Binding characteristics of molecularly imprinted polymers based on fungicides in hydroalcoholic media

An iprodione‐imprinted polymer was prepared by copolymerization of methacrylamide and ethylene glycol dimethacrylate using a noncovalent imprinting approach. Methacrylamide was chosen using molecular dynamics simulations. To concentrate iprodione from hydro‐alcoholic solutions, batch sorption of iprodione on the imprinted polymer were conducted. The equilibrium time for iprodione sorption is 20 min, and the corresponding kinetic mechanism follows the pseudo‐second order indicating a strong interaction between iprodione and the imprinted polymer. Langmuir, Freundlich, and Dubinin–Radushkevich models were used to fit the isotherm of iprodione sorption. The imprinted polymer was found to be more efficient than the nonimprinted polymer for the uptake of iprodione, as revealed by its higher adsorption energy, affinity, and capacity. Finally, a selectivity study was conducted on the imprinted and the nonimprinted polymers to sorb three fungicides. It shows that the imprinted polymer could be used as a preconcentration phase in a multiresidue analysis of fungicides in hydroalcoholic medium.     

Preferred conformations of enol ethers in solution: Detection of an equilibrium by kinetic nuclear overhauser effects

n.O.e. difference spectra reveal that the preferred solution conformation of methyl enol ethers has the methyl group $\text{syn}$-periplanar to the double bond; n.O.e kinetics in a methoxy—heptatriene demonstrate the presence of both possible periplanar conformations, the energy difference being $\text{ca}$ 1 kcal/mole.     

Comparison of the separation of aziridine isomers applying heptakis(2,3-di-O-methyl-6-sulfato)beta-CD and heptakis(2,3-di-O-acetyl-6-sulfato)beta-CD in aqueous and nonaqueous systems

Aziridines are attracting interest as protease inhibitors, which might be used, e.g., for treatment of parasitic diseases. Within the framework of greater projects dealing with the search of new selective protease inhibitors, a huge number of aziridines with two stereogenic centers will be synthesized. Thus, a fast and reliable screening method for the evaluation of the isomeric composition is needed. Robust baseline separations were obtained using heptakis(2,3-di-O-acetyl-6-sulfato)beta-CD (HDAS) in acidic methanol and sulfated beta-CD in acidic phosphate buffer. With HDAS the resolutions were higher and migration times shorter. Thus, the method will be used as a screening method for further isomeric mixtures of aziridines.     

A host-guest optical sensor for aliphatic amines based on lipophilic cyclodextrin

A host-guest optical sensor for the determination of aliphatic amines as exemplified by octylamine is proposed. It is based on the reversible fluorescence enhancement of heptakis(2,6-di-O-isobutyl)-β-cyclodextrin(DOB-β-CD) hosting tetraphenylporphyrin (TPP) immobilized in poly(vinyl chloride) (PVC) membrane by aliphatic amine extracted from aqueous phase into membrane phase. The optimum membrane contained 1.15 wt % TPP, 6.15 wt % DOB-β-CD as sensing reagent and other membrane materials. The fluorescence enhancement of the membrane resulted from the formation of a stable three-component complex among DOB-β-CD, TPP, and aliphatic amines. With the optimum conditions described, the fluorescence response of the sensor to octylamine shows a good correlation with the theoretically derived equation in the range 1.0 × 10^–6 to 8.0 × 10^–4 mol/L. The response characteristics including reversibility, response time, reproducibility and lifetime and selectivity of this optical device are also discussed in detail. This sensor has also been applied for the determination of octylamine in water samples containing interferents with satisfactory recovery. Received: 21 November 1999 / Revised: 10 January 2000 / Accepted: 15 January 2000     

Development and validation of a separation method for the diastereomers and enantiomers of aziridine-type protease inhibitors

Aziridine derivatives are attracting pharmacological interest as protease inhibitors. Due to their two centers of chirality, the aziridines studied here are mixtures of two diastereomers and corresponding enantiomers. Applying cyclodextrin-modified capillary electrophoresis resulted in a baseline separation of the four isomers. The most robust separation was obtained by means of 2 mM sulfated beta-cyclodextrin in 50 mM phosphate buffer of pH 2.5. Using this method, 0.25% of the trans-diastereomers aziridine could be precisely and accurately quantified in the presence of 99.75% of the cis-isomers. The corrected peak-area ratios, migration times, and resolutions were found to be robust with respect to small variations of voltage, buffer concentrations, pH, temperature, chiral selector concentration, and different lots.