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101.
Roth A Buchholz A Rudolph M Schütze E Kothe E Plass W 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(5):1571-1583
A series of bimetallic zinc(II) and nickel(II) complexes based on the novel dinucleating unsymmetric double-Schiff-base ligand benzoic acid [1-(3-{[2-(bispyridin-2-ylmethylamino)ethylimino]methyl}-2-hydroxy-5-methylphenyl)methylidene]hydrazide (H(2)bpampbh) has been synthesized and structurally characterized. The metal centers reside in two entirely different binding pockets provided by the ligand H(2)bpampbh, a planar tridentate [ONO] and a pentadentate [ON(4)] compartment. The utilized ligand H(2)bpampbh has been synthesized by condensation of the single-Schiff-base proligand Hbpahmb with benzoic acid hydrazide. The reaction of H(2)bpampbh with two equivalents of either zinc(II) or nickel(II) acetate yields the homobimetallic complexes [Zn(2)(bpampbh)(mu,eta(1)-OAc)(eta(1)-OAc)] (ZnZn) and [Ni(2)(bpampbh)(mu-H(2)O)(eta(1)-OAc)(H(2)O)](OAc) (NiNi), respectively. Simultaneous presence of one equivalent zinc(II) and one equivalent nickel(II) acetate results in the directed formation of the heterobimetallic complex [NiZn(bpampbh)(mu,eta(1)-OAc)(eta(1)-OAc)] (NiZn) with a selective binding of the nickel ions in the pentadentate ligand compartment. In addition, two homobimetallic azide-bridged complexes [Ni(2)(bpampbh)(mu,eta(1)-N(3))]ClO(4) (NiNi(N(3))) and [Ni(2)(bpampbh)(mu,eta(1)-N(3))(MeOH)(2)](ClO(4))(0.5)(N(3))(0.5) (NiNi(N(3))(MeOH)(2)) were synthesized. In all complexes, the metal ions residing in the pentadentate compartment adopt a distorted octahedral coordination geometry, whereas the metal centers placed in the tridentate compartment vary in coordination number and geometry from square-planar (NiNi(N(3))) and square-pyramidal (ZnZn and NiZn), to octahedral (NiNi and NiNi(N(3))(MeOH)(2)). In the case of complex NiNi(N(3)) this leads to a mixed-spin homodinuclear nickel(II) complex. All compounds have been characterized by means of mass spectrometry as well as IR and UV/Vis spectroscopies. Magnetic susceptibility measurements show significant zero-field splitting for the nickel-containing complexes (D=2.9 for NiZn, 2.2 for NiNi(N(3)), and 0.8 cm(-1) for NiNi) and additionally a weak antiferromagnetic coupling (J=-1.4 cm(-1)) in case of NiNi. Electrochemical measurements and photometric titrations reveal a strong Lewis acidity of the metal center placed in the tridentate binding compartment towards external donor molecules. A significant superoxide dismutase reactivity against superoxide radicals was found for complex NiNi. 相似文献
102.
Carrick L Tassieri M Waigh TA Aggeli A Boden N Bell C Fisher J Ingham E Evans RM 《Langmuir : the ACS journal of surfaces and colloids》2005,21(9):3733-3737
Photon correlation spectroscopy is used to study the internal dynamics of self-assembled charged peptide fibrils. Short neutral and charged polymeric aggregates have diffusive modes due to whole macromolecular motion. For long semiflexible fibrils the logarithm of the intermediate scattering function follows a q(2)t(3/4) scaling at long times consistent with a Kratky-Porod free energy and preaveraged Oseen hydrodynamics. Persistence lengths on the order of micrometers are calculated for the peptide fibrils consistent with estimates from the liquid-crystalline phase behavior. Fibril diameters (5-35 nm) calculated from the initial decay of the correlation functions are in agreement with transmission electron microscopy measurements. 相似文献
103.
McCarthy FO Chopra J Ford A Hogan SA Kerry JP O'Brien NM Ryan E Maguire AR 《Organic & biomolecular chemistry》2005,3(16):3059-3065
Beta-sitosterol is the most prevalent plant cholesterol derivative (phytosterol) and can undergo similar oxidation to cholesterol, leading to beta-sitosterol oxides. The biological impact of phytosterol oxides has only been evaluated in a phytosterol blend (usually of beta-sitosterol, campesterol, stigmasterol and dihydrobrassicasterol). The lack of pure phytosterols, including beta-sitosterol, hinders the collection of significant toxicity data on the individual beta-sitosterol oxides. An efficient synthetic route to multi-gram quantities of pure beta-sitosterol is described here, together with the first syntheses and characterisation of pure beta-sitosterol oxides. 相似文献
104.
J. H. Merkin D. B. Ingham 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1987,38(1):102-116
The mixed convection boundary layer on a horizontal plate is considered for the two separate cases when there is a uniform free stream with the plate held fixed and when there is no outer flow but the plate is moving continuously with a uniform velocity along its length. In both cases we assume that power law temperature distribution on the plate which enables the governing equations to be reduced to similarity form. For the first problem we consider the range of buoyancy parameter for which there are dual solutions, showing how these dual solutions arise from a bifurcation and how the lower branch of solutions terminate as the buoyancy parameter tends to zero. For the second problem we show that there is a unique solution for all positive values of the buoyancy parameter and that for negative values the solution terminates at a singular solution with algebraic decay.
