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61.
Alexander Orth Dr. Ludger Johannes Prof. Dr. Winfried Römer Prof. Dr. Claudia Steinem 《Chemphyschem》2012,13(1):108-114
The architecture of the plasma membrane is not only determined by the lipid and protein composition, but is also influenced by its attachment to the underlying cytoskeleton. Herein, we show that microscopic phase separation of “raft‐like” lipid mixtures in pore‐spanning bilayers is strongly determined by the underlying highly ordered porous substrate. In detail, lipid membranes composed of DOPC/sphingomyelin/cholesterol/Gb3 were prepared on ordered pore arrays in silicon with pore diameters of 0.8, 1.2 and 2 μm, respectively, by spreading and fusion of giant unilamellar vesicles. The upper part of the silicon substrate was first coated with gold and then functionalized with a thiol‐bearing cholesterol derivative rendering the surface hydrophobic, which is prerequisite for membrane formation. Confocal laser scanning fluorescence microscopy was used to investigate the phase behavior of the obtained pore‐spanning membranes. Coexisting liquid‐ordered‐ (lo) and liquid‐disordered (ld) domains were visualized for DOPC/sphingomyelin/cholesterol/Gb3 (40:35:20:5) membranes. The size of the lo‐phase domains was strongly affected by the underlying pore size of the silicon substrate and could be controlled by temperature, and the cholesterol content in the membrane, which was modulated by the addition of methyl‐β‐cyclodextrin. Binding of Shiga toxin B‐pentamers to the Gb3‐doped membranes increased the lo‐phase considerably and even induced lo‐phase domains in non‐phase separated bilayers composed of DOPC/sphingomyelin/cholesterol/Gb3 (65:10:20:5). 相似文献
62.
The synthesis, characterization and crystal structure analysis of the ammonium salt of the dioxovanadium(V) complex NH4[VO2(salhyph)] with the tridentate Schiff base ligand derived from salicylaldehyde and benzoic acid hydrazide (H2salhyph) is reported. NH4[VO2(salhyph)] crystallizes in the monoclinic space group Pn with a = 708.8(2), b = 1444.3(3), c = 717.1(2) pm and β = 101.09(2)°. The vanadium atom of the dioxovanadium(V) moiety has a distorted square‐pyramidal coordination geometry. Extensive hydrogen bonding is observed between the ammonium cation and the oxygen atoms coordinated to the vanadium atom yielding to a two‐dimensional network, where the complex anions are arranged in a bilayer. Additional crystal packing within the bilayer appears to be controlled mostly by π stacking between the aromatic rings of the ligand. The reactions of NH4[VO2(salhyph)] with several proton acidic compounds including water, methanol, and proton acids lead to neutral monooxovanadium(V) and dioxovanadium(V) complexes ([VO2(Hsalhyph)], [V2O3(salhyph)2] and [VO(OMe)(salhyph)(HOMe)]). 相似文献
63.
64.
Baron A Herrero C Quaranta A Charlot MF Leibl W Vauzeilles B Aukauloo A 《Chemical communications (Cambridge, England)》2011,47(39):11011-11013
Spectroscopic, electrochemical and theoretical characterisations of photoactive systems readily assembled via click-chemistry show an efficient bi-directional charge shift through the triazole link. 相似文献
65.
Enzymatic Conversion of Flavonoids using Bacterial Chalcone Isomerase and Enoate Reductase 下载免费PDF全文
Dipl.‐Biol. Mechthild Gall Dipl.‐Biochem. Maren Thomsen Dipl.‐Biochem. Christin Peters Dr. Ioannis V. Pavlidis M. Sc. Patrick Jonczyk M. Sc. Philipp P. Grünert Dr. Sascha Beutel Prof. Dr. Thomas Scheper Egon Gross Dr. Michael Backes Dr. Torsten Geißler Dr. Jakob P. Ley Dr. Jens‐Michael Hilmer Dr. Gerhard Krammer Dr. Gottfried J. Palm Prof. Dr. Winfried Hinrichs Prof. Dr. Uwe T. Bornscheuer 《Angewandte Chemie (International ed. in English)》2014,53(5):1439-1442
Flavonoids are a large group of plant secondary metabolites with a variety of biological properties and are therefore of interest to many scientists, as they can lead to industrially interesting intermediates. The anaerobic gut bacterium Eubacterium ramulus can catabolize flavonoids, but until now, the pathway has not been experimentally confirmed. In the present work, a chalcone isomerase (CHI) and an enoate reductase (ERED) could be identified through whole genome sequencing and gene motif search. These two enzymes were successfully cloned and expressed in Escherichia coli in their active form, even under aerobic conditions. The catabolic pathway of E. ramulus was confirmed by biotransformations of flavanones into dihydrochalcones. The engineered E. coli strain that expresses both enzymes was used for the conversion of several flavanones, underlining the applicability of this biocatalytic cascade reaction. 相似文献
66.
