For chromatographic separation,the reasonable modulation of stationary phases is the key factor to achieve high separation performance.We proposed that developing MOF stationary phases through precisely modulating the...For chromatographic separation,the reasonable modulation of stationary phases is the key factor to achieve high separation performance.We proposed that developing MOF stationary phases through precisely modulating the thermodynamic interactions between MOFs and analytes is conducive to improving the separation resolution.MIL-125,MIL-125-NH_(2),MIL-143-BTB,and MIL-143-TATB were developed as stationary phases with the careful modulation of organic ligands.MIL-125-NH_(2)and MIL-143-TATB coated columns exhibited much better separation performance than their counterparts,MIL-125 and MIL-143-BTB,respectively.The investigation of the separation mechanism indicated that thermodynamic interaction,rather than kinetic diffusion,was responsible for the separation improvement.MIL-125-NH_(2)and MIL-143-TATB provided stronger and distinguishable interactions with targets than corresponding MIL-125 and MIL-143-BTB,respectively,resulting in enhanced separation performance.This work demonstrates a guide to improving the separation performance of MOF stationary phases by increasing the thermodynamic interactions between MOFs and analytes.展开更多
An ionic liquid assisted hydrogel modified silica was synthesized using a one-pot polymerization and physical coating technique and subsequently applied to mixed-mode liquid chromatography.Analytical techniques,includ...An ionic liquid assisted hydrogel modified silica was synthesized using a one-pot polymerization and physical coating technique and subsequently applied to mixed-mode liquid chromatography.Analytical techniques,including Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),and elemental analysis,etc.,confirmed the successful prepared of this innovative stationary phase.The unique combination of amide,long alkyl chain,and imidazole ring in the hydrogel coating enables the stationary phase to function effectively in hydrophilic/reversed-phase/ion exchange liquid chromatography.Notably,the stationary phase exhibited superior separation performance owing to the synergistic effect of the ionic liquid and hydrogel.This was particularly evident when analyzing various analytes such as organic acids,nucleosides/bases,polycyclic aromatic hydrocarbons(PAHs)and anions.Furthermore,under our operating conditions,an excellent column efficiency of 53,642.9 plates/m was achieved for theobromine.In summary,we have proposed a straightforward strategy to enhance the separation performance of hydrogel coatings in liquid chromatography,thereby broadening the potential applications of hydrogels in the field of separation.展开更多
A series of optically active copolymers with various feed ratios have been synthesized through helix-sense-selective copolymerization catalyzed by[Rh(norbornadiene)Cl]2-triethylamine.This process involves two proline-...A series of optically active copolymers with various feed ratios have been synthesized through helix-sense-selective copolymerization catalyzed by[Rh(norbornadiene)Cl]2-triethylamine.This process involves two proline-derived acetylene monomers,(S)-N-(4-chlorophenyl)carbamoyl-2-ethynyl pyrrolidine(MCl)and(S)-N-(tert-butoxycarbonyl)-2-ethynyl pyrrolidine,followed by acidic deprotection and neutralization.These copolymers adopt helical conformations with a preferred handedness,as demonstrated by nuclear magnetic resonance spectroscopy and a series of spectroscopic analyses.The chiroptical activity intensity of copolymer has been found to increase with MCl content.Consequently,the enantioseparation capabilities of copolymers containing 95 mol%,90 mol%,and 85 mol%MCl units have been assessed as chiral stationary phases in high-performance liquid chromatography because of their good chiroptical activities.These chiral stationary phases effectively enantioseparate racemic alcohols,sulfoxides,amides,and metal complexes.Notably,the copolymer with 90 mol%MCl shows superior chiral recognition ability,especially for 1-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl)ethanol(α=1.19)and 4-methylbenzenesulfinamide(α=1.47).Insights from molecular dynamic simulation and autodock analysis indicate that hydrogen bonding andπ-πstacking interactions between the chiral stationary phases and enantiomers play a key role for successful chiral separation.Our contribution not only demonstrates the importance of hydrogen bonding donor and copolymer chiroptical activity of chiral stationary phases for chiral resolution,but will also provide valuable insights for the future development of novel stationary phases.展开更多
