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141.
On the basis of the data on the distribution of various neutral solutes between sodium dodecyl sulfate (SDS) micelles and water, the control of separation selectivity in micellar electrokinetic chromatography (MEKC) by modification of the micellar phase with organic additives has been proposed and applied to the separation of simple model compounds. It was found that the distribution constants between the micelles and water (Kd,mc), which were determined by means of MEKC, of the solutes possessing hydrophilic functional groups are much larger than those between heptane and water (Kd,hep), whereas the Kd,mc values of the solutes possessing no hydropholic groups are comparable to their Kd,hep values. This indicates that the former solutes are preferentially solubilized in the Stern layer of the micelles and that the latter are located in the hydrocarbon core. In MEKC separations of aromatic compounds and metal acetylacetonates, considerable changes in separation selectivity were caused by the addition of compounds possessing both hydrophilic functional groups such as alcohols, phenol and ketones to the SDS micellar solution. The variations of the retention factors of the analytes could be explained in terms of saturation of the solubilization sites in the Stern layer with the modifiers, specific interaction of the modifiers with the analytes via hydrogen bonding in the micelles, and expansion of the core volume with the hydrocarbon parts of the modifiers. Such effects of the micellar modification could improve the resolution as well as the selectivity of MEKC separations. 相似文献
142.
The acid dissociation constants of 1,2-bis(cis-aminophenoxy)ethane-N,N,N′,N′;-tetraacetic acid (H4BAPAT or H4Z), and the stability constants of its chelates with tripositive rare-earth metal ions have been determined by the potentiometric titration and mercury indicator electrode methods at 15°, 25′ and 35°C and an ionic strength of 0.1 (KNO3). The existence of a monohydrogen chelate species, LnHZ, and the normal chelate, LnZ?, is illustrated. Enthalpy and entropy changes characterizing the formation of the normal chelates and the dissociation of the last two protons of chelating acid have been calculated at 25°C. These functions have been compared with corresponding values for related chelating agents. 相似文献
143.
S. O. Bondareva V. V. Lisitskii N. I. Yakovtseva Yu. I. Murinov 《Russian Chemical Bulletin》2004,53(4):803-807
The kinetics of hydrolysis of 1,2-disubstituted imidazolines in aqueous media was studied (pH 2.0—12.5, T = 25—90 °C) by UV spectroscopy. The hydrolysis products were identified. The introduction of a branched substituent into position 2 of the imidazoline ring increases the hydrolytic stability of the compounds. The effect of the pH on the hydrolysis rate of imidazolines is discussed. 相似文献
144.
Petr Barták Petr Bedná? Michael Lämmerhofer Zdeněk Stránský 《Analytica chimica acta》2004,506(1):105-113
Intermolecular association and ion-pair formation, respectively, between a cationic chiral selector, viz. o-9-(tert-butylcarbamoyl) quinine (CQN), and the both enantiomers of anionic N-(3,5-dinitrobenzoyl)leucine, (R)-DNB-Leu and (S)-DNB-Leu, were investigated by affinity capillary electrophoresis (ACE). Thus, binding constants of the both diastereomeric ion-pairs, (R) and (S)-DNB-Leu/CQN associates, were determined by different experimental setups and correction of nonlinear effects. A reciprocal setup was employed for the high-affinity (S)-enantiomer, and the experimental mobility data obtained for CQN at variable (S)-DNB-Leu concentrations in the background electrolyte were linearized and evaluated by advanced statistical model. A binding constant of KS=125.1 l mol−1 was afforded. The constant for the (R)-enantiomer, which is outside the range suitable for direct affinity CE, was obtained from indirect affinity CE utilizing the separation of the DNB-Leu racemate at a single appropriate CQN concentration in the BGE (resolution method) taking advantage of the known constant for the (S)-enantiomer yielding a binding constant of KR=2.51 l mol−1. Thereby, the so-called “constant time method” was adopted for the required precise measurement of the effective mobilities of the both enantiomers. A combined approach of reciprocal affinity CE with racemic DNB-Leu as additive and the resolution method confirmed the results. The resulting constants evidence excellent enantioselectivity of the tert-butylcarbamoyl derivative of the cinchona alkaloid quinine as chiral selector for N-(3,5-dinitrobenzoyl) derivatives of amino acids. 相似文献
145.
Mohamed GG Omar MM Hindy AM 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):1140-1150
Metal complexes of Schiff base derived from 2-thiophene carboxaldehyde and 2-aminobenzoic acid (HL) are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The ligand dissociation as well as the metal-ligand stability constants were calculated pH metrically at 25 degrees C and ionic strength mu=0.1 (1M NaCl). The complexes are found to have the formulae [M(HL)2](X)n.yH2O (where M=Fe(III) (X=Cl, n=3, y=3), Co(II) (X=Cl, n=2, y=1.5), Ni(II) (X=Cl, n=2, y=1) and UO2(II) (X=NO3, n=2, y=0)) and [M(L)2] (where M=Cu(II) (X=Cl) and Zn(II) (X=AcO)). The molar conductance data reveal that Fe(III) and Co(II), Ni(II) and UO2(II) chelates are ionic in nature and are of the type 3:1 and 2:1 electrolytes, respectively, while Cu(II) and Zn(II) complexes are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a terdentate manner with ONS donor sites of the carboxylate O, azomethine N and thiophene S. From the magnetic and solid reflectance spectra, it is found that the geometrical structure of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species. 相似文献
146.
