Pataj Zoltán, Berkecz Robert, Ilisz István, Misicka Aleksandra, Tymecka Dagmara, Fülöp Ferenc, Armstrong Daniel W, Péter Antal
Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Hungary.
Chirality. 2009 Oct;21(9):787-98. doi: 10.1002/chir.20670.
Reversed-phase high-performance liquid chromatographic methods were developed for the separation of enantiomers of eleven unnatural beta(2)-homoamino acids on chiral stationary phases containing macrocyclic glycopeptides (teicoplanin-containing Chirobiotic T and T2) or the macrocyclic peptide teicoplanin aglycone (Chirobiotic TAG) as chiral selectors. The effects of the organic modifier, the mobile phase composition, temperature, and the structures of the analytes on the separations were investigated. Separations were carried out at constant mobile phase compositions in temperature range 7-45 degrees C and the changes in enthalpy, Delta(DeltaH(o)), entropy, Delta(DeltaS(o)), and free energy, Delta(DeltaG(o)), were calculated. The -Delta(DeltaG(o)) values obtained on the three columns indicated that Chirobiotic TAG, without sugar units, may promote the interactions of the enantiomers of beta(2)-homoamino acids with branched alkyl or aryl side-chains, whereas for beta(2)-homoamino acids with alkyl side-chains Chirobiotic T and T2 seem to be more favorable. The elution sequence was determined in some cases and was observed to be R < S.
开发了反相高效液相色谱法，用于在含有大环糖肽（含替考拉宁的手性固定相T和T2）或大环肽替考拉宁苷元（手性固定相TAG）作为手性选择剂的情况下，分离11种非天然β(2)-高氨基酸的对映体。研究了有机改性剂、流动相组成、温度以及分析物结构对分离的影响。在7-45℃的温度范围内，在恒定流动相组成下进行分离，并计算焓变（Δ(ΔH°)）、熵变（Δ(ΔS°)）和自由能变（Δ(ΔG°)）。在三根色谱柱上获得的-Δ(ΔG°)值表明，不含糖单元的手性固定相TAG可能促进具有支链烷基或芳基侧链的β(2)-高氨基酸对映体之间的相互作用，而对于具有烷基侧链的β(2)-高氨基酸，手性固定相T和T2似乎更有利。在某些情况下确定了洗脱顺序，观察到为R < S。
