高效液相色谱直接光学拆分手性农药(英文)

Enantiomer separation is one of the most important prerequisites for the investigation of environmental enantioselective behavior for chiral pesticides.The enantiomeric separation of three chiral pesticides,indoxacarb,lambda-cyhalothrin,and simeconazole,were studied on cellulose tris-(3,5-dimethylphenyl-carbamate)-coated chiral stationary phase(CDMPC-CSP) using high-performance liquid chromatography under normal phase condition.The effects of chromatographic conditions,such as the mobile phase composition including the concentration and type of alcohol modifiers in hexane,flow rate and column temperature,on enantiomer separation were examined.The thermodynamical mechanism of enantioseparation and chiral recognition mechanism were discussed.Better separation were achieved using 20% n-propanol for indoxacarb,2% iso-butanol for lambda-cyhalothrin,and 20% iso-propanol for simeconazole as modifiers in hexane at 25℃ with the selectivity factor(a) of 1.69,1.82 and 1.70,respectively.The resolution factor(Rs) decreased as the flow rate increased from 0.4 to 1.1 ml·min-1.The retention factor(k’) and selectivity factor for the enantiomers of analytes decreased as temperature increased.The lna-1/T plots for racemic chiral pesticides were linear in the range of 15-35℃ in hexane/iso-propanol and the chiral separation was controlled by enthalpy.Hydrogen bonding,π-π and dipole-dipole interactions between enantiomers and CDMPC-CSP play an important role in chiral identification,and the fitting of the asymmetric portion of solutes in a chiral cavity or channel of the CSP is also important.     

Kinetics of lipase catalyzedenantioselective esterification of racemic ibuprofen in isooctane

The kinetics of Candida rugosa lipase catalyzed esteritlcation of racemic ibuprofen with n-butanol in isooctane was studied. The kinetic study was carried out with the addition of 0.1% and 2% (by volume) of water for enzyme activation respectively when celite was added into isooctane for enzyme dispersion. The specific initial rate for S-ibuprofen can be fitted with the Ping Pong Bi Bi mechanism with dead-end competitive inhibition by the alcohol. The time courses of the enantioselective esteriflcation of the two ibuprofen enantiomers with different initial substrate concentrations and water contents were simulated with a model in which both effects of enzyme inactivation by long term reaction and reversed hydrolytic reaction under high water content were taken into consideration.     

Quantitative determination of triacylglycerol profile of structured lipid by capillary supercritical fluid chromatography and high-temperature gas chromatography

Two analytical methods have been developed for the qualitative and quantitative analyses of triacylglycerol profile of structured lipid (SL)-containing medium-chain and long-chain fatty acids. Supercritical fluid chromatography (SFC) was used in the first method. The SL was dissolved in chloroform/methanol, 95:5 (vol/vol), and analyzed directly using a super-critical fluid chromatograph equipped with temperature and density programming capabilities. No derivatization was required for sample preparation. An SB-methyl-100 capillary column (10 m, 100 μ i.d., 0.25 μ film thickness) was used for the separation of the triacylglycerol species and a flame-ionization detector (FID) was used for the detection. Supercritical fluid carbon dioxide was used as the mobile phase. In the second method, the SL was hydrogenated to complete saturation prior to analysis using gas chromatography at high temperatures of up to 375°C. A DB-5HT capillary column (30 m × 0.32 mm i.d., 0.1 μ film thickness) was used for the separation. FID was used for the detection and helium gas was used as mobile phase. The triacylglycerol species were separated and identified based on their equivalent carbon number (ECN), the total carbon number of the acyl side chains. A calibration curve was constructed using a triacylglycerol mixture containing known amounts of monoacyltriacylglycerol standard materials ranging from ECN 18 (trihexanoin) to ECN 66 (tridocosanoin). The novel triacylglycerol species, ECN 32–43, created by the interesterification of medium-chain triacylglycerol (MCT) and long-chain triacylglycerol (LCT) were separated and identified based on their retention times. These triacylglycerols, ECN 32–43, were absent in the physical mixture of MCT and LCT. The unique triacylglycerol specieis, ECN 32-43, were therefore selected as the fingerprinting region for the qualitative identification of the SL. Quantitation of the novel triacylglycerol species in the SL was achieved by using the integrated peak area of the new species. Both methods were employed successfully to distinguish the physical mixture from the corresponding interesterified SL. Results generated by the two methods were compared and found to be in good agreement.     

模拟移动床色谱手性分离过程的非线性非理想模型

A non-linear non-ideal model,taking into account non-linear competitive isotherms,axial disperison,film mass transfer,intraparticle diffusion,and port periodic switching,was developed to simulate the dynamics of simulated moving bed chromatography(SMBC),The model equations were solved by a new efficient numerical technique of orthogonal collocation on finite elements with periodical movement of conceantration vector,The simulated SMBC performance is in accordance with the experimental results reported in the literature for separation of 1,1‘‘‘‘‘‘‘‘-bi-2-naphtol enantiomers using SMBC,This model is useful for design,operation ,optimization and scale-up of non-linear SMBC for chiral separations with significant non-ideal effects,especially for high solute concentration and small intraparticle diffusion coefficient or large chiral stationary phase particle.     

