Study of the retention behavior of small polar molecules on different types of stationary phases used in hydrophilic interaction liquid chromatography

The retention behavior of a large group of analytes (35) with varied properties (pK_a and logP) was studied on eight hydrophilic interaction LC columns with different surfaces, stationary phase chemistries, and types of particles. The acetonitrile content (5–95%), buffer concentration (0.5–200 mM), and pH of the mobile phase (3.8 and 6.8) were evaluated for their effects on the retention behavior. The type of stationary phase had a significant impact on the selectivity and retention time of the tested analytes. Completely different selectivity was observed on the aminopropyl stationary phase. In this study, the influence of the buffer concentration was similar for all tested columns, except for the aminopropyl stationary phase. Increasing the buffer concentration led to decreased retention times for the basic compounds and increased retention times for the acidic compounds, while the inverse behavior was observed on the aminopropyl stationary phase. The selectivity of the individual stationary phases was evaluated at pH 3.8 and 6.8. Much lower selectivity differences between the stationary phases were observed at pH 6.8 than pH 3.8. Bare silica stationary phases were used in the comparison of the particles (fused‐core and fully porous particles of 3 and 1.7 μm) and the columns provided by different manufacturers.     

Medical radioisotope 89Zr production with RFT-30 cyclotron

Journal of Radioanalytical and Nuclear Chemistry - 89Zr is an emerging radionuclide with promising application in nuclear medicine for the non-invasive diagnosis of various cancers with PET...     

Mechanism of enhanced conversion of 1,2,3-trichloropropane by mutant haloalkane dehalogenase revealed by molecular modeling

1,2,3-Trichloropropane (TCP) is a highly toxic, recalcitrant byproduct of epichlorohydrin manufacture. Haloalkane dehalogenase (DhaA) from Rhodococcus sp. hydrolyses the carbon–halogen bond in various halogenated compounds including TCP, but with low efficiency (k _cat/K _m = 36 s^-1 M^-1). A Cys176Tyr-DhaA mutant with a threefold higher catalytic efficiency for TCP dehalogenation has been previously obtained by error-prone PCR. We have used molecular simulations and quantum mechanical calculations to elucidate the molecular mechanisms involved in the improved catalysis of the mutant, and enantioselectivity of DhaA toward TCP. The Cys176Tyr mutation modifies the protein access and export routes. Substitution of the Cys residue by the bulkier Tyr narrows the upper tunnel, making the second tunnel “slot” the preferred route. TCP can adopt two major orientations in the DhaA enzyme, in one of which the halide-stabilizing residue Asn41 forms a hydrogen bond with the terminal halogen atom of the TCP molecule, while in the other it bonds with the central halogen atom. The differences in these binding patterns explain the preferential formation of the (R)- over the (S)-enantiomer of 2,3-dichloropropane-1-ol in the reaction catalyzed by the enzyme.     

Photoinitiated RAFT polymerization of vinyl acetate

A photoinitiation process was investigated to develop a rapid and well‐controlled RAFT polymerization method applied to vinyl acetate (VAc) using methyl (ethoxycarbonothioyl)sulfanyl acetate (MESA) and bis(2,4,6‐trimethylbenzoyl)phenylphosphine oxide as the RAFT agent and photoinitiator, respectively. MESA was selected as the photochemically inert RAFT agent to minimize photolysis of the thiocarbonylthio groups during polymerization. Poly(vinyl acetate) with a prespecified well‐controlled molecular weight (MW) and a narrow MW distribution was successfully synthesized. The polymerization reaction proceeded as a living polymerization and was remarkably rapid compared with approaches that use thermally initiated processes with a very short induction period. A detailed kinetic study of the mechanism underlying the polymerization reaction, however, revealed that the chain ends containing xanthate moieties were not perfectly stable upon UV‐irradiation, and they generated radicals via homolytic cleavage. This reaction appeared to proceed by a combination of a degenerative transfer RAFT mechanism and a dissociation‐combination mechanism. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Direct evaluation of baryon numbers of empty chiral bags

Goldstone and Jaffe proved using very general arguments that for a chiral bag surrounded by a Skyrme soliton, the baryon number of the Dirac vacuum inside the bag exactly cancels the (known) baryon number of the soliton outside. Their analysis applies to massless quarks. In order to obtain a formalism easier to generalize to massive quarks, we rederive the result for spherical bags by solving the Dirac equations for the inside of the bag and explicitly performing the required summations over the energy levels.     

Kinetics of the fluorescence of poly(N-vinylcarbazole) and poly(N-vinylcarbazole) with 2,4,7-trinitrofluorenone in the solid state

The fluorescence decay time measurements by the stroboscopic method have been made on films of amorphous poly(N-vinylcarbazole) (PVCA) and PVCA doped with 2,4,7-trinitrofluorenone (TNF). The obtained lifetimes of two excimer species have at 77 K and at 300 K values of about 43 ns and 9 ns, which are similar to other measurements. The kinetics of excimer fluorescence and energy transfer in PVCA films are described by a simple model of the Stern-Volmer type. It assumes the fast migration of localized singlet excitons and their trapping in two species of excimer traps.We propose a modified kinetic model for films of PVCA with TNF. In this model we assume besides the exciton migration and trapping on excimer and impurity traps also the direct energy transfer from two excimer species to charge transfer complexes of PVCA with TNF by the Förster dipole-dipole mechanism. The estimated critical distance of this transfer are about 10 Å.     

Convergence analysis of implicit iterative algorithms for asymptotically nonexpansive mappings

In this paper, we consider the weak and strong convergence of an implicit iterative process with errors for two finite families of asymptotically nonexpansive mappings in the framework of Banach spaces. Our results presented in this paper improve and extend the recent ones announced by many others.