Description
Depuis l’isolement de la creatine par CHEVREUL, en 1832, dans les extraits de viande (44) et son identification par LIEBIG, en r847, l’attention des biochimistes a porte principalement, pendant longtemps, sur le role de l’arginine dans la production de l’uree (I28), sur le cyde de l’ureo genese (I34) et sur celui de la phosphocreatine (7I) et de la phospho arginine (r68, I69) dans la contraction musculaire. A la suite de la mise en evidence, d’une part des reactions de trans amidination expliquant la convertibilite entre l’arginine et un certain nombre de derives guanidiques (28,29,33,73,25, 29I, 292), et, d’autre part, du mecanisme complexe de la biosynthese de l’arginine (34, 45, 46, I95, I96) , l’importance du groupement guanidique dans la fixation et le transfert de l’azote organique est devenue beaucoup plus manifeste. Par ailleurs, l’isolement de nouvelles substances dont certaines: la phosphotaurocyamine, la phosphoglycocyamine (280-282), la phospho- 10mb ricine (270), jouent le meme role de phosphagenes que le creatine et l’argininephosphate (257), amis en evidence la part importante que les derives guanidiques prennent dans la chimie du musde. L’etude de leur biogenese a montre en outre que leur role n’est pas seulement equivalent a l’arginine dans la fixation de l’azote du groupe amidinique, mais qu’ils sont capables de jouer egalement de role de regulateurs du metabolisme azote (258). I. Structure et formation. / Contents / Table des matires.- Die Actinomycine.- I. Einleitung.- II. Gewinnung und Eigenschaften der Actinomycine.- 1. Trennung von Actinomycingemischen.- 2. Von Streptomyces-Arten produzierte Actinomycingemische.- Die Actinomycingemische C, X und I.- Actinomycingemisch Z.- Actinomycin bildende Streptomyces-Arten.- Identifizierung frher beschriebener Actinomycingemische.- Actinomycingemische der dirigierten Biosynthese.- 3. Nomenklatur der Actinomycine.- Nomenklatur nativer Actinomycingemische.- Nomenklatur reiner Actinomycine.- 4. Eigenschaften und Aminosuregehalt reiner Actinomycine.- Physikalische Eigenschaften.- Chemische Eigenschaften.- Molekulargewicht.- Aminosuregehalt.- III. Die Konstitution der Actinomycine.- 1. Die Konstitution des Chromophors.- Despeptido-actinomycin.- Konstitution des Despeptido-actinomycins.- Synthese des Despeptido-actinomycins.- Farbige Abbauprodukte der Surehydrolyse.- Actinocinin.- Konstitution des Actinomycin-Chromophors.- Synthese des Actinomycin-Chromophors.- Reaktionen des Actinomycin-Chromophors.- 2. Die Konstitution des Peptidteils.- Actinomycin C3.- Actinomycin C1 (I1 X1, D).- Actinomycin C2.- Actinomycin X2.- Actinomycin X0?.- Actinomycin X0?.- 3. Struktur-Variationen des Peptidteils.- IV. Derivate der Actinomycine.- 1. Derivate, die durch Vernderung des Peptidteils entstehen.- 2. Derivate, die durch Vernderung des Chromophors entstehen.- Natrlich vorkommende Nitroverbindungen..- I. Chloramphenicol.- 1. Isolierung und Konstitutionsermittlung.- 2. Synthesen.- 3. Herstellung des Chloramphenicols auf biologischem Wege.- 4. Bestimmung des Chloramphenicols.- II. ?-Nitropropionsure.- III. Aristolochiasuren.- 1. ber ltere Arbeiten.- 2. Neuere Arbeiten zur Isolierung, Reindarstellung und Konstitutionsermittlung.- 3. Konstitution der Aristolochiasure-I.- 4. Konstitution der Aristolochiasure-II.- 5. Weiteres Vorkommen von Aristolochiasuren und Isolierung und Charakterisierung von strukturell verwandten Naturstoffen.- Drivs guanidiques biologiques..- I. Structure et formation.- 1. Structure.- 2. Nomenclature.