This investigation describes a new precise, sensitive and accurate stereoselective RP-HPLC method for determination of the enantiomers of a novel α- and β-receptor blocking agent, 1-[4-(2-methoxyethyl) phenoxy]-3-...This investigation describes a new precise, sensitive and accurate stereoselective RP-HPLC method for determination of the enantiomers of a novel α- and β-receptor blocking agent, 1-[4-(2-methoxyethyl) phenoxy]-3-[[2-(2- methoxyphenoxy) ethyl]amino]-2-propanol (T J0711), in rat plasma. GITC was used for precolunm derivatization of T J0711 enantiomers. Enantiomeric resolution was achieved on a Eurospher-100 C18 column (250 mm×4.6 mm ID, 5-μm particle size), with UV detection at 255 nm, and the mobile phase consisted of acetonitrile and water (58:42, v/v) containing 0.02% glacial acetic acid (v/v). Using the chromatographic conditions described, T J0711 enantiomers were well resolved with mean retention time of 10.2 and 11.5 min, respectively. Linear response (r〉0.999) was observed over the range of 0.125-12.5 μg/mL of TJ0711 hydrochloride enantiomers. The mean relative standard deviation (RSD%) of the results of within-day precision was ≤ 10%. The proposed method was found to be suitable and accurate for the quantitative determination of T J0711 enantiomers in rat plasma, and it can be used in pharmacokinetic studies.展开更多
The stereoselective hydrolysis of esmolol in whole blood and in its separated components from rat,rabbit and human was investigated.Blood esterase activities were variable in different species in the order of rat>r...The stereoselective hydrolysis of esmolol in whole blood and in its separated components from rat,rabbit and human was investigated.Blood esterase activities were variable in different species in the order of rat>rabbit>human.Rat plasma showed the high esterase activity and had no stereoselectivity to enantiomers.Rabbit red blood cell(RBC) membrane,RBC cytosol and plasma all hydrolyzed esmolol but with different esterase activity,whereas the hydrolysis in RBC membrane and cytosol showed significant stereoselectivity towards R-(+)-esmolol.Esterase in RBC cytosol from human blood mainly contributed to the esmolol hydrolysis,which was demonstrated with no stereoselctivity.Esterase in human plasma showed a low activity,but a remarkable stereoselectivity with R-(+)-esmolol.In addition,the protein concentration affected the hydrolysis behavior of esmolol in RBC suspension.Protein binding of esmolol enantiomers in human plasma,human serum albumin(HSA) and α;-acid glycoprotein(AGP) revealed that there was a significant difference in bound fractions between two enantiomers,especially for AGP.Our results indicated that the stereoselective protein binding might play a role in the different hydrolysis rates of esmolol enantiomers in human plasma.展开更多
A high-performance liquid chromatography coupled with mass spectrometry(HPLC–MS) method was established for the separation and determination of acetyl-glutamine enantiomers(acetylL-glutamine and acetylD-glutamine) si...A high-performance liquid chromatography coupled with mass spectrometry(HPLC–MS) method was established for the separation and determination of acetyl-glutamine enantiomers(acetylL-glutamine and acetylD-glutamine) simultaneously. Baseline separation was achieved on Chiralpak AD-H column(250 mm ×4.6 mm, 5 μm). n-Hexane(containing 0.1% acetic acid) and ethanol(75:25, v/v) were used as mobile phase at a flow rate of 0.6 m L/min. The detection was operated in the negative ion mode with an ESI source. [M-H]-m/z187.0540 for enantiomers and [M-H]-m/z 179.0240 for aspirin(IS) were selected as detecting ions. The linear range of the calibration curve for each enantiomer was 0.05–40 μg/m L. The precision of this method at concentrations of 0.5–20 μg/m L was within 7.23%, and the accuracy was 99.81%–107.81%. The precision at LOQ(0.05 μg/m L) was between 16.28% and 17.56%, which was poor than that at QC levels. The average extraction recovery was higher than 85% for both enantiomers at QC levels. The pharmacokinetics of enantiomers was found to be stereoselective. There was not chiral inversion in vivo or in vitro between enantiomers.展开更多
Aim The present study developed a CYP3A4-expressed Caco-2 monolayer model at which effects of the efflux-metabolism alliance on the transport and uptake of clausenamide(CLA) enantiomers as CYP3A4 substrates were inv...Aim The present study developed a CYP3A4-expressed Caco-2 monolayer model at which effects of the efflux-metabolism alliance on the transport and uptake of clausenamide(CLA) enantiomers as CYP3A4 substrates were investigated. The apparent permeability coefficients (Papp) of ( - ) and ( + )CLA were higher in the ab- sorptive direction than those in the secretory direction with efflux ratios(ER) of 0. 709 ± 0.411 and 0. 867± 0. 250 ( Х10^-6 -1 cm · s ), respectively. Their bidirectional transports were significantly reduced by (75.6 ± 87.5)% af- ter treatment with verapamil ( a P-glycoprotein inhibitor) that increased the rate of metabolism by CYP3 A4, whereas the CYP3A4 inhibitor ketoconazole treatment markedly enhanced the basolateral to apical flux of ( - ) and ( + ) CLA with ERs being 2. 