Synthesis of covalently bonded cellulose derivative chiral stationary phases with a bifunctional reagent of 3-(triethoxysilyl)propyl isocyanate

A bifunctional reagent of 3-(triethoxysilyl)propyl isocyanate (TEPI) was initially adopted as a spacer reagent to prepare the bonded types of chiral stationary phases (CSPs) with cellulose derivatives. The silica-based CSPs were chemically prepared with non-regioselective and regioselective approaches and their chiral resolving capabilities were evaluated in terms of HPLC resolution of test enantiomers. It was observed that the chiral recognition capabilities of the non-regioselectively prepared CSPs were influenced by the amount of TEPI used. And also, the regioselectively prepared CSP generally showed a slightly higher resolution power than the non-regioselectively prepared CSP, while the non-regioselective procedures were highly advantageous to rapid preparation. In addition, chiral recognition of the prepared CSPs was affected by the properties of the used silica matrices. (C) 2003 Elsevier B.V. All rights reserved.

Molecularly imprinted monolithic stationary phases for liquid chromatographic separation of enantiomers and diastereomers

The method for preparation of molecularly imprinted monolithic stationary phase has been improved to achieve liquid chromatographic separation of enantiomers and diastereomers. By adopting low polar porogenic solvents of toluene and dodecanol and optimal polymerization conditions, the molecularly imprinted monolithic stationary phases with good flow-through properties and high resolution were prepared. Enantiomers of amino acid derivatives and diastereomers of cinchona alkaloids were completely resolved using the monolithic stationary phases. The influence of porogenic composition, monomer-template ratio and polymerization conditions on the chromatographic performance was investigated. Some chromatographic conditions such as the composition of the mobile phase and the temperature were characterized. Scanning electron microscopy showed that the molecularly imprinted monolithic stationary phase has a large through-pore structure to allow the mobile phase to flow through the column at very low backpressure. Accelerated separations of enantiomers and diastereomers were therefore achieved at elevated flow rates. Finally, the chiral recognition performance of the prepared stationary phase in aqueous media was investigated. Hydrophobic interaction, and ionic and/or hydrogen bonding interactions were proposed to be responsible for the recognition mechanism. (C) 2002 Elsevier Science B.V. All rights reserved.

Synthesis and characteristics of composite chiral stationary phases based on cellulose derivatives

Composite chiral stationary phases (CSPs) were prepared on the basis of cellulose derivatives coated or bonded onto silica. "Molecular exterior" type CSPs were prepared by mixing together two different cellulose tris-derivatives before or after being coated or bonded onto silica, and the "molecular interior" type was obtained by synthesizing non-regioselectively heterosubstituted cellulose derivatives coated or bonded onto silica. For the sake of comparison, the individual phases were also prepared with corresponding cellulose derivatives by coating or bonding approaches, respectively. All of the prepared CSPs were characterized and their chiral recognition properties were evaluated by HPLC with several test racemates. The experimental results demonstrated that the "molecular exterior" CSPs generally exhibit chiral recognition capacities intermediate between those of the two individual phases. However, in the separation of some racemates higher enantioselectivity may be achieved on the "molecular interior" phases than on individual phases, thus broadening the application range of a single cellulose-based CSP.

Transient state of chiral recognition in a binary mixture of cyclodextrins in capillary electrophoresis

The transient state (as the defined point where no enantioseparation is obtained in a dual chiral selector system) of chiral recognition of aminoglutethimide in a binary mixture of neutral cyclodextrins (CDs) was studied by capillary electrophoresis (CE). The following three dual selector systems were used: alpha-cyclodextrin (alpha-CD) and beta-cyclodextrin (beta-CD); alpha-CD and heptakis(di-O-methyl-beta-cyclodextrin) (DM-beta-CD); alpha-CD and heptakis(tri-O-methyl-beta-cyclodextrin) (TM-beta-CD). The S-(-) enantiomer of the analyte was more strongly retained in the presence of either alpha-CD or TM-beta-CD at pH 2.5, 100 mM phosphate buffer, while the R-(+) enantiomer was more strongly retained in the presence of either P-CD or DM-P-CD. In the more simple case, the elution order is invariably kept if the enantiomers have the same elution order in either one of the two hosts of the binary mixture. In contrast, the elution order may be switched by varying the concentration ratio of two hosts that produce opposite elution order for this particular analyte. In such a dual selector system, the enantioselectivity will disappear at the transient state at a certain ratio of host,:host, Moreover, the migration times of the two enantiomers with host, alone (diluted in buffer) is approximately equal to the migration times at the corresponding concentration of host, alone (diluted in buffer), where the ratio of concentrations of host,:host, is the same as in the binary mixture at the transient state. As found by nuclear magnetic resonance experiments, the analyte is forming a 1:1 complex with either one of the CDs applied. From this finding, a theoretical model based on the mobility difference of the two enantiomers was derived that was used to simulate the transient state. (C) 2000 Elsevier Science B.V. All rights reserved.

