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51.
Variations of densities and viscosities with temperature and composition are reported for binary liquid mixtures containing propionic acid+aniline (I),+o-toluidine (II),+o-anisidine (III), and+o-chloroaniline (IV). Entropies S
m and enthalpies H
m of activation as functions of the composition of the mixtures, as well as free energies of activation G
m at 10, 20, 30, 40, and 50°C and different compositions were calculated by means of Eyring's equation. The formation of activated complexes between the components of these binary mixtures is postulated and claimed to result from acid-base and hydrogen bonding exchange interactions. 相似文献
52.
Nonaqueous CE and field-amplified sample stacking have been used in the determination of complex mixtures of polar aromatic sulfonates (AS; mainly benzene- and naphthalenesulfonates) of environmental concern. The analytical procedure consists of an on-column aqueous sample enrichment, followed by the nonaqueous electrophoretic determination of stacked aromatic sulfonates. Various organic solvents were used as separation medium, acetonitrile and N-methylformamide gave the best results. Optimum capillary electrophoresis separation is obtained with ammonium acetate (25 mM) dissolved in N-methylformamide-methanol (90:10) as background electrolyte. This combined method was applied to the analysis of surface water samples spiked with selected aromatic sulfonates derivatives. 相似文献
53.
Maria Luisa Moyá Antonio Barrios Maria del Mar Graciani Rafael Jiménez Ernestina Muñoz Francisco Sánchez John Burgess 《Transition Metal Chemistry》1991,16(2):165-168
Summary The kinetics of replacement of 4,4-bipyridine, (4,4-bipy), and 4-cyanopyridine, (4-CNpy), by cyanide in [Fe(CN)5-(4,4-bipy)]3-. at 298 K have been studied in binary aqueous mixtures containing different amounts of t-butanol, methanol, glycerol, ethyleneglycol and sucrose. The plots of logarithms of the limiting rate constantsversus the mole fraction of water are linear over the entire composition range studied, showing the importance of solvation phenomena. A different straight line of log (kL/s–1)versus XH2O is obtained for each mixture, indicating the influence of other solvent parameters on the reaction rate. A multiparameter regression of G
exp
with A (acidity vector), B (basicity vector) and GE is used for both reactions; plots of G
calc
versus G
exp
are linear with slopes of near unity. 相似文献
54.
We analyze a variant of the EPRB experiment within a framework for quantum mechanics that rests on a radical interpretation of the sum over histories. Within this framework, reality is (just as classically) a single history, e.g. a definite collection of particles undergoing definite motions; and quantum dynamics appears as a kind of stochastic law of motion for that history, a law formulated in terms of non-classical probability-amplitudes. No state vectors enter this framework, and their attendant nonlocality is therefore absent as well.1. That is, before pair creations and annihilations were discovered. (The electronic and nuclear spins might also be regarded as new aspects of their kinematics. But perhaps spin is better construed, within the sum-over-histories framework, as a quality of a more dynamical character, namely as a generalized sort of probability-amplitude.)2. A possible escape would be the so-called Everett interpretation, in which the collapse never occurs, but its effects are supposed to be recovered via a more careful analysis of closed systems in which measurement-like processes take place. Among other things, this approach tends to lead either to the view that nothing really happens [1] or to the view that everything really happens [2] (which perhaps is not that different from the former view).3. For example, the rule, collapse occurs along the past light cone (in the Heisenberg picture), appears to be consistent.4. And Bell's inequality shows thatany theory formulated in terms of an instantaneous state evolving in time would encounter the same trouble. Indeed, the trouble shows up even more glaringly if one adapts Bell's argument to spin-1 systems, using the results of Kochen and