Comparison and evaluation of copper complex-containing siloxane polymers as stationary phases for capillary gas chromatography.

Two metallomesogenic polymers. P-C11CuC18 and P-C11CuC12 consisting of flexible aliphatic side chains with copper carboxylate complexes have been synthesized on the basis of addition reactions with polysiloxane. The applicability of the prepared columns to the analysis of phthalate esters that are of environmental concern was assessed. For preparation of the capillary column with its wall coated with the metallomesogenic polymer, both static and dynamic methods were employed. Factors affecting the retention and the sample selectivity on both columns were examined. A better separation of phthalates was achieved with P-C11CuC18 than P-C11CuC12. The former phase showed a higher solute-solvent interaction than the latter. With static coating, the wall-coated P-C11CuC18 capillary column (15 m x 250 microm I.D.) showed that the baseline separation of all 14 phthalates could be achieved within 38 min with high reproducibility. The calibration graphs for phthalate ester determination were linear over the range of 10-625 microg ml(-1). The mass detection limits were lower than the ng range based on three times the standard deviation of seven measurements of the lowest peak that could be detected.

Synthesis and analytical properties of a novel columnar metallomesogenic polymer.

A metallomesogenic side-chain polymer with copper carboxylato discotic units in stacks prepared by covalent bonding of 14-pentadecenoic acid, stearic acid and poly(methylhydrosiloxane) is described. The physico-chemical and thermal properties of both monomeric and polymeric metallomesogens were determined by elemental analysis, IR, polarizing optical microscopy, thermal gravimetric analysis and differential scanning calorimetry. The polymeric states showed a discotic lamellar phase at 50-95 degrees C and an ordered discotic hexagonal phase at 95-200 degrees C. By dynamic coating, the metallomesogenic polymer was crosslinked to the capillary wall via benzoyl peroxide. The wall-coated capillary columns (15 m x 0.25 mm I.D.) were used for the separation of phenols. Factors affecting the retention and the sample selectivity were examined. Van 't Hoff plots as a function of temperature indicated that phase transitions were occurring. Thermodynamic properties of the analytes in this system were also studied. For the determination of a mixture of 3-aminophenol, 2-chlorophenol, 2-nitrophenol, 4-nitrophenol, o-methylphenol, m-methylphenol, p-methylphenol, 2,4-dichlorophenol, 2,4-dimethylphenol, 2,4-dinitrophenol, 2,4,6-trichlorophenol, 2,4,6-trimethylphenol, 4-bromophenol, 3-methyl-4-chlorophenol, pentachlorophenol, and unsubstituted phenol, the calibration graphs for most phenols were linear over the range of 10-1000 microg ml(-1) and the mass detection limits were in the ng range based on three times standard deviation of seven measurements of the lowest peak that could be detected.