Synthesis and characteristics of the human serum albumin-triazine chiral stationary phase

Human serum albumin (HSA) was successfully bonded to silica with s-triazine as activator. The coupling reaction by this method was rapid and effective. The triazine-activated silica is relatively stable and can be installed for at least 1 month without obvious loss of reactivity when stored below 30 degreesC, pH below 7. It was observed that the amount of bound HSA reached 120 mg/g silica calculated from the UV absorbance difference of the HSA solution. d,l-tryptophan was selected as the probe solute to characterize the properties of HSA bonded s-triazine chiral stationary phase, and separation factor of 9.4 was obtained for d,l-tryptophan. Furthermore, the amount of effective HSA on silica was measured by high-performance frontal analysis, and only 16.8 mg/g silica was responsible for the resolution of d,l-tryptophan. These results indicate that the amount of both the bound and effective HSA on silica with triazine as activator was much higher than those by the Schiff base coupling method. Different kinds of enantiomers were resolved successfully on the aminopropylsilica-bonded HSA s-triazine chiral stationary phase. (C) 2000 Wiley-Liss, Inc.

Synthesis of a silica-bonded bovine serum albumin s-triazine chiral stationary phase for high-performance liquid chromatographic resolution of enantiomers

A novel method of synthesizing protein chiral stationary phase (protein-CSP) is proposed with 2,4,6-trichloro-1,3,5-triazine as the activator. The bovine serum albumin (BSA) based chiral columns (150x4.6 mm I.D.) were prepared successfully within 8 h. With tryptophan as the probe solute, it was observed that the BSA immobilized by this method had a better ability to distinguish enantiomers than that activated by glutaric dialdehyde. This may be due to the well-maintained BSA conformation and the larger amount of BSA immobilized on the silica gel. The BSA-CSP prepared by this method was relatively stable under experimental conditions, and the resolution of 13 chiral compounds was achieved. The coupling reaction in this method is mild, reliable and reproducible; it is also suitable for the immobilization of various biopolymers in the preparation of bioreactor, biosensor and affinity chromatography columns. (C) 2000 Elsevier Science B.V. All rights reserved.

Direct enantiomer separation of 2-phenylcyclopropanecarboxylate esters on cyclodextrin derivatives stationary phases in GC

Direct enantiomeric separation of all four optical isomers of 2-phenylcyclopropane carboxylate ester was first achieved on each of the three different beta-cyciodextrin chiral stationary phases (CSPs) in GC. Using these CSPs, enantiomeric excess of the products of enantioselective cyclopropanation can be determined directly, conveniently and fast.

New cocktail functional monomers in making molecule imprinting polymer with high chiral selectivity

in order td produce molecule imprinting polymer (MIP) with high chiral selectivity against N-c-protected amino acid, new cocktail functional monomers acrylamide (AM) + 2-vinylpyridine (2-VP) and AM + methacrylic acid (MAA) were investigated. AM + 2-VP was found to be more efficient in improving the selectivity and resolution of the molecule imprinting polymer.

Numerical Simulation of Particle Separation in An Oil-Sand Separator

The gathering systems of crude oil are greatly endangered by the fine sand and soil in oil. Up to now , how to separate sand from the viscid oil is still a technical problem for oil production home or abroad. Recently , Institute of Mechanics in Chinese Academy of Sciences has developed a new type of oil-sand separator , which has been applied successfully in oil field in situ. In this paper, the numerical method of vortex-stream function is used to predict the liquid-solid separating course and the efficiency for this oil-sand separator. Results show that the viscosity and particle diameter have much influence on the particle motion. The calculating separating efficiency is compared with that of experiment and indicates that this method can be used to model the complex two-phase flow in the separator.