This work utilizes on-column ligand synthesis and affinity capillary electrophoresis (ACE) to determine binding constants (Kb) of 9-flourenylmethyloxy carbonyl (Fmoc)-amino acid derivatives to the glycopeptide antibiotics ristocetin (Rist) and teicoplanin (Teic). In this technique, two separate plugs of sample are injected on to the capillary column and electrophoresed. The initial sample plug contains a d-Ala-d-Ala terminus peptide and either one or two non-interacting standard(s). The second plug contains a Fmoc-amino acid-N-hydroxysuccinimide (NHS) ester. The electrophoresis is then carried out with an increasing concentration of Rist or Teic in the running buffer. Upon electrophoresis the initial d-Ala-d-Ala peptide reacts with the Fmoc-amino acid yielding a new Fmoc-amino acid-d-Ala-d-Ala peptide derivative. Continued electrophoresis results in the binding of Rist or Teic to the Fmoc-amino acid-d-Ala-d-Ala peptide derivatives. Analysis of the change in the relative migration time ratio (RMTR) or electrophoretic mobility () of the Fmoc-amino acid-d-Ala-d-Ala peptide derivatives relative to the non-interacting standards, as a function of the concentration of Rist and Teic, yields a value for
Kb. These findings demonstrate the advantage of coupling on-column ligand synthesis to ACE for estimating binding parameters between antibiotics and ligands.Abbreviations Rist
Ristocetin
- Teic
Teicoplanin
- ACE
Affinity capillary electrophoresis
- RMTR
Relative migration time ratio 相似文献
147.
An attempt has been made to apply Green’s function and partitioning technique to the case of XY2Z (ClO2F) pyramidal type molecule belonging toC, point group. The isotopic rules have been formulated. The force constants, rotation distortion constants and mean amplitude
of vibration have been computed and compared with other observed and calculated values whichever is available. 相似文献
148.
The electronic spectrum of VCr has been studied using the complete-active-space self-consistent field complete-active-space second-order perturbation theory approach. Potential-energy curves for 12 electronic states have been computed. Transition energies, with respect to the X2 ground state, for some of the calculated electronic states are (with possible experimental values within parentheses) 0.53 eV (0.56) for A2+, 1.03 eV (1.14) for A4, 1.20 eV (1.14) for B2, 1.45 eV (1.51) for B4, 1.60 eV (1.51, 1.78) for C2, and 1.61 eV (1.63) for A4–.
AcknowledgementsThe research reported in this communication was supported by a grant from the Swedish Natural Science Research Council (NFR). S. Alex and D.G. Leopold are acknowledged for providing results from their negative ion photoelectron spectroscopy on VCr.Contribution to Björn Roos Honorary Issue 相似文献
149.
The hydrogen abstraction reaction of O(^3P) with Si2H6 has been studied theoretially. Two transition states of ^3A″ and ^3A′ symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 leve with 6-311G (d) basis set. G3MP2 has been used for the final single-point energy calculation. The rate constants have been calculated over a wide temperature range of 200-3000K using canonical variational transition-state sheory (CVT) with small curvature tunneling effect(SCT). The calculated CVT/SCT rate constants match well with the experimental value. 相似文献
150.
Reactions of OH radicals and some one-electron oxidants with 2-aminopyridine (2-AmPy) and 3-aminopyridine (3-AmPy) were studied in aqueous solutions using pulse radiolysis technique. The OH adduct of 2-AmPy at pH 9 has an absorption maximum at 360 nm along with a weak absorption band in the visible region and was found to be reactive with oxygen. The rate constant for its reaction with O2 was determined to be 1.0×108 dm3 mol−1 s−1. At pH 4 also, the OH adduct of 2-AmPy has an absorption band at 360 nm. However, there are differences in the absorption at other wavelengths. From the plot of ΔOD vs. pH at 340 nm, the pKa of the OH adduct was determined to be 6.5. Among the specific oxidants, only SO4−√ radicals were able to oxidize 2-AmPy. In the case of 3-aminopyridine (3-AmPy), the transient species formed by OH radical reaction at pH 9 has an absorption maximum at 410 nm with shoulder bands on both the sides. Its absorption spectrum at pH 4 was different indicating the existence of a pK value for the OH adduct. pKa of 3-AmPy-OH radical adduct species was evaluated to be 5.7. This adduct species was also found to be reactive with oxygen (k=7.6×106 dm3 mol−1 s−1). Specific one-electron oxidants like N3√, Br2−√ C2−√ and SO4−√ were able to oxidize 3-AmPy indicating that it is easier to oxidize 3-AmPy as compared to 2-AmPy. 相似文献