Preface ......................................................... v
Abbreviations, Symbols and Definitions ......................... xv
Introduction ................................................. xvii
The Beginning of the Chemical Study of Bioluminescence .... xix
Luciferin .................................................. xx
Photoprotein .............................................. xxi
Chemical Studies on Bioluminescence in the Last One
Hundred Years ............................................ xxii
Chemical Study of Bioluminescence in the Future .......... xxiv
The Contents of this Book ................................ xxvi
1. The Fireflies and Luminous Insects .......................... 1
1.1. The Fireflies ......................................... 3
1.1.1. Essential Factors in the Firefly
Luminescence Reaction ......................... 3
1.1.2. Firefly Luciferin and Oxyluciferin ............ 5
1.1.3. Firefly Luciferase ............................ 8
1.1.4. Assays of Luciferase Activity, ATP and
Luciferin .................................... 11
1.1.5. General Characteristics of the
Bioluminescence of Fireflies ................. 12
1.1.6. Mechanisms of the Bioluminescence ............ 15
1.1.7. Light Emitters in the Firefly
Luminescence System .......................... 17
1.1.8. A Note on the Dioxetanone Pathway and the
l8O-incorporation Experiment ................. 19
1.2. Phengodidae and Elateroidae .......................... 23
1.2.1. Phengodidae .................................. 24
1.2.2. Elateridae ................................... 24
1.3. Diptera .............................................. 25
1.3.1. The Glow-worm Arachnocampa ................... 25
1.3.2. The American Glow-worm Orfelia ............... 27
2. Luminous Bacteria .......................................... 30
2.1. Factors Required for Bioluminescence ................. 31
2.2. Bacterial Luciferase ................................. 33
2.3. Long-chain Aldehyde .................................. 35
2.4. Mechanism of Luminescence Reaction ................... 37
2.5. Assay of Luciferase Activity ......................... 39
2.6. Quantum Yield of Long-chain Aldehydes ................ 41
2.7. In vivo Luminescence of Luminous Bacteria ............ 41
3. The Ostracod Cypridina (Vargula) and Other Luminous
Crustaceans ................................................ 47
3.1. The Ostracod Cypridina ............................... 49
3.1.1. Overview of Ostracoda ........................ 49
3.1.2. Cypridina hilgendorfii Müller ................ 51
3.1.3. Research on Cypridina Luminescence
before 1955 .................................. 53
3.1.4. Purification and Crystallization of
Cypridina Luciferin .......................... 55
3.1.5. Properties of Cypridina Luciferin ............ 58
3.1.6. Oxyluciferin and Etioluciferin ............... 62
3.1.7. Purification and Molecular Properties
of Cypridina Luciferase ...................... 62
3.1.8. Luciferin-luciferase Luminescence
Reaction ..................................... 64
3.1.9. Quantum Yield ................................ 69
3.2. Euphausiids Euphausia pacifica and Meganyctiphanes
norvegica ............................................ 71
3.2.1. Involvement of the Fluorescent Compound F
and Protein P ................................ 71
3.2.2. Fluorescent Compound F ....................... 74
3.2.3. Protein P .................................... 79
3.2.4. Luminescence Reaction ....................... 80
3.3. The Decapod Shrimp Oplophorus gracilirostris ......... 82
3.3.1. Oplophorus Luciferase ........................ 82
3.3.2. Coelenterazine-luciferase Reaction ........... 83
3.4. Copepoda ............................................. 88
4. The Jellyfish Aequorea and Other Luminous Coelenterates .... 90
4.1. The Hydrozoan Medusa Aequorea aequorea ............... 92
4.1.1. History of the Biochemical Study of
Aequorea Bioluminescence ..................... 94
4.1.2. Extraction and Purification of Aequorin ...... 95
4.1.3. Properties of Aequorin ...................... 100
4.1.4. Discovery of the Coelenterazine Moiety
in Aequorin ................................. 111
4.1.5. Regeneration of Aequorin from Apoaequorin ... 113
4.1.6. Recombinant Aequorin ........................ 116
4.1.7. Semisynthetic Aequorins ..................... 118
4.1.8. The In Vivo Luminescence of Aequorea ........ 129
4.2. The Hydroid Obelia (Hydrozoan) ...................... 133
4.2.1. Natural Obelins ............................. 133
4.2.2. Recombinant Obelin .......................... 134
4.3. The Hydrozoan Medusa Phialidium gregarium ........... 137
4.4. Other Bioluminescent Hydrozoans ..................... 138
4.5. The Scyphozoans Pelagia and Periphylla .............. 140
4.5.1. Pelagia noctiluca ........................... 140
4.5.2. Periphylla periphylla ....................... 140
4.6. The Anthozoan Renilla (Sea Pansy) ................... 147
4.7. Green Fluorescent Protein (GFP) ..................... 151
4.8. The Ctenophores ..................................... 154
5. The Coelenterazines ....................................... 159
5.1. Discovery of Coelenterazine ......................... 159
5.2. Occurrence of Coelenterazine ........................ 160
5.3. Properties of Coelenterazine and its Derivatives .... 165
5.4. Chemi- and Bioluminescence Reactions of
Coelenterazine ...................................... 168
5.5. Chemical Reactions of Coelenterazine ................ 173
5.6. Synthesis of Coelenterazines ........................ 176
5.7. Coelenterazine Luciferases .......................... 176
6. Luminous Mollusca ......................................... 180
6.1. The Limpet Latia .................................... 182