934 ± 1. 432 and 1. 877 ± 0. 148 ( Х 10^-6 cm/s) respectively. These changes could be blocked by the duel CYP3A4/P-glycoprotein inhibitor cyclosporine A, consequently, Papp values for CLA enanti- omers in both directions were significantly greater than those obtained by using verapamil or ketoconazole, and their ERs were similar to those following ( - ) or ( + )-isomer treatment alone. Furthermore, the uptake of ( - )CLA was more than that of ( + )CLA in the transfected cells. Incubation with ketoeonazole decreased the intracellular concentrations of the two enantiomers. This effect disappeared in the presence of a CYP3A4 inducer dexametha- sone. These results indicated that CYP3A4 could influence P-gp efflux, transport and uptake of CLA enantiomers as CYP3A4 substrates and that a duel inhibition to CYP3A4/ P-glycoprotein could enhance their absorption and bioavailability, which provides new insight into the efflux-metabolism alliance and will benefit the clinical pharma- cology of (?) CLA as a candidate drug for treatment of Alzheimer' s disease.展开更多
Gatifloxacin (GFX) is a kind of chiral fluoroquinolones compound due to the methyl group at the C-3 position of the piperazine ring[1]. Although the enantiomers of GFX show similar levels of antimicrobial activity a...Gatifloxacin (GFX) is a kind of chiral fluoroquinolones compound due to the methyl group at the C-3 position of the piperazine ring[1]. Although the enantiomers of GFX show similar levels of antimicrobial activity and pharmacokinetics[2], the other biological activities (i.e., toxicity or enantioselective recognition to various receptors in vivo) of GFX enantiomers have not yet been studied. With this in mind, we developed a rapid and cost-effective high performance liquid chromatographic (HPLC) separation procedure for GFX enantiomers with a pre-column esterification strategy.展开更多
Distribution behavior of terbutaline enantiomers was examined in the aqueous and organic solvent of a two-phase system containing L-dibenzoyltartaric acid and lipophilic phase transfer reagent of Na-tetraphenylborate....Distribution behavior of terbutaline enantiomers was examined in the aqueous and organic solvent of a two-phase system containing L-dibenzoyltartaric acid and lipophilic phase transfer reagent of Na-tetraphenylborate. The influences of pH, organic solvents, concentrations of Na-tetraphenylborate and L-dibenzoyltartaric acid on the partition coefficients and enantioselectivity of terbutaline enantiomers, were investigated. The results show that tetraphenylborate lipophilic anion and terbutaline enantiomers form two lipophilic salt complexes , which facilitates the solubility of the enantiomers in the organic phase. L-dibenzoyltartaric acid forms more stable complexes with enantiomer Ⅱ than with enantiomer I . Enantioselectivity and partition coefficient increase with the addition of the length of alkyl chain of alcohols. pH and concentrations of lipophilic anion and L-dibenzoyltartaric acid influence them obviously and differently.展开更多
A method of high performance liquid chromatographic separation of clausenamide enantiomers with chiral-AGP(α_1-acid glycoprotein) stationary phases has been established.The absolute configurations of(-)clausenami...A method of high performance liquid chromatographic separation of clausenamide enantiomers with chiral-AGP(α_1-acid glycoprotein) stationary phases has been established.The absolute configurations of(-)clausenamide and(+)clausenamide are 3S, 4R,5R,6S and 3R,4S,5S,6R,respectively.The present method has been used to analyze the(-)clausenamide and(+)clausenamide and its analogues such as the major metabolite and synthetic derivatives of clausenamide.展开更多
Enantiomers of a-substituted-(2-pyridyl)-methylarfdnes uere separated on SC -7 gas chromatograph with a 20m×0.25mm Chirasil-Val capIlary column,Carrier gas was nitro- gen or hydrogen.The resolution factors(ri.s) ...Enantiomers of a-substituted-(2-pyridyl)-methylarfdnes uere separated on SC -7 gas chromatograph with a 20m×0.25mm Chirasil-Val capIlary column,Carrier gas was nitro- gen or hydrogen.The resolution factors(ri.s) were 1.02 to 1.06.Enantiomers of pyridyl anines were separated to and near to base line.展开更多
Silica gel thin-layer plates covered with L-arginine and copper acetate were used for the separation of amino acid enantiomers, The chromatographic selectivity and the effects of plate different preparation methods, s...Silica gel thin-layer plates covered with L-arginine and copper acetate were used for the separation of amino acid enantiomers, The chromatographic selectivity and the effects of plate different preparation methods, sample molecular structure and solvent compositions on resolution performance were also discussed.展开更多
