Methacryloylpropyl–βcyclodextrin and vinylpyrrolidone copolymers: Synthesis and characterization as potential chiral selector

Abstract

ABSTRACT:The free radical copolymerization of vinylpyrrolidone (VP) with 2-hydroxy-3-methacryloyloxypropyl ␤-cyclodextrin (␤W7 MAHP), a derivative of hydroxypropyl ␤-cyclodextrin (CD) substituted by polymerizable methacryloyl groups, is carried out in water by varying the molar ratio of the comonomers. It is found that the higher the molar ratio of ␤W7 MAHP to VP, the larger the molar mass of the water-soluble copolymer. A size exclusion chromatography analysis coupled with multiangle laser light scattering detection (SEC-MALLS) suggests that VPrich copolymers with a mass-average molar mass (MM) of about 2.5 ϫ 10 4 g mol Ϫ1 may consist of ␤W7 MAHP dimers, trimers, and oligomers containing few CD units whereas ␤W7 MAHP rich copolymers with an MM of about 5.5 ϫ 10 6 g mol Ϫ1 are likely to be dominated by crosslinked polymer materials. ␤W7 MAHP-co-VP copolymers coated on porous silica are used as high-performance liquid chromatography chiral selectors. The effects of the structural features of the guest molecule and the characteristics of the chiral stationary phases on the retention and resolution are evaluated. SEC-MALLS detection shows that, by varying the comonomer feed, copolymers with different molar masses and macromolecular structures are formed. The chiral separation ability of Copo VP is evaluated toward enantiomers having one or more aromatic rings as a function of the amount of copolymer adsorbed onto the silica surface, the ␤W7 MAHP content, and the concentration of solute. It is clear that the column combining the greater amounts of adsorbed copolymer and ␤W7 MAHP exhibits better resolving power. Moreover, the size, geometry, and functionality of the guest molecule are important factors that strongly affect the enantioselectivity.

Water-soluble polymeric derivatives of β-cyclodextrin

“…Thus, CD derivatives based on the initial copolymer VP-AA are water soluble at a low content of CD residues (0.6-1.2 mol %, 6-12 wt %) (Table 3, experiments 11,12,[17][18]. An increase in the CD content in the polymer to 6.7 mol % (43 wt %) ( Table 3, experiment 16) leads to the loss of polymer solubility in water.…”

“…In particular, soluble poly meric derivatives of cyclodextrins based on poly(acrylic acid) [5], on copolymers of acrylic acid (AA) and acrylamide [6], and on polyallylamine [7] and crosslinked polymers [8] were synthesized via reactions in polymer chains. Soluble and crosslinked cyclodextrin containing polymers were prepared through the radical copolymerization of unsaturated derivatives of cyclodextrins with some monomers, including N vinylpyrrolidone (VP) [4,[9][10][11][12][13][14]. It was 1 shown that the polymeric derivatives of cyclodextrins can form inclusion complexes.…”

Distribution of grafted β-cyclodextrin in porous particles for bone tissue engineering

“…Matrices consisting of porous particles have a large area of interaction with the liquid phase, which is a key element in efficient separation. Cyclodextrins and derivatives hereof grafted to porous particles, for example silica gel, have gained some attention as cyclodextrins are able to facilitate the separation of structural isomers [16][17][18]. Commonly used methods to characterize cyclodextrin modified particles include Fourier Transformed Infrared Spectroscopy (FTIR) [13,19,20], Raman Spectroscopy [16,21], Scanning Electron Microscope (SEM) [13,16,20,22], Elemental Analyses [21,23,24] and Thermo Gravimetric Analysis (TGA).…”

Synthesis and characterization of macroporous silica modified with optically active poly[N‐(oxazolinylphenyl)acrylamide] derivatives for potential application as chiral stationary phases

“…1,2 In addition to brush-type CSPs based on low-molecular-mass selectors, [3][4][5][6][7][8] a large number of CSPs containing surface-adsorbed polysaccharide derivatives, especially cellulose and amylose carbamates, have been used extensively at the analytical and preparative levels because they can resolve the enantiomers of a wide range of racemic compounds by high-performance liquid chromatography (HPLC). [9][10][11][12][13][14][15][16][17] At the same time, research on CSPs based on synthetic, optically active polymers has also been rapidly evolving. [18][19][20][21][22][23][24][25][26] Some columns packed with polymeric CSPs have been commercial-ized.…”

“…The chromatographic separation of enantiomers of chiral stationary phases (CSPs) has attracted great attention as one of the most efficient separation techniques 1, 2. In addition to brush‐type CSPs based on low‐molecular‐mass selectors,3–8 a large number of CSPs containing surface‐adsorbed polysaccharide derivatives, especially cellulose and amylose carbamates, have been used extensively at the analytical and preparative levels because they can resolve the enantiomers of a wide range of racemic compounds by high‐performance liquid chromatography (HPLC) 9–17. At the same time, research on CSPs based on synthetic, optically active polymers has also been rapidly evolving 18–26.…”