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  • 1
    ISSN: 1365-2958
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Biology , Medicine
    Notes: We previously identified HpuB, an 85 kDa Fe-repressible protein required for utilization of Fe from, and binding to, haemoglobin and the haemoglobin–haptoglobin complex. The gene for hpuB was cloned from Neisseria meningitidis strain DNM2 and the predicted amino acid sequence indicates that HpuB is an outer membrane receptor belonging to the TonB family of high-affinity transport proteins. A second open reading frame, predicted to encode a 34.8 kDa lipoprotein, was discovered 5′ to hpuB, and was designated hpuA. HpuA was identified in a total-membrane-protein preparation by construction of a mutant lacking HpuA. Acylation of HpuA was confirmed by [3H]-palmitic acid labelling of meningococci. Consensus promoter sequences were not apparent 5′ to hpuB. The hpuA insertion mutation exerted a polar effect, abolishing expression of hpuB, suggesting that hpuA and hpuB are co-transcribed. The 3.5 kb polycistronic hpuAB mRNA was identified and shown to be transcriptionally repressed by iron. The transcriptional start site was identified 33 nucleotides 5′ to the hpuA translational start site, appropriately positioned around consensus promoter and ferric uptake regulator (Fur)-box sequences. The structure of this operon suggests that HpuA–HpuB is a two-component receptor analogous to the bipartite transferrin receptor TbpB–TbpA.
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  • 2
    ISSN: 1365-2486
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Geography
    Notes: Models of mass and energy exchanges between the biosphere and the atmosphere generally contain a nonlinear dependence between fluxes and model parameters, and thus estimation of these parameters from measurements in a heterogeneous landscape depends on the scale of the observations. The scale-dependence of a typical surface-exchange model (the CSIRO Biospheric Model, CBM) is examined using the diurnal variation of hourly fluxes of CO2, latent heat, sensible heat and soil heat. The fluxes were measured using micrometeorological techniques over six sites in a grazing/pasture system in SE Australia during a period of three weeks in 1995. Nonlinear parameter inversion was used to determine model parameters.Analysis of the covariance of the estimates of the parameters and the unexplained residuals of the model showed that a maximum of three or four parameters could be determined independently from the observations for all six sites. Estimates of a key model parameter, jmax, the mean of maximum potential electron transport rate of all leaves within the canopy, was best determined by the measurements of net CO2 flux at all sites examined. Measurements of ground heat flux provide little information about any of the model parameters in CBM.Because of nonlinearities in the surface exchange model, calculated fluxes will be in error if parameters for the component vegetation types are simply averaged in proportion to their areal fraction. The magnitude of these errors was examined for CBM using a hypothetical land surface consisting of two surface types, each with different parameter values. Predictions of net CO2, latent heat and ground heat fluxes using a linear combination of model parameters for the two surface types were quite similar with those found using optimal estimates of the parameters for the landscape, but were significantly poorer for sensible heat fluxes.
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  • 3
    ISSN: 1365-2958
    Source: Blackwell Publishing Journal Backfiles 1879-2005
    Topics: Biology , Medicine
    Notes: Rhizobium melioti DctD activates transcription from the dctA promoter by catalysing the isomerization of closed complexes between σ54-RNA polymerase holoenzyme and the promoter to open complexes. DctD must make productive contact with σ54-holoenzyme and hydrolyse ATP to catalyse this isomerization. To define further the activation process, we sought to isolate mutants of DctD that had reduced affinities for σ54-holoenzyme. Mutagenesis was confined to the well-conserved C3 region of the protein, which is required for coupling ATP hydrolysis to open complex formation in σ54-dependent activators. Mutant forms of DctD that failed to activate transcription and had substitutions in the C-terminal half of the C3 region were efficiently cross-linked to σ54 and the β-subunit of RNA polymerase, suggesting that they bound normally to σ54-holoenzyme. In contrast, some mutant forms of DctD with amino acid substitutions in the N-terminal half of the C3 region had reduced affinities for σ54 and the β-subunit in the cross-linking assay. These data suggest that the N-terminal half of the C3 region of DctD contains a site that may contact σ54-holoenzyme during open complex formation.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991), S. 1833-1843 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental study of the dynamics of electrodissolution of iron in sulfuric acid is reported. The experiments were done under potentiostatic conditions with a rotating disk electrode as a function of two parameters, potential and electrode diameter. The dynamic behavior depends strongly on the latter parameter; with increasing electrode size we observe transitions from periodic oscillations to low-order chaos to higher-order chaos. The attractor dimension increases with increasing electrode size. In addition, for the large electrodes at more positive potentials, a secondary higher frequency oscillation also arises.
