments 126References 1278 In Situ Studies of Carotenoids in Plants and Animals 131Malgorzata Baranska, Jan Cz. Dobrowolski, and Grzegorz Zajac8.1 Introduction 1318.2 Plants 1318.3 Animals 1348.4 Humans 1378.4.1 Skin 1378.4.2 Macular pigment 1398.4.3 Carotenoids in single human cells 1408.5 Perspectives 142Acknowledgments 143References 1439 Carotenoids in Pigment–Protein Complexes: Relation between Carotenoid Structure and Function 147Wieslaw I. Gruszecki9.1 Biological functions of carotenoids 1479.2 Carotenoids in pigment–protein complexes 1499.3 Final remarks 1549.4 Perspectives 155Acknowledgments 155References 155Part III Technology 15910 Carotenoid Biosynthesis and Regulation in Plants 161Rafal Baranski and Christopher I. Cazzonelli10.1 Biosynthetic pathways 16110.1.1 Occurrence in nature 16110.1.2 Cellular localization and compartmentalization 16210.1.3 Pathways to generate isoprenoid precursors for carotenoid biosynthesis 16310.1.4 The main pathway toward carotenoid biosynthesis 16510.1.5 Specialty branches of the pathway 16910.2 Regulation of carotenoid biosynthesis 17010.2.1 Cross]talk between and within the carotenoid and MEP pathways 17110.2.2 Environmental and developmental control 17110.2.3 Regulation by epigenetic and posttranscriptional mechanisms 17210.2.4 Carotenoids in plastid biogenesis, differentiation, and control 17310.2.5 Enzyme localization and metabolon compartmentalization 17410.2.6 Carotenoid degradation and production of signaling metabolites 17510.3 Biofortification and health perspectives 178Acknowledgments 179References 17911 Carotenoid Bioavailability from the Food Matrix: Toward Efficient Extraction Procedures 191Hartwig Schulz11.1 Introduction 19111.2 Occurrence of carotenoids in food materials 19311.3 Bioavailability and bioefficiency of carotenoids 19411.4 Extraction of carotenoids from various food matrices 19711.5 Conclusions 21011.6 Perspectives 211References 21112 Carotenoid Production by Bacteria, Microalgae, and Fungi 217Ralf Martin Schweiggert and Reinhold Carle12.1 Introduction 21712.2 Microbial biosynthesis of carotenoids 21812.3 Carotenoid]rich microorganisms 22312.3.1 Microalgae 22312.3.2 Yeasts and filamentous fungi 22512.3.3 Bacteria 22612.4 Selected examples of biotechnological carotenoid production 22812.4.1 Production of β]carotene 22812.4.2 Production of astaxanthin 23012.4.3 Production of lycopene 23212.4.4 Production of lutein and zeaxanthin 23312.5 Perspectives and conclusions 234References 23513 Impact of Stress Factors on Carotenoid Composition, Structures, and Bioavailability in Microbial Sources 241Agnieszka Kaczor and Marta Z. Pacia13.1 Introduction 24113.2 Light 24213.3 Temperature 24613.4 Carbon and nitrogen sources 24913.5 Aerobic versus anaerobic conditions 25013.6 Inorganic and organic salts 25013.7 Other chemical agents 25313.8 pH 25313.9 Multiple stress factors 25413.10 Perspectives and conclusions 254Acknowledgments 255References 25514 Syntheses with Carotenoids 261Hans]Richard Sliwka and Vassilia Partali14.1 Introduction 26114.2 Reaction with double bonds 26314.2.1 Hydrogenation 26314.2.2 Halogenation 26314.2.3 Oxidation 26314.2.4 Electron transfer from and to carotenoids 26414.2.5 Iron carbonyl 26414.2.6 Nitration 26514.2.7 In]chain modification 26514.3 Transformation of substituents 26514.3.1 −C=O → −C=C− 26514.3.2 −CH=O → CH=S 26714.3.3 −C=O → −C=S 26814.3.4 −C=O → −C−OH 26814.3.5 Inversion of −OH 26914.3.6 −OH → −F, −Cl, −Br, and −I 26914.3.7 −OH → −SR, −SCN, −SH, −N2, −NH2, and −SeR 26914.3.8 −OH → −OR 27014.3.9 −OH → glycosides 27114.3.10 Reactions with carotenoid epoxides 27114.3.11 Reactions with halogen carotenoids 27114.3.12 Metal complexes with carotenols, carotenals, and carotenones 27214.4 Preparative derivatization 27214.5 Syntheses with carotenoid acids and carotenols 27214.5.1 −COOH → −COCl 27314.5.2 −COOH → COO− M+ 27314.5.3 −COOH → COOR 27314.5.4 −COOR → −COOH 27714.5.5 −COOH → −CONH2 27914.5.6 −COOH → −CO−O−OC− (carotenoid anhydrides) 27914.6 Carotenoid reactions with Au 28014.7 Valuation and conclusion 281Acknowledgments 282References 283Index 291