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891.
Efficient and convenient three-component couplings of an aryl halide, isocyanide, and an amino alcohol under palladium catalysis provide a range of oxazolines and benzoxazoles in excellent yield. 相似文献
892.
Hamilton JM Anhorn MJ Oscarson KA Reibenspies JH Hancock RD 《Inorganic chemistry》2011,50(7):2764-2770
Some metal-ion-complexing properties of the ligand 2,2',6',2'-terpyridyl (terpy) in aqueous solution are determined by following the π-π* transitions of 2 × 10(-5) M terpy by UV-visible spectroscopy. It is found that terpy forms precipitates when present as the neutral ligand above pH ~5, in the presence of electrolytes such as NaClO(4) or NaCl added to control the ionic strength, as evidenced by large light-scattering peaks. The protonation constants of terpy are thus determined at the ionic strength (μ) = 0 to avoid precipitation and found to be 4.32(3) and 3.27(3). The log K(1) values were determined for terpy with alkali-earth metal ions Mg(II), Ca(II), Sr(II), and Ba(II) and Ln(III) (Ln = lanthanide) ions La(III), Gd(III), and Lu(III) by titration of 2 × 10(-5) M free terpy at pH >5.0 with solutions of the metal ion. Log K(1)(terpy) was determined for Zn(II), Cd(II), and Pb(II) by following the competition between the metal ions and protons as a function of the pH. Complex formation for all of these metal ions was accompanied by marked sharpening of the broad π-π* transitions of free terpy, which was attributed to complex formation affecting ligand vibrations, which in the free ligand are coupled to the π-π* transitions and thus broaden them. It is shown that log K(1)(terpy) for a wide variety of metal ions correlates well with log K(1)(NH(3)) values for the metal ions. The latter include both experimental log K(1)(NH(3)) values and log K(1)(NH(3)) values predicted previously by density functional theory calculation. The structure of [Ni(terpy)(2)][Ni(CN)(4)]·CH(3)CH(2)OH·H(2)O (1) is reported as follows: triclinic, P1, a = 8.644(3) ?, b = 9.840(3) ?, c = 20.162(6) ?, α = 97.355(5)°, β = 97.100(5)°, γ = 98.606(5)°, V = 1663.8(9) ?(3), Z = 4, and final R = 0.0319. The two Ni-N bonds to the central N donors of the terpy ligands in 1 average 1.990(2) ?, while the four peripheral Ni-N bonds average 2.107(10) ?. This difference in the M-N bond length for terpy complexes is typical of the complexes of smaller metal ions, while for larger metal ions, the difference is reversed. The significance of the metal-ion size dependence of the selectivity of polypyridyl ligands, and the greater rigidity of ligands based on aromatic groups such as pyridyl groups, is discussed. 相似文献
893.
The classical analytical method for gaseous carbonyl measurements based on solid sorbent coated with 2,4-dinitrophenylhydrazine (DNPH) and analysis by HPLC/UV suffers from limited resolution of carbonyls with similar molecular structures and high molecular weights. In this paper, we report the development of a sensitive and reliable analytical method for simultaneous determination of 21 airborne carbonyls within the C1-C9 range. Carbonyls were collected on a sampling tube filled with 100 mg Tenax TA (60-80 mesh) sorbent coated with 1 μmol pentafluorophenyl hydrazine (PFPH), followed by solvent desorption and analysis by gas chromatography (GC)/mass spectrometry (MS). Common carbonyl gases including formaldehyde, acetaldehyde, butyraldehyde, hexaldehyde and benzaldehyde at ppbv levels were collected with efficiency greater than 90% onto sampling tubes at a flow rate of 100 mL min−1. The limits of detection (LODs, signal/noise = 3) of the tested carbonyls were in the range of 0.08-0.20 ppbv for a sampled volume of 24.0 L. These limits are less than or comparable with those that can be obtained using the DNPH-HPLC method. The method has been field-tested both in ambient air of York and in diluted cigarette smoke. Comparing field tests with the classical DNPH-HPLC method, good agreement was displayed between the two methods for the same carbonyls, but with more carbonyl species detected by the PFPH-GC/MS method. The PFPH-GC/MS method provides better molecular separation for carbonyls with similar structures, is highly sensitivity and gives confirmation of identification by structures when detected using MS. 相似文献
894.
