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Various Metallopheophorbides As Substrates for Chlorophyll Synthetase

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Various Metallopheophorbides As Substrates for Chlorophyll Synthetase Various Metallopheophorbides as Substrates for Chlorophyll Synthetase Michael Helfrich and Wolfhart Rüdiger Botanisches Institut, Universität München, Menzinger Straße 67, D-W-8000 München 19 Z. Naturforsch. 47c, 231-238 (1992); received January 29, 1992 Chlorophyllide, Zincpheophorbide a, Copperpheophorbide a, Cobaltpheophorbide a, Nickel- pheophorbide a Pheophorbide a was prepared from a mixture of chlorophylls a and b by differential extrac­ tion with HC1 and saponification. The insertion of the following metal ions was investigated: Mg, Zn, Co, Cu, Ni. In the enzyme test with chlorophyll synthetase, the metallopheophorbides fall into two categories: the Mg- and Zn-complexes are good substrates, the Co-, Cu- and Ni-complexes are neither substrates nor competitive inhibitors for the enzyme reaction. This corresponds to two categories of complex structures: Mg- and Zn-porphyrins prefer penta- coordinate square-pyramidal structures, Co-, Cu- and Ni-porphyrins prefer tetracoordinate square-planar structures. A model for substrate binding to chlorophyll synthetase is proposed. Introduction Since chemical reactions of chlorophyllides, e.g. The last step of chlorophyll biosynthesis is the modifications of the side chains, result easily in a prenylation of chlorophyllide with either geranyl- loss of the central magnesium, we investigated the geranyl diphosphate or phytyl diphosphate [1]. insertion of several metal ions into pheophorbide a The activity of chlorophyll synthetase - the en­ and the possible acceptance of the resulting metal zyme which catalyzes this step - was at first de­ complexes as substrates or competitive inhibitors tected in dark-grown (“etiolated”) seedlings [1 a, 2] of chlorophyll synthetase. but was later also described in green plants [3, 4]. Chlorophyll synthetase activity does not depend Materials and Methods on light whereas the previous biosynthetic step, Thin-layer chromatography (TLC) was per­ hydrogenation of protochlorophyllide to chloro­ formed on silica gel RP8 F254 plates (Merck) with phyllide requires continuous irradiation in An- methanol/acetone/water (64:20:16, v:v:v). For giosperms. Etiolated Angiosperm seedlings accu­ preparative separations by column chromatogra­ mulate protochlorophyllide in the dark. Proto­ phy, silica gel C-l8 (reverse phase, 55-105|i chlorophyllide is neither a substrate nor a 125 Ä, Waters) was used with the elution solvent competitive inhibitor for chlorophyll synthetase. 65% acetone containing 2 m M Hepes-KOH and Broken etioplasts prepared from dark-grown oat 1 m M Na2S20 4. Electronic absorption spectra were seedlings which contain protochlorophyllide and measured with a Lambda 2 spectrophotometer chlorophyll synthetase have therefore been incu­ (Perkin Elmer). !H NMR spectra were recorded bated with various exogenous chlorophyllides in on a 360 MHz instrument (Bruker). FAB mass order to test the substrate specificity of the enzyme spectra were obtained with a CH7a instrument [5]. It was found in these experiments that struc­ (Varian MAT). tural variations of substituents at ring A and the All operations were carried out under dim light. isocyclic ring are tolerated by the enzyme. Remov­ The solvents were saturated with argon before use. al of the central magnesium ion, i.e. formation Oxygen was removed from all reaction vessels with of pheophorbide led to nearly complete loss of argon or nitrogen. acceptance as a substrate [5]. Preparation of pheophorbide a (1) Abbreviations: Hepes, 2-[4-(2-hydroxyethyl)-l-piper- Green leaves of spinach ( Spinacea oleracea L.) azino]ethane sulfonic acid; HPLC, high performance or pea ( Pisum sativum L.) were used for isolation liquid chromatography; MS, mass spectrum; TLC, thin- layer chromatography. of a mixture of chlorophylls a + b according to Iri- yama et al. [6]. Briefly, 1 kg of leaves were frozen Verlag der Zeitschrift für Naturforschung, D-W-7400 Tübingen in liquid nitrogen, pulverized and extracted several 0939-5075/92/0300-0231 $01.30/0 times with acetone (total volume 4.5 1). The crude 232 M. Helfrich and W. Rüdiger • Metallopheophorbides as Substrates for Chlorophyll Synthetase extract was cleared by filtration and mixed with move the acetone, traces of acetic acid and excess dioxane (270 ml). Water was added slowly to this of Cu salt. Yield 2.3 jimol (51%) blue-green pig­ mixture at 0 °C until the absorption band of chlo­ ment, ?imax in CHC13 (relative absorption coeffi­ rophyll at 660 nm disappeared from the superna­ cients) = 400 (0.92), 424 (1.0), 507 (0.09), 656 tant (usually 800-900 ml H20 were needed). The (0.80) nm. TLC revealed 