Search results for "dimer"
showing 10 items of 558 documents
Refinement of a structural model of a pigment-protein complex by accurate optical line shape theory and experiments.
2007
Time-local and time-nonlocal theories are used in combination with optical spectroscopy to characterize the water-soluble chlorophyll binding protein complex (WSCP) from cauliflower. The recombinant cauliflower WSCP complexes reconstituted with either chlorophyll b (Chl b) or Chl a/Chl b mixtures are characterized by absorption spectroscopy at 77 and 298 K and circular dichroism at 298 K. On the basis of the analysis of these spectra and spectra reported for recombinant WSCP reconstituted with Chl a only (Hughes, J. L.; Razeghifard, R.; Logue, M.; Oakley, A.; Wydrzynski, T.; Krausz, E. J. Am. Chem. Soc. U.S.A. 2006, 128, 3649), the "open-sandwich" model proposed for the structure of the pig…
Pigment−Pigment and Pigment−Protein Interactions in Recombinant Water-Soluble Chlorophyll Proteins (WSCP) from Cauliflower
2007
Plants contain water-soluble chlorophyll-binding proteins (WSCPs) that function neither as antennas nor as components of light-induced electron transfer of photosynthesis but are likely constituents of regulatory protective pathways in particular under stress conditions. This study presents results on the spectroscopic properties of recombinant WSCP from cauliflower reconstituted with chlorophyll b (Chl b) alone or with mixtures of Chl a and Chl b. Two types of experiments were performed: (a) measurements of stationary absorption spectra at 77 and 298 K and CD spectra at 298 K and (b) monitoring of laser flash-induced transient absorption changes with a resolution of 200 fs in the time doma…
Pigment Binding, Fluorescence Properties, and Oligomerization Behavior of Lhca5, a Novel Light-harvesting Protein
2005
A new potential light-harvesting protein, named Lhca5, was recently detected in higher plants. Because of the low amount of Lhca5 in thylakoid membranes, the isolation of a native Lhca5 pigment-protein complex has not been achieved to date. Therefore, we used in vitro reconstitution to analyze whether Lhca5 binds pigments and is actually an additional light-harvesting protein. By this approach we could demonstrate that Lhca5 binds pigments in a unique stoichiometry. Analyses of pigment requirements for light-harvesting complex formation by Lhca5 revealed that chlorophyll b is the only indispensable pigment. Fluorescence measurements showed that ligated chlorophylls and carotenoids are arran…
Amino acids in the second transmembrane helix of the Lhca4 subunit are important for formation of stable heterodimeric light-harvesting complex LHCI-…
2007
Photosynthetic light-harvesting complexes (LHCs) are assembled from apoproteins (Lhc proteins) and non-covalently attached pigments. Despite a considerable amino acid sequence identity, these proteins differ in their oligomerization behavior. To identify the amino acid residues determining the heterodimerization of Lhca1 and Lhca4 to form LHCI-730, we mutated the poorly conserved second transmembrane helix of the two subunits. Mutated genes were expressed in Escherichia coli and the resultant proteins were refolded in vitro and subsequently analyzed by gel electrophoresis. Replacement of the entire second helix in Lhca4 by the one of Lhca3 abolished heterodimerization, whereas it had no eff…
Localization of the N-terminal Domain in Light-harvesting Chlorophyll a/b Protein by EPR Measurements
2005
The conformational distribution of the N-terminal domain of the major light-harvesting chlorophyll a/b protein (LHCIIb) has been characterized by electron-electron double resonance yielding distances between spin labels placed in various domains of the protein. Distance distributions involving residue 3 near the N terminus turned out to be bimodal, revealing that this domain, which is involved in regulatory functions such as balancing the energy flow through photosystems (PS) I and II, exists in at least two conformational states. Models of the conformational sub-ensembles were generated on the basis of experimental distance restraints from measurements on LHCIIb monomers and then checked f…