Enantioseparation of 3-chlorophenylglycine enantiomers using Mandyphos-Pd as chiral extractant

Chiral extractant plays a key role in chiral extraction, and considerable efforts have been undertaken for the development of new and efficient chiral extractants in recent years. This work demonstrated for the first time that chiral ferrocenyl diphosphine ligand(Mandyphos-Pd) had considerable ability to enantioseparate 3-Chlorophenylglycine enantiomers with separation factor(α) of 2.64. Mandyphos-Pd concentration and p H had significant influences on enantioselectivity, while operating temperature showed less influence. The extraction experiments can be performed at room temperature(20 °C) which had the advantage of energy saving. After optimization, the highest performance factor(pf, 0.08376) was obtained at the condition of p H 7.8 and Mandyphos-Pd concentration 1.2 mmol·L~(-1). According to the experimental results, the possible recognition mechanism was discussed.     

水溶性β-环糊精反应萃取分离苯基琥珀酸对映体的平衡研究

This paper deals with the enantioseparation of phenylsuccinic acid (H2A) enantiomers by liquid-liquid reactive extraction using β-CD derivatives as aqueous selectors. Cyclodextrin and its derivatives can interact with guest molecules selectively to form complexes with different stabilities. Cyclodextrin derivatives are not soluble in organic liquids, but highly soluble in water. In this work, hydroxypropyl-β-cyclodextrin (HP-β-CD), hydroxyethyl- β-cyclodextrin (HE-β-CD) and methyl-β-cyclodextrin (Me-β-CD) were selected as chiral selectors in aqueous phase for the reactive extraction of phenylsuccinic acid enantiomers from organic phase to aqueous phase. The results show that the efficiency of the extraction depends, often strongly, on a number of process variables, including the types of organic solvents and β-CD derivatives, the concentrations of the extractants and H2A enantiomers, pH and temperature. HP-β-CD, HE-β-CD and Me-β-CD have stronger recognition abilities for R-phenylsuccinic acid than for S-phenylsuccinic acid. Among the three kinds of β-CD derivatives, HP-β-CD has the strongest separation ability. Excellent enantio-separation was achieved under the optimal conditions of pH of 2.5 and temperature of 5°C with a maximum enantioselectivity (a) of 2.38. Reactive extraction of enantiomers with hydrophilic β-CD derivatives is of strong chiral separation ability and can be hopeful for separations of various enantiomers at a large-scale.     

Hybridization of metal–organic framework and monodisperse spherical silica for chromatographic separation of xylene isomers

Metal–organic frameworks(MOFs) packed in the column have been a promising candidate as the stationary phase for high performance liquid chromatography(HPLC). However, the direct packing of irregular MOF powder could raise some problems like high back pressure and low column efficiency in the HPLC separation. In this work, UiO-66 capable of separating xylenes was supported effectively on the surface of the monodisperse spherical silica microspheres by one-pot method. The hybridization of Ui O-66 and silica microspheres(termed UiO-66@SiO_2 shell–core composite) was prepared by stirring the suspension of the precursors of Ui O-66 and\\COOH terminated silica in the N,N-dimethylformamide with heating. The shell–core composite material UiO66@SiO_2 was characterized by SEM, TEM, PXRD and FTIR. Then, it was used as a packing material for the chromatographic separation of xylene isomers. Xylene isomers including o-xylene, m-xylene and p-xylene were efficiently separated on the column with high resolution and good reproducibility. Moreover, the Ui O-66@SiO_2 shell–core composites packed column still remained reverse shape selectivity as Ui O-66 possessed, and the retention of xylenes was probably ascribed to the hydrophobic effect between analytes and the aromatic rings of the Ui O-66 shell. The Ui O-66@SiO_2 shell–core composites obtained in this study have some potential for the separation of structural isomers in HPLC.     

Quality Control of 1-Alkyl-3-methylimidazolium Ionic Liquid Precursors with HPLC

A high performance liquid chromatography (HPLC) method was proposed to monitor the synthesis and purification of the 1-alkyl-3-methylimidazolium ionic liquid precursors from alkylation of 1-methylimidazole with alkyl halides and determine the purity of final products. The results showed that separation of 1-methylimidazole from the precursors could be obtained under the HPLC performance conditions such as cation exchange column, acetonitrile/KH2PO4 aqueous solution and 209 nm wavelength. The content of unreacted 1-methylimidazole in the precursors could be easily calculated from their corresponding HPLC peak areas with the calibration curve of 1-methylimidazole. The retention times of the 1-alkyl-3-methylimidazolium ionic liquid precursors decreased with their increasing alkyls, and the ionic liquids with the same cation and different anions had almost the same retention times.     

