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11.
The first molal hydrolysis quotient, Q1.1, of Mg2+ was measured potentiometrically from 1 to 250°C at ionic strengths of 0.11, 0.31, 1.01, and 5.0 mol-kg-1 in an aqueous NaCl medium using a hydrogen-electrode, concentration cell. Only hydrolysis of the first four percent of the
magnesium in solution could be followed before precipitation of brucite, Mg(OH)2(cr), occurred. The log Q1.1 values were fitted as a function of temperature and ionic strength using four adjustable parameters. The resulting constants
are compared with the limited existing low temperature data. At infinite dilution and 25°C the following quantities are reported:
logK
1.1 = -11.68±0.05, †Hso = 70.1±1.2 kJ-mol-1, †So = 11±4 J-K-1-mol-1, and †C
p
o
= 0 J-K-1-mor-1. At each ionic strength, including the values extrapolated to infinite dilution, the heat capacity change for the hydrolysis
reaction was zero,i.e., logQ
1.1 was found to be a linear function of the reciprocal temperature in Kelvin, at least over the measured range of l-250°C. The
hydrolysis constants at infinite dilution were modeled to 550°C and two kbar pressure with a function incorporating solvent
density using published results obtained at these extreme conditions. 相似文献
12.
Actin-containing liposomes were prepared via extrusion through 400 and 600 nm pore diameter membranes at different monomeric actin concentrations in low ionic strength buffer (G-buffer). After subjecting the liposome dispersions to high ionic strength polymerization buffer (F-buffer), topological changes in liposome structure were studied using atomic force microscopy (AFM). Paired dumbbell, horseshoelike, and disklike assemblies were observed for actin-containing liposomes extruded through 400 and 600 nm pore diameter membranes. The topology of actin-containing liposomes was found to be highly dependent on both liposome size and actin concentration. At 1 mg/mL actin, the actin-containing liposomes transformed into a disklike shape, whereas, at 5 mg/mL actin, the actin-containing liposomes retained a spherical shape. On the basis of these observations, we hypothesize that actin could either polymerize on the surface of the inner leaflet of the liposome membrane or polymerize in the aqueous core of the liposome. We explain the associated shape changes induced in actin-containing liposomes on the basis of the hypothesized mechanism of actin polymerization inside the liposomes. At higher actin concentrations (5 mg/mL), we observed membrane-induced actin self-assembly in G-buffer, which implies that G-actin is able to interact directly with lipid bilayers at sufficiently high concentrations. 相似文献
13.
Rhodium(I) complexes trans-[RhCl(CO)(PR(2)[NC(4)H(3)C(O)Me-2])(2)] (R = Ph, NC(4)H(4)) react with water to give the diphosphoxane-bridged dimers [Rh(2)Cl(2)(CO)(2)(mu-PR(2)OPR(2))(2)] following cleavage of the P-N bonds to the 2-acetyl-N-pyrrolyl groups. The two dimers have been crystallographically characterized and show a number of structural differences, with the PPh(2)OPPh(2) compound possessing semibridging chloride and carbonyl ligands whereas the P(NC(4)H(4))(2)OP(NC(4)H(4))(2) compound contains only terminal chlorides and carbonyls. No evidence for cleavage of the P-N bonds involving the unfunctionalized N-pyrrolyl groups in trans-[RhCl(CO)(P[NC(4)H(4)](2)[NC(4)H(3)C(O)Me-2])(2)] was observed. 相似文献
14.
Pandey S Redden RA Hendricks AE Fletcher KA Palmer CP 《Journal of colloid and interface science》2003,262(2):579-587
Solubilization environment afforded by several of the novel allyl glycidyl ether-modified methylhydrosiloxane polymers are investigated using a common polycyclic aromatic hydrocarbon fluorescence probe, pyrene. The backbone of the polymer has been modified by the addition of an alkyl chain of varying length (either C8, C12, or C18) and to differing degrees of substitution. The nomenclature adopted for the purposes of these studies is as follows: "AGENT" represents the backbone polymer with no alkyl substitution, and "OAGENT", "DAGENT", and "SAGENT" are substituted with n-octyl, n-dodecyl, and n-octadecyl, respectively. The percentage of alkyl substitution is designated as 10, 15, and 20%. The pyrene polarity scale (defined as the ratio of the intensity of peak I to peak III) was used to determine the relative dipolarity of the cybotactic region provided by approximately 1 w/w% aqueous polymer solutions compared to 10 mM sodium dodecylsulfate (SDS) micellar solution. Results indicate that 10-15% DAGENT afforded the most hydrophobic solubilization site, followed by 15% OAGENT and 15% SAGENT. In addition, as the degree of alkyl substitution of DAGENT increased from 10 to 20%, the cybotactic region appeared to become more hydrophobic. Furthermore, a deeper investigation into the relative size of the solubilization site revealed that all alkyl-substituted polymers promoted excimer formation at relatively low pyrene concentrations, indicating the possibility of localized concentration enhancement within the solvation pockets and/or compartmentalization of the solute molecules. The pyrene fluorescence excitation data strongly indicates ground-state heterogeneity that is most prominent in AGENT and decreases as the alkyl chain length is increased. This provides a relative sense of the size and shape of the solvation pockets afforded by each polymer solution. An overall analysis of the collected data indicated that these alkyl-substituted polymers may provide a more selective and efficient pseudostationary phase in electrokinetic chromatography with better solvation capacity for hydrophobic compounds compared to SDS. 相似文献
15.
