Use of tert-butylbenzoylated tartardiamide chiral stationary phase for the enantiomeric resolution of acidic compounds by nano-liquid chromatography.
Several racemic acidic compounds of pharmaceutical and environmental interest have been separated into their enantiomers by nano-liquid chromatography (nano-LC) employing a tert-butylbenzoylated tartardiamide chiral stationary phase (CHI-TBB). CHI-TBB was packed into a fused silica capillary of 100 microm id and retained by two frits made with a heated wire; detection was on-column at a window (about 0.5 cm) prepared by removing the polyimide layer. The normal phase mode was selected for eluting the studied acidic compounds and therefore n-hexane/2-propanol/acetic acid (89/10/1, v/v/v) was used as mobile phase. Working at a flow rate of 220 nL/min a good resolution was obtained for mecoprop, dichlorprop, diclofop, fenoxaprop (herbicides) and for DF 1738Y, DF 1770Y, DF 2008Y (drugs under evaluation). In order to optimize the chiral resolution we modified the polarity of the mobile phase by adding several polar additives such as ethyl acetate, dichloromethane, tert-butyl methyl ether. Better results were obtained for some herbicides on working with 2-propanol/CH2Cl2/n-hexane/acetic acid (8/4/87/1, v/v/v/v). The influence of the capillary temperature on chiral resolution was studied for two herbicides with different chemical structures, namely mecoprop and haloxyfop in the temperature range between 10 and 40 degrees C and with n-hexane/2-propanol/1% acetic acid (89/10/1, v/v/v) as the mobile phase. Linear correlation of ln k vs 1/T and In alpha vs 1/ T was observed; deltaH degrees values were negative, demonstrating that retention of analytes was an exothermic process. A decrease in resolution was observed with rising temperature, showing that enantioresolution was mainly influenced by selectivity factors.
Fanali
Salvatore
S
Istituto di Metodologie Chimiche, C. N. R., Monterotondo Scalo (Roma), Italy. fanali@imc.cnr.it
D'Orazio
Giovanni
G
Rocco
Anna
A
D000894:Anti-Inflammatory Agents, Non-Steroidal / Q000737:chemistry; D001555:Benzene Derivatives / Q000737:chemistry*; D002853:Chromatography, Liquid / Q000295:instrumentation / Q000379:methods*; D003958:Diamide / Q000737:chemistry*; D006540:Herbicides / Q000737:chemistry; D015394:Molecular Structure; D036103:Nanotechnology; D013237:Stereoisomerism; D013644:Tartrates / Q000737:chemistry*; D013696:Temperature
D000894:Anti-Inflammatory Agents, Non-Steroidal; D001555:Benzene Derivatives; D006540:Herbicides; D013644:Tartrates; D003958:Diamide; C063841:tert-butylbenzene; C029768:tartaric acid