Specker[10]. In order to use the Kochen-Specker results in the EPR manner one needs a scheme for measuring the relevant observables, but this can be accomplished by means of suitably concatenated Stern-Gerlach analyzers with recombining beams [13]. Then, as Allen Stairs has pointed out [14], even the perfect correlations become impossible to reproduce, and no reference to probability theory is needed to establish a contradiction with locality. Recently, an analogous experiment using three spin 1/2 particles instead of two spin 1 particles has also been given [15].5. No technical problem obstructs an extension to fermionic fields (indeed the functional integral formalism for Quantum Field Theory is probably the most popular at present), but the realistic interpretation of the individual histories seems to get lost. One way out would be if all fermions were composites or collective excitations of fields quantized according to bosonic commutation relations. Another would be if the particle formulation were taken as basic, with the complementary field formulation being merely a mathematical artifice (at least for fermions).6. In the approach of Gell-Mann-Hartle and Griffiths for example, only a small subset of the possible partitions is granted meaning, in such a way that all interference terms are suppressed and quantum probabilities reduce to classical ones.7. In stating these rules we consider an idealized situation in which the spatio-temporal indeterminacy of particle-locationwithin a given one of our trajectories is ignored; or if you prefer, you can take the experiment as only a Gedanken one affording a simplified illustration of how EPR-like correlations are understood within the sum-over-histories framework. In this connection recall also that the semiclassical propagator is in fact exact for a free particle.8. This can be interpreted either as part of the specification of the initial conditions, or (as suggested by a referee) merely as an example of relativization of probabilities.9. Thus a state vector may be defined as an equivalence-class of sets of partial histories.10. One such generalization applies to open systems, for example to a particle in contact with a heat reservoir. For this example see [11], wherein the two-way path formalism of §5 above is used, and the influence of the reservoir results in an effective dynamics for the particle in which the forward and backward portions of its world-line are coupled to each other by a certain interaction term in the amplitude. In this type of situation a density-operator (though not a state vector ) can still be introduced, but it no longer summarizes all the relevant information about the past (and correspondingly its evolution lacks the Markov property that(t + dt) is determined by(t) alone). For quantum gravity, it may be that not even such a non-Markov will be exactly definable, and only the global probabilities themselves will make sense.11. Ironically it is just this property of the amplitudes which, as mentioned above, makes possible the introduction of the state vectors whose collapse then introduces such a strong appearance ofnonlocality into the theory. 相似文献
55.
Ikejiri M Bernardo MM Meroueh SO Brown S Chang M Fridman R Mobashery S 《The Journal of organic chemistry》2005,70(14):5709-5712
[structure: see text] Matrix metalloproteinases (MMPs), of which 26 are known, have been implicated in a number of pathological conditions, including tumor metastasis. We have previously described the first mechanism-based inhibitor for MMPs (J. Am. Chem. Soc. 2000, 122, 6799-6800), which in chemistry mediated by the active site zinc ion selectively and covalently inhibits MMP-2, -3, and -9. Computational analyses indicated that this selectivity in inhibition of MMPs could be improved by design of new variants of the inhibitor class. We report herein the syntheses of methyl 2-(4-{4-[(2-thiiranylpropyl)sulfonyl]phenoxy}phenyl)acetate (3) and 2-(4-{4-[(2-thiiranylpropyl)sulfonyl]phenoxy}phenyl)acetic acid (4), and show that compound 3 serves as a mechanism-based inhibitor exclusively for MMP-2. This molecule should prove useful in delineating the functions of MMP-2 in biological systems. 相似文献
56.
