Recent applications and chiral separation development based on stationary phases in open tubular capillary electrochromatography(2019–2022)

Capillary electrochromatography(CEC)plays a significant role in chiral separation via the double separation principle,partition coefficient difference between the two phases,and electroosmotic flow-driven separation.Given the distinct properties of the inner wall stationary phase(SP),the separation ability of each SP differs from one another.Particularly,it provides large room for promising applications of open tubular capillary electrochromatography(OT-CEC).We divided the OT-CEC SPs developed over the past four years into six types:ionic liquids,nanoparticle materials,microporous materials,biomaterials,non-nanopolymers,and others,to mainly introduce their characteristics in chiral drug separation.There also added a few classic SPs that occurred within ten years as supplements to enrich the features of each SP.Additionally,we discuss their applications in metabolomics,food,cosmetics,environment,and biology as analytes in addition to chiral drugs.OT-CEC plays an increasingly significant role in chiral separation and may promote the development of capillary electrophoresis(CE)combined with other instruments in recent years,such as CE with mass spectrometry(CE/MS)and CE with ultraviolet light detector(CE/UV).

Three Cinnamyl β-Cyclodextrins Used as GC Stationary Phases

Aim To study the chromatographis beheviors of three new cinnamyl cyclodextrin derivative stationary phases. Mehtods Three new cinnamyl β-cyclodextrins, heptakis-(2, 6-di-O-cinnamyl-3-O-methyl)-β-CD, heptakis-(2, 6-di-O-cinnamyl-3-O-acetyl-)-β-CD and heptakis-2, 6-di-O-cirinamyl-3-O-trifluoroacetyl)-β-CD were synthesized and coatal on fused-silica capillary columns . Results The new stationary phases have better thermal stability, good column efficiency and excellent mpaxation power for some sutstituted benzene positional isomers. It was found that the introduction of cinnamyl groups has a significant effect on these stationary phases. Conclusion There new subetituted β-CD compounds are very suitable to be ed as gas chromatographic stationary phases.

Effect of Single-walled Carbon Nanotubes on Cellulose Phenylcarbamate Chiral Stationary Phases

Single-walled carbon nanotubes（SWNTs） have a high adsorption ability and nanoscale interactions. Cellulose trisphenylcarbamates possess high enantioseparation ability in high-performance liquid chromatography（HPLC）. Single-walled carbon nanotubes mixed with cellulose trisphenylcarbamate are coated on the silica gel as chiral stationary phases and higher enantioseparation factors are obtained. After a single-walled carbon nanotube is linked to the 6-pesition of cellulose 2,3-bisphenylcarbamate, its enantioseparation resolution increases compared to that of the cellulose trisphenylcarbamate. It is the first time that SWNTs have been applied to enantioseparation. The results indicate that the single-walled carbon nanotubes are good promoters of chiral recognition. This method can be used to improve the enantioseparation efficiency of the polysaccharide chiral stationary phases.

Glucose,cellobiose,lactose and raffinose used as chiral stationary phases in HPLC

This paper presents the enantioseparation using glucose, cellobiose, lactose and raffinose as chiral selector bonded to silica gel via an arm in HPLC. Surprisingly, they also possess high enantioseparation selectivity, may be used in normal-phase and reversed- phase mode, and there is a big chiral discriminating complementary. This work indicates that oligosaccharides could soon become very attractive as a new class of chiral stationary phase for HPLC.

Synthesis of novel chiral stationary phases for high-performance liquid chromatography

Three novel chiral selectors 4a-c were synthesized from （S）-amino acids and （R）-1-phenyl-2-（4-methylphenyl）ethylamine. 4a-c were connected to 3-aminopropylsilanized silica gel to be used as the chiral stationary phase for HPLC. Five amino acid derivatives and two pyrethroid insecticides were fairly resolved on these three new chiral stationary phases under normal phase condition.

Novel guanidinium-based ionic liquids as stationary phases for capillary gas chromatography

The present study describes guanidinium-based ionic liquids（GBILs） as stationary phases for capillary gas chromatography （CGC） and to the best of our knowledge,no related reports are available up to now.In this study,a hexaalkylguanidinium ionic liquid（DOTMG-NTf;） was synthesized and coated statically onto capillary columns.Selectivity of the stationary phase was evaluated by separating Grob test mixture,test mixture,alcohols mixture,and fatty acid methyl esters mixture,and thermal stability was investigated as well.The present study demonstrates that GBILs as CGC stationary phases exhibit satisfactory selectivity and thermal stability and have a great potential as new candidates for CGC stationary phases.

