Chlorophylls (eBook)

Gilbert R. Seely, Leo P. Vernon (Herausgeber)

eBook Download: PDF | EPUB

2014 | 1. Auflage
696 Seiten
Elsevier Science (Verlag)
978-1-4832-6772-2 (ISBN)

Infos

The Chlorophylls reviews developments in study of chlorophylls, and at the same time summarizes the state of knowledge in the more established areas of the physics, chemistry, and biology of chlorophylls. The book is organized into four sections. The first section deals with the chlorophylls as chemical entities, and treats their isolation, analysis, chemistry, and synthesis. The second concerns chlorophylls in real and colloidal solution and in the solid state in vitro, and includes the effects of aggregation on visible, infrared, and NMR spectral properties. The third section treats the biosynthesis, organization, and properties of chlorophylls in the plant and bacterial cell, and the fourth is concerned with the photochemical and photophysical behavior of chlorophylls in vitro and in vivo. It is hoped that this work will help those investigating selected aspects of chlorophyll to keep abreast of other methods and approaches, and will provide the interested scientist with a modern, conceptually organized treatment of the subject.

Inhalt

Front Cover 1
The Chlorophylls 4
Copyright Page 5
Table of Contents 10
List of Contributors 3
Contributors 6
Preface 8
List of Abbreviations 16
Section I: Isolation and Chemistry 18
Chapter 1. 
20 
I. Introduction 20
II. Chemical Structures 23
III. Function 33
REFERENCES 36
Chapter 2. Extraction, Separation, Estimation, and Isolation of the Chlorophylls 38
I. Basis of Interest in Analytical Methods 39
II. Nature of Chlorophylls 40
III. Individual Chlorophylls 47
IV. Desiderata for Estimation of Chlorophylls 58
V. Alteration Products 59
VI. Extraction of Chlorophylls 64
Vll. Estimation of Chlorophylls 66
VIII. Preparation of Chlorophylls 70
ACKNOWLEDGMENT 78
REFERENCES 78
Chapter 3. The Structure and Chemistry of Functional Groups 84
I. General Aspects 84
II. Chemistry of Functional Groups 93
REFERENCES 120
Chapter 4. Recently Characterized Chlorophylls 128
l. Introduction 128
II. Chlorophyll d 128
III. Chlorobium Chlorophylls 650 and 660 129
IV. Chlorophyllide(s) c 133
V. Bacteriochlorophyll b 133
VI. Seed-Coat Protochlorophyll 133
VII. "P750" of Blue-Green Algae 134
VIII. ''F698'' 134
IX. Chlorophyll e 134
REFERENCES 134
Chapter 5. 
136 
I. Introduction 136
II. Hans Fischer's Work on the Synthesis of Chlorophyll a 137
III. Woodward's Synthesis of Chlorophyll a 146
REFERENCES 160
Section II: 
162 
Chapter 6. Visible Absorption and Fluorescence of Chlorophyll and Its Aggregates in Solution 164
I. Absorption and Fluorescence Spectra of Monodisperse Chlorophylls and Pheophytins 164
II. Absorption and Fluorescence Spectra of Chlorophyll Aggregates 189
III. Fluorescence and Other Luminescence Properties of Chlorophylls and Analogs 192
REFERENCES 198
Chapter 7. Infrared and Nuclear Magnetic Resonance Spectroscopy of Chlorophyll 202
I. Introduction 203
II. Infrared Spectra 205
III. Nuclear Magnetic Resonance Spectra 232
IV. Applications of Infrared and Nuclear Magnetic Resonance Spectroscopy 252
V. Concluding Remarks 265
ACKNOWLEDGMENTS 266
REFERENCES 266
Chapter 8. Some Properties of Chlorophyll Monolayers and Crystalline Chlorophyll 270
I. Introduction 270
II. Chlorophyll Monolayers 272
III. Crystalline Chlorophyll 288
REFERENCES 295
Section III: 
298 
Chapter 9. 
300 
I. Introduction 300
II. The Chloroplast as a Complete Photosynthetic System 301
III. Structure of Chloroplasts As Revealed by Light Microscopy 303
IV. Structure of Chloroplasts As Revealed by Electron Microscopy 308
V. Distribution of Function within Chloroplasts 315
REFERENCES 326
Chapter 10. 
330 
I. Introduction 330
II. Structure 331
III. Control of Photopigment Synthesis 349
REFERENCES 356
Chapter 11. Spectral Characteristics of Chorophyll in Green Plants 360
I. Introduction 360
II. Early Evidence for an ''Inactive'' Form of Chlorophyll a 362
III. Absorption Spectroscopy 364
IV. Two Photosynthetic Pigment Systems 371
V. Chlorophyll Transformation during Chloroplast Development 374
VI. Fluorescence 381
VII. Orientation of Chlorophyll in Vivo 391
VIII. Conclusion 393
REFERENCES 393
Chapter 12. Absorption and Fluorescence Spectra of Bacterial Chlorophylls in Situ 398
I. Introduction 398
II. Bacteriochlorophylls 400
III. Chlorobium Chlorophylls 410
IV. Discussion 413
ACKNOWLEDGMENTS 413
REFERENCES 413
Chapter 13. 
416 
Part I: Complexes Derived from Green Plants 416
I. Natural Chlorophyll-Protein Complexes 416
II. Artificial Chlorophyll-Protein Complexes 425
REFERENCES 427
Chapter 13 A. Chlorophyll-Protein Complexes 430
Part II: Complexes Derived from Green Photosynthetic Bacteria 430
I. Introduction 430
II. Bacteriochlorophyll-Protein Complex from Chloropseudomonas ethylicum 432
III. Modified Complex 438
ACKNOWLEDGMENT 442
REFERENCES 442
Chapter 13 B. Chlorophyll-Protein Complexes 444
Part III: Optical Rotatory Dispersion of Chlorophyll-Containing Particles from Green Plants and Photosynthetic Bacteria 444
REFERENCES 453
Chapter 14. 
454 
I. Introduction 454
II. Properties of Protochlorophyll 456
III. Protochlorophyll in Vivo 462
IV. Protochlorophyll Holochrome in Vitro 473
REFERENCES 493
Chapter 15. 
498 
I. Pathways in the Formation of Chlorophylls 498
II. The Control of Chlorophyll Metabolism 519
ACKNOWLEDGMENTS 523
REFERENCES 523
Chapter 16. 
528 
I. Introduction 528
II. Chlorophylls of Oxygen-Evolving Photosynthetic Organisms 529
III. Bacterial Chlorophylls 533
IV. Concluding Remarks 534
REFERENCES 535
Section IV: 
538 
Chapter 17. 
540 
I. Introduction 540
II. The Initiation of Photochemical Processes by Chlorophylls 541
III. Photochemical Reactions of Chlorophylls 560
REFERENCES 578
Chapter 18. Photochemistry of Chlorophyll in Vivo 586
I. Introduction 586
II. Photoreactions Associated with Pigment System I of Plants 588
III. Photoreactions Associated with Pigment System II 596
IV. Photoreactions Associated with the Bacterial Systems 600
V. Mechanism of Photochemical Reactions in Vivo 605
REFERENCES 620
Chapter 19. 
626 
I. Photosynthetic Units: Light-Harvesting Pigments and Photochemical Reaction Centers 627
II. Mechanisms for the Transfer and Utilization of Energy Absorbed in Photosynthetic Tissues 635
III. The Significance of Light Emitted by Chlorophylls in Vivo 644
IV. Conclusions 655
REFERENCES 656
Author Index 660
Subject Index 688

