Chlorophylls and bacteriochlorophylls : biochemistry, biophysics, functions and applications /

Editorial p. v
Contents p. xi
Preface p. xxii
Author Index p. xxix
Color Plates p. CP1
Part 1 Structures, Chemistry, Analysis
1 An Overview of Chlorophylls and Bacteriochlorophylls: Biochemistry, Biophysics, Functions and Applications Hugo Scheer p. 1
Summary p. 1
I Introduction p. 2
II Structures p. 4
III Why Chlorophylls? p. 12
IV Functions p. 16
Acknowledgments p. 19
References p. 19
2 Synthesis, Reactivity and Structure of Chlorophylls Mathias O. Senge and Arno Wiehe and Claudia Ryppa p. 27
Summary p. 27
I Basic Structure and Reactivity of Chlorophylls p. 28
II Conformational Flexibility of Hydroporphyrins p. 28
III Chemical Synthesis of Chlorophylls and Bacteriochlorophylls p. 29
IV Chemical Modifications p. 30
Acknowledgments p. 35
References p. 35
3 Chlorophyll c Pigments: Current Status Manuel Zapata and Jose L Garrido and Shirley W. Jeffrey p. 39
Summary p. 40
I Introduction p. 40
II Chemistry of Chlorophyll c Pigments p. 41
III Biochemistry of Chlorophyll c Pigments p. 46
IV Distribution p. 47
V Applications and Future Directions p. 47
Note Added in Proof p. 50
Acknowledgments p. 50
References p. 50
4 Unusual Tetrapyrrole Pigments of Photosynthetic Antennae and Reaction Centers: Specially-tailored Chlorophylls Masami Kobayashi and Machiko Akiyama and Hideo Kise and Tadashi Watanabe p. 55
Summary p. 56
I Introduction p. 56
II Specially-tailored Chlorophylls in a Limited Number of Organisms p. 56
III Specially-tailored Chlorophylls Associated with Reaction Centers p. 59
Acknowledgments p. 63
References p. 63
5 [Heavy metal]-Chlorophylls Formed in Vivo During Heavy Metal Stress and Degradation Products Formed During Digestion, Extraction and Storage of Plant Material Hendrik Kupper and Frithjof C. Kupper and Martin Spiller p. 67
Summary p. 67
I Introduction p. 68
II Substitution of the Central Mg[superscript 2+] Ion Under Elevated Heavy Metal Concentrations in vivo p. 68
III Occurrence of Partially Degraded and Transmetalated Chlorophyll Derivatives in Marine Invertebrates p. 72
IV Chlorophyll Degradation Products Formed During Storage and Extraction of Plant Material p. 73
Acknowledgments p. 75
References p. 75
6 Spectroscopy and Structure Determination Masami Kobayashi and Machiko Akiyama and Hiromi Kano and Hideo Kise p. 79
Summary p. 79
I Introduction p. 80
II Absorption Spectra p. 80
III Fluorescence Spectra p. 85
IV Circular Dichroism Spectra p. 87
V Mass Spectra p. 88
VI Nuclear Magnetic Resonance Spectra p. 90
Acknowledgments p. 93
References p. 93
7 Spectrometric Assays for Plant, Algal and Bacterial Chlorophylls Robert J. Porra p. 95
Summary p. 95
I Introduction p. 96
II Modern Spectrophotometric Assays of Chlorophylls a and b p. 96
III Choice of Extractant and Determination of Accurate Extinction Coefficients for Chlorophylls a and b in Such Solvents p. 96
IV Reliable Simultaneous Equations for the Accurate Assay of Chlorophylls a and b p. 99
V The Unacceptable Errors and Consequences of Using the Arnon Equations p. 100
VI Other Spectrophotometric Assays for Chlorophylls a and b in Association with Their Derivatives or Other Pigments p. 101
VII Spectrophotometric Assays for Chlorophylls in Chlorophyll c-containing Algae p. 101
VIII Spectrophotometric Data for the Assay of Bacteriochlorophylls p. 101
IX Spectrofluorimetric Assays for Chlorophylls a and b p. 103
