Synthesis of a chiral stationary phase with poly[styrene‐b‐cellulose 2,3‐bis(3,5‐dimethylphenylcarbamate)] by surface‐initiated atom transfer radical polymerization and its chiral resolution efficiency

Abstract

A chiral stationary phase (CSP) with poly[-styrene-b-cellulose 2,3-bis(3,5-dimethylphenylcarbamate)] was synthesized by the surface-initiated atom transfer radical polymerization (SI-ATRP) of cellulose 2,3-bis(3,5-dimethylphenylcarbamate)-6-acrylate after the SI-ATRP of styrene on the surface of silicon dioxide supports in pyridine. The successful preparation of the CSP with poly[styrene-b-cellulose 2,3-bis(3,5-dimethylphenylcarbamate)] was confirmed via Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray photoelectron spectroscopy, elemental analysis, and thermal analysis. The applicability for the chiral resolution of the CSP with poly[styrene-b-cellulose 2,3-bis(3,5-diphenylcarbamate)] was evaluated with high-performance liquid chromatography with 10 racemates under various mobile phases of hexane/alcohol, hexane/tetrahydrofuran (THF), and hexane/chloroform. The results show that the CSP with poly[styrene-b-cellulose 2,3-bis(3,5-diphenylcarbamate)] could be used in THF and chloroform as eluents. The chiral resolutions of the commercial Chiracel OD, the CSP with cellulose 2,3-bis(3,5-dimethylphenylcarabmate), and the CSP with poly[styrene-b-cellulose 2,3-bis(3,5-dimethylphenylcarbamate)] prepared by SI-ATRP were examined.

Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes

“…Hydrophilic monomers with potential use in biomedical applications include N -acryloylmorpholine (NAM), , 4-hydroxyphenylethyl methacrylate (HPEMA), , N -( p -vinylbenzyl)-phthalimide (VBP) and a dendronized form of PEGMA . Monomers with pendant carbohydrate residues such as 2-(2,3,4,6-tetra-O-acetyl-β- d -glucosyloxy)­ethyl methacrylate (AcGEMA), glucosylureaethyl methacrylate (GUMA), 4-vinylbenzenesulfonamidoethyl 1-thio-β-D-saccharides (VBSAEZ), N -2–4-(vinylbenzenesulfonamido)­ethyl lactobionamide (VBSAELA), , 2′-acrylamidoethyl D-pyranosides (AAEP), − glucosamine-derivatized GMA and cellulose derivatives , offer novel platforms for biosensors and chiral stationary phases due to specific interactions with biomolecules, such as proteins.…”

“…Choi and co-workers prepared chiral stationary phases by SI-ATRP of vinylated cellulose 2,3-bis­(3,5-dimethylphenylcarbamate). These polymer brushes were grown either directly from silica or from silica grafted with an initial polystyrene block . The authors demonstrated enantiomer separation of stilbene oxide, benzoin, 2-phenylcyclohexanone, cobalt­(III) trisacetylacetonate, d , l -sec-phenylethyl alcohol, Tröger’s base, 2,2,2-trifluoro-1-(9-anthryl)­ethanol and flavanonein.…”

“…These polymer brushes were grown either directly from silica 276 or from silica grafted with an initial polystyrene block. 277 The authors demonstrated enantiomer separation of stilbene oxide, benzoin, 2-phenylcyclohexanone, cobalt(III) trisacetylacetonate, D,L-sec-phenylethyl alcohol, Troger's base, 2,2,2-trifluoro-1-(9-anthryl)ethanol and flavanonein. Polymer brushes produced by SI-CRP have also been explored as high binding capacity coatings on MALDI-TOF MS sample plates to allow enrichment of the analytes.…”

Enantioseparation in high performance liquid chromatography: preparation and evaluation of a vancomycin-based chiral stationary phase via surface-initiated atom transfer radical polymerization

“…As one of the most popular routes, SI-ATRP is a convenient and useful method for synthesizing polymers with well-controlled molecular weights and distributions. 35,36…”

“…As one of the most popular routes, SI-ATRP is a convenient and useful method for synthesizing polymers with well-controlled molecular weights and distributions. 35,36 Generally speaking, macrocyclic glycopeptides have the disadvantage of large steric hindrance for CSP synthesis as chiral selectors. Thus, Zhang et al 37 prepared a vancomycinbonded CSP by the immobilization of vancomycin onto amino-containing silica using glutaraldehyde as a spacer arm.…”