Preparation of uniformly sized molecularly imprinted polymers for phenolic compounds and their application to the assay of bisphenol A in river water.

Uniformly sized molecularly imprinted polymers, which can recognize bisphenol A (BPA), have been prepared by a multi-step swelling and polymerization method using BPA or a structurally related analogue of BPA [p-t-octylphenol (OP) or p-t-butylphenol (BP)] as the template molecule, 4-vinylpyridine as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. The BP-imprinted polymer showed higher molecular recognition ability for BPA than the OP-imprinted polymer. The BPA- and BP-imprinted polymers were applied for the assay of a trace amount of BPA in river water using column-switching HPLC with fluorescence detection: A BPA-imprinted polymer was used for removal of BPA from the pretreatment eluent as the trap column, and a BP-imprinted polymer was used for selective pretreatment and enrichment of BPA in river water as the pretreatment column. The calibration graph, constructed from peak area data plotted versus BPA concentration, was linear with a correlation coefficient of >0.999 in the concentration ranges of 25-1000 ppt. The limit of quantitation was 25 ppt with a 5-ml injection. The column-switching HPLC system was successfully applied for the assay of BPA in river water.     

Ultrasonic irradiation effect in the quenched benzene

On slow cooling, a precursor phenomenon in supercooled benzene was probed by longitudinal absorption. On quenching, in-situ observation of ultrasonic measurements was carried out at the fixed temperature. Sequence of the transmitted waves was multiple scattered in quenched benzene. The dynamic ultrasound scattering is sensitive to the local strain and dynamic inhomogeneous fluctuations. The quenched benzene shows the maximum value of longitudinal absorption at incubation time, t_inc. Crystal domain growth/coarsening is promoted by the ultrasonic irradiation at t_inc < t. In addition, t_inc depends on the quenching temperature. Ultrasonic irradiation and quenching effects dominate the extraordinal nucleation and growth process of benzene in spite of simple and non-polar molecular liquid.     

Direct injection analysis of bisphenol A in serum by combination of isotope imprinting with liquid chromatography-mass spectrometry

A restricted access media-molecularly imprinted polymer was prepared using bisphenol A (BPA)-d16 as a template molecule, and was successfully applied to direct injection analysis of BPA in serum combined with column-switching LC-MS.     

Strain-Induced “Band Flips” in Cyclodecaamylose and Higher Homologues

The cavity of the larger molecule has less space for guests! Unlike the structure of the smaller annular cyclodextrins, that of the higher homologues of cycloamyloses (CAs) with more than ten glucose units contains a 90° kink between adjacent glucose residues within one half of the molecule and a 180° band flip between adjacent units in different halves (see depicted section of the CA14 structure) to yield butterfly-shaped structures with narrow, groovelike cavities.     

Isolation and characterization of cyclic alpha-(1-->4)-glucans having degrees of polymerization 9-31 and their quantitative analysis by high-performance anion-exchange chromatography with pulsed amperometric detection.

Cyclic alpha-(1-->4)-glucans with degrees of polymerization (DPs) 9-31 were isolated from a mixture of cyclization products formed in the early stage of the action of cyclodextrin glucanotransferase (CGTase) on synthetic amylose, and characterized by matrix-assisted laser desorption ionization time-of-flight MS, 13C-NMR and HPLC of their partial acid hydrolyzates. High-performance anion-exchange chromatography (HPAEC) with pulsed amperometric detection for an accurate estimation of cyclic alpha-(1-->4)-glucans was developed using those isolate glucans as quantification standards, and by HPAEC, the time course of the cyclization reaction of CGTase from an alkalophilic Bacillus sp. A2-5a on synthetic amylose was determined.     

Retentivity and enantioselectivity of uniformly-sized molecularly imprinted polymers for (S)-nilvadipine in aqueous and non-aqueous mobile phases.

Uniformly-sized molecularly imprinted polymers (MIPs) for (S)-nilvadipine have been prepared by a multi-step swelling and polymerization method using methacrylic acid or 4-vinylpyridine (4-VPY) as a functional monomer, ethylene glycol dimethacrylate (EDMA) as a cross-linker, and toluene, chloroform, cyclohexanol or phenylacetonitrile as a porogen. The chiral recognition abilities of the MIPs for nilvadipine were evaluated using aqueous and non-aqueous mobile phases. Among the MIPs, the (S)-nilvadipine-imprinted 4-VPY-co-EDMA polymers prepared using toluene as a porogen showed the highest recognition ability for nilvadipine in both aqueous and non-aqueous mobile phases. In addition to molecular shape recognition, hydrogen-bonding interactions of the NH proton of nilvadipine with a pyridyl group of the (S)-nilvadipine-imprinted 4-VPY-co-EDMA polymers could play an important role in the retention and chiral recognition of nilvadipine in aqueous and non-aqueous mobile phases. Furthermore, the MIP for (S)-nilvadipine gave the highest molecular recognition ability when a porogenic solvent during polymerization was used as the mobile phase modifier.     