X Concluding Remarks p. 105
Acknowledgments p. 105
References p. 105
8 Chlorophyll Analysis by New High Performance Liquid Chromatography Methods Jose L. Garrido and Manuel Zapata p. 109
Summary p. 109
I Introduction p. 110
II New Bonded Phase Columns p. 110
III Mass Spectrometry as High Performance Liquid Chromatography Detection Technique Applied to Chlorophylls p. 112
IV Applications p. 113
V Future Directions in the High Performance Liquid Chromatography Analysis of Chlorophylls p. 115
Acknowledgments p. 119
References p. 119
9 Large Scale Chlorophyll Preparations Using Simple Open-Column Chromatographic Methods Yuzo Shioi p. 123
Summary p. 124
I Introduction p. 124
II Extraction of the Pigments p. 124
III Precipitation of Chlorophylls p. 126
IV Column Chromatographic Methods p. 127
Acknowledgments p. 130
References p. 131
Metabolism
10 Chlorophyll Metabolism, an Overview Wolfhart Rudiger and Bernhard Grimm p. 133
Summary p. 133
I Introduction p. 134
II The Diversity of Tetrapyrrole Metabolic Pathways p. 134
III Subcellular Location of Enzymes p. 140
IV Regulation of Chlorophyll Biosynthesis p. 140
V Incorporation into Proteins p. 142
VI Chlorophyll Degradation p. 143
VII Concluding Remarks p. 143
References p. 143
11 Biosynthesis of 5-Aminolevulinic Acid Samuel I. Beale p. 147
Summary p. 147
I Alternate Pathways for 5-Aminolevulinic Acid Biosynthesis p. 147
II 5-Aminolevulinic Acid Biosynthesis from Glycine and Succinyl-Coenzyme A p. 148
III 5-Aminolevulinic Acid Biosynthesis from Five-Carbon Precursors p. 149
IV Phylogenetic Distribution and Evolutionary Implications of the Two 5-Aminolevulinic Acid Biosynthetic Pathways in Photosynthetic Species p. 154
Acknowledgments p. 154
References p. 154
12 Transfer RNA-Dependent Aminolevulinic Acid Formation: Structure and Function Of Glutamyl-tRNA Synthetase, Reductase and Glutamate-1-Semialdehyde-2, 1-Aminomutase Dieter Jahn and Jurgen Moser and Wolf-Dieter Schubert and Dirk W. Heinz p. 159
Summary p. 159
I Two Pathways for 5-Aminolevulinic Acid Biosynthesis p. 160
II Glutamyl-tRNA Synthetase Forms Glutamyl-tRNA for Protein and Tetrapyrrole Biosynthesis p. 160
III Glutamyl-tRNA p. 160
IV Glutamyl-tRNA Synthetase p. 160
V Glutamyl-tRNA Reductase p. 163
VI Glutamate-1-Semialdehyde-2, 1-Aminomutase p. 166
VII Metabolic Channeling of Glutamate-1-Semialdehyde p. 167
VIII Concluding Remarks p. 167
Acknowledgments p. 168
References p. 168
13 The Pathway from 5-Aminolevulinic Acid to Protochlorophyllide and Protoheme Elena Yaronskaya and Bernhard Grimm p. 173
Summary p. 173
I Introduction p. 174
II Enzymes of Porphyrin Synthesis p. 174
III The Chlorophyll-synthesizing Branch p. 178
IV The Protoheme-synthesizing Branch p. 182
V Concluding Remarks p. 183
References p. 183
14 Biosynthesis of Chlorophylls a and b: The Last Steps Wolfhart Rudiger p. 189
Summary p. 189
I Introduction p. 190
II Protochlorophyllide Reduction p. 190
III Metabolism of Chlorophyll b and Chlorophyllide b p. 193
IV Esterificatlon p. 195
Supplement p. 197
Note Added in Proof p. 197
Acknowledgments p. 197
References p. 197
15 Bacteriochlorophyll Biosynthesis in Green Bacteria Niels-Ulrik Frigaard and Aline Gomez Maqueo Chew and Julia A. Maresca and Donald A. Bryant p. 201
Summary p. 201
I Introduction p. 202
II Approach to Elucidating Bacteriochlorophyll Biosynthesis in Green Bacteria p. 203
III Overview of Proposed Pathways p. 206