This study presents and validates a theoretical model for estimating the number of double bonds in triglyceride molecules using magnetic resonance imaging. The model enables reliable estimation of the number of double bonds from a small number of time points, as are typically acquired with chemical shift imaging. Prior knowledge from the US Department of Agriculture (USDA) is used to constrain the properties of triglyceride. Validation in oil phantoms shows agreement between the measured number of double bonds and USDA reference values (correlation 0.95, significance P=.0003, slope 0.95±0.31, intercept 0.08±1.24). Feasibility in a human subject was demonstrated using a long breath-hold (43 s) scan. 相似文献
895.
Klochan O Micolich AP Hamilton AR Trunov K Reuter D Wieck AD 《Physical review letters》2011,107(7):076805
We report the observation of Kondo physics in a spin-3/2 hole quantum dot. The dot is formed close to pinch-off in a hole quantum wire defined in an undoped AlGaAs/GaAs heterostructure. We clearly observe two distinctive hallmarks of quantum dot Kondo physics. First, the Zeeman spin splitting of the zero-bias peak in the differential conductance is independent of the gate voltage. Second, this splitting is twice as large as the splitting for the lowest one-dimensional subband. We show that the Zeeman splitting of the zero-bias peak is highly anisotropic and attribute this to the strong spin-orbit interaction for holes in GaAs. 相似文献
896.
S. K. G. Peters S. R. Kehl R. E. Martinelli M. W. Tamblin T. F. Hamilton 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(1):209-214
The Marshall Islands Program at the Lawrence Livermore National Laboratory has completed a series of radiological surveys at Bikini, Rongelap, Utrōk, and Enewetak Atolls in the Marshall Islands designed to take a representative sample of food supplies with emphasis on determining 137Cs activity concentrations in common food plants. Coconuts (Cocos nucifera L.) are the most common and abundant food plant, and provided a common sample type to characterize the level and variability of activity concentrations of 137Cs in plant foods collected from different islands and atolls. Other dominant food types included Pandanus (Pandanus spp.) and breadfruit (Actocarpus spp.). In general, the activity concentration of 137Cs in food plants was found to decrease significantly between the main residence islands on Bikini, Rongelap, Utrōk, and Enewetak Atolls. The mean activity concentration of 137Cs measured in drinking coconut meat and juice was 0.72 (95 % CI 0.68–0.77) and 0.34 (95 % CI 0.30–0.38) Bq g?1, respectively, on Bikini Island; 0.019 (95 % CI 0.017–0.021) and 0.027 (95 % CI 0.023–0.031) Bq g?1, respectively, on Rongelap Island; 0.010 (95 % CI 0.007–0.013) and 0.007 (95 % CI 0.004–0.009) Bq g?1, respectively, on Utrōk Island; and 0.002 (95 % CI 0.0013–0.0024) and 0.002 (95 % CI 0.001–0.0025) Bq g?1, respectively, on Enewetak Island. High levels of variability are reported across all islands. These results will be used to improve the accuracy and reliability of predictive dose assessments, help characterize levels of uncertainty and variability in activity concentrations of fallout radionuclides in plant foods, and allow atoll communities to make informed decisions about resettlement and possible options for cleanup and rehabilitation of islands and atolls. 相似文献
897.
Eduardo Rezende Graminho Ronivaldo Rodrigues da Silva Tatiana Pereira de Freitas Cabral Eliane Candiani Arantes Nathalia Gonsales da Rosa Luiz Juliano Debora Noma Okamoto Lilian Caroline Gonçalves de Oliveira Marcia Yuri Kondo Maria Aparecida Juliano Hamilton Cabral 《Applied biochemistry and biotechnology》2013,169(1):201-214
The purpose of this work was to purify a protease from Penicillium waksmanii and to determine its biochemical characteristics and specificity. The extracellular protease isolated that was produced by P. waksmanii is a serine protease that is essential for the reproduction and growth of the fungus. The protease isolated showed 32 kDa, and has optimal activity at pH 8.0 and 35 °C towards the substrate Abz-KLRSSKQ-EDDnp. The protease is active in the presence of CaCl2, KCl, and BaCl, and partially inhibited by CuCl2, CoCl2 and totally inhibited by AlCl3 and LiCl. In the presence of 1 M urea, the protease remains 50 % active. The activity of the protease increases 60 % when it is exposed to 0.4 % nonionic surfactant-Triton X-100 and loses 10 % activity in the presence of 0.4 % Tween-80. Using fluorescence resonance energy transfer analysis, the protease showed the most specificity for the peptide Abz-KIRSSKQ-EDDnp with k cat/K m of 10,666 mM?1?s?1, followed by the peptide Abz-GLRSSKQ-EDDnp with a k cat/K m of 7,500 mM?1?s?1. Basic and acidic side chain-containing amino acids performed best at subsite S1. Subsites S2, S3, S′ 2, and S′ 1, S′ 3 showed a preference for binding for amino acids with hydrophobic and basic amino acid side chain, respectively. High values of k cat/K m were observed for the subsites S2, S3, and S′ 2. The sequence of the N-terminus (ANVVQSNVPSWGLARLSSKKTGTTDYTYD) showed high similarity to the fungi Penicillium citrinum and Penicillium chrysogenum, with 89 % of identity at the amino acid level. 相似文献
898.