Human blood serum of cancer, cancer-recovered and healthy patients contains laevorotatory and dextrorotatory B2 active molecules. The laevorotatory B2 active carriers in patient serum carry information on the cancer s...Human blood serum of cancer, cancer-recovered and healthy patients contains laevorotatory and dextrorotatory B2 active molecules. The laevorotatory B2 active carriers in patient serum carry information on the cancer status while the dextrorotatory B2 active carriers carry information on the recovered and/or healthy patient status. Their magneto-optical characteristic is analysed by the B2 Magneto Optical Circular Birefringence. By applying the MOCB experimental technique, it is possible to differentiate between the cancer and non-cancer patients. The paper introduces a purely molecular physics approach for description of the cancer/recovered and also non-cancer patients status.展开更多
[Objectives]To establish an ultra performance convergence chromatography(UPC2)method to determine the content of enantiomers in(R)-2-methoxyethyl1-(1-phenylethyl)-1H-imidazole-5-carboxylate hydrochloride(ET-26 HCl).[M...[Objectives]To establish an ultra performance convergence chromatography(UPC2)method to determine the content of enantiomers in(R)-2-methoxyethyl1-(1-phenylethyl)-1H-imidazole-5-carboxylate hydrochloride(ET-26 HCl).[Methods]ChiralpakAD-3 chromatographic column(4.6 mm×100 mm,3μm)was used,with 0.1%diethylamine methanol solution-supercritical carbon dioxide(1∶9)as mobile phase;flow rate 2.0 mL/min;back pressure 2000 psi,detection wavelength 240 nm,and column temperature 35℃.[Results]ET-26-HCl was completely separated from the enantiomers,and the linear relationship was good;the detection limit was 1.5μg/mL.[Conclusions]This method is suitable for the determination of the content of enantiomers in ET-26-HCl.展开更多
A packed column supercritical fluid chromatography (SFC) method for the separation of clopidogrel enantiomers on a chiral stationary phase and CO2 with modifier as mobile phase has been developed at an analytical scal...A packed column supercritical fluid chromatography (SFC) method for the separation of clopidogrel enantiomers on a chiral stationary phase and CO2 with modifier as mobile phase has been developed at an analytical scale. Among 11 different 2 stationary phases the Chiral cel OD-H column showed by far the best separation properties. The influence of different modifiers, injection solvents, temperature, and pressure, and density of the fluid, respectively, on the separation behaviour has been studied. It was found that the separation behaviour strongly depends on the type of modifier and the modifier content. Temperature and pressure are of less influence.展开更多
An insoluble β cyclodextrin polymer cross linked with epichlorohydrin was prepared, and its structure was identified with infrared spectrum. Colloid stationary phase was prepared by dissolving the polymer in the mixe...An insoluble β cyclodextrin polymer cross linked with epichlorohydrin was prepared, and its structure was identified with infrared spectrum. Colloid stationary phase was prepared by dissolving the polymer in the mixed solvent of diisopropyl ether, methylene dichloride and benzene and treated for 0.5 h by ultrasonication, and then was coated on a fused silica capillary column. The optimun reaction conditions are as follows: the mole ratio of epichlohydrin to β cyclodextrin is 12.1∶1, reacting at 65 ℃ for 24 h. The Chromatographic performance such as column efficiency, thermal stabilities and polarity were studied, two kinds of disubstituted benzene isomers and eight pairs of enantiomers were separated on the capillary column. The results show that the β cyclodextrin polymer is suitable for use as a capillary gas chromatographic stationary phase, and possess excellent chromatographic properties in separating enantiomers and position isomers.展开更多
In Korea and China,ilaprazole is a widely used proton pump inhibitor in the treatment of gastric ulcers.In this study,a specific and sensitive LC-MS/MS method has been developed and validated for the quantification of...In Korea and China,ilaprazole is a widely used proton pump inhibitor in the treatment of gastric ulcers.In this study,a specific and sensitive LC-MS/MS method has been developed and validated for the quantification of ilaprazole enantiomers in the rat plasma,using R-lansoprazole as the internal standard.The enantioseparation was achieved on a CHIRALPAK AS-RH column(4.6 mm×150 mm,i.d.5 mm),with a mobile phase composed of 10 m M ammonium acetate aqueous solution and acetonitrile(60:40,V/V),at a flow-rate of 0.5 m L/min.The method was validated over the concentration range of 0.5 e300 ng/m L for both,R-and S-ilaprazole.The lower limit of quantification was 0.5 ng/m L for both enantiomers.The relative standard deviation(RSD)of intra-and inter-day precision of R-ilaprazole and S-ilaprazole was less than 10.9%,and the relative error accuracy(RE)ranged fromà0.5%e2.0%.Finally,the method was successfully evaluated in rats in a stereoselective pharmacokinetic study of the ilaprazole racemate.展开更多
Both enantiomers R-1 and S-1 of a chiral C60 derivative were synthesized by the reactions of C60 with 1, 1'-bi-2-naphthol bis(azidoacetates) and characterized by FD-MS, fT-IR,1H NMR, 13C NMR, UV-VIS, CD spectra.