- 3. Formation par voie chimique.- 4. Biogense.- a. Formation par amidination successive: cas de l’arginine.- b. Formation par transformation d’autres composs guanidiques.- c. Formation par transamidination.- II. Proprits gnrales.- 1. Basicit.- 2. Formation des sels.- 3. Stabilit et hydrolyse.- 4. Cyclisation.- 5. Oxydation.- 6. Dgradation biochimique.- a. Dguanidylation.- b. Dsamidination totale.- c. Ds-amidination partielle.- III. Mthodes gnrales d’analyse et de preparation.- 1. Ractions d’identification et de dosage.- a. Raction au diactyle.- b. Raction l’?-naphtol.- c. Raction au nitroprussiate ferrique.- d. Raction la ninhydrine.- 2. Chromatographie sur papier et sur colonne. Electrophorse.- IV. Rpartition des drivs guanidiques.- Conclusions.- Bibliographie.- Naturally Derived isoThiocyanates (Mustard Oils) and Their Parent Glucosides..- I. Introduction.- II. Historical Development.- III. Parent Glucosides.- 1. General Properties.- 2. Distribution in Plant Tissues.- 3. Detection, Isolation, Separation and Determination.- a. Paper Chromatography.- b. Isolation and Separation Methods.- c. Quantitative Determination.- 4. Chemical Structure.- a. Earlier Formulation.- b. Revised Structures.- c. Synthesis.- 5. Individual Glucosides.- IV. Enzymic Hydrolysis.- 1. Distribution of Myrosinase.- 2. Properties of Myrosinase.- V. Naturally Derived isoThiocyanates.- 1. General Properties.- 2. Detection, Isolation, Separation and Determination.- a. Chromatographic Methods.- b. Isolation.- c. Separation.- d. Quantitative Determination.- 3. Chemical Structure.- a. Saturated Alkyl isoThiocyanates.- b. Unsaturated Alkyl isoThiocyanates.- c. ?-Methylthioalkyl isoThiocyanates and Related Sulphoxides and Sulphones.- Stereochemistry.- d. Aromatic isoThiocyanates.- e. Hydroxy-substituted iso-Thiocyanates.- f. isoThiocyanates of Doubtful Structure.- VI. Botanical Distribution of isoThiocyanate Glucosides.- VII. Biological Properties of isoThiocyanates and Their Parent Glucosides.- VIII. Tables.- 1. Crystalline isoThiocyanate Glucosides, Known at the End of 1959.- 2. Crystalline isoThiocyanate Glucoside Tetraacetates, Known at the End of 1959.- 3. isoThiocyanate Glucosides with Established Side-chains, Known at the End of 1959.- 4. Molecular Rotations of Sulphoxide isoThiocyanates of Natural Origin, Some Derivatives and Related Compounds.- 5. The Occurrence of isoThiocyanates or Their Parent Glucosides in Species of the Family Cruciferae.- 6. The Occurrence of isoThiocyanates or Their Parent Glucosides in Families Other than Cruciferae.- References.- Die Farbstoffe im Gefieder der Vgel..- I. Einleitung.- II. Carotinoide (Lipochrome).- 1. Lutein (Xanthophyll).- 2. Kanarienxanthophyll.- 3. Zeaxanthin.- 4. Picofulvin.- 5. Astaxanthin bzw. Astacin.- 6. Rhodoxanthin.- 7. Rote Carotinoide unbekannter Struktur.- 8. Physiologische Grundlagen der Carotinoid-Ablagerung.- III. Die gelben und roten Federfarbstoffe der Papageien.- IV. Fluoreszierende, gelbe Federfarbstoffe.- 1. Bei Papageien.- 2. Bei anderen Arten.- V. Pyrrolfarbstoffe.- 1. Koproporphyrin.- 2. Turacin.- 3. Pyrrolfarbstoffe im Stoffwechsel der Vgel.- VI. Chemisch ungeklrte Federpigmente.- VII. Rckblick.- Cis-trans Isomeric Carotenoid Pigments..- I. Introduction.- Nomenclature.- Some Historical Remarks on Stereoisomerism of Polyenes.- II. Number and Types of cis Carotenoids. Steric Hindrance.- III. Some Properties of cis Carotenoids.- 1. Relative Stabilities.- Sterically Unhindered cis Forms.- Sterically Hindered cis Forms.- Polycis Forms.