IV Early Steps in Porphyrin Biosynthesis p. 209
V Bacteriochlorophyll a Biosynthesis p. 209
VI Chlorophyll a Biosynthesis p. 210
VII Bacteriochlorophyll c Biosynthesis p. 211
VIII Bacteriochlorophyll d Biosynthesis p. 215
IX Bacteriochlorophyll e Biosynthesis p. 215
X Bacteriochlorophyll c Biosynthesis in Green Filamentous Bacteria p. 216
XI Future Directions p. 217
Note added in Proof p. 217
Acknowledgments p. 217
References p. 217
16 Involvement of Tetrapyrroles in Cellular Regulation Christoph F. Beck and Bernhard Grimm p. 223
Summary p. 223
I Introduction p. 224
II Intra-organellar Regulation by Tetrapyrroles p. 225
III Role for Tetrapyrroles in Inter-organellar Signaling p. 226
IV Transport of Tetrapyrroles p. 230
V Concluding Remarks p. 230
References p. 232
17 Chlorophyll Catabolites and the Biochemistry of Chlorophyll Breakdown Bernhard Krautler and Stefan Hortensteiner p. 237
Summary p. 237
I Introduction p. 238
II Chlorophyll Breakdown and Chlorophyll Catabolites in Higher Plants p. 239
III Chlorophyll Breakdown and Chlorophyll Catabolites in Green Algae p. 254
IV Chlorophyll Catabolites from Marine Organisms p. 255
V Conclusions and Outlook p. 256
Note Added in Proof p. 256
Acknowledgments p. 257
References p. 257
18 The Evolution of Chlorophylls and Photosynthesis Anthony W. D. Larkum p. 261
Summary p. 261
I Introduction p. 262
II The Early Earth and the Origins of Photosynthesis p. 262
III Evolution of the Pathway to the Earliest Photosynthetic Pigments p. 263
IV Evolution of Extant Photosynthetic Pigments and Early Photosynthetic Organisms p. 267
V Reaction Centers p. 272
VI Evolution of Oxygenic Photosynthesis p. 275
VII Light-Harvesting Chlorophyll Proteins p. 277
VIII Outlook p. 278
References p. 278
The Native Environment
19 The Influence of Protein Interactions on the Properties of the Bacteriochlorophyll Dimer in Reaction Centers James P. Allen and JoAnn C. Williams p. 283
Summary p. 283
I Introduction p. 284
II Protein Interactions that Influence the Properties of the Dimer p. 285
III Modeling the Effect of Protein Interactions on the Electronic Structure of the Dimer p. 288
IV The Effect of Protein Interactions on Electron Transfer p. 290
V Conclusions p. 292
Acknowledgments p. 292
References p. 293
20 Magic Angle Spinning Nuclear Magnetic Resonance of the Chlorosomes Ido de Boer and Huub J. M. de Groot p. 297
Summary p. 297
I Introduction p. 297
II Aggregated Hydrated Chlorophyll (Chl a/H[subscript 2]O) as a Model for Magic Angle Spinning Nuclear Magnetic Resonance Technology Development p. 298
III Self-organization of Bacteriochlorophyll is the Main Structural Feature of the Chlorosomal Antennae p. 300
IV A 3-Dimensional Model for the Structure of the Chlorosomal Antennae p. 303
V Conclusions and Future Prospects p. 304
Note Added in Proof p. 305
References p. 305
21 Single Molecule Spectroscopy of Pigment Protein Complexes from Purple Bacteria Jurgen Kohler and Thijs J. Aartsma p. 309
Summary p. 309
I Introduction p. 310
II Spectroscopy of Individual Light-harvesting Complexes p. 312
Acknowledgments p. 319
References p. 319
22 Effects of Axial Coordination, Electronic Excitation and Oxidation on Bond Orders in the Bacteriochlorin Macrocycle, and Generation of Radical Cation on Photo-Excitation of in vitro and in vivo Bacteriochlorophyll a Aggregates: Resonance Raman Studies Yasushi Koyama and Yoshinori Kakitani and Leenawaty Limantara and Ritsuko Fujii p. 323
