High-resolution performance of pillar[6]arene functionalized with imidazolium ionic liquids for gas chromatography.

Pillar[n]arenes (P[n]A, n = 5-10) have attracted much attention because of their highly symmetric pillar-shaped architecture with π-electron rich cavity. Nevertheless, the use of ionic liquid functionalized P[n]A in chromatography has not been reported up to data. This work reports the investigation of the imidazolium ionic liquids functionalized pillar[6]arene (P6A-C10-IM-C8[NTf2]) as the stationary phase for gas chromatography (GC). The statically coated P6A-C10-IM-C8[NTf2] column (0.25 mm i.d.) showed moderate polarity and high column efficiency of 4733 plates/m determined by n-dodecane at 120 °C (k = 2.29). Owing to its unique amphiphilic conformation, the P6A-C10-IM-C8[NTf2] showed good column inertness and resolving capability for a wide range of analytes and isomers. Particularly, the P6A-C10-IM-C8[NTf2] column exhibited distinctly advantageous performance for the challenging isomers of halogenated benzenes, benzaldehydes, phenols and anilines over the common commercial columns, namely 5% phenyl methyl polysiloxane (HP-5) and 35% phenyl methyl polysiloxane (HP-35). In addition, it exhibited good column repeatability and reproducibility with RSD values on the retention times less than 0.05% for run-to-run, 0.38% for day-to-day and 2.94% for column-to-column, respectively. This work demonstrates the promising future of ionic liquid P[n]A stationary phases for chromatographic separations.

Hydroxyl-functionalized pillar[5]arene with high separation performance for gas chromatography.

Here we report the first example of employing hydroxyl-functionalized pillar[5]arene (P5A-C10-OH) as stationary phase for capillary gas chromatographic (GC) separations. The statically coated P5A-C10-OH capillary column possessed moderate polarity and column efficiency of 3233 plates per m determined by n-dodecane. As a result, the P5A-C10-OH column exhibited high-resolution capability for the mixture of 17 analytes from apolar to polar nature. Importantly, it exhibited advantageous performance for high resolution of the challenging isomers of bromonitrobenzene, chloroaniline, bromoaniline, iodoaniline and dimethylaniline with good peak shapes over the P5A-C10 and commercial HP-35 columns. In addition, eight cis-/trans-isomers with diverse types were baseline separated on the P5A-C10-OH column. And the application of detecting isomeric impurities in real samples gave strong evidence of its potential and feasibility for the viable GC analysis.

Multipurpose new gas chromatography column based on pillararenes functionalized with imidazolium ionic liquids.

BACKGROUND: Gas chromatography is worldwide recognized as one of the most important analytical techniques, due to its high versatility and reliability. The heart of a gas chromatograph is the column, that allows analyte peak separations and, consequently, accurate qualitative and qualitative analyses. New and more efficient columns are always requested to satisfy new and challenging analytical needs. RESULTS: In this work, imidazolium ionic liquids functionalized pillar [5] arenes have been used for the first time as gas chromatographic stationary phases, considering their highly symmetric pillar-shaped architecture with cavities rich in π-electrons. Four imidazolium ionic liquids functionalized pillar [5] arenes have been tested as stationary phases with numerous analytes and isomers. In particular, one of these showed superior performances if compared to commercial columns, enabling challenging isomeric separations of halogenated benzenes, aromatic aldehydes, and aromatic anilines. SIGNIFICANCE AND NOVELTY: To our knowledge, this is the first report on the use of the ionic liquid P[n]A as a stationary phase in chromatography, either in GC or liquid chromatography (LC) separations. This work demonstrates the promising potential of ionic liquid P[n]A stationary phases for chromatographic separations.

A New Capillary Gas Chromatography Column Based on Poly(ethylene glycol) Methyl Ether-Functionalized Calix[4]arene.

In this work, a novel capillary column (C4A-mPEG) with a calixarene-based polymer stationary phase (poly(ethylene glycol) methyl ether-functionalized 4-tert-butylcalix[4]arene) was designed and used for gas chromatographic (GC) separations. The C4A-mPEG capillary column, prepared by the static coating method, showed moderate polarity and a column efficiency of 2332 plates/m, determined by 1-octanol at 120 °C. The separation features of C4A-mPEG stationary phase, resulting from its unique structure and multiple molecular recognition processes with analytes, including π-π, H-bonding, dipole-dipole, and van der Waals interactions, allowed to obtain high-resolution performances for a wide range of compounds and their isomers, especially benzaldehydes, phenols, and anilines. Moreover, compared with 4-tertbutyl calix[4]arene (C4A) and polyethylene glycol (PEG) stationary phases, a higher resolving capability was also observed for the separation of toluidine and xylidine isomers.

Performance and selectivity of amphiphilic pillar[5]arene as stationary phase for capillary gas chromatography.