快速纯化在大肠杆菌中表达的增强型绿色荧光蛋白

As an excellent reporter molecule, enhanced green fluorescent protein （eGFP） was widely used for gene expression and regulation and was generally expressed in Escherichia coli strain. A rapid procedure consisting of ammonium sulfate precipitation, size exclusion chromatography, and anion exchange chromatography was developed for the purification of eGFP. Based on the proposed procedure, recombinant eGFP with an electrophoretic purity was achieved in combination with an overall yield of 66% and a purification factor of 17.9. The fluorescent spectrometry of purified eGFP and lysate from E. coli strain expressing eGFP exhibited the same wavelength of excitation and emission maxima, indicating that the purification procedure did not influence the construct and fluorescent characteristics of desired protein. The procedure mentioned was easy to scale up for the purification of large quantities of eGFP.     

THEORY FOR STEP AND PULSE METHOD OF SUPERCRITICAL FLUID CHROMATOGRAPHY

1 INTRODUCTIONSupercritical fluid chromatography(SFC),employing supercritical fluid as mobilephase,originated in the 1960's [1-4].Since 1980's extensive research work has beenperformed on SFC,chiefly for analytical purposes [5,6].SFC was then adopted for thedetermination of thermodynamic properties such as partial molar volume,and partialmolar enthalpy of solutes in both mobile phase and stationary phase and the solutedistribution coefficient between two phases [7- 11].Partial molar properties can be de-     

拟除虫菊酯类农药在超临界流体色谱中的对映体分离

[目的]获得单一对映体对于低毒高效的农药生产和环境安全具有重要意义。[方法]使用超临界CO2色谱,对6种拟除虫菊酯类农药在Sino-Chiral OJ柱上进行对映体分离研究,考察了改性剂种类(甲醇、乙醇和异丙醇)及体积分数(1%、3%、5%)对其分离的影响。[结果]高效氯氟氰菊酯在3种改性剂条件下都得到了基线分离;氯菊酯只在甲醇作为改性剂时得到分离;氰戊菊酯只在3%乙醇改性条件下实现部分分离;氯氰菊酯在乙醇作为改性剂时取得了最优分离,得到8个异构体中的7个出峰;联苯菊酯和溴氰菊酯均只得到2个对映体出峰。[结论]在手性分离过程中,对映体与手性固定相之间的偶极-偶极和π-π作用对菊酯类农药的分离起较大作用,同时卤素取代基的电负性大小对分离也有较大影响。     

用于制备规模的超临界流体色谱分离对映体受到青睐

综述了超临界流体色谱应用于手性药物的进展。超临界流体色谱正在从单纯地对对映体进行鉴定的分析规模,转向能生产几毫克到几百克物质的半制备或制备规模。快速筛选手性固定相和调节剂是成功应用超临界流体色谱于制备过程的关键。     

超(亚)临界流体色谱拆分布洛芬对映体的热力学

引　言布洛芬 (ibuprofen) ,化学名 (RS) 2 (4 异丁基苯基 )丙酸 ,属非甾体抗炎药 ,兼具明显的解热、镇痛作用 ,其α位含有一个手性碳原子 ,如图 1所示 ,存在一对光学异构体 ,其中S ( ) 构　型具有生理活性 ,而R (- ) 构型活性低或无活性[1] .Fig 1　Structureofibuprofen　　　超临界CO2 通常用于萃取[2 ] .利用超临界CO2作流动相 ,采用色谱方法分离混合物是最近几年才出现的新技术[3] .利用手性固定相的高效液相色谱法直接拆分布洛芬对映体已有报道[4 ] .而超 (亚 )临界流体色谱法由于具有体系的黏度低、扩散和传质速率高、拆分…     

超临界流体色谱法测定固体在二氧化碳中的溶解度

开发了一种测定超临界二氧化碳中大分子溶质的溶解度的方法。这一方法将微型超微界流体萃取直接与超临界色谱相耦合，超临界流体色谱采用ＦＩＤ作为检测器。实验中两者具有同一压力、温度及同样的ＣＯ２流速度。     

超临界CO2色谱拆分手性农药的研究进展

综述了国内外超临界CO2色谱拆分手性农药的研究进展,概述了超临界CO2技术的优越性以及色谱的手性固定相、流动相和操作条件,并介绍了制备型超临界CO2色谱的应用.     