Summary p. 224
I The 5- and 6-Coordinated States of Bacteriochlorophyll a in the S[subscript 0], T[subscript 1] and D[subscript 0] Electronic States as Probed by the Ring-Breathing Frequency p. 324
II Changes in Bond Orders as Scaled by Stretching Force Constants in the Conjugated Systems of Bacteriochlorophyll a, Bacteriopheophytin a and Carotenoid: Implication of the Arrangement of Those Pigments in the Reaction Center p. 329
III Generation of the T[subscript 1] State and Subsequent Transformation into the D[subscript 0] State upon Photo-Excitation of in vitro and in vivo Bacteriochlorophyll a Aggregates p. 331
Acknowledgments p. 334
References p. 335
23 Mapping the Global Ring Currents in Porphyrins and Chlorins Erich Steiner and Patrick W. Fowler p. 337
Summary p. 337
I Introduction p. 337
II Electronic Structure and Spectra p. 337
III Ring Currents p. 339
IV Orbital Model of Ring Currents p. 341
V The Four-Orbital Model of the Ring Current in Porphyrins p. 341
VI Pathways p. 342
VII Porphin and Magnesium Porphin p. 342
VIII Chlorins p. 346
Appendix p. 346
Note Added in Proof p. 346
References p. 346
24 Bacteriochlorophyll Protein Maquettes Dror Noy and Christopher C. Moser and P. Leslie Dutton p. 349
Summary p. 349
I Protein Maquette Tools for Exploring Natural Design of Chlorophyll- and Bacteriochlorophyll-Proteins p. 350
II Essentials of De Novo Designing Protein Maquettes p. 352
III Adapting Natural LHs to Maquettes p. 353
IV Concluding Remarks p. 360
Acknowledgments p. 360
References p. 360
25 Molecular Assembly of Bacteriochlorophyll Complexes Using Synthetic Light-Harvesting Model Polypeptides Mamoru Nango p. 365
Summary p. 365
I Introduction p. 365
II Molecular Assembly of Bacteriochlorophylls with Isolated Light-Harvesting Subunits from Rhodobacter sphaeroides and Synthetic Models p. 367
III Molecular Assembly of Bacteriochlorophyll a Complex and Its Analogues by Synthetic 4[alpha]-Helix Polypeptides p. 369
IV Concluding Remarks p. 371
Acknowledgments p. 372
References p. 372
26 Reconstitution and Pigment Exchange Harald Paulsen p. 375
Summary p. 375
I Introduction p. 376
II Reconstitution p. 376
III Pigment Exchange p. 379
IV Concluding Remarks p. 381
Note Added in Proof p. 381
References p. 382
27 Assembly of Model Bacteriochlorophyll Proteins in the Native Lipid Environment Adela Garcia-Martin and Lee Gyan Kwa and Mathias von Jan and C. Neil Hunter and Paula Braun p. 387
Summary p. 387
I Introduction p. 388
II Bacteriochlorophyll Proteins with Model Transmembrane Helices p. 388
III Assembly Motifs of (Bacterio)chlorophyll Proteins p. 391
Acknowledgments p. 394
References p. 394
Functions
28 Photosynthetic Functions of Chlorophylls Alexander N. Melkozernov and Robert E. Blankenship p. 397
Summary p. 397
I Introduction p. 398
II Structure of Chlorophylls and Their Relevance to Photosynthetic Functions p. 398
III Chlorophyll-Sensitized Electron Transfer p. 399
IV Light-harvesting and Energy Transfer p. 402
V Structural Function p. 408
V Photoprotective Function of Chlorophylls p. 408
Acknowledgments p. 410
References p. 410
29 Excitation Energy Transfer Between (Bacterio)Chlorophylls-the Role of Excitonic Coupling Dieter Leupold and Heiko Lokstein and Hugo Scheer p. 413
Summary p. 413
I Introduction p. 414
II Excitation Energy Transfer in Purple Bacteria p. 415
III Excitation Energy Transfer in Light-Harvesting Complex II-type Complexes of Higher Plants p. 420
