Temperature-induced isomerization of violaxanthin in organic solvents and in light-harvesting complex II

Three main xanthophyll pigments are bound to the major photosynthetic pigment-protein complex of Photosystem II (LHCII): lutein, neoxanthin and violaxanthin. Chromatographic analysis of the xanthophyll fraction of LHCII reveals that lutein appears mainly in the all-trans conformation, neoxanthin in the 9'-cis conformation and major fraction of violaxanthin in the all-trans conformation. Nevertheless, a small fraction of violaxanthin appears always in a cis conformation: 9-cis and 13-cis (approximately 4% and 2% in the darkness, respectively). Illumination of the isolated complex (5 min, 445 nm, 250 micromolm-2s-1) results in the substantial increase in the concentration of the cis steric conformers of violaxanthin: up to 6% of 9-cis and 4% of 13-cis. Similar effect can be obtained by dark incubation of the same preparation for 30 min at 60 degrees C. Heating-induced isomerization of the all-trans violaxanthin can also be obtained in the organic solvent system but the formation of the 9-cis stereoisomer has not been observed under such conditions. The fact that the appearance of the 9-cis form of violaxanthin is specific for the protein environment suggests that violaxanthin may replace neoxanthin in LHCII in the N1 xanthophyll binding pocket and that the protein stabilizes this particular conformation. The analysis of the electronic absorption spectra of LHCII and the FTIR spectra of the protein in the Amid I band spectral region indicates that violaxanthin isomerization is associated with the disaggregation of the complex. It is postulated that this reorganization of LHCII provides conditions for desorption of violaxanthin from the pigment protein complexes, its diffusion within the thylakoid membrane and therefore, availability to the enzymatic deepoxidation within the xanthophyll cycle. It is also possible that violaxanthin isomerization plays the role of a security valve, by consuming an energy of excessive excitations in the antenna pigment network (in particular, exchanged at the triplet state levels).     

Complexes of heteroscorpionate trispyrazolylborate ligands. Part VI. Carboxylate induced conversion of mono-ligand Tp′M(L) into bis-ligand Tp′2M complexes (M=Co(II) and Cu(II))

A series of homoleptic complexes of hexacoordinate cobalt(II) and copper(II) complexes with 3,5-disubstituted homo- and heteroscorpionate tris(pyrazolyl)borate anionic ligands (Tp′) were synthesized, i.e. bis[hydrotris(3-phenyl,5-methylpyrazol-1-yl)borato]cobalt(II), bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]cobalt(II) and bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]copper(II) and their structures were elucidated crystallographically. The complexes were also formed spontaneously during attempted metathesis of the corresponding Tp′M(NCS) complexes into Tp′M(OOCCH(OH)CH₃) complexes. In the case of the analogous conversion applied for the thiocyanato [hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3,5-dimethylpyrazol-1-yl)boratocobalt(II) complex with sodium carboxylates (lactate, pyruvate and 2-hydroxybutyrate), the cross-transfer of pyrazolyl residues between starting anionic ligands was observed resulting in formation of bis-ligand homo- and heteroleptic Tp′CoTp″ complexes, where Tp′, Tp″ were tris(pyrazolyl)borates composed of n 3(5)-phenyl,5(3)-methylpyrazolyl and (3−n) 3,5-dimethylpyrazolyl residues (n=0–3) identified by mass spectrometry. Metathesis of thiocyanate in thiocyanato hydrotris(3-phenyl,5-methylpyrazol-1-yl)boratocobalt(II) into pyruvate led to the isolation of stable the pyruvato hydrotris(3-phenyl,5-methylpyrazol-1-yl)boratocobalt(II) complex, the structure of which was determined crystallographically. The Tp′ ligands are η³ coordinated to metal ions in every case, whereas the pyruvate anion is coordinated through carboxylate and carbonyl oxygen atoms to the cobalt center. Two rotational isomers distinguishable by ¹H NMR spectroscopy for the hexacoordinate bis[hydrobis(3-phenyl,5-methylpyrazol-1-yl)(3-methyl,5-phenylpyrazol-1-yl)borato]cobalt(II) complex were detected in solution.     

Dünnschicht-Chromatographie höherer Fettsäuren

Zusammenfassung Die Dünnschichtchromatographie von Fettsäuren wurde mit der Papierchromatographie solcher Säuren hinsichtlich ihrer Trennwirkung verglichen. Ein Verfahren zur quantitativen Bestimmung auf Dünn-schichten getrennter Fettsäuren wurde ausgearbeitet.

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Summary The thin layer chromatography of fatty acids was compared with the paper chromatography of such acids with respect to their separation. A method was worked out for the quantitative determination of fatty acids separated on thin layers.

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Résumé On compare la chromatographie en couche mince des acides gras avec celle sur papier, du point de vue de leur pouvoir de séparation. On a mis au point un procédé de dosage quantitatif des acides gras séparés sur couches minces.

     

Influence of the Bulk and Donor-Acceptor Properties of Solvent on Ligand Field Spectra

The influence of solvents on the electronic absorption spectra of chromium (III) complexes was investigated. The dependence of the crystal field parameter Dq on dielectric constant as well as Gutmann donor number DN of solvent was found and described. By using the proposed model, unknown in the literature donor numbers for a few alcohols were estimated.     

Lipozyme-Mediated Regioselective Esterification of Isosorbide Under Solvent-Free Conditions

Abstract: Monoesters of isosorbide were obtained with high regioselectivity in Lipozyme catalysed esterification by fatty acids under solvent-free conditions.     

Novel (R)-(+)-limonene-derived ligands: synthesis and application in asymmetric transfer hydrogenations

(R)-(+)-Limonene was transformed into mono-N-tosylated-1,2-diamine derivatives using an N-tosylaziridination procedure followed by sodium azide treatment and reduction on Pd/C. The ligands obtained proved effective in the asymmetric transfer hydrogenation protocol on aromatic ketones.     

Monosaccharides with Phosphorus in the Sugar Ring

Abstract

In recent years attention has been directed toward the synthesis of modified sugars wherein the oxygen atom in the sugar ring is replaced by sulfur, selenium or phosphorus. Synthesis of sugar analogs with phosphorus as the ring heteroatom is interesting from the point of view of their possible biological activity.     

Absolute configurations of C34 and C35 of antibiotic niphimycin A

The relative configurations of four stereogenic centers of the C33‐C42 fragment of niphimycin A were assigned as 2S*, 3R*, 4S* and 6S*, based upon ¹H NMR analysis with double‐quantum filtered COSY and nuclear Overhauser spectroscopy experiments. These data were then correlated with absolute configurations at C36 and C38 of niphimycin A, which were declared previously as 36S and 38S [3]. This allowed for the assignment of the absolute configurations at C34 and C35 of niphimycin A as 34S and 35R. Copyright © 2012 John Wiley & Sons, Ltd.     

Digital model of a vacuum circuit breaker for the analysis of switching waveforms in electrical circuits

The article presents a method of modelling a vaccum circuit breaker in the ATP/EMTPpackage, the results of the verification of the correctness of the developed digitalcircuit breaker model operation and its practical usefulness for analysis of overvoltagesand overcurrents occurring in commutated capacitive electrical circuits and also examplesof digital simulations of overvoltages and overcurrents in selected electricalcircuits.