- 2. Melting Points.- 3. Rotatory Power.- 4. Relative Adsorption Affinities.- IV. Cis-trans Isomerism and UV Spectra.- 1. Some Remarks on the Spectra of all-trans Carotenoids.- 2. Spectral Effect of trans ? cis Isomerization in the Visible Region.- 3. Spectral Effect of trans ? cis Isomerization in the Near Ultraviolet Region: the cis-Peak.- 4. A Theoretical Interpretation of Spectral Phenomena, Especially of the cis-Peak Effect.- 5. Spectra at Extremely Low Temperatures.- V. Preparation of cis Carotinoids by Direct Rearrangement of the All-trans Form.- 1. Thermal Methods of cis-trans Isomerization.- (a) Spontaneous Rearrangement in Solution at Room Temperature.- (b) cis-trans Isomerization in Refluxed Solutions.- (c) cis-trans Isomerization by Melting Crystals.- 2. Photochemical cis-trans Isomerization in the Absence of Catalysts.- 3. cis-trans Isomerization by Iodine Catalysis, in Light.- 4. cis-trans Isomerization by Acid Catalysis.- 5. cis-trans Isomerization by Contact with Active Surfaces.- 6. cis-trans Isomerization via Boron Trifluoride Complexes.- 7. Bio-stereoisomerization.- VI. Preparation of cis Carotenoids by Total Synthesis.- VII. Naturally Occurring cis and Polypcis Carotenoids.- 1. Mono- and Dicis Carotenoids.- 2. Polycis Carotenoids.- Prolycopene.- Further Polycis Lycopenes.- Proneuro-sporene (Protetrahydrolycopene, Neoneurosporene P).- Pro-?-carotene.- VIII. Some General Remarks on Configurational Assignments.- 1. Stereoisomeric Types.- 2. Number and Location of cis Double Bonds.- 3. Configuration and Infrared Spectrum.- IX. Configurational Assignments in Certain Stereoisomeric Sets.- 1. Stereoisomeric Sets with Two Hydroaromatic Terminal Groups.- ?-Carotene Set.- Cryptoxanthin Set.- Zeaxanthin Set.- Isozeaxanthin Set.- Echinenone Set.- Can-thaxanthin Set.- ?-Carotene Monoepoxide Set.- ?-Carotene Diepoxide Set.- 3,4-Dehydro-?-carotene and 3,4,3?,4?-Bisdehydro-?-carotene Sets.- 16,16?-Homo-?-caxotene Set.- 13,13?-Bis-desmethyl-?-carotene Set.- retro-Dehydrocarotene Set.- ?-Carotene Set.- ?-Cryptoxanthin (Physoxanthin) Set.- Lutein Set.- Trollixanthin Set.- 3,4-Dehydro-?-carotene Set.- Taraxanthin Set.- 2. Stereoisomeric Sets with One Hydroaromatic and One Aliphatic Terminal Group.- ?-Carotene Set.- Gazaniaxanthin Set.- Celaxanthin Set.- Capsanthin Set.- Torularhodin Set.- 3. Stereoisomeric Sets with Two Aliphatic Terminal Groups.- Lycopene Set.- Neurosporene Set.- Phytofluene Set.- Rhodoviolascin (Sprilloxanthin) Set.- Capsorubin Set.- Fucoxanthin Set.- 4. Stereoisomeric Sets with Two Aromatic Terminal Groups.- 1,18-Diphenyl-3,7,12,16-tetramethyl-octadecanonaene Set.- Renieratene and Isorenieratene Sets.- 1,3,7,12,16,18-Hexaphenyl-octadecanonaene Set.- “Naphthyl-carotene” Set.- X. Lower-molecular Weight Cartenoid-carboxylic Acids: Bixin and Crocetin.- Bixin Set.- Crocetin Set.- XI. Cis-trans Isomerism and Provitamin a Effect of Carotenoids..- References.- The Gibberellins..- I. Introduction.- II. The Chemistry of the Gibberellins.- 1. General Remarks.- 2. Nomenclature.- 3. The Chemistry of Gibberellic Acid.- A. Structure of Gibberene.- B. Structure of Gibberic Acid.- (a) Gibberic Acid.- (b) epiGibberic Acid.- C. Structure and Stereochemistry of allo Gibberic Acid.- (a) allo Gibberic Acid.- (b) Absolute Configuration.- (c) epiallo Gibberic Acid.- D. Structure and Stereochemistry of Gibberellic Acid.- (a) Gibberellic Acid.- (b) Epimerisation at Position 2 in Gibbanes.- (c) Rearrangement of Gibb-3-ene 1 ? 4a Lactones.- (d) Absolute Configuration.