Adrian E. Ion Eike T. Spielberg Lorenzo Sorace Axel Buchholz Winfried Plass 《Solid State Sciences》2009,11(4):766-771
Reaction of the copper precursor [Cu(MeOsaltn)(H2O)] (H2MeOsaltn = N,N′-bis(3-methoxysalicylidene)-1,3-diaminopropane) with Ln(NO3)3·6H2O (Ln = Sm and Tb) and pyrazine-2,3-dicarboxylic acid (H2pyrdic) results in the formation of 1D zigzag chains with the general formula of [Cu(MeOsaltn)Ln(NO3)(pyrdic)]n·nDMF. X-ray crystal structures reveal that the samarium and terbium compounds are isostructural and crystalize in the orthorhombic space group Pbcn. The chains are composed of heterodinuclear copper–lanthanide building blocks which are linked by the pyrazine-2,3-dicarboxylate bridging units. Temperature-dependent susceptibility measurements indicate antiferromagnetic exchange interactions for the samarium–copper chain whereas for the terbium–copper compound ferromagnetic interactions are observed. 相似文献
67.
The sugar-modified Schiff base ligand benzyl 2-deoxy-2-salicylideneamino-alpha-D-glucopyranoside H 2L, prepared by condensation of salicylaldehyde and the monomeric chitosan analogue benzyl 2-deoxy-2-amino-alpha-D-glucopyranoside, reacts with copper(II) acetate to form a self-assembled, alkoxo-bridged tetranuclear homoleptic copper(II) complex [{Cu(L)}4] (4) with Cu4O4 heterocubane core. The chiral complex 4 crystallizes in the space group P2 12 12 1. The tetranuclear complex 4 is composed of two dinuclear {Cu(L)}2 entities linked by the four mu 3-bridging C-3 alkoxide oxygen atoms of the sugar backbone. The preorganization of the dimeric {Cu(L)}2 entities is enforced by strong hydrogen bonds between the phenolate oxygen atom and the C-4 hydroxy group of the two constituting chiral monomeric building blocks. Therefore the Cu4O4 core can be classified as a type I or 2 + 4 cubane. The chirality of the structure is confirmed by circular dichroism (CD) spectra, which reveal a significant dichroism associated with the copper centered transitions at around 600 nm. Temperature dependent magnetic susceptibility measurements indicate ferromagnetic exchange interactions in complex 4. Fitting of the experimental data with a two J model based on the 2 + 4 topology ( H = - J1(S1S3 + S2S4) - J2(S1 + S3)(S2 + S4)) leads to exchange coupling constants of J1 = 64 and J2 = 4 cm(-1). The observed ferromagnetic coupling can be attributed to the very small Cu-O-Cu bridging angles within the Cu2O2 core of the constituting dimeric entities, which are a result of the conformational requirements introduced by the sugar backbone. 4 is not only the first example of an alkoxo-bridged tetranuclear copper(II) complex with Cu4O4 core representing the 2 + 4 cubane class with ferromagnetic ground state but also a rare example for the class of molecules combining a ferromagnetic ground state with optical activity. The ferromagnetic S = 2 ground state of 4 is confirmed by magnetization measurements and ESR spectroscopy. 相似文献
68.
Winfried K. Grassmann Steve Drekic 《Methodology and Computing in Applied Probability》2008,10(1):73-83
A number of authors have recently suggested solving quasi birth-and-death (QBD) processes through the use of eigenvalue-based
methods. These methods take on a special form when there are multiple eigenvalues present. We investigate this problem in
a general setting as well as in the context of a specific preemptive priority queueing model.
相似文献
69.
70.
To describe electron localization in substitutionally random alloysA
c
B
1–c
the coherent potential approximation (CPA) is incorporated into the self-consistent theory of Anderson localization in the form developed by Vollhardt and Wölfle. Modifications of the localization theory arise from the tight-binding model with bimodal diagonal disorder of arbitrary strength. The mean-free path, correlation and localization lengths, and the zero-temperature conductivity are calculated at dimensionalityd=3. The metal-insulator transition is studied numerically for a CPA-induced band structure under semielliptical model assumptions. 相似文献