PMID- 22960793 OWN - NLM STAT- MEDLINE DCOM- 20130705 LR - 20191210 IS - 1618-2650 (Electronic) IS - 1618-2642 (Linking) VI - 405 IP - 2-3 DP - 2013 Jan TI - Exploiting thermodynamic data to optimize the enantioseparation of underivatized amino acids in ligand exchange capillary electrophoresis. PG - 951-9 LID - 10.1007/s00216-012-6298-7 [doi] AB - Stereoselective amino acid analysis has increasingly moved into the scope of interest of the scientific community. In this work, we report a study on the chiral separation of underivatized D,L-His by ligand exchange capillary electrophoresis (LECE), utilizing accurate ex ante calculations. This has been obtained by the addition to the background electrolytes (BGE) of NaClO(4) which renders the separations "all in solution processes", allowing to accurately calculate in advance the concentrations of the species present in solution and to optimize the system performances. To this aim, the formation of ternary complexes of Cu(2+) ion and L-lysine (L-Lys) or L-ornithine (L-Orn) with L- and D-histidine (His), and histamine (Hm) have been studied by potentiometry and calorimetry at 25 degrees C and with 0.1 mol dm(-3) (KNO(3)) in aqueous solution. The ternary species [Cu(L)(L-His)H](+) and [Cu(L)(D-His)H](+) (where L = L-Lys or L-Orn) show a slight but still detectable stereoselectivity, and the determination of DeltaH degrees and DeltaS degrees values allowed the understanding of the factors which determine this phenomenon. The stereoselectivity showed by the protonated ternary species has been exploited to chirally separate D,L-His in LECE, by using the binary complexes of copper(II) with L-Lys or L-Orn as background electrolytes added with the appropriate amounts of NaClO(4). FAU - Contino, Annalinda AU - Contino A AD - Dipartimento di Scienze Chimiche, Universita degli Studi di Catania, Catania, Italy. acontino@unict.it FAU - Maccarrone, Giuseppe AU - Maccarrone G FAU - Remelli, Maurizio AU - Remelli M LA - eng PT - Evaluation Study PT - Journal Article PT - Research Support, Non-U.S. Gov't DEP - 20120815 PL - Germany TA - Anal Bioanal Chem JT - Analytical and bioanalytical chemistry JID - 101134327 RN - 0 (Amino Acids) SB - IM MH - Amino Acids/*chemistry MH - Electrophoresis, Capillary/*methods MH - Stereoisomerism MH - Thermodynamics EDAT- 2012/09/11 06:00 MHDA- 2013/07/06 06:00 CRDT- 2012/09/11 06:00 PHST- 2012/06/19 00:00 [received] PHST- 2012/07/23 00:00 [accepted] PHST- 2012/07/19 00:00 [revised] PHST- 2012/09/11 06:00 [entrez] PHST- 2012/09/11 06:00 [pubmed] PHST- 2013/07/06 06:00 [medline] AID - 10.1007/s00216-012-6298-7 [doi] PST - ppublish SO - Anal Bioanal Chem. 2013 Jan;405(2-3):951-9. doi: 10.1007/s00216-012-6298-7. Epub 2012 Aug 15.