Comparing columns for gas chromatography with the two-parameter model for retention prediction

The retention times of selected compounds in temperature programmed gas chromatography were predicted using a two-parameter model, on the basis of thermodynamic data obtained from isothermal runs on seven capillary columns, primarily substituted with 5% diphenylsiloxane. The scope for using thermodynamic data obtained from isothermal runs on one column to optimize separation on a different column or a different instrument setup was investigated. Additionally, the predictive utility of thermodynamic data obtained using a DB-5 column that had been in use for three years was compared to that of a new column of the same model. It was found that satisfactory separation could be achieved on one capillary column or instrument setup on the basis of thermodynamic data obtained using a different column or instrument set-up.     

Adsorption in a stratified column bed packed with porous particles having partially fractal structures and a distribution of particle diameters

Stratified column bed systems whose sections are formed by packing adsorbent particles with a partially fractal structure are proposed and studied. The simulation results clearly show that the breakthrough times and the shape of the breakthrough curves obtained from stratified column beds are significantly larger and sharper than those obtained from conventional columns. The stratified column beds provide, to the designer and user of chromatographic column systems, more degrees of freedom with respect to the number of parameters and variables that could be controlled in the design, construction, and operation of efficient chromatographic adsorption systems. Furthermore, the results suggest that the stratified column beds could provide a higher dynamic adsorptive capacity than conventional columns when it is required to increase the column throughput.     

Polyvinylacetate Gel Permeation Chromatography of H-Coal Liquids and Model Compounds. Comparison with Rigid Gel,Reversed Phase and Normal Phase Chromatography

Abstract

This paper reports the application of polyvinylacetate gel (Fractogel) for size fractionation of the H-Coal liquids and model aromatic hydrocarbons. The four H-Coal liquids were each divided into three classes according to solubility in hexane, benzene, and pyridine. A model mixture of eight compounds when applied to the Fractogel column yielded four fractions; a similar performance was given by a prepacked, Toyo Soda microparticulate column containing styrene-divinylbenzene copolymer. Regarding the twelve H-Coal solvent fractions, the chromatograms obtained from the Fractogel column were analogous to those from the Toyo Soda column. By making further use of model compounds, the Fractogel results are compared with those obtained from reversed phase chromatography on a Partisil ODS column and those from normal phase chromatography on a LiChrosorb silica column. These comparisons reveal the usefulness in separating certain aromatic hydrocarbons by the Fractogel column. Furthermore, judging from the chromatograms of a hexane-soluble H-Coal fraction obtained by the reversed phase and normal phase methods, the ODS column will complement the Fractogel column in fractionating the H-Coal liquids.     

Characteristics of elution profile in radial chromatography under linear conditions

Radial chromatography is one of the most efficient tools for the fast analytical and preparative separation of complex samples. Compared to conventional axial liquid chromatography, it has obvious advantage espe- cially in the preparation of biological sa…     

Chromatography in fluidized beds

Summary Chromatography is carried out under the conditions of fluidization, in long, straight tubes under organized and non-organized conditions. Under non-organized conditions the column is filled only with a sorbent. In organized conditions, either metal coils are added into the column or a segmented column is utilized with metal grids. The results obtained are compared to those obtained under fixed-bed conditions when the column is completely filled with the sorbent. Organized fluidized beds provide a significant decrease in longitudinal bandspreading.     

The use of phospholipid modified column for the determination of lipophilic properties in high performance liquid chromatography

A new chromatographic stationary phase obtained by coating a reversed phase amide column with phosphatidylcholine based liposomes solution to yield a phospholipid modified column (PLM). The modification is achieved by the dynamic coating method which recycles the coating solution through the column in a closed loop for a period of 24 h. The chromatographic properties of the new column have changed significantly as compared to the original amide column due to the phospholipid coating. A good correlation was observed between n-octanol/water logP values and the logarithm of the retention factor obtained on the PLM column for a large number of solutes. In addition the PLM column was characterized using the linear solvation energy relationship (LSER). The values of the LSER system constants for the PLM column were calculated and were found to be very close to those of the n-octanol/water extraction system thus suggesting that the PLM column can be used for the estimation of n-octanol/water partition coefficient and serve as a possible alternative to the shake-flask method for lipophilicity determination. In addition, the results suggest that the PLM column can provide an alternative to other phospholipid-based column such as the IAM and the DPC columns.     