Andrew D. Hamilton Erkang Fan Scott Van Arman Cristina Vicent Fernando Garcia Tellado Steven J. Geib 《Supramolecular chemistry》2013,25(3-4):247-252
Abstract In recent years there has been intense activity in the design of synthetic molecules capable of enzyme-like recognition and binding of small substrates.1 Two fundamental approaches have been taken. The first has generally involved non-directional binding forces (such as solvophobic, π-stacking and dispersion interactions) in water-soluble cyclophane frameworks.2 This approach led to extremely important quantitative insights into the hydrophobic effect and the enthalpic and entropic contributions of solvent reorganization to binding.3 However, the weakly oriented nature of the binding interactions has resulted in only moderate substrate selectivity beyond the shape recognition permitted by the cavity. In nature such selectivity is a prerequisite for the chiral recognition and catalytic activity of enzymes and is achieved by hydrogen bonding and electrostatic interactions. The second major approach to artificial receptors makes use of these more directional interactions by incorporating several hydrogen bonding groups into a cleft or cavity of defined geometry.4 The resulting hosts form strong and selective complexes to those substrates with complementary shape and hydrogen bonding characteristics.5 In these cases, however, the binding free energy is solvent dependent, diminishing to zero as the polarity of the medium increases, due to the strong solvation of the hydrogen bonding sites. A central goal in contemporary molecular recognition research must be to develop receptors that effectively use directed hydrogen bonding interactions in competitive solvents. Success will probably require combining strong (possibly charged) hydrogen bonding groups with hydrophobic sites capable not only of effective apolar association with the substrate but also of protecting the polar sites from full solvation. 相似文献
899.
Pietro P. Lopes Bruno C. Batista Guilherme A. Saglietti Hamilton Varela Edson A. Ticianelli 《Journal of Solid State Electrochemistry》2013,17(7):1851-1859
A number of fuel cell relevant reactions are known to undergo kinetic instabilities under certain conditions. The majority of the experiments in such systems have been performed in liquid electrolyte systems on half-cell setups. Results for proton exchange membrane fuel cells fed with H2/CO mixtures at the anode show that there can be a range of gas flow rate and current density where spontaneous potential oscillations take place. Despite the recent developments in this area, there are still many mechanistic aspects underlying the emergence of electrochemical oscillations that remain unknown. In the present contribution, we report results on the CO2 production during the oxidation of carbon monoxide-containing hydrogen in a proton exchange membrane fuel cell, as measured by online mass spectrometry. By extensive fitting and careful consideration of the proposed mechanism, we were able to estimate the coverage of hydrogen and CO during the oscillations. As no other approach seems capable to probe the adsorbate coverage in an operando fuel cell, our analyses access experimental hidden information that can be of high value for fuel cell research. 相似文献
900.
Robert Hamilton Maeve O'leary Brian Walker Brian J. Walker 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract α-Aminoalkylphosphonic acids are analogues of natural aminoacids and as such have been the subject of much research effort over past years1. The diphenyl esters of α- aminoalkylphosphonic acids are particularly potent and show high selectivity as irreversible inhibitors of serine proteinases. Thus far, α-aminoalkylphosphonic acid ester analogues of a number of aliphatic- and aromatic aminoacids have been prepared including valine, phenylalanine, tryptophan, and tyrosine2, and the basic aminoacids ornithine, lysine. etc.3. We have now also prepared the a-diphenyl phosphonate analogues of the acidic aminoacids, aspartic and glutamic4. These have been examined as potential inactivators of serine proteinases exhibiting a P1 specificity for aspartate and glutamate, e.g. S. aureus V8 protease and granzyme B. 相似文献