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971.
Yu Yang Maya Belghazi Arnaud Lagadec David J. Miller Steven B. Hawthorne 《Journal of chromatography. A》1998,810(1-2):149-159
The intermolecular interactions between organic solutes and sorbent matrices under subcritical water conditions have been investigated at a pressure of 50 bar and temperatures ranging from 50 to 250°C. Both polar and nonpolar organics (chlorophenols, amines, n-alkanes, and polycyclic aromatic hydrocarbons) and five different sorbent matrices (glass beads, alumina, Florisil, silica-bonded C18, and polymeric XAD-4 resins) were used. From the same matrix, the polar solutes always eluted at lower temperatures, while the moderately polar and nonpolar solutes only eluted at higher temperatures. Similar to matrix effects previously observed using supercritical carbon dioxide, the sorbent type greatly influenced the elution efficiency under subcritical water conditions. Lower temperatures are sufficient to elute a particular solute from glass beads, alumina, and Florisil, but higher temperatures (less polar water) are needed to elute the same solute from silica-bonded C18. The highest temperatures were required to elute aromatic organics from XAD-4. These matrix effects demonstrate that, while low temperature water can break inert or dipole interactions between solutes and glass beads, alumina, and Florisil, higher temperature water is required to interrupt the van der Waals attractions between solutes and silica-bonded C18, and even higher temperatures needed to overcome the π-electron interactions between aromatic solutes and XAD-4. 相似文献
972.
A. S. Balueva E. I. Ayupova G. N. Nikonov Yu. T. Struchkov A. P. Pisarevskii 《Russian Chemical Bulletin》1994,43(9):1561-1567
Fused 1,3,2-dioxaborinanes, derivatives of 4-diphenylphosphino- and 4-diphenylphosphoryl-4H-1, 3-dioxa-2-boraphenanthrenes, and their complexes with amines have been synthesized. According to X-ray diffraction data, the complex of 2-phenyl-4-diphenylphosphoryl-4H-1, 3-dioxa-2-boraphenanthrene with butylamine exists as a dimer due to the formation of intermolecular hydrogen bonds.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1649–1655, September, 1994.The present work was financially supported by the International Science Foundation (grant No. RHBOOO). 相似文献
973.
Summary The chelation behaviour of the complexes of La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Y3+, Tb3+, Dy3+, Ho3+ with biologically active 2-Hydroxy-1-naphthaldehyde semicarbazone (HNAS) has been studied potentiometrically in 75% (v/v) dioxane-water medium at various ionic strengths. The method of Bjerrum and Calvin, as modified by Irving and Rossotti has been used to find out the values of n andpL. The formation constants of metal chelates and the values ofS
min have been calculated. The order of formation constants of chelates was found to be: La3+3+3+3+3+3+3+3+3+3+3+.
Physikochemische Untersuchungen zur Komplexierung von biologisch aktivem 2-Hydroxy-1-naphthaldehyd-Semicarbazon (HNAS) mit Lanthanoiden
Zusammenfassung Das Chelierungsverhalten von La3+, Ce3+, Pr3+, Nd3+, Sm3+, Eu3+, Gd3+, Y3+, Tb3+, Dy3+ und Ho3+ mit 2-Hydroxy-1-naphthaldehydsemicarbazon (HNAS) wurde potentiometrisch in 75% (v/v) Dioxan-Wasser bei verschiedenen Ionenstärken untersucht. Die Werte für n undpL wurden nach der Methode von Bjerrum und Calvin in der Modifikation von Irving und Rossotti bestimmt. Die Komplexbildungskonstanten der Metallchelate und die WerteS min wurden ermittelt. Die Reihung der Komplexbildungskonstanten war La3+相似文献3+ 3+ 3+ 3+ 3+ 3+ 3+ 3+ 3 3+.
974.
The stoichiometric pK
1
*
and pK
2
*
for the ionization of carbonic acid has been determined from emf measurements in NaCl soluions to 6.0m at 25°C. Our results at low concentrations are in good agreement with the results of Harned and Bonner, of Dyrssen and Hansson and of Roy et al. The calculated values of pK
1
*
using Pitzer's equations agree with the measured values to ±0.01 pK units provided higher order terms are used. It was necessary to use a triplet interaction parameter () and higher order electrostatic terms (E) to calculate reliable values of pK
2
*
(±0.03 pK units) over the entire concentration range. These results demonstrate the reliability of the Pitzer equations to estimate activity coefficients in concentrated salt solutions. 相似文献
975.
