Possibility of large volume injection and band focusing in UHPLC.

New shell-type stationary phases are widely used in fast chromatographic measurements. These columns provide more efficient separation, when applied in a conventional high-performance liquid chromatography instrument, than columns with fully porous particles, and the volume overload of core-shell particles is 60% of the value obtained for fully porous particles. Additionally, to achieve adequate sensitivity, the injection volume cannot be significantly decreased. This study presents a systematic evaluation of the possibilities of large volume injection onto columns packed with 2.6 µm Kinetex C18 shell particles. The effect of volume overload on performance of columns with different lengths (50, 100 and 150 mm) is studied. Column efficiency is compared under isocratic, pulse gradient and gradient conditions. The application of large volume injection in practice is also reported. The most suitable among the tested large volume injection techniques was the gradient elution, which was applied to determine amino acid enantiomers from fruit juice.

Oxidative N-dealkylation in cobalt-bispidine-H2O2 systems.

The reaction of the Co(II) complex with the rigid bispidine ligand L1 with two tertiary amine and two pyridine donors, [Co(II)(L1)(OH2)2]2+, with H2O2 and O2 produces [Co(II)(L2)(OH2)2]3+, where L2 is demethylated at one of the amine donors, and CH2O.

Hydrolysis of natural and artificial phosphoesters using zinc model compound with a histidine-containing pseudopeptide.

Zinc(II) complex with histidine-containing pseudopeptide derived from N,N'-bis(benzylhistidyl) diethylenetriamine L was examined as catalyst for the hydrolysis of bis(p-nitrophenyl) phosphate (BNPP), p-nitrophenyl phosphate (NPP), adenylyl-(3'-5')adenosine (ApA), thymidylyl-(3'-5') thymidine (TpT) and PBR 322 supercoiled DNA. The stepwise protonation constants of the ligand, stability constants for its zinc(II) complex LZn have been determined potentiometrically in aqueous solution. LZn efficiently hydrolyzed BNPP and NPP and their pseudo-first-order rate constants k(obs) are 1.1 x 10(-5) s(-1) and 2.1 x 10(-5) s(-1), respectively. Bell-shaped pH-k(obs) profile was seen in BNPP hydrolysis around pH 7. Kinetic parameters were obtained from temperature dependence of hydrolysis rate constants where entropy of activation showed considerably high negative value. ApA and TpT as RNA-type and DNA-type dinucleotides were slowly hydrolyzed by LZn. On the basis of the kinetic evidence of bell-shaped pH-k(obs) profile and species distribution curve, we propose a mechanism for LZn-promoted hydrolysis of BNPP as well as ApA where cooperative achieve of zinc-hydroxo and zinc-aqua complex species may be responsible for enzymatic activity. The agarose gel electrophoresis and AFM demonstrated that LZn performed good activity on the selective cleavage of pBR322 supercoiled DNA at pH 7.0 providing evidence for its probable applicability.