Simultaneous determination of bisphenol A and its halogenated derivatives in river water by combination of isotope imprinting and liquid chromatography-mass spectrometry

A restricted access media-molecularly imprinted polymer (RAM-MIP) for [2H16]bisphenol A (BPA-d16) was prepared by a multi-step swelling and polymerization method using 4-vinylpyridine as a functional monomer and ethylene glycol dimethacrylate as a cross-linker, followed by hydrophilic surface modification using glycerol dimethacrylate and glycerol monomethacrylate as hydrophilic monomers. The obtained RAM-MIP showed excellent molecular recognition abilities for BPA and BPA-d6 as well as BPA-d16 used as the template molecule, and good ones for tetrachlorobisphenol A (Cl4-BPA) and tetrabromobisphenol A (Br4-BPA). Next, the RAM-MIP was utilized for selective on-line pretreatment and enrichment of BPA, Cl4-BPA and Br4-BPA in a river water sample, followed by their separation and determination by LC-MS. The calibration graphs of BPA, Cl4-BPA and Br4-BPA, constructed using BPA-d6 as an internal standard, showed good linearity in the range of 12.5-200 pg/mL (r > 0.999) with a 2-mL injection of a river water sample. The inter-day precision data for the assay of BPA, Cl4-BPA and Br4-BPA at 25 pg/mL were 1.08, 3.67 and 1.58%, respectively. Furthermore, this method was successfully applied for the simultaneous determination of BPA and its halogenated derivatives in river water.     

Uniformly Sized Molecularly Imprinted Polymers: Their Applications to Chiral Separation and Bioanalysis

Molecular recognition plays an important role in biological and chemical processes. Since molecular imprinting techniques can afford complementary binding sites for a target molecule, the molecularly imprinted polymer (MIP) for the target molecule has been used for its specific recognition as chromatographic media, solid-phase ex-     

Molecularly imprinted polymers for triazine herbicides prepared by multi-step swelling and polymerization method. Their application to the determination of methylthiotriazine herbicides in river water

Uniformly-sized, molecularly imprinted polymers (MIPs) for atrazine, ametryn and irgarol were prepared by a multi-step swelling and polymerization method using ethylene glycol dimethacrylate as a cross-linker and methacrylic acid (MAA), 2-(trifluoromethyl) acrylic acid (TFMAA) or 4-vinylpyridine either as a functional monomer or not. The MIP for atrazine prepared using MAA showed good molecular recognition abilities for chlorotriazine herbicides, while the MIPs for ametryn and irgarol prepared using TFMAA showed excellent molecular recognition abilities for methylthiotriazine herbicides. A restricted access media-molecularly imprinted polymer (RAM-MIP) for irgarol was prepared followed by in situ hydrophilic surface modification using glycerol dimethacrylate and glycerol monomethacrylate as hydrophilic monomers. The RAM-MIP was applied to selective pretreatment and enrichment of methylthiotriazine herbicides, simetryn, ametryn and prometryn, in river water, followed by their separation and UV detection via column-switching HPLC. The calibration graphs of these compounds showed good linearity in the range of 50-500 pg/mL (r > 0.999) with a 100 mL loading of a river water sample. The quantitation limits of simetryn, ametryn and prometryn were 50 pg/mL, and the detection limits were 25 pg/mL. The recoveries of simetryn, ametryn and prometryn at 50 pg/mL were 101%, 95.6% and 95.1%, respectively. This method was successfully applied for the simultaneous determination of simetryn, ametryn and prometryn in river water.     

Restricted access media-molecularly imprinted polymer for propranolol and its application to direct injection analysis of beta-blockers in biological fluids

A restricted access media-molecularly imprinted polymer (RAM-MIP) for propranolol (PRP) has been prepared for direct injection analysis of beta-blockers in biological fluids. First, the MIP for PRP was prepared using methacrylic acid and ethylene glycol dimethacrylate as the functional monomer and cross-linker, respectively, by a multi-step swelling and polymerization method. Next, a 1:1 mixture of glycerol monomethacrylate and glycerol dimethacrylate was used for hydrophilic surface modification, and added directly to the MIP for PRP after 4 h from the start of polymerization. Then further polymerization was carried out for 20 h. The obtained RAM-MIP for PRP showed excellent molecular recognition ability for PRP, good ones for alprenolol (ALP) and pindolol, and fair ones for other beta-blockers. The RAM-MIP was applied for direct injection analysis of ALP enantiomers in a rat plasma sample by a column-switching HPLC system using a beta-cyclodextrin phenylcarbamate-bonded silica column as the analytical column. The calibration graph, constructed from peak area versus each ALP enantiomer concentration, was linear with a correlation coefficient of > 0.999 over the concentration ranges of 12.5-250 ng ml(-1). The limit of quantitation was 12.5 ng ml(-1) with a 50 microl injection. This method could be applicable for the assay of ALP enantiomers at the therapeutic plasma levels, and have wide applicability for the assay of beta-blockers in biological fluids.