Textauszug

2

Extraction, Separation, Estimation, and Isolation of the Chlorophylls*

HAROLD H. STRAIN and WALTER A. SVEC,     Argonne National Laboratory, Argonne, Illinois

Publisher Summary

This chapter discusses extraction, separation, estimation, and isolation of the chlorophylls. From the analytical standpoint, the principal photosynthetically functional green pigments extractable from autotrophic and photo heterotrophic organisms with organic solvents are regarded as chlorophylls. These pigments are products of the autotrophic and photo heterotrophic growth of various organisms. The various green and gray-brown products formed from the natural green pigments when cells are injured or killed, subjected to various reagents, or exposed to various unfavorable conditions are regarded as chlorophyll alteration products. Most analytical methods are not suited to the identification and estimation of chlorophylls within the chloroplasts. In many chromatographic separations, green zones of the common chlorophylls a and b serve as reference standards. Additional green zones may be misinterpreted as indicative of new chlorophylls, although in fact they may be because of chlorophyll alteration products or to anomalous zone formation. Chromatographic separations may be qualitative or quantitative, on an ultramicroscale or on a preparative scale. Qualitative methods reveal the number, the sequence, and the identity of the pigments. Quantitative methods provide individual pigments that may be estimated fluorimetrically, calorimetrically, or spectrophotometrically. Chromatographic methods may be employed in many different modifications, namely, columnar chromatography, one-way paper chromatography, two-way paper chromatography, radial paper chromatography, and also with acceleration by centrifugal force, and thin-layer chromatography.