Amino acids(AAs)including D-and L-enantiomers are a group of organic nitrogen species in ambient aerosol.Due to the low abundances of AAs(level of ng/m^(3))and the matrix effects by coexistent components,it is challen...Amino acids(AAs)including D-and L-enantiomers are a group of organic nitrogen species in ambient aerosol.Due to the low abundances of AAs(level of ng/m^(3))and the matrix effects by coexistent components,it is challenging to quantify AA enantiomers in ambient aerosols especially under pollution conditions.In this study,we present an optimized method for analyzing AA enantiomers in atmospheric aerosol samples including a pretreatment process and the detection by high performance liquid chromatography coupled to a fuorescence detector(HPLC-FLD).Matrix effects caused by coexistent chemicals on AA enantiomers analysis in ambient aerosol samples were investigated especially for those collected in pollution episodes.The results revealed that the determination of AA enantiomers is significantly affected by the coexistent organic carbon(as a proxy of organic matter)and water-soluble ion of NH_(4)^(+).To remove the matrix effects,we applied a pretreatment using the solid phase extraction column coupled with alkaline adjustment to sample extract.After pretreatment,18 AAs including 6 pairs of D-and L-enantiomers(i.e.,leucine,isoleucine,valine,alanine,serine,and aspartic acid)can be successfully separated and quantified in aerosol samples by HPLC-FLD.The recoveries are in the range of 67%-106%.This method was successfully applied to the urban aerosol samples from pollution and non-pollution periods for AA enantiomers determination.We suggest that the concentrations of D-AAs and the ratio of D-AA/L-AA are indicative of the contribution of bacterial sources and the infuence of biomass burning.展开更多
This paper presents a new chiral separation technology: two-phase (O/W) recognition chiral extraction. Distribution behavior of α-cyclohexyl-mandelic acid enantiomers was studied in the extraction system with D(L)-is...This paper presents a new chiral separation technology: two-phase (O/W) recognition chiral extraction. Distribution behavior of α-cyclohexyl-mandelic acid enantiomers was studied in the extraction system with D(L)-isobutyl tartrate in 1,2-dichloroethane organic phase and β-CD derivatives in aqueous phase, and the influence of the kind and concentration of extractant and pH on extraction performance was investigated. The experimental results indicate that two-phase (O/W) recognition chiral extraction is of strong chiral separation ability. HP-β-CD, HE-β-CD and Me-β-CD have higher recognition ability for S-CHMA than that for R-CHMA, among which HP-β-CD has the strongest ability; whereas, D-isobutyl tartrate has reversed recognition ability for them. In the extraction system containing HP-β-CD and D-isobutyl tartrate, e.e.% of S-CHMA in aqueous phase reached 27.6% by one stage extraction, and the distribution ratio for R-CHMA(kR) and for S-CHMA(kS) and separation factor (α) are 2.44, 0.89 and 2.49, respectively. Meanwhile, pH and concentration of extractant have great effects on chiral separation ability. Two-phase (O/W) recognition chiral extraction has great significance for preparative separation of racemic compounds.展开更多
In order to obtain a better enantioselectivity of phenylalanine enantiomers and establish the optimal chiral ex- traction conditions, the distribution behavior was investigated in aqueous two-phase systems which were ...In order to obtain a better enantioselectivity of phenylalanine enantiomers and establish the optimal chiral ex- traction conditions, the distribution behavior was investigated in aqueous two-phase systems which were composed of polyethylene glycol and ammonium sulfate containing combinatorial chiral selector: β-cyclodextrin and HP-β-cyclodextrin. The influence of the molar concentration ratio of combinatorial chiral selectors, the total molar concentration of combinatorial chiral selectors, pH value, buffer type and its concentration were thoroughly studied, respectively. The results show that the enantioselectivity reaches 1.53 under the optimal chiral extraction conditions This extraction is a potential economical and effective way for chiral resolution.展开更多