Covalent organic frameworks(COFs)have demonstrated great potential in chromatographic separation because of unique structure and superior performance.Herein,single-crystal three-dimensional(3D)COFs with regular morpho...Covalent organic frameworks(COFs)have demonstrated great potential in chromatographic separation because of unique structure and superior performance.Herein,single-crystal three-dimensional(3D)COFs with regular morphology,good monodispersity and high specific surface area,were used as a stationary phase for high-performance liquid chromatography(HPLC).The single-crystal 3D COFs packed column not only exhibits high efficiency in separating hydrophobic molecules involving substituted benzenes,halogenated benzenes,halogenated nitrobenzenes,aromatic amines,aromatic hydrocarbons(PAHs)and phthalate esters(PAEs),but also achieves baseline separation of acenaphthene and acenaphthylene with similar physical and chemical properties as well as environmental pollutants,which cannot be quickly separated on commercial C18 column and a polycrystalline 3D COFs packed column.Especially,the column efficiency of 17303-24255 plates/m was obtained for PAEs,and the resolution values for acenaphthene and acenaphthylene,and carbamazepine(CBZ)and carbamazepine-10,11-epoxide(CBZEP)were 1.7and 2.2,respectively.This successful application not only confirmed the great potential of the singlecrystal 3D COFs in HPLC separation of the organic molecules,but also facilitates the application of COFs in separation science.展开更多
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 ex...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.展开更多
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 ...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.展开更多
Effective enantioseparation of Naftopidil and its derivatives by HPLC was accomplished using several different polysaccharide-based chiral stationary phases（CSPs）.In normal-phase mode,the compounds were eluted on fo...Effective enantioseparation of Naftopidil and its derivatives by HPLC was accomplished using several different polysaccharide-based chiral stationary phases（CSPs）.In normal-phase mode,the compounds were eluted on four coated-and two immobilized-columns with the mixture of n-hexane,isopropanol and diethylamine（DEA）.Polysaccharide tris（3,5- dimethylphenyl carbamate） was shown to be the best enantiomer selector.In addition,the immobilized column packed with Chiralpak IA or IB was applied under polar-organic and reversed-phase conditions,both of which exhibited excellent enantioselectivity for Naftopidil and its derivatives.Furthermore,the underlying possible chiral recognition mechanisms were discussed.展开更多
Six newly synthesized racemic 1-（substituted phenyl）-4-[3-（indole-4-yl-oxy）-2-hydroxypropyl]-piperazine 1-6 were successfully resolved by carbon dioxide supercritical fluid chromatography （SFC） on an analytical ...Six newly synthesized racemic 1-（substituted phenyl）-4-[3-（indole-4-yl-oxy）-2-hydroxypropyl]-piperazine 1-6 were successfully resolved by carbon dioxide supercritical fluid chromatography （SFC） on an analytical scale column packed with immobilized polysaccharide-based chiral stationary phases （CSPs）. We found that separation on the Chiralpak IA CSP was superior to the other two immobilized CSPs （Chiralpak IB and Chiralpak IC）, and isopropanol （IPA） was a superior modifier compared to the other five solvents including ethanol, methanol, tetrahydrofuran, acetonitrile and dichloromethane. The effects of organic modifier composition, back pressure, and column temperature for enantioseparation of all six compounds were studied. Of the physical parameters studied, modifier composition had the greatest impact on retention. Changing temperature generally had less impact on retention but produced the greatest selectivity changes. The optimum condition was found as follows： Chiralpak IA column, column temperature 35 ~C, back pressure 120 bar, 35% IPA containing 0.1% diethylamine （v/v） in mobile phase, flow rate of mobile phase 3.0 mL/min, UV detection 283 nm. Separation of all six racemic compounds was completed within 10 rain and excellent resolution was obtained. Thus, SFC was found to be the methodology of choice for resolving the enantiomers of this class of compounds.展开更多
It is a new strategy to immobilize cells on the inner wall of a capillary column and use affinity capillary electrophoresis（ACE） to study receptor-ligand interactions or to screen natural products and compounds synt...It is a new strategy to immobilize cells on the inner wall of a capillary column and use affinity capillary electrophoresis（ACE） to study receptor-ligand interactions or to screen natural products and compounds synthesized by combinatorial chemistry. In this paper, we developed a new method of immobilizing HEK293 cells on the inner wall of a capillary column. Four important experimental conditions were optimized, including cell injection density, PLL concentration, cell culturing time and sterile processing method. Immobilized cell-coated capillary columns prepared under the optimized experimental conditions exhibited good uniformity, stability and durability, which were suitable for capillary electrophoresis. The method could also be used to immobilize HEK293 cells over-expressing certain membrane receptors on the inner wall of a capillary. In this way, cell-coated capillary columns could be applied to ACE drug screening targeting certain membrane proteins.展开更多