6.2. The Clam Pholas dactylus ............................ 192
6.3. Luminous Squids (Cephalopoda) ....................... 199
6.3.1. The Firefly Squid Watasenia scintillans ..... 200
6.3.2. The Purpleback Flying Squid
Symplectoteuthis oualaniensis (Tobi-ika) .... 204
6.3.3. The Luminous Flying Squid Symplectoteuthis
luminosa (Suji-ika) ......................... 210
7. Annelida .................................................. 216
7.1. The Tubeworm Chaetopterus variopedatus .............. 216
7.1.1. Biochemistry of the Luminescence of
Chaetopterus variopedatus ................... 218
7.1.2. Properties of the Chaetopterus
Photoprotein and its Luminescence
Reaction .................................... 221
7.2. The Bermuda Fireworm Odontosyllis ................... 225
7.3. Luminous Earthworms (Oligochaeta) ................... 234
7.4. Polynoid Scaleworm Harmothoö lunulata .............. 242
7.5. The Polychaete Tomopteris .......................... 246
8. Dinoflagellates and Other Protozoa ........................ 248
8.1. Radiolarians ........................................ 248
8.2. Dinoflagellates ..................................... 249
8.2.1. Cultivation and Harvesting of
Dinoflagellates ............................. 251
8.2.2. Scintillons ................................. 251
8.2.3. The Luciferase of Gonyaulax polyedra ........ 252
8.2.4. Extraction and Purification of
Dinoflagellate Luciferin .................... 256
8.2.5. Properties of Dinoflagellate Luciferin ...... 258
8.2.6. Chemical Structures of Dinoflagellate
Luciferin and its Oxidation Products ........ 260
8.2.7. Chemical Mechanism of Dinoflagellate
Bioluminescence ............................. 263
8.2.8. Luciferin Binding Protein of
Dinoflagellates ............................. 264
9. Luminous Fungi ............................................ 266
9.1. An Overview on Fungal Bioluminescence ............... 266
9.2. Early Studies on the Biochemistry of Luminous
Fungi ............................................... 268
9.3. Role of Superoxide in Fungal Luminescence ........... 271
9.4. Studies on Panellus stipticus ....................... 275
9.4.1. Panal ....................................... 277
9.4.2. Activation Products of Panal ................ 279
9.4.3. PS-A and PS-B ............................... 282
9.4.4. Activation of PS-A and PS-B ................. 283
9.4.5. Mechanism of the in vivo Bioluminescence
of P. stipticus ............................. 289
9.4.6. Synthetic Studies of Panellus Luciferin ..... 291
9.5. Studies on Mycena citricolor ........................ 294
9.5.1. Luciferin Obtained by Kuwabara and
Wassink ..................................... 294
9.5.2. Studies on the Mycena citricolor
Luminescence by the Author .................. 294
9.6. Summary on the Chemistry of Fungal Luminescence ..... 298
10. Other Luminous Organisms .................................. 301
10.1. Ophiuroidea: Brittle Stars .......................... 301
10.1.1. The Brittle Star Ophiopsila californica ..... 302
10.1.2. The Brittle Star Ampbiura fillformis ........ 307
10.2. Millipede Luminodesmus sequoiae (Diplopoda) ......... 307
10.3. Centipede Orphaneus brevilabiatus (Chilopoda) ....... 314
10.4. Hemicordata ......................................... 315
10.4.1. The Acorn Worm Balanoglossus biminiensis .... 315
10.4.2. The Luciferin of Ptychodera flava ........... 318
10.5. Tunicates (Phylum Chordata) ......................... 319
10.6. The Luminous Fishes ................................. 322
10.6.1. Coastal and Shallow-water Fishes that
Utilize Cypridina Luciferin ................. 323
10.6.2. Oceanic Deep-sea Luminous Fishes ............ 327
10.6.3. Future Research on Fish Bioluminescence ..... 330
Appendix ...................................................... 333
A Taxonomic Classification of Selected Luminous
Organisms ............................................ 333
В Lists of Luciferins, Luciferases and Photoproteins
Isolated ............................................. 340
С Miscellaneous Technical Information .................. 349
C1 Basic Principle of the Isolation of
Bioluminescent Substances ........................ 349
С1.1. Reversible Inhibition of Bioluminescence ... 350
C1.2. Extraction of Luciferin-luciferase
Systems .................................... 353
C1.3. Solubilization of Proteins ................. 353
C1.4. Purification ............................... 355
C2. Storage of Samples ............................... 356
C3. Measurement of Luminescence ...................... 360
C4. Calibration of Luminometer and the Measurement
of Quantum Yield ................................. 361
C5. Measurements of Coelenterazine, its
Derivatives, and other Important Substances
in Bioluminescence ............................... 363
C5.1. Assay of Coelenterazine .................... 363
C5.2. Assay of the Coelenterazine Luciferase
Activity ................................... 364
C5.3. Assay of the Stabilized Forms of
Coelenterazine ............................. 365
C5.4. Assay of Dehydrocoelenterazine ............. 366
C5.5. Assay of Cypridina Luciferin ............... 366
C5.6. Assay of Cypridina Luciferase .............. 367
C5.7. Assay of Ca2+-sensitive Photoproteins ... 368
C5.8. Measuring Bioluminescence in the Field ..... 369
C6. l8O-Labeling of the Reaction Product CO2 ......... 370
C7. Glass Blowing .................................... 374
D Advice to Students Who are Interested in Studying
the Chemistry of Bioluminescence ..................... 375
References .................................................... 379
Index ......................................................... 455
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