Zusammenfassung Die Grenzschicht an einer horizontalen Platte mit gemischter Konvektion wird für zwei Fälle untersucht: Für eine ruhende Platte bei gleichförmiger Außenströmung und für eine Platte, die sich kontinuierlich mit konstanter Geschwindigkeit in ihrer eigenen Ebene bewegt, ohne Außenströmung. Für beide Fälle wählen wir ein Potenzgesetz für die Temperaturverteilung entlang der Wand, für welche die Grundgleichungen eine Ähnlichkeitslösung zulassen. In der ersten Problemstellung betrachten wir einen Bereich des Auftriebsparameters, für den zweifache Lösungen existieren. Wir zeigen, wie diese doppelten Lösungen aus einer Bifurkation entstehen und wie der untere Lösungszweig endet, wenn der Auftriebsparameter gegen Null strebt. Für die zweite Problemstellung zeigen wir, daß eine eindeutige Lösung existiert für alle positiven Werte des Auftriebsparameters und daß für negative Werte eine singuläre Lösung mit algebraischem Zerfall erreicht wird.相似文献
105.
W. Brückner B. Granz D. Ingham K. Kilian U. Lynen J. Niewisch B. Pietrzyk B. Povh H.G. Ritter H. Schröder 《Physics letters. [Part B]》1977,67(2):222-224
Annihilation and elastic cross-sections of p have been measured between 400 and 850 MeV/c. In both cross-sections a resonance is observed at a mass of 1939 ± 3 MeV. For its natural width τ ? 4 MeV is obtained. 相似文献
106.
H. Umesha Shetty Eileen M. Daly Nigel H. Greig Stanley I. Rapoport Timothy T. Soncrant 《Journal of the American Society for Mass Spectrometry》1991,2(2):168-173
An automatic reaction control chemical ionization technique in an ion trap detector (lTD) was used to quantitate the levels of the cholinergic drug, arecoline, in plasma of treated patients with Alzheimer’s disease. The chemical ionization reaction was carried out with acetonitrile. The protonated molecules of arecoline (m I z 156) and the internal standard, homoarecoline (m / z 170), were monitored. Human plasma samples were extracted with a readily evaporable solvent mixture, the residues reconstituted and injected along with a tertiary amine-carrier into a capillary gas chromatograph interfaced with the ITD. Standard curves for plasma-extracted arecoline between 20-ng/mL and 156-pg/mL levels were linear (r> 0.9980). Satisfactory precision (relative standard deviation < 20%) and accuracy (relative error < 15%) at the limit of quantitation, 156 pg/mL arecoline, were achieved. Optimal conditions for handling of blood samples obtained by venipuncture were determined. The assay was successfully applied for the therapeutic monitoring of Alzheimer patients treated intravenously with arecoline. 相似文献
107.
Mauro Panunzio Emiliano Tamanini Elisa Bandini Eileen Campana Antonio D''Aurizio Paola Vicennati 《Tetrahedron》2006,62(52):12270-12280
The synthesis of 5-phenylthio-1,3-oxazinan-4-ones, through a hetero Diels–Alder strategy, is described. The cycloadducts thus prepared have been shown to be useful intermediates for the synthesis of 1,3-aminoalcohols, valuable intermediates in the preparation of biologically significant molecules, e.g., optically active Duloxetines and Fluoxetines. In the course of this elaboration a novel microwave assisted desulfurization reaction is reported. 相似文献
108.
Spencer C Alford Joel D Pearson Amanda Carette Robert J Ingham Perry L Howard 《BMC biochemistry》2009,10(1):9-11
Background
α-Sarcin is a protein toxin produced by Aspergillus giganteus. It belongs to a family of cytotoxic ribonucleases that inactivate the ribosome and inhibit protein synthesis. α-Sarcin cleaves a single phosphodiester bond within the RNA backbone of the large ribosomal subunit, which makes the ribosome unrecognizable to elongation factors and, in turn, blocks protein synthesis. Although it is widely held that the protein synthesis inhibition caused by the toxin leads to cell death, it has not been directly shown that catalytically inactive mutants of α-sarcin are non-toxic when expressed directly within the cytoplasm of cells. This is important since recent studies have cast doubt on whether protein synthesis inhibition is sufficient to initiate apoptosis. 相似文献109.
Sylvie Pailloux Iris Binyamin Lorraine M. Deck Benjamin P. Hay Eileen N. Duesler Lev N. Zakharov W. Scott Kassel Arnold L. Rheingold Robert T. Paine 《Polyhedron》2009,28(18):3979-3984
The lanthanide coordination chemistry of the new ligand 2-hydroxy-2-(1-oxy-pyridin-2-yl)-N,N-diphenyl acetamide (5) has been examined. X-ray crystal structure determinations for the free ligand 5 and for one complex, [La(5)6] (NO3)3·7H2O, have been completed and the latter reveals an unexpected bidentate chelation mode for 5 that involves the amide carbonyl oxygen atom and the 2-hydroxy oxygen atom of each ligand. The six bidentate ligands generate an icosohedral inner coordination sphere. The N-oxide oxygen atom of each ligand also hydrogen bonds with a 2-hydroxyl hydrogen atom in a neighboring ligand molecule in the same molecular unit. 相似文献
110.