976.
A new separation system of capillary electrophoresis for the simultaneous determination of metals by using ethylenediamine tetraacetic acid (EDTA) as complexing agent and employing vancomycin as complex selector was described. The Z-shape cell capillary electrophoresis was used to enhance the sensitivity for the determination of the complexes of Cu(Ⅱ), Ni(Ⅱ), Co(Ⅱ) and Fe(Ⅲ) with EDTA. The partial filling method (co-current mode) was used in order to increase the selectivity of the electrophoretic method, meanwhile vancomycin was not present at the detector path during the detection of metal-EDTA complexes. The vancomycin concentration, phosphate concentration and pH of the buffer strongly influenced mobility, resolution and selectivity of the studied analytes. Under the optimal condition, the relative standard deviations (n=5) of the migration time and the peak area were less than 3.14% and 7.35%, respectively. Application of the Z-shape cell capillary electrophoresis method with UV detection and vancomycin loading led to the reliable determination of these metal ions in tap water and the recoveries were 97%-101%. The detection limits based on a signal to noise ratio of 3 : 1 were found in the range of 2-10 μg·L^-1. 相似文献
977.
978.
L. Ya. Zakharova F. G. Valeeva A. R. Ibragimova L. A. Kudryavtseva Yu. F. Zuev L. V. Avvakumova V. I. Kovalenko A. I. Konovalov 《Russian Chemical Bulletin》2007,56(1):62-69
The kinetics of alkaline hydrolysis of O-ethyl O-p-nitrophenyl chloromethylphosphonate in a sodium bis(2-ethylhexyl)sulfosuccinate—n-nonane—polyethylene glycol—water reverse micellar system was studied in a wide range of concentrations of the surfactant
and water. The sign of the catalytic effect of micelles is inverted in the presence of the polymer. A sharp change in the
apparent rate constant of hydrolysis of the phosphonate was found in a region of the temperature percolation threshold.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 60–67, January, 2007. 相似文献
979.
A new technique of searching the conformational space of transition states was used to explore the cause of the rate acceleration in the gem-dialkyl effect in intramolecular cyclization reactions. Several previous hypotheses were discarded and a new hypothesis was advanced based on this new data. This hypothesis, the “Facilitated Transition” hypothesis, states that increased steric hindrance reduces the overall activation energy by facilitating rotation through the transition state. The older “Reactive Rotamer” hypothesis was eliminated by generating all conformations of the starting materials using the
and
computer programs and demonstrating that no relationship is found between rate increase and a change in the concentration of “reactive rotamers”. 相似文献
980.
笼形聚偕胺肟树脂的研究HX/ACAO树脂吸附贵金属 总被引:3,自引:0,他引:3
氢卤酸、硝酸、硫酸、磷酸和硼酸处理的笼形聚偕胺肟树脂(HX/A-CAO)对Ag+和等贵金属离子的吸附能力按如下顺序:PdCl42-:H3BO3/ACAO>BCAO>H3PO4/ACAO>HI/ACAO>H2SO4/ACAO>HCl/ACAO>HNO3/ACAO>HF/ACAO.IrCl62-:BCAO>H3PO4/ACAO>H3BO3/ACAO>HCl/ACAO>HF/ACAO>HI/ACAO>H2SO4/ACAO≥HNO3/ACAO.PtCl62:BCAO>H3BO3/ACAO>H2SO4/ACAO>HNO3/ACAO>HCl/ACAO>HF/ACAO>H3PO4/ACAO>HI/ACAO.Ag+:BCAO>H3BO3/ACAO>HI/ACAO>H2SO4/ACAO>HF/ACAO>HCl/ACAO>H3PO4/ACAO>HNO3/ACAO.AuCl4-:BCAO>H3BO3>H3PO4/ACAO>HF/ACAO>HCl/A-CAO>H2SO4/ACAO>HI/ACAO>HNO3/A-CAO.研究了H3BO3/ACAO树脂对Ag+和离子的吸附动力学,讨论了吸附机理. 相似文献