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71.
Sottini S Abbruzzetti S Spyrakis F Bettati S Ronda L Mozzarelli A Viappiani C 《Journal of the American Chemical Society》2005,127(49):17427-17432
Biphasic geminate rebinding of CO to myoglobin upon flash photolysis has been associated to ligand distribution in hydrophobic cavities, structurally detected by time-resolved crystallography, xenon occupancy, and molecular simulations. We show that the time course of CO rebinding to human hemoglobin also exhibits a biphasic geminate rebinding when the protein is entrapped in wet nanoporous silica gel. A simple branched kinetic scheme, involving the bound state A, the primary docking site C, and a secondary binding site B was used to calculate the microscopic rates and the time-dependent population of the intermediate species. The activation enthalpies of the associated transitions were determined in the absence and presence of 80% glycerol. Potential hydrophobic docking cavities within the alpha and beta chains of hemoglobin were identified by computational modeling using xenon as a probe. A hydrophobic pocket on the distal side of the heme, corresponding to Xe4 in Mb, and a nearby site that does not have a correspondence in Mb were detected. Neither potential xenon sites on the proximal side nor a migration channel from the distal to proximal site was located. The small enthalpic barriers between states B and C are in very good agreement with the location of the xenon sites on the distal side. Furthermore, the connection between the two xenon sites is relatively open, explaining why the decreased mobility of the protein with viscosity only slightly perturbs the energetics of ligand migration between the two sites. 相似文献
72.
Silvia?Faranda Giorgia?Foca Andrea?Marchetti Lorenzo?TassiEmail author Alessandro?Ulrici Claudia?Zucchi 《Journal of solution chemistry》2004,33(10):1181-1197
Kinematic viscosities were measured for 2-butanone + 2-butanol binary liquid mixtures with a capillary Ubbelohde routine viscometer in the temperature range from 273.15 to 353.15 K at atmospheric pressure, and covering the whole miscibility field (0xi1). Experimental data have been correlated by means of different empirical or semiempirical relationships, such as =(T), =(xi), and =(T, xi). Viscosity deviations, , from ideal behavior are negative at all experimental conditions, confirming that structure breaking effects prevail in the liquids. Furthermore, the thermodynamics of viscous flow and excess Gibbs energy of activation of viscous flow, G*E, have been calculated. As an alternative and complementary approach to such investigations, the fluidity () of this binary system has been analyzed by the modified—Batschinski theory. The results are discussed in terms of the specific molecular interactions between the mixture components. 相似文献
73.
Rapid determination of minority organic acids in honey by high-performance liquid chromatography 总被引:8,自引:0,他引:8
Suárez-Luque S Mato I Huidobro JF Simal-Lozano J Sancho MT 《Journal of chromatography. A》2002,955(2):207-214
A rapid high-performance liquid chromatographic method for the determination of organic acids in honey is reported. Malic, maleic, citric, succinic and fumaric acids were identified and quantified in 15 min. First time repeatibility, reproducibility and recoveries were determined out for these acids in honey samples. Maleic acid was also quantified for first time by a chromatographic method. The organic acids were removed from honey by using a solid-phase extraction procedure with anion-exchange cartridges. Previously, the solution of honey was adjusted to pH 10.50 with 0.1 M NaOH and stirred for 15 min at room temperature. Then, this solution was adjusted to pH 5.00 with 0.1 M H2SO4. This procedure was carried out to avoid interferences in the baseline. The chromatographic separation was achieved with only one Spherisorb ODS-2 S5 column thermostated at 25 degrees C. Metaphosphoric acid (pH 2.20) was used as mobile phase at a flow-rate of 0.7 ml/min. Organic acids were detected with a UV-vis detector (215 nm). The precision results showed that the relative standard deviations of the repeatability and reproducibility were < or =3.20% and < or =4.86%, respectively. The recoveries of the organic acids ranged from 62.9 to 99.4%. Under optimum conditions the detection limits ranged from 0.0064 to 7.57 mg/kg and the quantification limits ranged from 0.025 to 10.93 mg/kg. 相似文献
74.
