Capillary electrochromatography with monolithic poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase

A new kind of monolithic capillary electrochromatography column with poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase has been developed. The stationary phase was found to be porous by scanning electron microscopy and the composition of the continuous bed was proved by IR spectroscopy to be the ternary polymer of styrene, divinylbenzene, and methacrylic acid. The effects of operating parameters, such as voltage, electrolyte, and organic modifier concentration in the mobile phase on electroosmotic flow were studied systematically, The retention mechanism of neutral solutes on such a column proved to be similar to that of reversed-phase high performance liquid chromatography. In addition, fast analyses of phenols, chlorobenzenes, anilines, isomeric compounds of phenylenediamine and alkylbenzenes within 4.5 min were achieved.

Chiral separation of enantiomers of amino acid derivatives by high-performance liquid chromatography on a norvancomycin-bonded chiral stationary phase

A novel norvancomycin-bonded chiral stationary phase (NVC-CSP) was synthesized by using the chiral selector of norvancomycin. The chiral separation of enantiomers of several dansyl-amino acids by high-performance liquid chromatography (HPLC) in the reversed-phase mode is described. The effects of some parameters, such as organic modifier concentration, column temperature, pH and flow rate of the mobile phase, on the retention and enantioselectivity were investigated. The study showed that ionic, as well as hydrophobic interactions were engaged between the analyte and macrocycle in this chromatographic system. Increasing pH of buffers usually improved the chiral resolution for dansyl-alpha-amino-n-butyric acid (Dns-But), dansyl-methionine (Dns-Met) and dansyl-threonine (Dns-Thr), but not for dansyl-glutamic acid (Dns-Glu) which contains two carboxylic groups in its molecular structure. The natural logarithms of selectivity factors (In alpha) of all the investigated compounds depended linearly on the reciprocal of temperature (1/T), most processes of enantioseparation were controlled enthalpically. Interestingly, the process of enantioseparation for dansyl-threonine was enthalpy-controlled at pH of 3.5, while at pH of 7.0, it was entropy-controlled according to thermodynamic parameters Delta(R,S)DeltaHdegrees and Delta(R,S)DeltaSdegrees afforded by Van't Hoff plots. In order to get baseline separation for all the solutes researched, norvancomycin was also used as a chiral mobile phase additive. In combination with the NVC-CSP remarkable increases in enanselectivity were observed for all the compounds, as the result of a "synergistic" effect. (C) 2003 Elsevier B.V. All rights reserved.

Time-dependent wavepacket approach to the influence of intense fields on the population of molecular excited states

The influence of laser-field parameters, such as intensity and pulse width, on the population of molecular excited state is investigated by using the time-dependent wavepacket method. For a two-state system in intense laser fields, the populations in the upper and lower states are given by the wavefunctions obtained by solving the Schrodinger equation through split-operator scheme. The calculation shows that both the laser intensity and the pulse width have a strong effect on the population in molecular excited state, and that as the common feature of light-matter interaction (LMI), the periodic changing of the population with the evolution time in each state can be interpreted by Rabi oscillation and area-theorem. The results illustrate that by controlling these two parameters, the needed population in excited state of interest can be obtained, which provides the foundation of light manipulation of molecular processes. (C) 2005 Elsevier B.V. All rights reserved.

Preparation of monolithic silica column with strong cation-exchange stationary phase for capillary electrochromatography

A monolithic silica based strong cation-exchange stationary phase was successfully prepared for capillary electrochromatography. The monolithic silica matrix from a sol-gel process was chemically modified by treatment with 3-mercaptopropyltrimethoxysilane followed by a chemical oxidation procedure to produce the desired function. The strong cation-exchange stationary phase was characterized by its substantial and stable electroosmotic flow (EOF), and it was observed that the EOF value of the prepared column remained almost unchanged at different buffer pH values and slowly decreased with increasing phosphate concentration in the mobile phase. The monolithic silica column with strong cation-exchange stationary phase has been successfully employed in the electrochromatographic separation of beta-blockers and alkaloids extracted from traditional Chinese medicines (TCMs). The column efficiencies for the tested beta-blockers varied from 210,000 to 340,000 plates/m. A peak compression effect was observed for atenolol with the mobile phase having a low phosphate concentration.

Improved procedure for preparation of covalently bonded cellulose tris-phenylcarbamate chiral stationary phases

The classical method for preparation of covalently boned cellulose derivative chiral stationary phases (CSP) with diisocyanate as spacer was improved. Diisocyanate was firstly allowed to react with 3-aminopropyltriethoxysilane, and the resulting product was then applied as the spacer reagent to immobilize cellulose derivatives onto silica gel. Influences of the amount and the length of the spacer on the optical resolution ability of the CSP were investigated. Comparing improved procedure to classical diisocyanate method, the cross-linking between the glucose units of the cellulose derivatives was avoided to the most extent. With the improved procedure, regio-nonselective ways could be adopted to prepare covalently bonded CSP, which showed an advantage for the rapid preparation.

Large-pore mesoporous SBA-15 silica particles with submicrometer size as stationary phases for high-speed CEC separation

A new mesoporous sphere-like SBA-15 silica was synthesized and evaluated in terms of its suitability as stationary phases for CEC. The unique and attractive properties of the silica particle are its submicrometer particle size of 400 nm and highly ordered cylindrical mesopores with uniform pore size of 12 nm running along the same direction. The bare silica particles with submicrometer size have been successfully employed for the normal-phase electrochromatographic separation of polar compounds with high efficiency (e.g., 210 000 for thiourea), which is matched well with its submicrometer particle size. The Van Deemeter plot showed the hindrance to mass transfer because of the existence of pore structure. The lowest plate height of 2.0 mu m was obtained at the linear velocity of 1.1 mm/s. On the other hand, because of the relatively high linear velocity (e.g., 4.0 mm/s) can be generated, high-speed separation of neutral compounds, anilines, and basic pharmaceuticals in CEC with C-18-modified SBA-15 silica as stationary phases was achieved within 36, 60, and 34 s, respectively.

Ab initio configuration-interaction study of the ground and low-lying electronic states of NiI

For the first time, we have studied the potential-energy curves, spectroscopic terms, vibrational levels, and the spectroscopic constants of the ground and low-lying excited states of NiI by employing the complete active space self-consistent-field method with relativistic effective core potentials followed by multireference configuration-interaction calculations. We have identified six low-lying electronic states of NiI with doublet spin multiplicities, including three states of Delta symmetry and three states of Pi symmetry of the molecule within 15 000 cm(-1). The lowest (2)Delta state is identified as the ground state of NiI, and the lowest (2)Pi state is found at 2174.56 cm(-1) above it. These results fully support the previous conclusion of the observed spectra although our computational energy separation of the two states is obviously larger than that of the experimental values. The present calculations show that the low-lying excited states [13.9] (2)Pi and [14.6] (2)Delta are 3 (2)Pi and 3 (2)Delta electronic states of NiI, respectively. Our computed spectroscopic terms, vibrational levels, and spectroscopic constants for them are in good agreement with the experimental data available at present. In the present work we have not only suggested assignments for the observed states but also computed more electronic states that are yet to be observed experimentally. (c) 2005 American Institute of Physics.