Analysis of polar peptides using a silica hydride column and high aqueous content mobile phases

The retention behavior of a set of polar peptides separated on a silica hydride stationary phase was examined with a capillary HPLC system coupled to ESI‐MS detection. The mobile phases consisted of formic acid or acetic acid/acetonitrile/water mixtures with the acetonitrile content ranging from 5 to 80% v/v. The effects on peptide retention of these two acidic buffer additives and their concentrations in the mobile phase were systematically investigated. Strong retention of the peptides on the silica hydride phase was observed with relatively high‐organic low‐aqueous mobile phases (i.e. under aqueous normal‐phase conditions). However, when low concentrations of acetic acid were employed as the buffer additive, strong retention of the peptides was also observed even when high aqueous content mobile phases were employed. This unique feature of the stationary phase therefore provides an opportunity for chromatographic analysis of polar peptides with water‐rich eluents, a feature usually not feasible with traditional RP sorbents, and thus under conditions more compatible with analytical green chemistry criteria. In addition, both isocratic and gradient elution procedures can be employed to optimize peptide separations with excellent reproducibility and resolution under these high aqueous mobile phase conditions with this silica hydride stationary phase.     

Miniaturized molecularly imprinted polymer extraction method for the gas chromatographic analysis of flavonoids

In this study, the use of monolithic molecularly imprinted polymers in a micropipette tip format allowing the simple and fast extraction of flavonoids from standard solutions and a black tea sample is demonstrated. The imprinted polymer employed quercetin, methacrylic acid or 4‐vinylpyridine, and ethylene glycol dimethacrylate as template, functional monomer, and cross‐linker, respectively. Surface morphologies of the quercetin‐imprinted polymers and the corresponding nonimprinted polymers were characterized by SEM. Extraction of flavonoid standards was performed to evaluate the selectivity and recovery with these imprinted and nonimprinted polymers. Flavonoid compositions in aliquots eluted from the tips were identified using fast GC with flame ionization detection. Maximum specific capacities of 0.2, 5.7, and 16.0 mg/g for catechin, morin, and quercetin, respectively, were obtained with the imprinted polymer prepared with methacrylic acid, with the corresponding recoveries of 99.8, 98.8, and 95.4%, respectively. Efficient extraction by the quercetin‐imprinted polymer of epicatechin, catechin, and quercetin from an apple‐flavored black tea sample was achieved, with GC–MS employed for compound identification for both the tea and extracted samples.     

Nonstationary Theory of Perturbations for Open-Shell Atoms in the Hartree–Fock Approximation

For a multielectron open-shell system exposed to an external time-dependent perturbation, the Hartree–Fock nonstationary equations are obtained in terms of density operators. Using them as a basis, equations of nonstationary coupled perturbation theory are suggested in orbital representation within the framework of the two-operator variant of the Roothaan method for an open shell. The perturbation theory corrections to the orbitals have been found in the form of expansions in unperturbed orbitals which are assumed to be calculated in the LCAO approximation in the basis of Slater-type atomic orbitals. The dynamic polarizability of open-shell atoms of substances from Li to F and Sc has been calculated as an even-power series of the frequency of incident radiation.     

Calculation of the ground state energy of neutral atoms (Z ≤ 54) by the algebraic variant of the Hartree-Fock method

High-precision calculations of the ground-state energy of atoms He through Xe are performed in the algebraic approximation of the Hartree-Fock method. The orbital exponents of Slater-type basis functions are optimized using the second-order minimization methods, which allows the virial theorem to be fulfilled to within 10^?15–10^?17 for the first time. The energies of atoms calculated with rather limited basis sets are, in terms of accuracy, as good as the results obtained by using the numerical procedure for solving the Hartree-Fock equations.     

Calculation of optical characteristics of atoms with a closed shell by the Hartree-Fock-Roothaan method

The transition frequencies, oscillator strengths, and Cauchy moments of the dipole dynamic polarizability are calculated for the Ar, Ca, Sr, and Xe atoms and their isoelectronic sequences.     

The Hartree–Fock Approximation Calculation of Electric Polarizability of Atoms with an Open Shell

Within the framework of the restricted Hartree–Fock method, equations of stationary coupled perturbation theory have been obtained for atomic-molecular systems with an open shell in orbital representation. Corrections to the Hartree–Fock orbitals are sought in the form of expansions in unperturbed orbitals which are assumed calculated in the LCAO approximation. The resulting inhomogeneous algebraic system for the expansion coefficients admits an exact solution. The static polarizability of atoms with an open shell from Li to Sc has been calculated with the use of an optimized basis set of Slater-type atomic orbitals.     

Liquid‐Phase Enantioselective Chromatographic Resolution Using Interpenetrated,Homochiral Framework Materials

Effective separation of mixtures of enantiomers is of continuing interest in analytical and preparative chromatography, with new materials frequently designed and tested. We report two new enantiomerically pure 2D→3D interpenetrated materials used as stationary liquid chromatographic (LC) phases that are shown to resolve selected racemic mixtures with enantiomeric and chemical selectivity. Dicarboxylate ligands derived from amino acids on naphthalene and perylene cores form 2D frameworks that interpenetrate to give 3D structures. Selectivity is initially tested by uptake from solution; subsequent LC methods show that the materials exhibit resolution of racemic analytes in ‘micro‐columns’ and that the two closely related materials show markedly different selectivity for different analytes with much greater activity than the ligands alone. Comparison with a close‐packed analogue suggests that the separation activity is largely due to surface effects.