Preparation of new hybrid organic/inorganic polymeric chiral stationary phases for ligand-exchange chromatography

Three new hybrid organic/inorganic polymeric ligand-exchange chiral stationary phases were developed by radical chain transfer reaction and surface grafting on silica gel, and successfully used for the enantioseparations of DL-amino acids and DL-hydroxyl adds. The resolutions were achieved by using water containing 2.0 × 10^-4 mol/L of CuAc2 as a mobile phase, column temperature of 40 ℃, flow rate of 1.0 mL/min and detection at UV 254 nm. The elution order of D-isomer before L-isomer was observed for all DL-amino acids resolved except DL-Pro.

Retention behaviors of novel ionic liquid stationary phases and their selectivity for capillary gas chromatography

One chloride-terminated ionic liquid（CTIL） and two hydroxyl-terminated ionic liquids（HTILs） were synthesized and used as stationary phases for capillary gas chromatography（CGC）.Molecular interactions of these stationary phases were evaluated by Abraham solvation parameter model,indicating that the CTIL exhibits remarkably strong H-bond basicity and the HTILs possess both H-bond basicity and acidity.The molecular interactions were further confirmed by separation of a complex mixture consisting of ketones,aldehydes,esters,alcohols and aromatic compounds.It was found that the obtained solvation parameters correlate well with the chromatographic performances of the analytes in terms of elution order and resolution.The well correlated relationship between the solvation parameters and the selectivity of the CTIL and HTILs stationary phases is quite helpful in predicting and understanding the retention behaviors of different types of analytes on these stationary phases.

Modification of Chiral Stationary Phases with L-Proline as a Selector for Ligand-exchange Chromatography via Introducing Hydrophobic Groups

Three chiral stationary phases（CSPl, CSP2 and CSP3） for ligand-exchange chromatography were prepared by firstly using dimethylchlorosilane as an endcapping reagent for decreasing residual silanol groups on the surface of silica gel, and then modifying the surface of silica gel with allyl glycidyl ether and alkenes through the hydrosilation reaction, and lastly introducing L-proline as a chiral selector. The enantiomer resolutions of 14 amino acids and 2 hydroxyl acids were completed on the CSPs by using an aqueous solution of Cu（Ac）2 as mobile phase at a flow rate of 1.0 mL/min and column temperature of 40 ℃ with detection at UV 254 nm. In terms of enantioseleetivity a, column efficiency and resolution Rs, the chromatographic behaviors of the analytes on the CSPs were discussed via comparing them to those on the CSP4 prepared via the reference method. The results show that enantioselectivity a, column efficiency and resolution Rs of the analytes on the CSPs could be improved by using the above modifying method.

Selectivity of New β-Cyclodextrin Derivatives as CGC Stationary Phases and Application for the Analysis of Volatile Compounds in Traditional Chinese Medicines

New cyclodextrin derivatives （CDs）, heptakis（2, 6-di- O-methyl-3- O-methoxymethyl）-β-CD （ Ⅰ ） and heptakis（2, 3, 6-tri-O-methoxymethyl）-β-CD （ Ⅱ ）, were investigated for their chromatographic performance as stationary phases for capillary gas chromatography （CGC）. Both of the CDs exhibited good selectivity and satisfactory separation for test mixtures and aromatic positional isomers, and volatile compounds from Ligusticurn chuanxiong Hort. Additionally, the selectivity and elution orders of major compounds were compared with a well-recognized commercial column on the basis of the results by gas chromatography-mass spectrometry （GC-MS）. The present work demonstrates the good selectivity of the two new CDs and can be used as GC stationary phases for the separation of positional isomers and analytes in complex samples.

AN EASY-TO-MAKE OZONE GENERATOR FOR THE IMMOBILIZATION OF STATIONARY PHASES IN GC CAPILLARY COLUMNS

An easy-to-make ozone generator which can be made with readily available materials is proposed. Concentration of the ozone prepared with this generator could reach that of ozone in equilibrium with oxygen. Cured with the ozone thus prepared, GC capillary columns with immobilized SE-54 phase and excellent chromatographic performance were successfully prepared.

Separation Properties of a New Polysiloxane-Anchored β-Cyclodextrin Derivative as Gas Chromatography Stationary Phase

A new capillary gas chromatography stationary phase, monokis (2,6 di O benzyl 3 O propyl (3’)) hexakis(2,6 di O benzyl 3 O methyl) β CD bonded polysiloxane, was synthesized. It exhibited separation abilities to disubstituted benzene isomers and some chiral solutes. It was also found that the polarity of CD derivatives can be lowered both by chemically bonding it to polysiloxane and by diluting it in polysiloxane. The separation abilities of the polysiloxane anchored CDs (SP CD) are higher than that of the unbonded CDs (S CD) and the diluted S CD at lower column temperature. Hydrosilylation reaction is one of the best methods to lower the operating temperature of CDs.