新型程序涂渍色谱柱程序效应的研究

新型程序涂渍色谱柱程序效应的研究许鸿生，洪辉（湘潭大学化学系，湘潭，４１１１０５）关键词新型程序柱，程序效应，气相色谱关于程序涂渍色谱柱的问题，国内外研究指数函数程序柱的较多［１～３］，色谱柱涂渍结构改变后，组分的保留行为及柱效能都发生较大变化．作者...     

电填充毛细管色谱柱性能的评价

报道了一种毛细管色谱柱的电填充技术,并进行了柱性能的评价研究。实验表明新的填充方法确保了色谱柱的柱效和重现性。     

Increased productivity in quantitative bioanalysis using a monolithic column coupled with high-flow direct-injection liquid chromatography/tandem mass spectrometry

The feasibility of using a monolithic column as the analytical column in conjunction with high-flow direct-injection liquid chromatography/tandem mass spectrometry (LC/MS/MS) to increase productivity for quantitative bioanalysis has been investigated using plasma samples containing a drug and its epimer metabolite. Since the chosen drug and its epimer metabolite have the same selected reaction monitoring (SRM) transitions, chromatographic baseline separation of these two compounds was required. The results obtained from this monolithic column system were directly compared with the results obtained from a previously validated assay using a conventional C18 column as the analytical column. Both systems have the same sample preparation, mobile phases and MS conditions. The eluting flow rate for the monolithic column system was 3.2 mL/min (with 4:1 splitting) and for the C18 column system was 1.2 mL/min (with 3:1 splitting). The monolithic column system had a run time of 5 min and the conventional C18 column system had a run time of 10 min. The methods on the two systems were found to be equivalent in terms of accuracy, precision, sensitivity and chromatographic separation. Without sacrificing the chromatographic separation, sensitivity, accuracy and precision of the method, the reduced run time of the monolithic column method increased the sample throughput by a factor of two.     

Polybutadiene-coated zirconia packing materials in solvating gas chromatography using carbon dioxide as mobile phase

Summary In this paper, practical considerations of column efficiency, separation speed, thermal stability, and column polarity of capillary columns packed with polybutadiene-coated zirconia were investigated under solvating gas chromatography (SGC) conditions using carbon dioxide as mobile phase. When compared with results obtained from conventional porous octadecyl obtained from conventional porous octadecyl bonded silica (ODS) particles, PBD-zirconia particles produced greater change in mobile phase linear velocity with pressure than conventional ODS particles under the same conditions. The maximum plate number per second (N_t) obtained with a 30 cm PBD-zirconia column was approximately 1.5 times higher than that obtained with an ODS column at 100 °C. Therefore, the PBD-zirconia phase is more suitable for fast separations than conventional ODS particles in SGC. Maximum plate numbers per meter of 76,900 and 63,300 were obtained using a 57 cm×250 μm i.d. fused silica capillary column packed with 3 μm PBD-zirconia at 50 °C and 100 °C, respectively. The PBD-zirconia phase was stable at temperatures up to 320 °C under SGC conditions using carbon dioxide as mobile phase. Polarizable aromatic compounds and low molecular weight ketones and aldehydes were eluted with symmetrical peaks from a 10 cm column packed with 3 μm PBD-zirconia. Zirconia phases with greater inertness are required for the analysis of more polar compounds by SGC.     