Pillar[n]arenes possess highly symmetrical and rigid pillar-shaped architecture with π-electron rich cavity that afford their reliable host-guest recognition interactions towards matched guests. In this work, a novel amphiphilic pillar[5]arene (P5A-C10-2NH2) was designed, synthesized and employed as the stationary phase for capillary gas chromatography. To date, they have not been reported in the field of chromatography. The P5A-C10-2NH2 capillary column (10 m × 0.25 mm i.d.) was prepared by static coating method. Its capillary column exhibited moderate polarity and column efficiency of 2265 plates/m determined by naphthalene at 120 °C. As evidenced, the P5A-C10-2NH2 column achieved advantageous separation performance for a mixture of 24 analytes of diverse types and exhibited different chromatographic selectivity from two pillar[5]arene derivatives columns and commercial HP-35 column with 35%-phenyl-methylpolysiloxane. Moreover, the P5A-C10-2NH2 column baseline resolved more than a dozen positional and cis-trans isomers. Furthermore, the separation mechanism of P5A-C10-2NH2 column was discussed by quantum chemical calculations. In addition, the P5A-C10-2NH2 column had high thermal stability and excellent separation repeatability 0.01-0.04% for run-to-run, 0.03-0.17% for day-to-day and 3.2-3.9% for column-to-column. The special amphiphilic structure and high resolution for various analytes reveal the good potential of pillararenes as a new class of stationary phases for chromatographic analyses. Moreover, the TPG column achieved improved thermal stability over the GIL column and excellent repeatability.

Amphiphilic Block Copolymer PCL-PEG-PCL as Stationary Phase for Capillary Gas Chromatographic Separations.

This work presents the first example of utilization of amphiphilic block copolymer PCL-PEG-PCL as a stationary phase for capillary gas chromatographic (GC) separations. The PCL-PEG-PCL capillary column fabricated by static coating provides a high column efficiency of 3951 plates/m for n-dodecane at 120 °C. McReynolds constants and Abraham system constants were also determined in order to evaluate the polarity and possible molecular interactions of the PCL-PEG-PCL stationary phase. Its selectivity and resolving capability were investigated by using a complex mixture covering analytes of diverse types and positional, structural, and cis-/trans-isomers. Impressively, it exhibits high resolution performance for aliphatic and aromatic isomers with diverse polarity, including those critical isomers such as butanol, dichlorobenzene, dimethylnaphthalene, xylenol, dichlorobenzaldehyde, and toluidine. Moreover, it was applied for the determination of isomer impurities in real samples, suggesting its potential for practical use. The superior separation performance demonstrates the potential of PCL-PEG-PCL and related block copolymers as stationary phases in GC and other separation technologies.

Performance and selectivity of lower-rim substituted calix[4]arene as a stationary phase for capillary gas chromatography.

This work presents the investigation of p-tert-butyl(tetradecyloxy)calix[4]arene (C4A-C10) as stationary phase for capillary gas chromatographic (GC) separations. The statically-coated C4A-C10 capillary column showed weak polarity and column efficiency of 2566 plates per m determined by n-dodecane at 120 °C. Impressively, the C4A-C10 column exhibited extremely high resolving capability for a wide range of analytes from nonpolar to polar, including n-alkanes, esters, ketones, aldehydes, alcohols and bromoalkanes. Most importantly, the C4A-C10 column exhibited an excellent separation performance for positional, structural and cis-/trans-isomers. Among them, the column displayed advantageous resolving capability over the commercial polysiloxane stationary phase for aromatic amine isomers. Moreover, the C4A-C10 column showed good column repeatability with RSD values below 0.06% for run-to-run, 0.12-0.27% for day-to-day and 2.8-5.3% for column-to-column.

Star-poly(ε-caprolactone) as the stationary phase for capillary gas chromatographic separation.

This work presents the separation performance of star-poly(ε-caprolactone) (star-PCL) as the stationary phase for capillary gas chromatography (GC). The statically coated star-PCL column showed a column efficiency of 3345 plates per m and moderate polarity. Importantly, the star-PCL column exhibited high selectivity and resolving capability for more than a dozen mixtures covering a wide-ranging variety of analytes and isomers. Among them, the star-PCL column displayed advantageous resolving capability over the commercial DB-1701 column for aromatic amine isomers such as toluidine, chloroaniline and bromoaniline. Moreover, it was applied for the determination of isomer impurities in real samples, showing good potential in GC applications.

Separation performance of p-tert-butyl(tetradecyloxy)calix[6]arene as a stationary phase for capillary gas chromatography.

This work presents the first example of the utilization of p-tert-butyl(tetradecyloxy)calix[6]arene (C6A-C10) as a stationary phase for capillary gas chromatographic (GC) separation. The statically coated C6A-C10 column showed a column efficiency of 3293 plates per m and had a nonpolar nature. Its selectivity and retention behaviour were investigated using a number of mixtures of diverse analytes and their isomers. As a result, the C6A-C10 column exhibited high resolving capability for aliphatic and aromatic analytes from apolar to polar nature, especially for positional, structural and cis-/trans-isomers. Moreover, the C6A-C10 column showed thermal stability up to 240 °C. In addition, it was applied for the determination of isomer impurities in real samples, proving its good potential for practical GC analysis.

Performance of palm fibers as stationary phase for capillary gas chromatographic separations.

Herein we report the first example of exploring bio-based materials, palm fibers (PFs), as a stationary phase for capillary gas chromatographic separations. The PFs capillary column was fabricated by the sol-gel coating method and showed a weak polar nature and high column efficiency over 4699 plates per m for n-dodecane, naphthalene and n-octanol. Importantly, the column exhibited high selectivity and resolving capability for more than a dozen mixtures covering a wide-ranging variety of analytes and isomers. In addition, it was applied for the determination of isomer impurities in real samples, proving its good potential for practical gas chromatographic analysis.