Magnetoelectric(ME)multiferroic materials have unique advantages in low-power and high-density information storage,because they can simultaneously display ferroelectricity and ferromagnetism.However,research on how to...Magnetoelectric(ME)multiferroic materials have unique advantages in low-power and high-density information storage,because they can simultaneously display ferroelectricity and ferromagnetism.However,research on how to construct air-stable highperformance ME single-molecule magnets(SMMs)is nonexistent.Herein,by introducing homochirality while reducing molecular symmetry,two doubledecker Dy(III)enantiomers adopting the polar space group P2_(1) and exhibiting excellent thermal stability were obtained.They displayed zero field SMM behavior with an anisotropy barrier(Ueff)of ca.100 cm^(−1).This work establishes a rational chemical design strategy for crystallizing SMMs in polar space groups and elucidates the direction for future research,that is,engineering small-size high-performance SMMs.展开更多
基金supported by a grant from a science andtechnology research program of Hubei provincial government(No.2003AA301B05)the Wuhan New Drug Development Program(No.20066002103)
文摘This investigation describes a new precise, sensitive and accurate stereoselective RP-HPLC method for determination of the enantiomers of a novel α- and β-receptor blocking agent, 1-[4-(2-methoxyethyl) phenoxy]-3-[[2-(2- methoxyphenoxy) ethyl]amino]-2-propanol (T J0711), in rat plasma. GITC was used for precolunm derivatization of T J0711 enantiomers. Enantiomeric resolution was achieved on a Eurospher-100 C18 column (250 mm×4.6 mm ID, 5-μm particle size), with UV detection at 255 nm, and the mobile phase consisted of acetonitrile and water (58:42, v/v) containing 0.02% glacial acetic acid (v/v). Using the chromatographic conditions described, T J0711 enantiomers were well resolved with mean retention time of 10.2 and 11.5 min, respectively. Linear response (r〉0.999) was observed over the range of 0.125-12.5 μg/mL of TJ0711 hydrochloride enantiomers. The mean relative standard deviation (RSD%) of the results of within-day precision was ≤ 10%. The proposed method was found to be suitable and accurate for the quantitative determination of T J0711 enantiomers in rat plasma, and it can be used in pharmacokinetic studies.
基金supported by National Major Projects of Ministry Science and Technology of China(2011CB710800,2012ZX09506001-004)Zhejiang Education Department(Y200909571)
文摘The stereoselective hydrolysis of esmolol in whole blood and in its separated components from rat,rabbit and human was investigated.Blood esterase activities were variable in different species in the order of rat>rabbit>human.Rat plasma showed the high esterase activity and had no stereoselectivity to enantiomers.Rabbit red blood cell(RBC) membrane,RBC cytosol and plasma all hydrolyzed esmolol but with different esterase activity,whereas the hydrolysis in RBC membrane and cytosol showed significant stereoselectivity towards R-(+)-esmolol.Esterase in RBC cytosol from human blood mainly contributed to the esmolol hydrolysis,which was demonstrated with no stereoselctivity.Esterase in human plasma showed a low activity,but a remarkable stereoselectivity with R-(+)-esmolol.In addition,the protein concentration affected the hydrolysis behavior of esmolol in RBC suspension.Protein binding of esmolol enantiomers in human plasma,human serum albumin(HSA) and α;-acid glycoprotein(AGP) revealed that there was a significant difference in bound fractions between two enantiomers,especially for AGP.Our results indicated that the stereoselective protein binding might play a role in the different hydrolysis rates of esmolol enantiomers in human plasma.
文摘A high-performance liquid chromatography coupled with mass spectrometry(HPLC–MS) method was established for the separation and determination of acetyl-glutamine enantiomers(acetylL-glutamine and acetylD-glutamine) simultaneously. Baseline separation was achieved on Chiralpak AD-H column(250 mm ×4.6 mm, 5 μm). n-Hexane(containing 0.1% acetic acid) and ethanol(75:25, v/v) were used as mobile phase at a flow rate of 0.6 m L/min. The detection was operated in the negative ion mode with an ESI source. [M-H]-m/z187.0540 for enantiomers and [M-H]-m/z 179.0240 for aspirin(IS) were selected as detecting ions. The linear range of the calibration curve for each enantiomer was 0.05–40 μg/m L. The precision of this method at concentrations of 0.5–20 μg/m L was within 7.23%, and the accuracy was 99.81%–107.81%. The precision at LOQ(0.05 μg/m L) was between 16.28% and 17.56%, which was poor than that at QC levels. The average extraction recovery was higher than 85% for both enantiomers at QC levels. The pharmacokinetics of enantiomers was found to be stereoselective. There was not chiral inversion in vivo or in vitro between enantiomers.