The stationary phase analysis of the Kirchhoff-type d emigrated field

In the literature,stationary phase analysis of Kirchhoff-type demigrated fields is carried out mainly under the following two conditions：（1） The considered isochrone and the target reflector are tangential to each other;（2） The spatial duration of the wavelet of the depthmigrated image is short.For the isochrones that are not tangential to the target reflector and for the depth-migrated images that have a large spatial duration,the published stationary phase equation for the demigrated field will become invalid.For performing the stationary phase analysis of the Kirchhoff-type demigrated field under the conditions that the considered isochrone and the target reflector are not tangential to each other and that the spatial duration of the wavelet of the depth-migrated image is not short（the general conditions）,I derive the formulas for the factors appearing in the stationary phase formula in two dimensions,from which I find that for different isochrones the horizontal coordinates of the stationary point of the depth difference function are different.Also,the equation for the Kirchhoff-type demigrated field consists of two parts.One is the true-amplitude demigrated signal and the other is the amplitude distortion factor.From these facts the following two conclusions can be drawn：（1） A demigrated signal is composed of many depth-migrated images and one depth-migrated image trace provides only one sample to the demigrated signal;and（2） The amplitude distortion effect is an effect inherent in the Kirchhoff-type demigration and cannot be eliminated during demigration.If this effect should be eliminated,one should do an amplitude correction after demigration.

Investigation on Two Novel Substituted β-Cyclodextrins Used as GC Stationary

Aim To study the chromatographic behaviors of two dipentyl cyclodextrin derivative stationary phases. Methods Two new β-cyclodextrin derivatives, heptakis-[2, 6-di-O-pentyl-3-O-(4-nitrobenzyl)] -β-CD and heptakis-[2, 6-di-O-pentyl-3 -O-(5 -hexenyl)]-β-CD, were synthesized and coatal on fed-silica capillary columns. The chromatographic behaviors of the columns were characterized . Results It was found that the she, polarity, and aromatic property of the substituted group at the 3-position of heptakis-(2, 6 - di - O - pentyl) - β - cyclodextrins greatly influenced their chromatographic properties and separation ability. The introduction of aromatic group or a group containing a double-bond may bring π-π interactions between the host and guest molecules, and therefore increases the separation ability of the β-CDs for substituted benzene isomers. Conclusion The new substituted β-CD compounds are very suitable for being used as gas chromatogaphic stationary phases.

High performance liquid chromatographic separation of thirteen drugs collected in Chinese Pharmacopoeia 2010(Ch.P2010) on cellulose ramification chiral stationary phase

The enantiomers separation of thirteen drugs collected in Ch.P2010 was performed on chiral stationary phase of cellulose ramification (chiralpak OD and chiralpak OJ) by high performance liquid chromatographic (HPLC) methods, which included ibuprofen (C1), ketoprofen (C2), nitrendipine (C3), nimodipine (C4), felodipine (C5), omeprazole (C6), praziquantel (C7), propranolol hydrochloride (C8), atenolol (C9), sulpiride (C10), clenbuterol hydrochloride (C11), verapamil hydrochloride (C12), and chlorphenamine maleate (C13). The mobile phase consisted of isopropanol and n-hexane. The detection wavelength was set at 254 nm and the fiow rate was 0.7 mL/min. The enantiomers separation of these thirteen racemates on chiralpak OD column and chiralpak OJ column was studied, while the effects of proportion of organic additives, alcohol displacer and temperature on the separation were studied. And the mechanism of some of racemates was discussed. The results indicated that thirteen chiral drugs could be separated onchiral stationary phase of cellulose ramification in normal phase chromatographic system. The chromatographic retention and resolution of enantiomers could be adjusted by factors including column temperature and the concentration of alcohol displacer and organic alkaline modifier in mobile phase. It was shown that the resolution was improved with reducing concentration of alcohol displacer. When concentration of organic alkaline modifier was 0.2% (v/v), the resolution and the peak shape were fairly good. Most racemates mentioned above had better resolution at column temperature of 25 1C. When racemates were separated, the temperature should be kept so as to obtain stable separation results.