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-...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.展开更多
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（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.展开更多
Chiral covalent organic frameworks(CCOFs) featuring chirality, stability, and good porosity have attracted a considerable amount of attention due to their important applications, such as asymmetric catalysis, chiral s...Chiral covalent organic frameworks(CCOFs) featuring chirality, stability, and good porosity have attracted a considerable amount of attention due to their important applications, such as asymmetric catalysis, chiral separation, and chiral recognition. In this study, a β-cyclodextrin(β-CD) covalent organic framework(β-CD-COF) diluted with polysiloxane OV-1701 was explored as a novel chiral stationary phase(CSP) for gas chromatography(GC) separation of racemates. The β-CD-COF coated capillary column had excellent selectivity, not only for the separation of linear alkanes, linear alcohols, fatty acid methyl esters mixture, the Grob mixture and positional isomers, but also for the resolution of chiral compounds, including chiral alcohols, aldehydes, ethers, and amino acid derivatives. In addition, the β-CD-COF-coated capillary column presented good repeatability and reproducibility. This work indicated the great potential of the CCOFs coated capillary column for the chromatographic separation of enantiomers.展开更多
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) m...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.展开更多
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 ...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.展开更多
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...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.展开更多
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...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.展开更多
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.G...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).展开更多
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 st...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.展开更多
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 up...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.展开更多
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 enantioseparati...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.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22174067,22204078,22374077,and 22474059)the Natural Science Foundation of Jiangsu Province of China(No.BK20220370)+2 种基金Jiangsu Provincial Department of Education(No.22KJB150009)Jiangsu Association for Science and Technology(No.TJ-2023-076)the Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘For chromatographic separation,the reasonable modulation of stationary phases is the key factor to achieve high separation performance.We proposed that developing MOF stationary phases through precisely modulating the thermodynamic interactions between MOFs and analytes is conducive to improving the separation resolution.MIL-125,MIL-125-NH_(2),MIL-143-BTB,and MIL-143-TATB were developed as stationary phases with the careful modulation of organic ligands.MIL-125-NH_(2)and MIL-143-TATB coated columns exhibited much better separation performance than their counterparts,MIL-125 and MIL-143-BTB,respectively.The investigation of the separation mechanism indicated that thermodynamic interaction,rather than kinetic diffusion,was responsible for the separation improvement.MIL-125-NH_(2)and MIL-143-TATB provided stronger and distinguishable interactions with targets than corresponding MIL-125 and MIL-143-BTB,respectively,resulting in enhanced separation performance.This work demonstrates a guide to improving the separation performance of MOF stationary phases by increasing the thermodynamic interactions between MOFs and analytes.
基金Innovation Groups of Basic Research in Gansu Province(No.23JRRA570)。
文摘An ionic liquid assisted hydrogel modified silica was synthesized using a one-pot polymerization and physical coating technique and subsequently applied to mixed-mode liquid chromatography.Analytical techniques,including Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),and elemental analysis,etc.,confirmed the successful prepared of this innovative stationary phase.The unique combination of amide,long alkyl chain,and imidazole ring in the hydrogel coating enables the stationary phase to function effectively in hydrophilic/reversed-phase/ion exchange liquid chromatography.Notably,the stationary phase exhibited superior separation performance owing to the synergistic effect of the ionic liquid and hydrogel.This was particularly evident when analyzing various analytes such as organic acids,nucleosides/bases,polycyclic aromatic hydrocarbons(PAHs)and anions.Furthermore,under our operating conditions,an excellent column efficiency of 53,642.9 plates/m was achieved for theobromine.In summary,we have proposed a straightforward strategy to enhance the separation performance of hydrogel coatings in liquid chromatography,thereby broadening the potential applications of hydrogels in the field of separation.
