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21.
A new flow electrical conductance instrument was constructed and tested on dilute NaCl solutions up to 458 K, and on more
concentrated solutions (maximum 0.436 mol⋅kg−1) at 373 K. The results of the new instrument agreed with those of previous authors within the estimated experimental errors.
The model of Bernard et al. (J. Phys. Chem. 96, 3833–3840 (1992), MSA) was found to represent the high-temperature results without introducing an ion-pairing equilibrium constant. The Fuoss–Hsia
conductance equation as given by Fernandez-Prini was found to represent the dilute concentrations with Λ° (NaCl) as the only adjustable parameter. It was found that Λ° (NaCl) could be expressed as a function of solvent viscosity and density by using three parameters found by regression of
literature results between 278.15 and 523 K. This equation along with the FHFP theory permits the equivalent conductivity
of dilute sodium chloride solutions to be calculated within the accuracy of the existing experimental measurements. 相似文献
22.
H. Eduardo Roman 《Journal of statistical physics》1990,58(1-2):375-382
Extensive Monte Carlo simulations of theant-in-the-labyrinth problem on randomL* L* L simple cubic lattices are performed, forL up to 960 on a CRAY-YMP supercomputer. The exponentk for the rms displacementr witht inrt
k
is found to bek=0.190±0.003. As a second approach, large percolation clusters with chemical shells up to 300 are generated on a simple cubic lattice at criticality. The diffusion equation is then solved by using the exact enumeration technique. The corresponding critical exponentd
w
is found to be 1/d
w
=0.250±0.003.On leave from I. Institut für Theoretische für Physik, Universität Hamburg, D-2000 Hamburg, Federal Republic of Germany. 相似文献
23.
Kim GN Kim EJ Son D Bacala A Imlay R Kirk P McNeil RR Metcalf W Cheng CP Mao ZP Yan Y Xu YT Zhu YC Abashian A Gotow K Kajino F Low E Naito F Piilonen L Childers R Darden C Lusin S Rosenfeld C Wilson S Frautschi M Kagan H Kass R Trahern CG Ko W Lander RL Maeshima K Malchow RL Higashi JR Kurihara Y Maki A Nozaki T Omori T Perez P Sagawa H Sakai Y Sugimoto Y Takaiwa Y Terada S Tsuchiya K Poling R Green J Park IH Sakamoto S Sannes F Schnetzer S Stone R Trentalange S Zimmerman D Miyano K Miyata H 《Physical review letters》1988,61(8):911-914
24.
Monotone Chemical Reaction Networks 总被引:2,自引:1,他引:2
Patrick De Leenheer David Angeli Eduardo D. Sontag 《Journal of mathematical chemistry》2007,41(3):295-314
We analyze certain chemical reaction networks and show that every solution converges to some steady state. The reaction kinetics
are assumed to be monotone but otherwise arbitrary. When diffusion effects are taken into account, the conclusions remain
unchanged. The main tools used in our analysis come from the theory of monotone dynamical systems. We review some of the features
of this theory and provide a self-contained proof of a particular attractivity result which is used in proving our main result. 相似文献
25.
The photochemistry of 13 4,4-diphenylcyclohexenones, substituted at carbon-6, was investigated in solution and in the crystalline state. The stereoselectivity was of particular interest. In the solution photochemistry of C-6 monosubstituted enones in benzene, there was a unique preference for migration of the cis-phenyl group with formation of bicyclo[3.1.0]hexanone photoproducts, with the original 6-substituent having an endo configuration at carbon-3 of the product. In methanol the reaction was diverted to afford 3,4-diphenylcyclohex-2-enes understood as arising from a hydrogen-bonded zwitterionic intermediate. The solid-state photochemistry was also investigated. There was a dramatic absence of the 3,4-diphenylcyclohex-2-ene products in accord with the absence of the hydrogen bonding encountered in methanol. Further, the solid-state reactivity correlated with a vector analysis using X-ray atomic coordinates. This established that the migrating phenyl group required an orientation facing the enone beta-carbon. While the interesting preference for the cis-endo migration was not intuitively predicted, ab initio computations on the alternative phenyl-bridged triplet intermediates did lead to an understanding of the selectivity. 相似文献
26.
Maria do Carmo B. Pimentel Eduardo Henrique M. Melo José Luiz Lima Filho William M. Ledingham Nelson Durán 《Applied biochemistry and biotechnology》1997,66(2):185-195
This work is a study of lipase production by a Brazilian strain ofPenicillium citrinum using an inexpensive and simple medium without organic nitrogen sources and of some important industrial properties, including
thermostability in relation to ionic strength. The maximal lipase activity (1585 U/L) was obtained whenPenicillium citrinum was cultured on 0.75% ammonium sulfate complemented with minerals salts instead of yeast extract. Although this activity
was about 55% lower than that produced in medium with yeast extract (2850 U/L), the specific activity (7.8 U/mg proteins)
was higher than that obtained with the yeast extract (4.9 U/mg proteins). The morphology of fungus changed totally, with yeast
extract there are smooth, solid, and spherical pellets whereas on ammonium sulfate there are small “hairy” pellets uniformly
suspended in the medium. The effect of ferrous (Fe++) ions was carried out using medium MA with and without Fe++ ions. Lipase production byPenicillium citrinum in medium MA requires Fe++ ions, the absence of which caused a decreased of about 50% in the specific activity (3.5 U/mg proteins). The utilization
of commercial, locally available oils as carbon sources, such as soybean oil (236 U/L) and corn oil (74 U/L) resulted in lower
activity compared to olive oil, showing that lipase production byPenicillium citrinum is specifically induced by olive oil. Potassium concentration in the medium can effects the production of lipase (1 mM (1585
U/L), 10 mM (1290 U/L), and 30 mM (1238 U/L), 50 mM (195 U/L), and 100 mM (2 U/L). The crude culture filtered was susceptable
to thermal deactivation. It was stable at pH 6.0, but was not stable at the optimum pH (8.0-8.5) at 50 mM. At the low ionic
concentration (1-25 mM) this lipase was stable at low pH (3.5-4.0). The activation energy was 22.4 ±2.2 Kcal. mol 1. 相似文献
27.