4 components with precipitate which consisted of mainly chlorophylls R f = 0.29, 0.33, 0.36 and 0.40. a + b was left in the suspension at 0 °C for 90 min. Ni complex: Pheophorbide a (4.5 jimol) was It was then removed by fast filtration at 0 °C with dissolved in 2 ml dimethylformamide and heated a precooled glass frit. The precipitate was dis­ under stirring with the saturated solution of solved in a few ml diethyl ether. A typical yield was NiCl2-6 H 20 in 1 ml dimethylformamide to 340 |imol chlorophyll a and 120 [imol chlorophyll 70-90 °C until no further spectral change oc­ b (61 % of the chlorophylls in the crude extract). curred (ca. 5 h). Workup with diethyl ether/water The preparation of pheophorbide a (1) was per­ as usual yielded 2.0 |amol (44%) green pigment. formed according to Hynninen and Lötjönen [7]. A.max in CHCI3 (relative absorption coefficients) = The mixture of chlorophylls a + b (300 |xmol) was 395 (1.02), 421 (1.0), 653 (1.04) nm. TLC revealed dissolved in 500 ml ice-cold diethyl ether. Ice-cold 1 main product (—90%) with RF = 0.28 and 3 by­ 30% aqueous HC1 (148 ml) was added to the solu­ products with R F = 0.24, 0.43 and 0.51. tion. Within 1 h under occasional shaking, pheo­ Co complex: Pheophorbide a (4.5 ^imol) was dis­ phorbide a accumulated in the lower (HC1) phase solved in 2 ml dimethylformamide and heated to whereas pheophytin b remained in the upper di­ 60 °C under stirring. The saturated solution of ethyl ether phase. After separation of the phases, CoCl 2 • 6 H20 in 1 ml dimethylformamide was the diethyl ether phase was reextracted three times added and the mixture heated to 60 °C for further with 30% HC1 (40 ml each). The combined HC1 10 min. Workup with diethyl ether/water yielded phases were diluted in a separatory funnel with the 1.9 |imol (42%) green pigment. A,max in CHC1 3 (re­ same volume (ca. 350 ml) ice-water. Ice-cold di­ lative absorption coefficients) = 405 (1.0), 641 ethyl ether (350 ml) was added. The pH value was (0.56) nm. TLC revealed 4 products with RF = 0, increased by drop wise addition of ice-cold 25% 0.20, 0.25 and 0.31. aqueous N H 3 until all pheophorbide a was trans­ Zn complex: Pheophorbide a (52 |amol) was dis­ ferred into the diethyl ether phase. The pigment solved in 10 ml CH 2C12 and heated to 35 °C. The was reextracted into 16% aqueous HC1 and from saturated solution of Zn(OAc )2 • 2 H 20 in 3 ml this phase into fresh diethyl ether after dilution of methanol was added. The mixture was refluxed for the lower phase with ice-water. The diethyl ether 10 min, cooled and poured into diethyl ether. phase was then washed with water until it was Workup with diethyl ether/water yielded 51 nmol acid-free, and dried with Na2S04. The yield of (98%) green pigment. Xmax in CHC1 3 (relative ab­ pheophorbide a (1) was 174 jxmol (78%). Analysis sorption coefficients) = 427 (1.0), 571 (0.09), 613 by HPLC (on a reverse phase C-l 8 column with (0.17), 659 (0.76) nm. TLC revealed 3 products 70% acetone) revealed minor amounts of pheo­ with R F = 0.39, 0.45 and 0.53. phorbide b (less than 2%) as the only contamina­ The mixture was separated by column chroma­ tion. tography. Pure products were obtained from the first and the last fraction. The most polar fraction proved to be 132-hydroxy-zinc-pheophorbide a Preparation of metallopheophorbides a (3a). A.max in CHC13 (relative absorption coeffi­ Various methods were applied for preparation cients) = 428 (1.0), 570 (0.08), 613 (0.15), 660 of various metallopheophorbides. (0.78) nm. MS: m/z 670 (59%, M +), 653 (100%), Cu complex [see ref. 8]: Pheophorbide a 611 (33%, M+-COOCH3) for MZn. The unpolar (4.5 (imol) was dissolved in 3 ml glacial acetic acid fraction was zinc-pheophorbide a (3). A.max in CHC1 3 and refluxed with 2 g Cu(II)acetate. After evapo­ (relative absorption coefficients) = 427 (1.0), 567 ration of the solvent, the residue was dissolved in (0.08), 611 (0.16), 659 (0.80) nm. MS: m/z 654 acetone/diethyl ether. The diethyl ether phase was (100%, M +), 595 (18%, M + -C O O C H 3), 577 washed several times with water in order to re­ (18%) for 64Zn. M. Helfrich and W. Rüdiger • Metallopheophorbides as Substrates for Chlorophyll Synthetase 233 Mg-complex: a) according to Strell and Urumov ments was obtained. The excess of 2,6-di-/-butyl- [9]: Pheophorbide a (3 ^imol) was dissolved in 5 ml 4-methylphenol was extracted with hexane. The dimethylsulfoxide and heated with 350 mg pigments were separated by column chromatogra­ Mg(OAc)2 -4 H20 to 190 °C for 10 min. The solu­ phy. Chlorophyllide a was eluted ahead of all tion was then cooled under a stream of N2. After by-products. It was compared with authentic chlo­ workup with diethyl ether/water, a green pigment rophyllide a prepared from etiolated oat seedlings (1.25 (imol, 42%) was obtained.
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