The gold(I) selenolate compound [Au(2)(SePh)(2)(mu-dppf)] (dppf = 1,1'-bis(diphenylphosphino)ferrocene) has been prepared by reaction of [Au(2)Cl(2)(mu-dppf)] with PhSeSiMe(3) in a molar ratio 1:2. This complex reacts with gold(I) or gold(III) derivatives to give polynuclear gold(I)-gold(I) or gold(I)-gold(III) complexes of the type [Au(4)(mu-SePh)(2)(PPh(3))(2)(mu-dppf)](OTf)(2), [Au(3)(C(6)F(5))(3)(mu-SePh)(2)(mu-dppf)], or [Au(4)(C(6)F(5))(6)(mu-SePh)(2)(mu-dppf)], with bridging selenolate ligands. The reaction of [Au(2)(SePh)(2)(mu-dppf)] with 1 equiv of AgOTf leads to the formation of the insoluble Ag(SePh) and the compound [Au(2)(mu-SePh)(mu-dppf)]OTf. The complexes [Au(4)(C(6)F(5))(6)(mu-SePh)(2)(mu-dppf)] and [Au(2)(mu-SePh)(mu-dppf)]OTf (two different solvates) have been characterized by X-ray diffraction studies and show the presence of weak gold(I)-gold(III) interactions in the former and intra- and intermolecular gold(I)-gold(I) inter-actions in the later. 相似文献
75.
76.
Lodi Andrea Nap Cees-Jan Metzger-Maurer Silvia Schwartzenberger Christelle 《Accreditation and quality assurance》2018,23(4):211-218
Accreditation and Quality Assurance - Two approaches were used to determine the mass fraction of a sample of folic acid, one indirect (mass balance) where the components other than folic acid were... 相似文献
77.
78.
Nontrivial Solutions for p-Laplace Equations with Right-Hand Side Having p-Linear Growth at Infinity
Silvia Cingolani 《偏微分方程通讯》2013,38(8):1191-1203
ABSTRACT The existence of a nontrivial solution for quasi-linear elliptic equations involving the p-Laplace operator and a nonlinearity with p-linear growth at infinity is proved. Techniques of Morse theory are employed. 相似文献
79.
Silvia Dulanská Boris Remenec Ján Bilohuštin Miroslav Labaška Dušan Galanda 《Journal of Radioanalytical and Nuclear Chemistry》2013,295(3):2189-2192
This paper describes the use of IBC’s AnaLig® Sr-01 molecular recognition technology product to effectively and selectively pre-concentrate, separate, and recover strontium from urine samples. This method uses two-stage columns separation consisting of two different commercial products Eichrom’s Pre-filter Material and AnaLig® Sr-01 column from IBC Advanced Technologies. This method does not involve co-precipitation of strontium as phosphates and oxalates from urine samples. The new rapid method separates strontium-90 with high chemical recovery. 相似文献
80.
Gabriella Ieronimo Alessandro Mondelli Francesco Tibiletti Angelo Maspero Giovanni Palmisano Simona Galli Stefano Tollari Norberto Masciocchi Kenneth M. Nicholas Silvia Tagliapietra Giancarlo Cravotto Andrea Penoni 《Tetrahedron》2013
The thermal reaction between nitrosoarenes and alkynes under alkylating conditions produces N-alkoxyindoles as the major products in moderate to good yields and excellent regioselectivity. Various electrophiles are used affording different N–O-protected hydroxyindoles in a multi-component fashion. Privileged acetylenic substrates used in reactions with substituted nitrosoarenes are arylalkynes or propiolates. Potentially bioactive compounds and other classes of highly functionalizable indole products were prepared. Reactions between o-carbomethoxy-nitrosoarenes and arylacetylenes provided tricyclic compounds containing an acylaziridine indoline skeleton. 相似文献