文摘Aim The present study developed a CYP3A4-expressed Caco-2 monolayer model at which effects of the efflux-metabolism alliance on the transport and uptake of clausenamide(CLA) enantiomers as CYP3A4 substrates were investigated. The apparent permeability coefficients (Papp) of ( - ) and ( + )CLA were higher in the ab- sorptive direction than those in the secretory direction with efflux ratios(ER) of 0. 709 ± 0.411 and 0. 867± 0. 250 ( Х10^-6 -1 cm · s ), respectively. Their bidirectional transports were significantly reduced by (75.6 ± 87.5)% af- ter treatment with verapamil ( a P-glycoprotein inhibitor) that increased the rate of metabolism by CYP3 A4, whereas the CYP3A4 inhibitor ketoconazole treatment markedly enhanced the basolateral to apical flux of ( - ) and ( + ) CLA with ERs being 2. 934 ± 1. 432 and 1. 877 ± 0. 148 ( Х 10^-6 cm/s) respectively. These changes could be blocked by the duel CYP3A4/P-glycoprotein inhibitor cyclosporine A, consequently, Papp values for CLA enanti- omers in both directions were significantly greater than those obtained by using verapamil or ketoconazole, and their ERs were similar to those following ( - ) or ( + )-isomer treatment alone. Furthermore, the uptake of ( - )CLA was more than that of ( + )CLA in the transfected cells. Incubation with ketoeonazole decreased the intracellular concentrations of the two enantiomers. This effect disappeared in the presence of a CYP3A4 inducer dexametha- sone. These results indicated that CYP3A4 could influence P-gp efflux, transport and uptake of CLA enantiomers as CYP3A4 substrates and that a duel inhibition to CYP3A4/ P-glycoprotein could enhance their absorption and bioavailability, which provides new insight into the efflux-metabolism alliance and will benefit the clinical pharma- cology of (?) CLA as a candidate drug for treatment of Alzheimer' s disease.
基金supported by Guangdong Natural Science Foundation(S2013030013338)the Ph D.Programs Foundation of Ministry of Education of China(20114404130002)Guangdong Planed Program in Science and Technology(cgzhzd0808,2013B051000072,2012A020100002)
文摘Gatifloxacin (GFX) is a kind of chiral fluoroquinolones compound due to the methyl group at the C-3 position of the piperazine ring[1]. Although the enantiomers of GFX show similar levels of antimicrobial activity and pharmacokinetics[2], the other biological activities (i.e., toxicity or enantioselective recognition to various receptors in vivo) of GFX enantiomers have not yet been studied. With this in mind, we developed a rapid and cost-effective high performance liquid chromatographic (HPLC) separation procedure for GFX enantiomers with a pre-column esterification strategy.
文摘Distribution behavior of terbutaline enantiomers was examined in the aqueous and organic solvent of a two-phase system containing L-dibenzoyltartaric acid and lipophilic phase transfer reagent of Na-tetraphenylborate. The influences of pH, organic solvents, concentrations of Na-tetraphenylborate and L-dibenzoyltartaric acid on the partition coefficients and enantioselectivity of terbutaline enantiomers, were investigated. The results show that tetraphenylborate lipophilic anion and terbutaline enantiomers form two lipophilic salt complexes , which facilitates the solubility of the enantiomers in the organic phase. L-dibenzoyltartaric acid forms more stable complexes with enantiomer Ⅱ than with enantiomer I . Enantioselectivity and partition coefficient increase with the addition of the length of alkyl chain of alcohols. pH and concentrations of lipophilic anion and L-dibenzoyltartaric acid influence them obviously and differently.
文摘A method of high performance liquid chromatographic separation of clausenamide enantiomers with chiral-AGP(α_1-acid glycoprotein) stationary phases has been established.The absolute configurations of(-)clausenamide and(+)clausenamide are 3S, 4R,5R,6S and 3R,4S,5S,6R,respectively.The present method has been used to analyze the(-)clausenamide and(+)clausenamide and its analogues such as the major metabolite and synthetic derivatives of clausenamide.
基金The project is supported by National Nature science Foundation of China.
文摘Enantiomers of a-substituted-(2-pyridyl)-methylarfdnes uere separated on SC -7 gas chromatograph with a 20m×0.25mm Chirasil-Val capIlary column,Carrier gas was nitro- gen or hydrogen.The resolution factors(ri.s) were 1.02 to 1.06.Enantiomers of pyridyl anines were separated to and near to base line.