Evidence for two spectroscopically different dimers of light-harvesting complex I from green plants
2000
A preparation consisting of isolated dimeric peripheral antenna complexes from green plant photosystem I (light-harvesting complex I or LHCI) has been characterized by means of (polarized) steady-state absorption and fluorescence spectroscopy at low temperatures. We show that this preparation can be described reasonably well by a mixture of two types of dimers. In the first dimer about 10% of all Q(y)() absorption of the chlorophylls arises from two chlorophylls with absorption and emission maxima at about 711 and 733 nm, respectively, whereas in the second about 10% of the absorption arises from two chlorophylls with absorption and emission maxima at about 693 and 702 nm, respectively. The…
Water soluble chlorophyll binding protein of higher plants: A most suitable model system for basic analyses of pigment–pigment and pigment–protein in…
2011
Abstract This short review paper describes spectroscopic studies on pigment–pigment and pigment–protein interactions of chlorophyll (Chl) a and b bound to the recombinant protein of class IIa water soluble chlorophyll protein (WSCP) from cauliflower. Two Chls form a strongly excitonically coupled open sandwich dimer within the tetrameric protein matrix. In marked contrast to the mode of excitonic coupling of Chl and bacterio-Chl molecules in light harvesting complexes and reaction centers of all photosynthetic organisms, the unique structural pigment array in the Chl dimer of WSCP gives rise to an upper excitonic state with a large oscillator strength. This property opens the way for thorou…
Sodium Congener of the Classical Lithium Methylchromate Dimer: Synthetic, X-ray Crystallographic, and Magnetic Studies of Me8Cr2[Na(OEt2)]4
2011
One of the milestone structures in the development of transition-metal complexes with metal metal bonds of multiple bond order was the lithium methylchromate dimer Me8Cr2[Li(donor)](4) (donor = THF or Et2O). Using a simple salt metathesis reaction mixing this compound with sodium tert-butoxide, the sodium congener Me8Cr2-[Na(OEt2)]4 has been synthesized as a green crystalline compound and isolated in 51% yield. Its solid-state structure was determined by single-crystal X-ray diffraction. Exhibiting exact crystallographic C-4h symmetry, this heavier alkali-metal chromate structure is also dimeric, formally comprising a (Me8Cr4)(4-) tetranionic core with four peripheral Na+ cations carrying s…
Effect of solute association on the apparent adsorption isotherm. A model of the separation of non-racemic mixtures of enantiomers in achiral chromat…
1996
This article discusses the effect of solute association on the apparent adsorption isotherm and on the chromatographic peak profile. The modelling performed has shown that dimerization of a solute in a chromatographic system gives rise to an apparent adsorption isotherm of the non-linear type. This results first of all in peak broadening. Tailing or a fronting can be observed depending on the relative retention of the monomer and the dimer. Secondly, the retention of the solute depends on the amount of sample because of the non-linear character of the adsorption isotherm. As a result, an excess of one of two analytes with absolutely identical adsorption properties i.e. optical isomers, can …
Exchange coupling across the cyanide bridge: structural and DFT interpretation of the magnetic properties of a binuclear chromium(III) complex.
2006
The reaction of [Cr(CN)6]3− with a mixture of trans-[Cr(cyclam)(OH)2]Cl, [Cr(cyclam)(OH)Cl]Cl and [Cr(cyclam)Cl2]Cl affords the cyanide bridged dimer, trans-[HO–Cr(cyclam)–NC–Cr(CN)5]−. The tetraphenylphosphonium salt of the anion crystallizes in space group P21/n and shows a bent arrangement of the Cr1–CN–Cr2 unit with the Cr1–CN bond angle at 166.9° and CN–Cr2 at 160.32°. The Cr2–O bond, trans to the hexacyanide fragment, is very short at 1.902 A. Two dimers are held together by two hydrogen bonds connecting the Cr2–OH group of each dimer with one of the NH groups of the cyclam ligand of an adjacent molecule, leading to an almost linear configuration. These dimers of dimers get packed par…