Based on the traditional scheme for a nonlinear system with multiple time scales,the enveloping slow-fast analysis method is developed in the paper,which can be employed to investigate the dynamics of nonlinear fields with multiple time scales with periodic excitation.Upon using the method,the behaviors of the kinetic model of CO oxidation on the platinum group metals have been explored in detail.Two typical bursting phenomena such as Fold/Fold/Hopf bursting and Fold/Fold bursting,are presented,the bifurcation mechanisms of which have been obtained.Furthermore,the dynamic difference between the two cases corresponding to relatively large and small perturbation frequencies,respectively,has been presented,which can be used to describe the influence of the frequencies involving in the evolution on the bursting behaviors in the system.
Inclusion behavior of oxybutynin (OBN) with hydroxypropyl-β-cyclodextrin (HP-β-CD) was investigated by ultraviolet absorption spectrum and fluorescence spectrum. A reliable determination of the complex stoichiometry was provided by the continuous variation technique. Alcohol was added to further investigate the mechanism of the inclusion behavior. Thermodynamic constants ΔG, ΔH and ΔS for inclusion interaction of OBN and HP-β-CD were determined. The results show that host-guest complex with molar ratio of 1-1 is formed, and inclusion stability constant between OBN and HP-β-CD is 54.9 L/mol determined by ultraviolet spectrum and 11.1 L/mol determined by fluorescence spectrum. OBN has weak binding ability with HP-β-CD in aqueous solution (stability constant <102 L/mol) and addition of alcohol leads to a decrease of stability constant, which indicates that the hydrophobic force contributes to the inclusion process. ΔG, ΔH and ΔS are all less than zero, which indicates that the inclusion process is a spontaneous and exothermic process.
This paper deals with the enantioseparation of phenylsuccinic acid(H2A)enantiomers by liquid-liquid reactive extraction usingβ-CD derivatives as aqueous selectors.Cyclodextrin and its derivatives can interact with guest molecules selectively to form complexes with different stabilities.Cyclodextrin derivatives are not soluble in organic liquids,but highly soluble in water.In this work,hydroxypropyl-β-cyclodextrin(HP-β-CD),hydroxyethyl- β-cyclodextrin(HE-β-CD)and methyl-β-cyclodextrin(Me-β-CD)were selected as chiral selectors in aqueous phase for the reactive extraction of phenylsuccinic acid enantiomers from organic phase to aqueous phase.The results show that the efficiency of the extraction depends,often strongly,on a number of process variables,including the types of organic solvents andβ-CD derivatives,the concentrations of the extractants and H2A enantiomers,pH and temperature.HP-β-CD,HE-β-CD and Me-β-CD have stronger recognition abilities for R-phenylsuccinic acid than for S-phenylsuccinic acid.Among the three kinds ofβ-CD derivatives,HP-β-CD has the strongest separation ability. Excellent enantioseparation was achieved under the optimal conditions of pH of 2.5 and temperature of 5°C with a maximum enantioselectivity(a)of 2.38.Reactive extraction of enantiomers with hydrophilicβ-CD derivatives is of strong chiral separation ability and can be hopeful for separations of various enantiomers at a large-scale.
The kinetics of the extraction of phenylsuccinic acid(PSA) enantiomers by hydroxypropyl-β-cyclodextrin(HP-β-CD) in a modified Lewis cell was studied,in which HP-β-CD dissolved in 0.1 mol L-1 NaH2PO4/H3PO4 buffer solution(pH = 2.5) was selected as the chiral extractant.PSA enantiomers were extracted from organic phase to aqueous phase in the extraction module.The theory of extraction accompanied by a chemical reaction has been used to obtain the intrinsic kinetics of this extraction module.The different parameters affecting the extraction rate such as agitation speed,interfacial area,initial concentration of PSA enantiomers in organic phase as well as HP-β-CD concentration in aqueous phase were separately studied.The experimental results demonstrate that the extraction reactions are fast.The reactions were found to be first order with respect to PSA and second order with respect to HP-β-CD with forward rate constants of 3.4 × 10-2 m6 mol-2 s-1 for R-PSA and 9.96 × 10?3 m6 mol-2 s-1 for S-PSA.These data will be useful in the design of extraction processes.
TANG KeWen1*,MIAO JiaBing2,ZHOU Tao2 & SONG LiTao2 1Department of Chemistry and Chemical Engineering,Hunan Institute of Science and Technology,Yueyang 414006,China 2College of Chemistry and Chemical Engineering,Central South University,Changsha 410083,China
Reactive extraction is an emerging technology for large-scale continuous resolution of drug enantiomers.The enantioselective extraction of R,S-naproxen by hydrophilic HP-β-CD in 1,2-dichloroethane was studied at 5 °C.The experimental data were described by a reactive extraction model with a homogeneous aqueous phase reaction of R,S-naproxen with HP-β-CD which couples a complete description of chemical equilibria in aqueous phase with the overall phase equilibria of the system.Important parameters of this model were determined experimentally.The physical distribution coefficients for molecular and ionic NAP were 0.041 and 1.730,respectively.Here we show that the efficiency of extraction depends strongly on two process variables including pH and HP-β-CD concentration.The model predictions are compared graphically with the results of previous experiments and there is a good agreement between each other.By the use of modeling and experiment,an optimized extraction condition with pH of 2.5 and HP-β-CD concentration of 0.1 mol/L was obtained with high enantioselectivity(α) of 1.59 and performance factor(pf) of 0.049.The model gives a good means of predicting enantiomers partitioning over a range of experimental conditions.