Stationary phase approximation in the ambient noise method revisited

The method of extracting Green＇s function between stations from cross correlation has proven to be effective theoretically and experimentally. It has been widely applied to surface wave tomography of the crust and upmost mantle. However, there are still controversies about why this method works. Snieder employed stationary phase approximation in evaluating contribution to cross correlation function from scatterers in the whole space, and concluded that it is the constructive interference of waves emitted by the scatterers near the receiver line that leads to the emergence of Green＇s function. His derivation demonstrates that cross correlation function is just the convolution of noise power spectrum and the Green＇s function. However, his derivation ignores influence from the two stationary points at infinities, therefore it may fail when attenuation is absent. In order to obtain accurate noise-correlation function due to scatters over the whole space, we compute the total contribution with numerical integration in polar coordinates. Our numerical computation of cross correlation function indicates that the incomplete stationary phase approximation introduces remarkable errors to the cross correlation function, in both amplitude and phase, when the frequency is low with reasonable quality factor Q. Our results argue that the dis- tance between stations has to be beyond several wavelengths in order to reduce the influence of this inaccuracy on the applications of ambient noise method, and only the station pairs whose distances are above several （〉5） wavelengths can be used.

COVALENTLY BONDING CHIRAL POLYURETHANE ON AMINATED SILICA GEL:A NEW STRATEGY TO PREPARE CHIRAL STATIONARY PHASE FOR HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

Two polyurethanes of different molecular weights were prepared by the copolymerization of phenyl diisocyanate and diisopropyl tartrate. The polyurethanes having terminal isocyanate groups were reacted with 3-aminopropyl silica gel to afford two chiral stationary phases. The M^- n of the two polyurethanes were 4057 g/mol and 6442 g/mol. The polyurethanes and the corresponding chiral stationary phases were characterized by FT-IR,^1 H NMR and elemental analysis. The loading capacities of the polyurethanes on silica gel were 0.68 mmol units/g and 0.61 mmol units/g, respectively. The separation performance and the influence of additives, triethylamine and trichloroacetic acid, on the separation of chiral compounds were investigated by HPLC. The chiral stationary phase prepared from polyurethane with M^- n of 4057 g/mol demonstrated better enantioseparation capability than that with M^- n of 6442 g/mol. Additionally, it was found that the addition of triethylamine and trichloroacetic acid in the mobile phases significantly improved the enantioseparation for these two chiral stationary phases.

Preparation and chiral recognitio of a novel chiral stationary phase for HPLC,based on mono(6~A-N-1-(2-hydroxyl)-phenylethylimino-6~A-deoxy)-β-cyclodextrin and covalently bonded silica gel

A novel chiral stationary phase （CSP） was prepared by immobilizing mono（6A-N-1-（2-hydroxyl）-phenylethylimino-6A- deoxy）-β-cyclodextrin onto the surface of silica gel via a longer spacer. This chiral stationary phase exhibited good enantioselectivity for a variety of chiral compounds under reversed-phase conditions.

The Optical Resolution of Chiral Tetrahedrone-type Clusters Contai- ning SCoFeM (M=Mo or W) Using High Performance Liquid Chromatography Chiral Stationary Phase

Amylose tris (phenylcarbamate) chiral stationary phase (ATPC-CSP) was prepared and used for optical resolution of clusters 1 and 2. n-Hexane/2-propanol ( 99/1; v/v) were found to be the most suitable mobile phase on ATPC-CSP.

MIL-53-based homochiral metal-organic framework as a stationary phase for open-tubular capillary electrochromatography

Homochiral metal-organic frameworks(MOFs)have attracted considerable attention in many fields of research,such as chiral catalysis and chiral chromatography.However,only few homochiral MOFs can be effectively used in capillary electrochromatography(CEC)and their performances are far from adequate.In this study,we successfully synthesized achiral nanocrystalline MIL-53.A facile post-synthetic modification strategy was then implemented to functionalize the product,yielding a homochiral MOF:L-His-NH-MIL-53.This MOF was then employed as a chiral coating in open-tubular CEC mode(OT-CEC),and,as such,it exhibited high enantioselectivities for several racemic drugs.The homochiral MOF and the fabricated capillary coating were systematically characterized using transmission electron microscopy,scanning electron microscopy(with energy-dispersive X-ray spectrometry),Fourier-transform infrared spectroscopy,X-ray diffractometry,thermogravimetric analysis,circular dichroism spectroscopy,Brunauer-Emmett-Teller surface area measurements,and X-ray photoelectron spectroscopy.This study is expected to provide a new strategy for the design and establishment of MOF-based chiral OT-CEC systems.