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Zeitschrift Für Naturfors Chung ZEITSCHRIFT FÜR NATURFORS CHUNG SECTIONC BIOSCIENCES Council Editorial Board E. BÜNNING, Tübingen A. HAGER, Tübingen A. BUTENANDT, München W. HESSELBACH, Heidelberg M. EIGEN, Gottingen P. KARLSON, Marburg F. KAUDEWITZ, München E. WECKER, Würzburg Advisory Editorial Board P. BÖGER, Konstanz H. SOHIMASSEK, Heidelberg D. BÜCKMANN, Ulm D. SCHULTE-FROHLINDE, Mülheim/R. K. Q. GÖTZ, Tübingen F. F. SEELIG, Tübingen G. GOTTSCHALK, Göttingen J. SEELIG, Bafel R. JAENICKE, Regensburg H. SIMON, München G. F. MEYER, Tübingen W. STEGLIOH, Bonn M. RAJEWSKY, Essen A. TREBST, Bochum EDITED IN COLLABORATION WITH THE INSTITUTES OF THE MAX-PLANCK-GESELLSCHAFT VOLUME 38c NUMBER7/8 JULY/AUGUST 1983 VERLAG DER ZEITSCHRIFT FÜR NATURFORSCHUNG TUBINGEN Contents Z. Naturforech. Vol. 38 c, Nö. 11/12, November/December 1983 Contents ofNos 1-12 I-XII Purification and Characterization of a Dissimilatory Nitrite Redüctase from the Phototrophic Bacteri- Original Communications um Rhodopseudomonas palustris M. PREUSS and J.-H. KLEMME 933 SJjS'^'^'-PentahydrOxyflaYaiione in the Bracts of Heiichrysum bracteatum Isolation and Fast Purification of Neocaizinostatin G. FORKMAKN v 891 by FPLC-Ion Exchange Chromatography D. DENKLAU, W. KÖHNLEIN, G. LÜDERS, and J. The Flavonesöf the European Species otSilene Sec- STELLMACH 939 tion Elisanthe O. MASTENBROEK, J. J. KNÖRR, R KAMPS-HEINS- 15N-Coprobiliverdin, ä New Model Chromophore BROEK, J. W. MAAS, J. M. STEYNS, and J. VAN BRE• H.-P. KÖST, E. BENEDIKT, E. CMIEL, and S. DERODE 894 SCHNEIDER 943 Isolation and Identification of Isoflavanone Phyto- Circulär Dichroism of Chromopeptides from Phyco- alexins froih Leaflets of Üiphysa robinioides eyanin J. L. INGHAM and S. TAHARA 899 C. SCHARNAGL, E. KÖST-REYES, S. SCHNEIDER, H- P. KÖST, and H. SCHEER 951 Wounding-Induced Increase of Quinolizidine Alka- loid AccuQiulation in Lupin Leaves Cytochromes and Anaerobic Sulfide Oxidation in M. WINK 905 the Purple Sulfur Bacterium ChromatiurHwarmin- Site of Äction of Growth Inhibitory Tryptophan U. WERMTER and U. FISCHER 960 Aiialogues in Catharanthus roseus Cell Suspen• sion Cultures Molecular Properties of High Potential Iron Sulfur F. SASSE, M. BUCHHOLZ, and J. BERLIN 910 Protein of Chromatium warmingii U. WERMTER and U. FISCHER 968 Selection öf Cell Lines of Catharanthus roseus with Ihcreased Tryptophan Decarboxylase Activity The Phycobiliproteids in Cyanophora paradoxa as F. SASSE, Ni. BUCHHOLZ, and J: BERLIN 916 Aecessoric Pigments and Nitrögen Storäge Pro• teins Structure of Ascorbic Acid and Its Biological Func• H. E. A. SCHENK, J. HANF, and M. NEU-MÜLLER tion: V. Transport of Ascorbate and Isoascorbate • '" ' 972 across Artificial Membranes as Studied by the Spin Label Technique The Influence of Cycloheximide and Chlorampheni- W. LOHMANN and J. WINZENBURG 923 coi on the Biosynthesis of the Photosynthetic Pig• ments in Cyanophora paradoxa. I. Photosynthetic On the Origin of the Non-Haemic Iron Transferrin Oxygen Evolution (In German) ESR Signal: ESR Investigätions on Histidine-Iron- H. E. A. SCHENK and M. NEU-MÜLLER 978 Citric Acid Systems W. LOHMANN, D. HOLZ, B. KIEFER, and D. The Influence of Cycloheximide and Chlorampheni- SCHMIDT 926 col on the Biosynthesis of the Photosynthetic Pig• ments in Cyanophora paradoxa. IL Carotenoids Enhancement Effect of Hydrophobie Vinyl Com• (In