The hydrolysis of chromate ion was studied potentiometrically in a concentration cell fitted with hydrogen electrodes by titrating basic NaCl–Na2CrO4 solutions with standardized HCl against a NaOH reference solution. The temperature was varied from 25 to 175°C at 25° intervals at the following ionic strengths (I): 0.1140, 0.2346, 0.5337, 0.9988, 2.940, and 5.239 (NaCl). Depending on the ionic strength, the molality of total chromium was varied from 0.001 to 0.100. The resulting titration curves could be resolved best in terms of three equilibria involving the formation of HCrO
4
–
(aq), Cr2O3– (aq), and CrO3Cl– (aq). The equilibrium quotients for all three reactions were fitted as a function of temperature and ionic strength, and the molal thermodynamic parameters that were computed from these relationships are tabulated at specific ionic strengths over the experimental temperature range. 相似文献
16.
ALKALINE QUENCHING OF BACTERIORHODOPSIN TRYPTOPHANYL FLUORESCENCE: EVIDENCE FOR AQUEOUS ACCESSIBILITY OR A HYDROGEN-BONDED CHAIN 总被引:3,自引:0,他引:3
Abstract— Comparison between Trp fluorescence yields of membrane-bound bacteriorhodopsin (BR) and retinylidene-free bacterioopsin (BO) is consistent with a model in which all eight Trp residues are active fiuorophores in the latter, while the emission of all but two residues in the former is lost by energy transfer to retinal. The visible chromophore of BR is progressively bleached with increasing pH. Up to pH 12 this bleaching is reversed on reneutralization; but above this the change is irreversible with the appearance of a new absorption band characteristic of free retinal. Emission yields for both proteins decrease with increasingly alkaline pH in a manner typical of energy transfer to weakly-fluorescent tyrosinate. The limiting yields, reached at a pH corresponding to that producing irreversible bleaching of the visible chromophore, agree with an integral value of one remaining active Trp fluorophore in BR and between one and two in BO and show that the bulk of Trp are within the 11 Å Förster energy-transfer distance of Tyr accessible to OH− . Current models of the native protein structure of BR arrange the polypeptide chain primarily in a bundle of seven helical segments with axes perpendicular to the lipid bilayer plane and with buried polar residues, including Trp and Tyr, located at intrahelical surfaces. An interpretation of the observed accessibility of buried Tyr to OH− is that an aqueous region exists within the protein structure. Moreover, this putative aqueous region must be close to the retinylidene chromophore and thus may be associated with the light-driven ion transport system. The results are also compatible with energy transfer to internal Tyr residues which are connected via a chain of phenolate hydrogen bonds to a surface Tyr. 相似文献
17.
Steady-state mass transfer experiments were done to determine whether certain strains of bacteria in homogeneous suspension will accumulate at the gas:liquid interface and thereby significantly increase the oxygen transfer rate to the suspension. In particular, with suspensions ofB. licheniformis, the measured transfer rates are as much as three times the rate expected for a uniform suspension. In contrast, suspensions ofM. luteus show no increase in oxygen flux above expected values. The fact thatB. licheniformis is motile, whereasM. luteus is not suggests that cell motility may play an important role in the accumulation process.
相似文献18.
Electrical conductance measurements of dilute (<0.1>0.1>–1) aqueous NaCl solutions were made primarily to quantify the degree of ion association which increases with increasing temperature and decreasing solvent density. These measurements were carried out at temperatures from 100 to 600°C and pressures up to 300 MPa with a modified version of the apparatus used previously in the high temperature study in this laboratory. Particular emphasis was placed on conditions close to the critical temperaturelpressure region of water, i.e., at 5° intervals from 370 to 400°C. The results verify previous findings that the limiting equivalent conductance Ao of NaCl increases linearly with decreasing density from 0.75 to 0.3 g-cm–1 and also with increasing temperature from 100 to 350°C. Above 350°C. Ao is virtually temperature independent. The logarithm of the molal association constant as calculated exclusively from the data400°C is represented as a function of temperature (Kelvin) and the logarithm of the density of water (g-cm–3) as follows:
相似文献
19.
David J. Wesolowski Donald A. Palmer George M. Begun 《Journal of solution chemistry》1990,19(2):159-173
Gibbsite, Al(OH)3, solubility studies in aqueous NaCl solutions at pH 9 demonstrate that the aluminate anion forms a strong complex with the neutral Bis-tris molecule 2,2-Bis(hydroxymethyl)-2,2,2-nitrilotriethanol, at low temperatures. The logarithm of the molal concentration quotient for the reaction
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