文摘Silica gel thin-layer plates covered with L-arginine and copper acetate were used for the separation of amino acid enantiomers, The chromatographic selectivity and the effects of plate different preparation methods, sample molecular structure and solvent compositions on resolution performance were also discussed.
文摘Human blood serum of cancer, cancer-recovered and healthy patients contains laevorotatory and dextrorotatory B2 active molecules. The laevorotatory B2 active carriers in patient serum carry information on the cancer status while the dextrorotatory B2 active carriers carry information on the recovered and/or healthy patient status. Their magneto-optical characteristic is analysed by the B2 Magneto Optical Circular Birefringence. By applying the MOCB experimental technique, it is possible to differentiate between the cancer and non-cancer patients. The paper introduces a purely molecular physics approach for description of the cancer/recovered and also non-cancer patients status.
文摘[Objectives]To establish an ultra performance convergence chromatography(UPC2)method to determine the content of enantiomers in(R)-2-methoxyethyl1-(1-phenylethyl)-1H-imidazole-5-carboxylate hydrochloride(ET-26 HCl).[Methods]ChiralpakAD-3 chromatographic column(4.6 mm×100 mm,3μm)was used,with 0.1%diethylamine methanol solution-supercritical carbon dioxide(1∶9)as mobile phase;flow rate 2.0 mL/min;back pressure 2000 psi,detection wavelength 240 nm,and column temperature 35℃.[Results]ET-26-HCl was completely separated from the enantiomers,and the linear relationship was good;the detection limit was 1.5μg/mL.[Conclusions]This method is suitable for the determination of the content of enantiomers in ET-26-HCl.
文摘A packed column supercritical fluid chromatography (SFC) method for the separation of clopidogrel enantiomers on a chiral stationary phase and CO2 with modifier as mobile phase has been developed at an analytical scale. Among 11 different 2 stationary phases the Chiral cel OD-H column showed by far the best separation properties. The influence of different modifiers, injection solvents, temperature, and pressure, and density of the fluid, respectively, on the separation behaviour has been studied. It was found that the separation behaviour strongly depends on the type of modifier and the modifier content. Temperature and pressure are of less influence.
文摘An insoluble β cyclodextrin polymer cross linked with epichlorohydrin was prepared, and its structure was identified with infrared spectrum. Colloid stationary phase was prepared by dissolving the polymer in the mixed solvent of diisopropyl ether, methylene dichloride and benzene and treated for 0.5 h by ultrasonication, and then was coated on a fused silica capillary column. The optimun reaction conditions are as follows: the mole ratio of epichlohydrin to β cyclodextrin is 12.1∶1, reacting at 65 ℃ for 24 h. The Chromatographic performance such as column efficiency, thermal stabilities and polarity were studied, two kinds of disubstituted benzene isomers and eight pairs of enantiomers were separated on the capillary column. The results show that the β cyclodextrin polymer is suitable for use as a capillary gas chromatographic stationary phase, and possess excellent chromatographic properties in separating enantiomers and position isomers.
基金the National Key Research and Development Program of China(2017YFC0908600)the National Natural Science Foundation of China(81773817)+1 种基金the National Key R&D Program of China(No.2017YFE0102200)the Fundamental Research Funds for the Central Universities(2017XZZX011-04)。
文摘In Korea and China,ilaprazole is a widely used proton pump inhibitor in the treatment of gastric ulcers.In this study,a specific and sensitive LC-MS/MS method has been developed and validated for the quantification of ilaprazole enantiomers in the rat plasma,using R-lansoprazole as the internal standard.The enantioseparation was achieved on a CHIRALPAK AS-RH column(4.6 mm×150 mm,i.d.5 mm),with a mobile phase composed of 10 m M ammonium acetate aqueous solution and acetonitrile(60:40,V/V),at a flow-rate of 0.5 m L/min.The method was validated over the concentration range of 0.5 e300 ng/m L for both,R-and S-ilaprazole.The lower limit of quantification was 0.5 ng/m L for both enantiomers.The relative standard deviation(RSD)of intra-and inter-day precision of R-ilaprazole and S-ilaprazole was less than 10.9%,and the relative error accuracy(RE)ranged fromà0.5%e2.0%.Finally,the method was successfully evaluated in rats in a stereoselective pharmacokinetic study of the ilaprazole racemate.
文摘Both enantiomers R-1 and S-1 of a chiral C60 derivative were synthesized by the reactions of C60 with 1, 1'-bi-2-naphthol bis(azidoacetates) and characterized by FD-MS, fT-IR,1H NMR, 13C NMR, UV-VIS, CD spectra.
