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991.
The aim of this paper is to prove that safe success in finding reaction paths (RPs) can only be expected from global path-determining methods. Some extensions of the mathematical arguments leading to the introduction of the DDRP (dynamically defined reaction path) method have been sketched. Four cases involving relaxation of analyticity, variability of the gradient field, minimum energy (reaction) paths (MEPs) and golf pocket holes on the potential energy surface (PES), and the rather strange consequences of the main theorem of the DDRP method giving a rigorous mathematical basis to chemical intuition in reaction kinetics have been discussed. The discussions show that the DDRP method - when changing the conditions and parameters - may, in essence, involve all other global methods. It has been shown that the DDRP method works in a stable way even for non-analytic though smooth energy functions; moreover, the gradient field can be replaced by other vector fields resulting in better convergence to the reaction path. As a by-product, the question of the existence of MEPs can safely be handled and golf pocket holes are constructed on the PES in order to prove that local methods have chance to search faithfully the RPs in complicated systems only if the energy function can be restored from its arbitrarily small pieces.This work was presented in parts at the 8th International Congress of Quantum Chemistry, Prague, Czech Republic, June 19–23,1994; Addendum to the Book of Abstracts of the 8ICQC: P/I-129. 相似文献
992.
Individual extraction constants of some dicarbollylcobaltate anions in the water-nitrobenzene system
E. Makrlík J. Rais K. Baše J. Plešek P. Vaňura 《Journal of Radioanalytical and Nuclear Chemistry》1995,198(2):359-365
Individual extraction constants of nine dicarbollylcobaltate anions in the two-phase water-nitrobenzene system were determined radiometrically assuming that the changes of Gibbs energy of the transfer of the tetraphenylarsonium cation, Ph4As+, and of the tetraphenylborate anion, BPh
4
–
, from the aqueous into the nitrobenzene phase are equal. The constants obtained by this method were correlated with Hansch's constants of hydrophobity. 相似文献
993.
Ludvík Beneš Vítězslav Zima 《Journal of inclusion phenomena and macrocyclic chemistry》1994,20(4):381-391
The course of intercalation of water into 1-VOPO4 has been studied by thermomechanical analysis and X-ray diffraction. Neither formation of vanadyl phosphate monohydrate nor staging were observed during the intercalation. The broadening and the shift of the positions of the lines in the diffractograms have been explained by the random stacking of intercalated and nonintercalated layers in the sample. 相似文献
994.
A. González P. Sánchez J. M. Pingarrón L. M. Polo 《Fresenius' Journal of Analytical Chemistry》1994,348(10):666-673
A polarographic study was carried out of the reduction processes of diethyl and dibutyl phthalate in micellar solutions with the cationic surfactant Hyamine 1622, and in an emulsified medium from aliquots of the phthalates dissolved in a diethyl ether: ethyl acetate (1:9) mixture and Hyamine 1622 as emulsifying agent. The characteristics of the reduction processes in both media were established. The number of electrons involved was higher for the base form of the electroactive species. Using dpp at E=–50 mV, the detection limits obtained in the emulsified medium were 6.7×10–8 and 7.4×10–7 moll–1 for diethyl phthalate and dibutyl phthalate, respectively. Interferences between the two phthalates were studied, and the possibility of carrying out the overall determination of both phthalates was demonstrated. Good results were obtained when applying the polarographic method developed in the emulsified medium to determine diethyl phthalate by dpp in spiked milk after extraction of the analyte with diethyl ether: ethyl acetate (1:9). 相似文献
995.
A fluorescence method involving sample pre-treatment is investigated concerning the determination of cefoxitin. A fluorescent product is formed when samples containing cefoxitin are subjected to alkaline hydrolysis with 1.0M sodium hydroxide and heated for 60 min at 90 degrees . The fluorescence is measured in ethanol/water medium (50% v/v) at approximately pH 2.0 provided by adding of 0.1M hydrochloric acid. The fluorescence excitation and emission maxima were 317 and 400 nm, respectively. The quantitative range is between 0.020 and 1.40 mug/ml. A detection limit of 2 x 10(-3) mug/ml was found. The proposed method has been applied to the determination of cefoxitin in commercial injections, saline and glucosed physiological serum. 相似文献
996.
A comparative electrochemical study of 2,4-dinitrophenol (DNP), albumin and DNP-albumin has been carried out at a hanging mercury drop electrode, in order to use DNP as a universal label in immunoelectrical assays. Several electrochemical techniques have been used. Differential pulse voltammetry has proved to be the most suitable. Wide dynamic linear ranges (more than three orders of magnitude for DNP-albumin) and low detection limits have been achieved (5 x 10(-10)M, 2 x 10(-10)M, 3 x 10(-12)M for DNP, albumin and DNP-albumin, respectively). Good reproducibility has been obtained in all cases (R.S.D. < 2.2%). 相似文献
997.
István Gyöngy 《Acta Appl Math》1994,35(1-2):165-177
We coasider a partially observable diffusion process (x
t,yt)t0 whose unobservable componentx
t lives on a submanifold M ofR
n
. We present some general conditions under which the conditional law ofx
t, given the observationsy
s
,s [0,t], admits a density w.r.t. a given measure on M. We characterize the analytical properties of this density by using appropriate Sobolev spaces.Research supported by the Hungarian National Foundation of Scientific Research No. 2290. 相似文献
998.
999.
V. Hnatowicz J. Kvítek V. Švorčík V. Rybka V. Popok 《Czechoslovak Journal of Physics》1994,44(6):621-627
Samples of polyethylene (PE) loaded with carbon black up to 8 wt.% and implanted with 150 keV Sb+ ions to the doses from 2×1013–2×1015 cm–2 were studied using standard Rutherford Back Scattering (RBS) technique. On the PE samples implanted to the doses above 2×1014 cm–2, a considerable surface carbonization is observed. The measured parameters of the Sb depth profile are compared with theoretical TRIM estimations. The projected range is by 25% lower than the theoretical one and the range straggling is about twice of that predicted. The differences are explained by stepwise polymer degradation during the ion bombardment. Strong oxidation of the ion implanted polymers is also observed. The oxygen depth profiles from the sample surface up to the depth comparable with Sb+ ion range evolve from nearly uniform one for low ion doses to highly non-uniform one for doses above 1×1015 cm–2. The total oxygen content in the sample surface layer 300 nm thick reaches a maximum for the doses of (1–2)×1014 cm–2.On leave from Belorussian State University, 220050 Minsk, Belarus.The authors thank the member of electrostatic accelerator group at INP for help during RBS measurements. The work was partly (V.H. and J.K.) supported by the Internal Grant Agency of the Academy of Sciences of Czech Republic under the grant No. 14805 and by the Internal Grant Agency of the Ministry of Education of Czech Republic under the grant No. 1002 (V.., V.R., V.H. and J.K.). In the final stage, the work was also supported by the Grant Agency of Czech Republic under the grant No. 202/93/0121. 相似文献
1000.
The so called toroidal distributions were obtained using the method previously employed to derive the other decompositions of the electric type transition operator used in literature. Some aspects of toroidal distributions are discussed. The condition is given which has to be imposed on the decomposition generating function in order that the Siegert's theorem holds. 相似文献