German) pounds in Enzymatic Hydrolysis of Waste Papers M. NEU-MÜLLER, H. E. A. SCHENK, and H. M. KUMAKURA and I. KAETSU 929 STRANSKY 984 Continued overleaf Contents Z. Naturforsch. Vol. 38c, No. 11/12, November/December 1983 The Influence of Cycloheximide and Chlorampheni- Notes col on the Biosynthesis of the Photosynthetic Pig• mente in Cyanophora paradoxa. III. Chlorophyll a Identification of the Major Anthocyanin of Carrot and Phycochromoproteids (In German) Cells in Tissue Culture as Cynidin 3-(Sinapoy/lxy- M. NEU-MÜLLER and H. E. A. SCHENK 990 losylglucosylgalactoside) J. B. HARBORNE, A. M. MAYER, and N. BAR-NHJN Distribution of Chlorophylls, Carotenoids and Qui- 1055 nones in Chloroplastsof Higher Plante •yS&&$WW, 996 Incorporation of 15N-Ammonia into Serotonin in Cotyledons of Maturing Walnuts Chlorophyll-Lipid-Interactions in Monomolecular W. GROSSE and F. ARTIGAS 1057 Layers H. HEITHIER and H. MÖHWALD 1003 N-Terminal Sequence of a Porphobilinogen-Synßtha- se (In German) Sex Pheromone Components of the Gamma Moth, B, LINGNER and T. KLEINSCHMIDT 1059 jiuiogräpha gamma (L.) (Lepidoptera: Nöctuidae) E DUNKELBLUM and S. GOTHILF 1011 Sequence Arialysis of the Cloned Cucumis melo Highly Repetitive Satellite DNA A Conförmational Transition of the Sarcoplasmic A. BRENNICKE and V. HEMLEBEN 1062 Reticulum Calcium Transport ATPase Induced by Vänadate Variation in Cephalic Volatile Substances in Rela• W. HASSELBACH, P. MEDDA, A. MIGALA, and B. tion to Worker Age and Behavior in the Stingless AGOSTTNI 1015 Bee, Scaptotrigona postica W. FRANCKE, W. SCHRÖDER, E. ENGELS, and W. Enzymatic Removal of Ofi-Ethylguanine versus Sta- ENGELS 1066 bility of 04-Ethylthynüne in the DNA of Rat Tis- sues Exposed to the Carcinogen Ethylnitrosourea: Antibodies against the a-Factor Pheromone of Sac- Possible Interference of Guanine-O6 Alkylation charomyces cerevisia with 5-Cytosine Methylation in the DNA of Repli- U. TILLMANN and H. HAHN 1069 cating Target Cells R MÜLLER and M. F. RAJEWSKY 1023 A New Cultural Methöd for Trichoplax adhaerem F. E. SCHULZE (In German) Rate of OH Radical Induced Strand Break Forma• K.G. GRELL 1072 tion in Single Stranded DNA under Anoxic Con- ditions. An Investigation in Aqueous Solutions SübjectTndex 1073 Usihg Conductivity Methods E. BQTHE, G. A. QURESHI, and D. SCHULTE-FROH- Authors Index 1095 LINDE 1030 The Intensity Dependence of the Receptor Potential of the Limulus Ventral Nerve Photoreceptor in Two Defined States of Light- and Dark Adapta• tion H. STIEVE, M. BRUNS, and H. GAUBE 1043 ISSN 0341-0382 Chemistry of Bacteriochlorophyll b: Identification of Some (Photo)Oxidation Products R. Steiner*, E. Cmiel**, and H. Scheer* * Botanisches Institut der Universität München, Menzingerstr. 67, D-8000 München 19 ** Institut für Physikalische und Theoretische Chemie, Technische Universität München, 8046 Garching Z. Naturforsch. 38c, 748-752 (1983); received June 15, 1983 Bacteriochlorophyll, Ethylidene Group, Isomerisation, Oxidation, Photosynthesis Photoreactions of bacteriochlorophyll b have been studied. They all arise from reactions at the A$,$l double-bond. The A7,8-isomerisation product 3 is formed under anaerobic conditions. Irradiation in the presence of oxygen leads to three products arising from an autoxidation reaction involving singlet oxygen. The structures of two of them (4,5) have been established from their methylpheophorbides 10 and 11 containing