- (e) Miscellaneous Reactions of Ring A.- 4. Biogenesis of the Gibberellins.- III. Occurrence of Gibberellins in Higher Plants.- IV. Effects on Plant Growth and Development.- 1. Stem Growth.- A. Day-neutral Annuals, etc.- B. Herbaceous Plants Sensitive to Vernalisation or Photoperiod.- C. Photoperiod-controlled Growth of Woody Plants.- D. Cell-extension or Cell-multiplication?.- E. Mode of Action Studies: Interactions with Auxins.- F. Mode of Action Studies: Interactions with Light.- G. Other Interactions.- 2. Leaf Growth.- 3. Root Growth.- A. Root Extension.- B. Root Initiation on Stem Cuttings.- C. Development of Root-nodules on Leguminous Plants.- 4. Flowering.- A. Rosette Plants Requiring Vernalisation or Long-days.- B. Caulescent Plants Induced to Flower by Vernalisation or Long-day Photoperiods.- C. Short-day Plants.- D. Discussion.- 5. Fertilisation and Fruit Growth.- A. Pollen Growth.- B. Parthenocarpy.- C. Fruit-swelling.- 6. Seed Germination.- A. Breaking of Dormancy.- B. Acceleration of Germination.- 7. Effects on Lower Plants.- 8. Discussion.- A. Hormonal Interactions.- B. The Rle of the Gibberellins as Plant Hormones.- V. Detection and Estimation of Gibberellins.- 1. Bioassay.- 2. Chemical and Physical Methods.- References.- Selected Subjects in Sedimentation Analysis, with Some Applications to Biochemistry..- Glossary of Terms.- I. Basic Theory.- 1. Charge Effects.- a) Diffusion.- b) Sedimentation.- 2. The Theory of Sedimentation Analysis.- a) Conservation of Mass. The Continuity Equation.- b) The Flow Equations.- 3. Velocity Equation for Two-Component, Incompressible Systems and Its Uses.- 4. The Differential Equation of the Ultracentn fuge and Its Solutions. Two Components.- II. The Sedimentation Velocity Experiment and the Determination of Molecular Weight. (Two-Component, Idealized Systems.).- 1. Definition and Evaluation of the Sedimentation Coefficient.- 2. Molecular Weights from Sedimentation and Diffusion.- 3. Molecular Weight Determination by Combination of Sedimentation Coefficient and Intrinsic Viscosity.- III. Heterogeneity and the Form of the Boundary Gradient Curve.- 1. Boundary Spreading: Negligible Diffusion, Constant Sedimentation Coefficient.- 2. Boundary Spreading: Appreciable Diffusion, Constant Sedimentation Coefficient.- 3. Boundary Spreading: Sharpening Effects of Concentration Dependence of Sedimentation Coefficient.- 4. The Johnston-Ogston Effect.- 5. Protein-Protein Interactions.- a) Monomer-Polymer Equilibria.- b) Bimolecular Associations.- c) Interconversion of Isomers.- IV. Three-Component Systems.- 1. Solvation.- 2. Sedimentation Equilibrium in a Density Gradient.- References.- Structure and Immunological Specificity of Polysaccharides..- I. Introduction.- II. Chemistry of Capsular Polysaccharides of Pneumococcus and O-Poly-saccharides of Salmonella.- III. Cross-reactions of Antipneumococcal Sera.- IV. Cross-reactions in Anti-Salmonella Sera.- V. Cross-reactions in Anti-Mycoplasma mycoides Serum.- VI. Conclusion.- VII. Tables.- 1. Specific Capsular Polysaccharides of Pneumococcus and Polysaccharides of Cross-reacting Microorganisms.- 2. Polysaccharides which Precipitate Antipneumococcal and Other Sera to Strongly Moderately.- 3. Cross-reactions of Polysaccharides of Microorganisms in Antipneumococcal and Other Antisera.- 4. Cross-reactions of Animal and Plant Polysaccharides in Antipneumococcal and Other Antisera.- References.- Namenverzeichnis. Index of Names. Index des Auteurs.- Sachverzeichnis. Index of Subjects. Index des Matires.