Distribution of solutes between polymer and supercritical fluid by inverse supercritical fluid chromatography

Two methods of inverse supercritical fluid chromatography (ISFC), frontal analysis supercritical fluid chromatography (SFC) and elution SFC, have been compared for the determination of distribution coefficients of solutes between a polymer and a supercritical CO₂. The logarithm of the distribution coefficient showed monotonic decrease with the density of the supercritical fluid (SF). The abnormal-maximum behavior of solute sorption in the polymer phase was explained by the fluid and solute properties, ϕ₂P/P ₂ ^sat . Interesting open-elliptic shapes of sorption and volume-fraction curves were obtained and explained with the fugacity coefficient. Correction to the capacity factor was employed to eliminate the retention due to the adsorption on the surface of the silica support. A model based on the Flory equation and the Peng-Robinson equation of state (EOS) successfully predicted the phase behavior of the ternary solutesupercritical fluid-polymer systems using only interaction parameters obtained from the binary systems. The solute distribution coefficient at infinite dilution was used to calculate the phase equilibrium at finite concentration using a ternary-phase diagram.     

5种芳氧苯氧丙酸类除草剂的超临界色谱手性分离

[目的]获得单一的高效异构体对于提高农药药效和减少环境污染具有重要意义。[方法]采用Sino-ChiralOJ柱在超临界色谱中以CO2为流动相对5种芳氧苯氧丙酸类除草剂进行手性分离。探索了系统温度(25-45℃)、流动相改性剂(甲醇、乙醇或异丙醇)及添加量(5%-15%)对分离效果的影响。[结果]唑禾草灵、吡氟禾草灵、喹禾灵获得了完全分离,其最大分离度分别为11.66、1.48、8.34,而禾草灵酸和吡氟氯禾灵均未获得分离。[结论]随着改性剂添加量的增大,唑禾草灵、吡氟禾草灵、喹禾灵的容量因子和分离度逐渐减小,而分离因子基本保持不变。在同一改性剂添加量下,容量因子按甲醇-乙醇-异丙醇的顺序基本逐渐增大,而分离因子基本保持不变。随着系统温度的升高,容量因子逐渐增大,分离因子和分离度逐渐减小。各物质结构上的差异导致分离效果不同。     

Supercritical fluid chromatography of North American ginseng extract

Supercritical fluid chromatography (SFC) using supercritical carbon dioxide (scCO₂) is considered as a “green” separation method, particularly suitable for the isolation of thermally unstable bioactive components. However, co-solvent and additives are often required in the mobile phase due to the poor solubility of polar components in scCO₂. In the present study, the effect of temperature and pressure on the separation of ginsenosides was studied with methanol being added to the CO₂ mobile phase. Acidic, basic, and ionic additives were introduced to the mobile phase, respectively, to study their effect on the separation of ginsenosides. The best separation conditions were achieved by adding trifluoroacetic acid in methanol (0.05% v/v) at 50 °C and 150 bar. A high-concentration component in the extracts from the supercritical fluid extraction of North American ginseng was isolated by SFC and identified as sucrose using NMR, HPLC, and ESI-MS. These results show that SFC is a promising technique for the separation, isolation, and identification of ginseng extracts.     

Separation of crude palm oil components by semipreparative supercritical fluid chromatography

Successful separation of triglycerides, diglycerides, free fatty acids, carotenes, tocopherol, and tocotrienols from crude palm oil has been achieved by supercritical fluid chromatography (SFC) with a combination of a C18 and a silica gel column. The separation was carried out by the programmed extraction elution method. Free fatty acids were separated into five components by gas-liquid chromatography; tocopherol and tocotrienols were also separated into four components by SFC analysis, and the pure fractionated carotenes were obtained by preparative SFC. Thus, by using supercritical fluid chromatography, crude palm oil components can be separated and fractionated, based on differences in their functional groups.     

Optimization of experimental parameters for separation of nonionic surfactants by supercritical fluid chromatography

A synthetic polymer generally consists of a mixture of many compounds that share the same repeating unit but have different degrees of polymerization. Because of its ability to cope with a wide range of molecular weights, supercritical fluid chromatography (SFC) is a powerful technique for separating the individual components of polymers. However, the separation conditions for SFC are more sensitive than those of other types of chromatography, and many experimental parameters need to be carefully selected to achieve high resolutions. Methods for optimizing the experimental parameters for SFC of a polymeric surfactant were investigated by chemometric techniques. Increases or decreases in peak resolution and elution times were measured for the separation by SFC of the nonionic surfactant poly(ethylene glycol) nonylphenyl ether for various column temperatures, flow-rate gradients of modifier, and modifier compositions. To maximize the separation efficiency, the experimental results were analyzed by using the chromatographic response function (CRF). This is a function of the desired peak resolution, the maximum acceptable elution time, and an arbitrary weighting factor that is adjusted to achieve an optimal balance between the peak separation and the elution time. Because the numerical value of the CRF changes in response to the chromatographic performance, it provides a means of identifying the conditions for achieving optimal separation for a particular SFC system.