an 8-acetyl and 8-(meth)oxyethyl-substituent, respectively, in addition to the isomerized A7,8-double bond. Introduction Materials and Methods Bacteriochlorophyll b (BCHL b) [1, 2] is the General methods photosynthetic pigment of only a few species of All solvents were reagent grade or distilled prior photosynthetic bacteria [3-7]. It is the Chlorophyll to use. HPLC was done as previously published for with the absorption at longest wavelengths (1020 nm Chlorophylls [7], but with a mixture of methanol/ in vivo), and it functions both as light harvesting aqueous sodium ascorbate = 93/7. Analytical tlc pigment in the antenna and as photoactive pigment was carried out on HPTLC-plates. The adsorbents in the reaction center [8-10]. were either silica gel (F254, Merck, Darmstadt; BCHL b is rather unstable due to the presence of carbon tetrachloride/acetone = 9/1 as eluent) or an exocyclic A8,8! ethylidene substituent [1]. It is RP8 reverse phase silica gel (Merck, Darmstadt; almost invariably contaminated with by-products methanol as eluent). Preparative tlc was done on absorbing around 680 nm, which are structurally self-coated plates (20x20 cm, 0.75 mm layer of silica related to the plant Chlorophylls. These products can H, Merck, Darmstadt) with the same eluents. arise from isomerisation and/or from oxidation Uv-vis spectra were recorded on ai DMR 22 (Zeiss, reactions which both lead from the bacteriochlorin Oberkochen) or a PE 320 (Perkin-Elmer, Überlin• to the chlorin conjugation System. There are ex- gen). The H-NMR spectra were recorded in CDC13 amples for both types of reactions in the literature with TMS as internal Standard. Mass spectra were [1, 2], but the chemistry of BCHL b is hitherto only obtained in the electron impact mode on a model insufficiently explored. Here we wish to report the CH7 (Varian-Mat, Bremen). identification of two of these products arising from Rp. viridis was grown anaerobically in 15 1 flasks oxidative isomerisation and present data on the on Gloe's medium [11] under incandescent light. solvent dependence and reaction mechanism. The cells were harvested after seven days and the BCHL b was isolated by the procedure of Strain and Svec [12], paying attention that the samples were kept in the darkness to inhibit any photoreac• tions. BCHL a was isolated [12] from photo- Abbreviations: BCHL, bacteriochlorophyll; Rp.y Rhodo- pseudomonas; Chi, Chlorophyll; UV-VIS-NIR, absorption in trophically grown Rp. spheroides R26 [11] and the ultraviolet, visible and near infrared spectral ränge; TLC, thin layer chromatography; HPLC, high pressure oxidized to 3-Acetyl-3-devinyl-chl a with DDQ [13]. liquid chromatography; DDQ, dichloro-dicyanobenzo- quinone. Photochemistry Reprint requests to Prof. Dr. H. Scheer. The pigment was dissolved in acetone or other 0341-0382/83/0900-0748 $01.30/0 solvents, and exposed to white light from a tungsten- R. Steiner et al. • Chemistry of Bacteriochlorophyll b 749 halogen lamp (20 mW/cm2). The reaction was (q, 8'-H); 4.52 (m, 18-H); 4.24 (m, 17-H); 3.93, 3.75, followed spectrophotometrically (decrease of the 3.70, 3.62, 3.44, 3.32, 3.23 (7s, 3H each, 2; 31; 7; 8l; 4 4 1 2 792 nm absorption peak of BCHL b, increase of a 12; 13 ; 17 -CH3); 1.81-2.38 (m, 17 , 17 ; CH2-CH2); 2 new band around 680 nm). Extinction coefficients of 2.15 (d, 8 -CH3); 1.85 ppm (d, 18-CH3).
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