基金supported by the National Natural Science Foundation of China(Nos.52273002 and 52333008)the funding of Boya Postdoctoral Fellowship at Peking University,BMS Junior Fellow Program and the National Funding Program for Postdoctoral Researchers(No.GZC20230031).
文摘A series of optically active copolymers with various feed ratios have been synthesized through helix-sense-selective copolymerization catalyzed by[Rh(norbornadiene)Cl]2-triethylamine.This process involves two proline-derived acetylene monomers,(S)-N-(4-chlorophenyl)carbamoyl-2-ethynyl pyrrolidine(MCl)and(S)-N-(tert-butoxycarbonyl)-2-ethynyl pyrrolidine,followed by acidic deprotection and neutralization.These copolymers adopt helical conformations with a preferred handedness,as demonstrated by nuclear magnetic resonance spectroscopy and a series of spectroscopic analyses.The chiroptical activity intensity of copolymer has been found to increase with MCl content.Consequently,the enantioseparation capabilities of copolymers containing 95 mol%,90 mol%,and 85 mol%MCl units have been assessed as chiral stationary phases in high-performance liquid chromatography because of their good chiroptical activities.These chiral stationary phases effectively enantioseparate racemic alcohols,sulfoxides,amides,and metal complexes.Notably,the copolymer with 90 mol%MCl shows superior chiral recognition ability,especially for 1-(2,4-dichlorophenyl)-2-(1H-imidazol-1-yl)ethanol(α=1.19)and 4-methylbenzenesulfinamide(α=1.47).Insights from molecular dynamic simulation and autodock analysis indicate that hydrogen bonding andπ-πstacking interactions between the chiral stationary phases and enantiomers play a key role for successful chiral separation.Our contribution not only demonstrates the importance of hydrogen bonding donor and copolymer chiroptical activity of chiral stationary phases for chiral resolution,but will also provide valuable insights for the future development of novel stationary phases.
基金the National Natural Science Foundation of China(No.22274021)Natural Science Foundation of Fujian Province(No.2022J01535)for financial support。
文摘Covalent organic frameworks(COFs)have demonstrated great potential in chromatographic separation because of unique structure and superior performance.Herein,single-crystal three-dimensional(3D)COFs with regular morphology,good monodispersity and high specific surface area,were used as a stationary phase for high-performance liquid chromatography(HPLC).The single-crystal 3D COFs packed column not only exhibits high efficiency in separating hydrophobic molecules involving substituted benzenes,halogenated benzenes,halogenated nitrobenzenes,aromatic amines,aromatic hydrocarbons(PAHs)and phthalate esters(PAEs),but also achieves baseline separation of acenaphthene and acenaphthylene with similar physical and chemical properties as well as environmental pollutants,which cannot be quickly separated on commercial C18 column and a polycrystalline 3D COFs packed column.Especially,the column efficiency of 17303-24255 plates/m was obtained for PAEs,and the resolution values for acenaphthene and acenaphthylene,and carbamazepine(CBZ)and carbamazepine-10,11-epoxide(CBZEP)were 1.7and 2.2,respectively.This successful application not only confirmed the great potential of the singlecrystal 3D COFs in HPLC separation of the organic molecules,but also facilitates the application of COFs in separation science.
文摘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.
基金supported by the National Natural Science Foundation of China (Grant No.40574052)
文摘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.
基金Guangzhou mega Projects of Science Research in 2009(Grant No.2009A1-E011-7)
文摘Effective enantioseparation of Naftopidil and its derivatives by HPLC was accomplished using several different polysaccharide-based chiral stationary phases（CSPs）.In normal-phase mode,the compounds were eluted on four coated-and two immobilized-columns with the mixture of n-hexane,isopropanol and diethylamine（DEA）.Polysaccharide tris（3,5- dimethylphenyl carbamate） was shown to be the best enantiomer selector.In addition,the immobilized column packed with Chiralpak IA or IB was applied under polar-organic and reversed-phase conditions,both of which exhibited excellent enantioselectivity for Naftopidil and its derivatives.Furthermore,the underlying possible chiral recognition mechanisms were discussed.