IV Excitation Energy Transfer in Chlorosomes p. 423
V Excitation Energy Transfer in the Fenna-Matthews-Olsen (FMO) Complex p. 424
Note Added in Proof p. 425
Acknowledgments p. 426
References p. 426
30 Mechanisms of Carotenoid-to-Bacteriochlorophyll Energy Transfer in the Light Harvesting Antenna Complexes 1 and 2: Dependence on the Conjugation Length of Carotenoids Yasushi Koyama and Yoshinori Kakitani p. 431
Summary p. 431
I Introduction p. 432
II Intrinsic Properties of Carotenoids' Excited-States p. 432
III Carotenoid-to-Bacteriochlorophyll Energy Transfer in Light Harvesting Complex 2 p. 434
IV Carotenoid-to-Bacteriochlorophyll Energy Transfer in Light Harvesting Complex 1 p. 438
V Comparison between the Light Harvesting Complexes 1 and 2 p. 439
Acknowledgments p. 442
References p. 443
31 Electron Transfer in Photosynthetic Reaction Centers Josef Wachtveitl and Wolfgang Zinth p. 445
Summary p. 445
I Introduction p. 446
II Dynamics and Energetics of the First Electron Transfer Reactions in Bacterial Reaction Centers p. 446
III Optimization of Photosynthesis p. 454
IV Concluding Remarks p. 455
References p. 455
Applications
32 Chlorophyll Sensitizers in Photodynamic Therapy Alexander S. Brandis and Yoram Salomon and Avigdor Scherz p. 461
Summary p. 462
I Introduction p. 462
II Photosensitizers Derived from Chlorophyll a p. 465
III Clinical Trials p. 476
Acknowledgments p. 476
References p. 476
33 Bacteriochlorophyll Sensitizers in Photodynamic Therapy Alexander S. Brandis and Yoram Salomon and Avigdor Scherz p. 485
Summary p. 486
I Introduction p. 486
II Photosensitizers Derived from Bacteriochlorophyll a p. 487
III Clinical trials p. 491
IV Conclusions and Perspectives p. 491
Acknowledgements p. 491
References p. 492
34 Metal-substituted Bacteriochlorophylls: Novel Molecular Tools Roie Yerushalmi and Idan Ashur and Avigdor Scherz p. 495
Summary p. 495
I Introduction p. 496
II From Porphyrins to Bacteriochlorophylls: An Experimental Benchmark for Theoretical Approaches p. 496
III Function-Oriented Chemical Modification of Bacteriochlorophylls p. 497
IV Applications p. 499
V Concluding Remarks p. 503
Acknowledgments p. 503
References p. 503
35 Chlorophyll Fluorescence as a Reporter on in vivo Electron Transport and Regulation in Plants Ladislav Nedbal and Michal Koblizek p. 507
Summary p. 507
I Introduction p. 508
II Time Scales p. 508
III Analysis of Chlorophyll Fluorescence Transients p. 511
IV Beyond the Conventional Analysis p. 515
V Prospects of the Technique and Instrumentation p. 516
Acknowledgments p. 516
References p. 516
36 Meeting the Challenge of Monitoring Chlorophyll in the Ocean from Outer Space Andre Morel p. 521
Summary p. 521
I Introduction p. 522
II Absorbing Substances in the Marine Environment p. 523
III Bio-optical Relationships in Oceanic Waters and Chlorophyll Algorithms p. 525
IV Reflectance of Oceanic Waters p. 528
V Phytoplankton Distribution and Primary Production p. 528
VI Sun-stimulated Fluorescence p. 531
VII Concluding Remarks: The Atmospheric Correction p. 531
Acknowledgments p. 532
References p. 533
37 Geochemistry of Chlorophylls Brendan J. Keely p. 535
Summary p. 536
I Introduction p. 536
II Chlorophyll Transformations p. 544
III Timing and Nature of Transformations p. 551
IV Transformation Scheme p. 553
V Applications p. 554
VI Concluding Remarks p. 556
Note Added in Proof p. 556
Acknowledgments p. 557
References p. 557
Index p. 563