基金supported by the Natural Science Foundation of China (No.41975156)。
文摘Amino acids(AAs)including D-and L-enantiomers are a group of organic nitrogen species in ambient aerosol.Due to the low abundances of AAs(level of ng/m^(3))and the matrix effects by coexistent components,it is challenging to quantify AA enantiomers in ambient aerosols especially under pollution conditions.In this study,we present an optimized method for analyzing AA enantiomers in atmospheric aerosol samples including a pretreatment process and the detection by high performance liquid chromatography coupled to a fuorescence detector(HPLC-FLD).Matrix effects caused by coexistent chemicals on AA enantiomers analysis in ambient aerosol samples were investigated especially for those collected in pollution episodes.The results revealed that the determination of AA enantiomers is significantly affected by the coexistent organic carbon(as a proxy of organic matter)and water-soluble ion of NH_(4)^(+).To remove the matrix effects,we applied a pretreatment using the solid phase extraction column coupled with alkaline adjustment to sample extract.After pretreatment,18 AAs including 6 pairs of D-and L-enantiomers(i.e.,leucine,isoleucine,valine,alanine,serine,and aspartic acid)can be successfully separated and quantified in aerosol samples by HPLC-FLD.The recoveries are in the range of 67%-106%.This method was successfully applied to the urban aerosol samples from pollution and non-pollution periods for AA enantiomers determination.We suggest that the concentrations of D-AAs and the ratio of D-AA/L-AA are indicative of the contribution of bacterial sources and the infuence of biomass burning.
基金Supported by the National Natural Science Foundation of China (Grant No. 20776038)
文摘This paper presents a new chiral separation technology: two-phase (O/W) recognition chiral extraction. Distribution behavior of α-cyclohexyl-mandelic acid enantiomers was studied in the extraction system with D(L)-isobutyl tartrate in 1,2-dichloroethane organic phase and β-CD derivatives in aqueous phase, and the influence of the kind and concentration of extractant and pH on extraction performance was investigated. The experimental results indicate that two-phase (O/W) recognition chiral extraction is of strong chiral separation ability. HP-β-CD, HE-β-CD and Me-β-CD have higher recognition ability for S-CHMA than that for R-CHMA, among which HP-β-CD has the strongest ability; whereas, D-isobutyl tartrate has reversed recognition ability for them. In the extraction system containing HP-β-CD and D-isobutyl tartrate, e.e.% of S-CHMA in aqueous phase reached 27.6% by one stage extraction, and the distribution ratio for R-CHMA(kR) and for S-CHMA(kS) and separation factor (α) are 2.44, 0.89 and 2.49, respectively. Meanwhile, pH and concentration of extractant have great effects on chiral separation ability. Two-phase (O/W) recognition chiral extraction has great significance for preparative separation of racemic compounds.
文摘In order to obtain a better enantioselectivity of phenylalanine enantiomers and establish the optimal chiral ex- traction conditions, the distribution behavior was investigated in aqueous two-phase systems which were composed of polyethylene glycol and ammonium sulfate containing combinatorial chiral selector: β-cyclodextrin and HP-β-cyclodextrin. The influence of the molar concentration ratio of combinatorial chiral selectors, the total molar concentration of combinatorial chiral selectors, pH value, buffer type and its concentration were thoroughly studied, respectively. The results show that the enantioselectivity reaches 1.53 under the optimal chiral extraction conditions This extraction is a potential economical and effective way for chiral resolution.
基金This work was supported by the National Natural Science Foundation of China(no.21871247)the Key Research Program of Frontier Sciences,CAS(no.ZDBSLY-SLH023)+2 种基金the Key Research Program of the Chinese Academy of Sciences(no.ZDRW-CN-2021-3-3)the Academy of Finland(grant no.332294)Computational resources were provided by CSC-IT Center for Science in Finland and the Finnish Grid and Cloud Infrastructure(persistent identifier urn:nbn:fi:research-infras-2016072533).
文摘Magnetoelectric(ME)multiferroic materials have unique advantages in low-power and high-density information storage,because they can simultaneously display ferroelectricity and ferromagnetism.However,research on how to construct air-stable highperformance ME single-molecule magnets(SMMs)is nonexistent.Herein,by introducing homochirality while reducing molecular symmetry,two doubledecker Dy(III)enantiomers adopting the polar space group P2_(1) and exhibiting excellent thermal stability were obtained.They displayed zero field SMM behavior with an anisotropy barrier(Ueff)of ca.100 cm^(−1).This work establishes a rational chemical design strategy for crystallizing SMMs in polar space groups and elucidates the direction for future research,that is,engineering small-size high-performance SMMs.