I Basis of Interest in Analytical Methods

A Significance of Chlorophylls

B Limitations of Analytical Methods

II Nature of Chlorophylls

A Properties of Chlorophylls

B Properties Useful for Analysis

C Examination by Partition and Chromatography

III Individual Chlorophylls

A Properties Required for Analytical Determinations

B Occurrence and Properties

C Natural Variants of Chlorophylls

D Nomenclature

E Criteria of Purity

IV Desiderata for Estimation of Chlorophylls

V Alteration Products

A Variation of Alteration Products

B Well-Defined, Green, Magnesium-Containing Alteration Products

C Poorly Defined, Green, Magnesium-Containing Alteration Products

D Well-Defined, Gray-to-Brown, Magnesium-Free Alteration Products

E Biological Modifications

VI Extraction of Chlorophylls

A Solvents for Extraction

B Treatment of Plant Material

VII Estimation of Chlorophylls

A Methods

B Estimation in Plant Extracts

C Estimation after Transference from the Extracts to Diethyl Ether

D Estimation after Transference to Nonpolar Solvents and Separation by Chromatography

E Calculation of Quantity of Chlorophyll per Unit of Plant Material

VIII Preparation of Chlorophylls

A Objectives

B Chlorophylls a and h

C Deuteriochlorophylls a and b

D Chlorophyll c

E Chlorophyll d

F Protochlorophyll

G Bacteriochlorophyll

H Deuteriobacteriochlorophyll

I Chlorobium Chlorophyll 660

References

I Basis of Interest in Analytical Methods

A Significance of Chlorophylls

Interest in analytical methods for the detection, estimation, and identification of the chlorophylls now arises in many diverse areas of investigation. Greenness or chlorophyll content is an indication of the quality of foods and fodders (1). It reveals the ripeness and quality of many fruits and vegetables (2). It reflects the keeping qualities of some foods (3), and it indicates various changes during the preparation, preservation, and storage of green vegetables (4–9).

In photosynthesis, the chlorophylls absorb the sunlight that is indispensable to the unique autotrophic activities of plants (10–13). They link the inorganic and the organic worlds. In the sea and on the land, the chlorophyll content of the native plants is a key to the production of oxygen (14) and of organic matter (15–22). Among agricultural plants, there is a relationship between the chlorophyll content (chlorophyll synthesis) and crop production, especially as influenced by the inorganic nutrition (23–35) and by pesticides (36).

The capacity of plants to maintain a functional pigment system with little variation throughout the long course of organic evolution has become of great interest to geneticists, taxonomists, and evolutionists (37). The occurrence of the same principal chlorophyll in all autotrophic (oxygen-producing) plants that have been examined points to a common origin for all these organisms (37, 38). Variations of the chlorophylls and the associated carotenoid pigments are related to the taxonomic classification of the organisms (37–45) (see Chapter 16). In the proliferation of plant material, the maintenance of these pigment systems depends upon the direct transmission of the chloroplast material to each new cell. Although remarkably constant in normal plants, the pigment system may be altered by irradiation, various chemical reagents (28, 31, 46), and genetic effects (47–52).

B Limitations of Analytical Methods

Progress in many studies of the chlorophylls depends upon the use of analytical methods for the identification and estimation of these pigments. As a consequence, there has been an increasing need for reliable analytical procedures (19, 53, 54).

In spite of a great deal of experimentation concerning the extraction and estimation of the chlorophylls, no one method combines simplicity, wide applicability, ready reproducibility, and high sensitivity. In fact, so many variable conditions affect the pigments, their extractability and their reactions, that the prospect for the selection of a single analytical procedure that will estimate all the green components of various plants and plant products with high precision is not very promising, as may be inferred from diverse investigations (38-66).

Several extensive reviews with numerous citations have already been devoted to the analytical chemistry of the chlorophylls (38, 62–66), to their structural chemistry and synthesis (55–61), and to their occurrence in various plants (37–43, 63, 65, 67, 68). To conserve space and avoid undue repetition, only the more recent and especially pertinent references are cited in this chapter. The objective of this summary is not to reproduce all the material that is readily available in the reviews (38, 63, 65, 67) and bibliographies (19, 69), but to evaluate the analytical procedures and consider the validity of the conclusions that result from the application of these methods. To this end, the properties of the natural chlorophylls most useful for analytical determinations will be considered. These properties include separability by extraction and chromatography, and the spectral absorption characteristics of the highly purified pigments and their frequently encountered alteration products.

II Nature of Chlorophylls

A Properties of Chlorophylls

From the analytical standpoint, the principal photosynthetically functional green pigments extractable from autotrophic (oxygen-producing) and photoheterotrophic organisms (68) with organic solvents are regarded as chlorophylls. These pigments are products of the autotrophic and photoheterotrophic growth of various organisms. By these criteria, the fully deuterated green pigments...

Produkt-Details

• Erscheint lt. Verlag: 28.6.2014
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Biologie ► Botanik
• Themenwelt: Naturwissenschaften ► Physik / Astronomie ► Angewandte Physik
• Themenwelt: Technik
• ISBN-10: 1-4832-6772-5 / 1483267725
• ISBN-13: 978-1-4832-6772-2 / 9781483267722