    Additional Material: 30 Ill.
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  • 5
    ISSN: 0947-6539
    Keywords: ab initio calculations ; carboranes ; electron diffraction ; rearrangements ; structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: closo-1,2-(SiMe3)2-1,2-C2B4H4 undergoes thermal conversion to 1,6-(SiMe3)2-1,6-C2B4H4. The reaction pathway was monitored by 11B NMR spectroscopy. The structures of the 1,2- and 1,6-isomers were optimized at the HF/6-31 G* ab initio level. Gas-phase electron diffraction studies for both isomers are reported, as well as low-temperature X-ray crystal structure determinations. Comparison of calculated structural data with the data obtained experimentally shows good agreement between theory and experiment.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 75 (1992), S. 269-275 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: From a MeOH extra of Psiadia trinervia, seven phenolic compounds were isolated by gel filtration and reversed-phase chromatography. Six of them are known compounds, namely 3,4-di-O-caffeoylquinic acid (2), 3,5-di-O-caffeoylquinic acid (3), caffeic acid, and three 3-methoxyflavonoids. Compound 1 is a 3,4-di-O-caffeoyl derviative of (1S,3R,4R,5R)-1,3,4, 5-tetrahydroxycyclohexanecarboxylic acid, a novel steroisomer of (-)-quinic acid. Following hydrolytic treatment of the MeOH extract, ethyl 3-O-caffeoylquinate (4), ethyl 3,4-di-O-caffeoylquinate (5), and ethyl 3,5-O-caffeoylquinate (6) were isolated. The latter three compounds are artifacts. The configuration of 1-3 was established by NMR and CD (exciton chirality method).
    Additional Material: 2 Ill.
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  • 7
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photooxygenation of (4R,4aS,7R)-4,4a,5,6,7,8-hexahydro-4,7-dimethyl-3H-2-benzopyran (16) was performed in (i) MeOH, (ii) acetaldehyde, and (iii) acetone at -78°. The products obtained respectively were (i) (2R)-2-[(1S,4R)-4-methyl-2-oxocyclohexyl]propyl formate (17; 72% yield), (ii) 17 (54.5%), (1R,4R,4aS,7R)-3,4,4a,5,6,7-hexahydro-4,7-dimethyl-1H-2-benzopyran-2-yl hydroperoxide (19; 16.7%), a 12:1 ratio of (3R,4aR,7R,7aS,10R,11aR)-7,7a,8,9,10,11-hexahydro-3,7,10-trimethyl-6H-[2]benzopyrano[1,8a-e]-1,2,4-trioxane (20) and its C(3)-epimer 21 (17%), together with evidence for the 1,2-dioxetane (22) originating from the addition of dioxygen to the re-re face of the double bond of 16, and iii) unidentified products and traces of 22. Addition of trimethylsilyl trifluoromethanesulfonate (Me3SiOTf) to the acetone solution of 16 after photooxygenation afforded (4aR,7R,7aS,10R,11aR)-7,7a,8,9,10,11-hexahydro-3,3,7,10-tetramethyl-6H-[2]benzopyrano[1,8a-e]-1,2,4,-trioxane (23, 40%). The photooxygenation of 16 in CH2Cl2 at -78° followed by addition of acetone and Me3SiOTf afforded 17 (11%), 23 (59%), and (4aR,7R,7aS,10R,11aR)-7,7a,8,9,10,11-hexahydro-3,3,7,10-tetramethyl-6H-[2]benzopyrano[8a,1-e]-1,2,4-trioxane (24; 5%. Repetition of the last experiment, but replacing acetone by cyclopentanone, gave 17 (16%), (4′aR,7′R,7′aS,10′R,11′aR)-7′,7′a,8′,9′,10′,11′-hexahydro-7′,10′-dimethylspiro[cyclopentane-1,3′-6′H-[2]benzopyrano[1,8a-e]-1,2,4-trixane] (25; 61%), and (4′aR,7′R,7′aS,10′R,11′aR)-7′,7′a,8′,9′,10′,11′-hexahydro-7′,10′-dimethylspiro[cyclopentane-1,3′-6′H-[2]benzopyrano[8a,1-e]-1,2,4-trixane] (26, 4%). The X-ray analysis of 23 was performed, which together with the NMR data, established the structure of the trioxanes 20, 21, 24, 25, and 26. Mechanistic and synthesis aspects of these reactions were discussed in relation to the construction of the 1,2,4-trioxane ring in arteannuin and similar molecules.