Chemical, structural, and thermal properties of Zn(II)-Cr(III) layered double hydroxides intercalated with sulfated and sulfonated surfactants 总被引:1,自引:0,他引:1
Crepaldi EL Pavan PC Tronto J Valim JB 《Journal of colloid and interface science》2002,248(2):429-442
Zn(II)-Cr(III)-LDHs (layered double hydroxides) containing sulfated or sulfonated surfactants as the interlamellar anion were synthesized by the coprecipitation method. The syntheses were conducted under various different experimental conditions, such as the Zn : Cr ratio, pH, and aging time. In each of the prepared materials, unlike previously reported data, the interlayer anion arrangement did not change, being consistent with a perpendicular monolayer. The thermal decomposition process of the prepared materials was studied by a set of analysis methods, such as TG/DTA, TG/MS, PXRD, and FT-IR. From the results obtained it was possible to conclude that, in an air atmosphere, the anions decomposed by a partial combustion, leading to the formation of sulfide. The results also showed that sulfonated surfactants containing LDHs are much more stable than those containing sulfated surfactants. A mechanism was proposed for the thermal decomposition of such LDHs based on the experimental results. 相似文献
28.
VISIBLE CHEMILUMINESCENCE ASSOCIATED WITH THE REACTION BETWEEN METHEMOGLOBIN OR OXYHEMOGLOBIN WITH HYDROGEN PEROXIDE 总被引:1,自引:0,他引:1
Eduardo A. Lissi Jorge Escobar Carlos Pascual Maria del Castillo Tais H. Schmitt Paolo Di Mascio 《Photochemistry and photobiology》1994,60(5):405-411
Abstract Visible chemiluminescence is emitted in the irreversible deactivation of hemoglobin or methemoglobin with excess H2 O2 . The emission takes place in two phases. The most intense one lasts a few seconds and is followed by a second phase of lower intensity that remains for longer periods. This second phase presents chaotic or sustained oscillations. Free radicals are implicated in the luminescent process since the emission can be reduced by free radical scavengers such as 6-hydroxy-2,5,7,8,-tetramethylchroman-2-carboxylic acid (Trolox) or ascorbic acid. These additives lead to a delay in reaching the maximum intensity, which can be related to their consumption, implying substantial recycling of the hemoprotein. Chemiluminescence is also observed in the oxidation of hemin by H2 O2 , suggesting a role for the heme group in the processes leading to the excited state production. The lower intensity observed in the presence of hemin can be related to the contribution of the globin chains. 相似文献
29.
Oscar E. Piro Eduardo E. Castellano Roberto C. V. Piatti Agustín E. Bolzn Alejandro J. Arvia 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m252-m255
The crystal structures of two salts of bis(thiourea)gold(I) complexes, namely bis(thiourea‐κS)gold(I) chloride, [Au(CH4N2S)2]Cl, (I), and bis[bis(thiourea‐κS)gold(I)] sulfate, [Au(CH4N2S)2]2SO4, (II), have been determined. The chloride salt, (I), is isomorphous with the corresponding bromide salt, although there are differences in the bonding. The AuI ion is located on an inversion centre and coordinated by two symmetry‐related thiourea ligands through the lone pairs on their S atoms [Au—S 2.278 (2) Å and Au—S—C 105.3 (2)°]. The sulfate salt, (II), crystallizes with four independent [Au(CH4N2S)2]+ cations per asymmetric unit, all with nearly linear S—Au—S bonding. The cations in (II) have similar conformations to that found for (I). The Au—S distances range from 2.276 (3) to 2.287 (3) Å and the Au—S—C angles from 173.5 (1) to 177.7 (1)°. These data are relevant in interpreting different electrochemical processes where gold–thiourea species are formed. 相似文献
30.
Ho-Shen Lin Ashraff A. Rampersaud Karen Zimmerman Mitchell I. Steinberg Donald B. Boyd 《中国化学会会志》1993,40(3):273-282
A series of nonpeptide angiotensin II receptor antagonists was synthesized via palladium-assisted cross coupling of aryl stannane and cycloalkenyl triflates and subsequent alkylation of silyl-protected imidazole. Our compounds, which have a terminal five- to seven-membered cycloalkenyl ring, are compared to DuPont EXP7711, an N-[(2′-carboxybiphenylyl)methyl]imidazole, which has a terminal phenyl moiety. Physicochemical properties of the compounds, such as lipophilicity, steric bulk, conformation, and the relative spatial proximity of the 2-carboxyl and the middle phenyl, are quantitated by computational chemistry. Potency in terms of binding affinity to AT1 receptors in rat adrenal glomerulosa and rabbit aorta is maximized when the terminal ring is aromatic. 相似文献