Muñoz-Espí R Qi Y Lieberwirth I Gómez CM Wegner G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(1):118-129
Polystyrene latex particles modified at the surface with different hydrophilic functional groups were prepared by miniemulsion polymerization and used as controlling agents in the crystallization of zinc oxide from aqueous medium. The effects of the chemical nature of the surface functionalization and the latex concentration on the crystal growth, morphology, and crystalline structure of the resulting zinc oxide were analyzed. Micro- and submicrosized crystals with a broad variety of morphologies depending on the functionalization were obtained. Among the different latexes studied, the acrylic-acid-derived particles were shown to be a convenient system for further quantitative investigations. In this case, as the additive concentration increases, the length-to-width ratio (aspect ratio) of the crystals decreases systematically. Preferential adsorption of the latex particles onto the fast-growing faces {001} of ZnO is assumed to follow a Langmuir-type isotherm, and interaction of the adsorbed particles with the growth centers will reduce the growth rate in [001]. This leads to a quantitative relationship linking the aspect ratio to the latex concentration at constant diameter and surface chemistry of the latex. The dependence of the aspect ratio on charge density of the latex can also be modeled by an algorithm in which attractive forces between the latex particle and the ZnO surface are balanced against repulsive forces of an osmotic nature. The latter are associated with the confined volume between the crystal and latex particle surfaces. 相似文献
57.
Eduardo Corts Corts Rafael Sosa Mendoza Maximiliano Santibez Gutirrez Olivia Garca‐Mellado De Corts 《Journal of heterocyclic chemistry》2004,41(2):273-276
The preparation and spectral properties often novel methyl 5‐[(o‐, m‐, and p‐substituted)‐phenylthio]‐2‐benzimidazolecarbamates with possible pharmacological activity as antihelmintics is described; by condensation and cyclization between 5‐methylthioures sulfate chloroformic acid methyl ester and 3,4‐diaminophenyl‐substituted‐phenylthio ether dissolved in ethanol. The structures of all final products were corroborated by ir; 1H‐nmr, 13C‐nmr and ms. 相似文献
58.
Rafael D. Sorkin Robert M. Wald Zhang Zhen Jiu 《General Relativity and Gravitation》1981,13(12):1127-1146
We examine the entropy of self-gravitating radiation confined to a spherical box of radiusR in the context of general relativity. We expect that configurations (i.e., initial data) which extremize total entropy will be spherically symmetric, time symmetric distributions of radiation in local thermodynamic equilibrium. Assuming this is the case, we prove that extrema ofS coincide precisely with static equilibrium configurations of the radiation fluid. Furthermore, dynamically stable equilibrium configurations are shown to coincide with local maxima ofS. The equilibrium configurations and their entropies are calculated and their properties are discussed. However, it is shown that entropies higher than these local extrema can be achieved and, indeed, arbitrarily high entropies can be attained by configurations inside of or outside but arbitrarily near their own Schwarzschild radius. However, if we limit consideration to configurations which are outside their own Schwarzschild radius by at least one radiation wavelength, then the entropy is bounded and we find Smax MR, whereM is the total mass. This supports the validity for self-gravitating systems of the Bekenstein upper limit on the entropy to energy ratio of material bodies. 相似文献
59.
Bernabé-Pineda M Ramírez-Silva MT Tapia-Benavides R Rojas-Hernández A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(5):1071-1076
The importance assigned to chelating agents in diverse areas has impelled studies concerning their development as related to metal ions representing a biological concern. The synthesis of di-isopropyliminodiacetoamide (D) is presented in this work. The acidity constant obtained for D was pKa = 5.79 +/- 0.04 with the aid of program SUPERQUAD. The equilibrium constants for D with Cu(II) were obtained with the aid of program SQUAD for CuD2+ and CuD2(2)+ species giving log beta1 = 4.795 +/- 0.002 and log beta2 = 8.374 +/- 0.004, respectively. 相似文献
60.
Rafael Rojas-Hernndez Juan Luis Díaz-de-Len-Santiago Grettel Barcel-Alonso Jorge Bautista-Lpez Valentin Trujillo-Mora Julio Csar Salgado-Ramírez 《Entropy (Basel, Switzerland)》2022,24(7)
This paper introduces a new method of compressing digital images by using the Difference Transform applied in medical imaging. The Difference Transform algorithm performs the decorrelation process of image data, and in this way improves the encoding process, achieving a file with a smaller size than the original. The proposed method proves to be competitive and in many cases better than the standards used for medical images such as TIFF or PNG. In addition, the Difference Transform can replace other transforms like Cosine or Wavelet. 相似文献