基金Science and Technology Program of Guangzhou City(Grant No.2010U1-E0531-2)
文摘Six newly synthesized racemic 1-（substituted phenyl）-4-[3-（indole-4-yl-oxy）-2-hydroxypropyl]-piperazine 1-6 were successfully resolved by carbon dioxide supercritical fluid chromatography （SFC） on an analytical scale column packed with immobilized polysaccharide-based chiral stationary phases （CSPs）. We found that separation on the Chiralpak IA CSP was superior to the other two immobilized CSPs （Chiralpak IB and Chiralpak IC）, and isopropanol （IPA） was a superior modifier compared to the other five solvents including ethanol, methanol, tetrahydrofuran, acetonitrile and dichloromethane. The effects of organic modifier composition, back pressure, and column temperature for enantioseparation of all six compounds were studied. Of the physical parameters studied, modifier composition had the greatest impact on retention. Changing temperature generally had less impact on retention but produced the greatest selectivity changes. The optimum condition was found as follows： Chiralpak IA column, column temperature 35 ~C, back pressure 120 bar, 35% IPA containing 0.1% diethylamine （v/v） in mobile phase, flow rate of mobile phase 3.0 mL/min, UV detection 283 nm. Separation of all six racemic compounds was completed within 10 rain and excellent resolution was obtained. Thus, SFC was found to be the methodology of choice for resolving the enantiomers of this class of compounds.
基金The National Natural Science Foundation(Grant No.81373372)Specialized Research Fund for the Doctoral Program of Higher Education of China(Grant No.20130001110059)
文摘It is a new strategy to immobilize cells on the inner wall of a capillary column and use affinity capillary electrophoresis（ACE） to study receptor-ligand interactions or to screen natural products and compounds synthesized by combinatorial chemistry. In this paper, we developed a new method of immobilizing HEK293 cells on the inner wall of a capillary column. Four important experimental conditions were optimized, including cell injection density, PLL concentration, cell culturing time and sterile processing method. Immobilized cell-coated capillary columns prepared under the optimized experimental conditions exhibited good uniformity, stability and durability, which were suitable for capillary electrophoresis. The method could also be used to immobilize HEK293 cells over-expressing certain membrane receptors on the inner wall of a capillary. In this way, cell-coated capillary columns could be applied to ACE drug screening targeting certain membrane proteins.
文摘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.
基金Supported by the National Natural Science Foundation of China(No.30160092)the Natural Science Foundation of Yunnan Province,China(No.2005E0006Z).
文摘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.
基金financially supported by the National Key R&D Program of China (No.2019YFA0904104)。
文摘Chiral covalent organic frameworks(CCOFs) featuring chirality, stability, and good porosity have attracted a considerable amount of attention due to their important applications, such as asymmetric catalysis, chiral separation, and chiral recognition. In this study, a β-cyclodextrin(β-CD) covalent organic framework(β-CD-COF) diluted with polysiloxane OV-1701 was explored as a novel chiral stationary phase(CSP) for gas chromatography(GC) separation of racemates. The β-CD-COF coated capillary column had excellent selectivity, not only for the separation of linear alkanes, linear alcohols, fatty acid methyl esters mixture, the Grob mixture and positional isomers, but also for the resolution of chiral compounds, including chiral alcohols, aldehydes, ethers, and amino acid derivatives. In addition, the β-CD-COF-coated capillary column presented good repeatability and reproducibility. This work indicated the great potential of the CCOFs coated capillary column for the chromatographic separation of enantiomers.
基金supported by the National Science and Technology Special Projects (No.2009zx09301-003-5 -1 and2009zx09301-003-7-1)
文摘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.
基金funded by the National Natural Science Foundation of China(Grant No.:82003705).
文摘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.
基金National Natural Science Foundation and Yunnan Province's Natural Science Foundation of China(No.20775066No.2005E0006Z).
文摘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.
基金the National Natural Science Foundation of China （No. 20472111） is gratefully acknowledged.
文摘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.
基金This study was funded by the Project of National Natural Science Foundation of China(Grant No.:82003705)the Shanghai Science and Technology Innovation Foundation(Grant Nos.:23010500200 and 23ZR1422700).
文摘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).
基金the National Nature Science Foundation of China(No.20675007)
文摘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.
基金supported by the National Natural Science Foundation of China (No. 40674027)CAS outstanding 100 research program,MOST program 2007FY220100
文摘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.
文摘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.