    Additional Material: 1 Tab.
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  • 8
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As one of the regulatory gene products in the HIV-1 genome, Rev protein must be translocated from the nucleus to the cytoplasm to exert its function. Therefore, inhibition of Rev protein translocation could be a useful target for HIV therapy. An extract from the Streptomyces strain A92-308902 with very potent inhibitory activity was found in the course of a high throughput screening with a Rev translocation assay (RTA). Bioassay-guided fractionation with gel filtration, normal-phase and reversed-phase chromatography yielded six RTA-active metabolites belonging to the leptomycin family, the known leptomycin A (1), leptomycin B (2), kazusamycin B (3), and kazusamycin A (4). and the hitherto unknown dilactonmycin (5) and delactonmycin (6), together with an inactive cyclic hexadepsipeptide L-156,620 (7). The structures were established mainly by spectroscopic methods (UV, FT-IR, FAB-MS, 1H-NMR, 13C-NMR(JMOD), DQ-COSY, ROESY, HSQC, and HMBC). The configuration of all C=C bonds of 1-6 was unambiguously established by analysis of coupling constants and ROESY spectra. All isolated leptomycins 1-6 inhibit Rev translocation at nanomolar concentrations. Six derivatives (2a-c and 4a-c) of leptomycin B (2) and kazusamycin A (4) were also prepared and tested in the RTA for preliminary investigations on structure-activity relationships.
    Additional Material: 5 Tab.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 58 (1995), S. 1585-1592 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polycyclotrimerization of a flexible aromatic dicyanate with a Schiff base structure was studied by means of differential scanning calorimetry (DSC). The study on dynamic DSC evaluated an apparent activation energy (Ea) of 75.8 kJ/mol and autocatalytic first-order kinetics with rate expression Af(α) = 1.96 X 105 (1 + 4.39 α) (1 - α) min-1. The kinetic feature can be explained by a proposed mechanism consisting of hydroxyl-catalyzed and autocatalytic paths. The lower value of Ea compared with other aromatic dicyanates is due to the electron-withdrawing linkage of the inherent imine ( - CH=N) structure. The kinetic feature is affected by the content of the residual impurities (e.g., phenols or absorbed water) in the corresponding sample. © 1995 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electroanalysis 9 (1997), S. 1422-1425 
    ISSN: 1040-0397
    Keywords: Riboflavin ; EQCM ; Adsorption ; Desorption ; pH ; Concentration ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemical and adsorption behaviors of riboflavin (RF) at gold electrodes has been studied by using an electrochemical quartz crystal microbalance (EQCM). Useful information is obtained not only about electrochemical behavior but also about mass changes on the electrode surface. The electrochemical properties and frequency shifts were investigated in RF solutions at different pH values, concentrations and scan rates. Reversible voltammograms were observed for pH ≤ 9.71. There was no electrochemical reaction for pH 〉 9.71. The maximum current response was obtained at about pH 8. The current response was proportional to the square root of scan rates when the concentration of RF was lower than 1.0 × 10-4 molL-1 (pH 6.92). On the contrary, at concentrations higher than 1.0 × 10-4 mol L-1 (pH 6.92), it was proportional to the scan rates.
    Additional Material: 5 Ill.
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