一氯醋酸的气相色谱分析

本文详细叙述了用气相色谱分析工业或重结晶—氯醋酸各组分含量、校正因子的方法为求得柱的高效对柱子和固定相进行了特殊处理,实验表明,用该色谱柱可得到令人满意的结果。     

Comparative Study of Packed and Capillary Column Chromatography for the Characterization of Vacuum Gas Oils

Gas chromatographic methods are of widespread use in the petroleum industry for assessing petroleum and derivatives quality. The feedstocks for catcracking processes are very sensitive to the n-paraffin contents, which can be accurately determined using capillary column chromatography. Nevertheless, packed column chromatography does have potential advantages, viz. sometimes shorter analysis times, lower costs, higher column capacity, for vacuum gas oil analysis. This paper presents a method for such a determination using a Dexsil-300 packed column. The results obtained (n-alkane contents, carbon number distribution) agree fairly well with those obtained on a 30 m × 0.25 mm DB-1 fused silica capillary column.     

Preparation of uniformly sized polymeric separation media potentially suitable for small-scale high-performance liquid chromatography and/or capillary electrochromatography.

Uniformly sized polymer particles were prepared by either a two-step swelling and polymerization method or a Shirasu porous glass (SPG) emulsification technique to compare their suitability as a uniformly sized packing material for small-scale high-performance liquid chromatography (HPLC) or capillary electrochromatography (CEC). The SPG emulsification technique afforded slightly worse size uniformity compared to the two-step swelling and polymerization technique. However, fairly nice spherical shapes with reproducible outward appearance and internal pore size distribution were obtained for both of 3- or 6-micron sized particles. On the other hand, the two-step swelling and polymerization method afforded broken particles with quite different outward appearances due to the polymeric porogen effects of seed polymer utilized as the shape template. In HPLC, the column packed with the 3-micron particles prepared with the SPG emulsification technique proved to have a fairly high column efficiency with good column stability, as assessed under repeated use in gradient elution. On the other hand, the column packed with the packing material obtained through the two-step swelling and polymerization method showed much poorer column stability, while initial column efficiency was compatible to that obtained using the SPG emulsification method. In addition, the packing material prepared with the SPG emulsification technique could be modified with ion-exchangeable monomers and showed fairly good column efficiency in the CEC mode.     

Ionic liquids as stationary phase solvents for methylated cyclodextrins in gas chromatography

Summary Room temperature ionic liquids (RTIL) are molten salts with melting points well below room temperature. 1-butyl-3-methylimidazolium chloride is a typical example of such RTIL. It was used as a solvent to dissolve permethylated-β-cyclodextrin (BPM) and dimethylated-?cyclodextrin (BDM) to prepare stationary phases for capillary columns in gas chromatography for chiral separation. The RTIL containing columns were compared to commercial columns containing the same chiral selectors. A set of 64 chiral compounds separated by the commercial BPM column was tested on the RTIL BPM column. Only 21 were enantioresolved. Similarly, a set of 80 compounds separated by the commercial BDM column was passed on the RTIL BDM column with only 16 positive separations. It is proposed that the imidazolium ion pair could make an inclusion complex with the cyclodextrin cavity, blocking it for chiral recognition. All the chiral compounds recognized by the RTIL columns had their asymmetric carbon that was part of a ring structure. The retention factors of the derivatized solutes were lower on the RTIL columns than those obtained on the commercial equivalent column. The peak efficiencies obtained with the RTIL capillary were significantly higher than that obtained with the commercial column. These observations may contribute to the knowledge of the mechanism of cyclodextrin-based GC enantioselective separations.     

Immobilization of Amylases on Silica Support to Study Breakdown Products of Potato Starch by HPLC

Abstract

Immobilization of α- and β-amylases on epoxypropylsilanized PartiSphere-5 was achieved. Hydrolysis of 2% potato starch solution yielded limit dextrin on α-amylase bound column while a mixture of limit dextrin, maltose and glucose was obtained from β-amylase bound column. The β-amylase bound column converted limit dextrin from α-amylase column into glucose.     

原位合成分子筛膜毛细管色谱柱的研制

吸附型多孔层毛细管柱既耐高温又对气体及烃类异构体有选择性，同时又具有毛细管色谱快速、高效等优点，是解决难分离组分的重要柱型．常用作气一固吸附色谱固定相的有强极性的硅、中极性的氧化铝、非极性的碳质及特殊吸附作用的分子筛．其中分子筛以其独特的吸附作用，在永久性气体和烃类碳数族组成分析中有重要地位．Pruecell和Soulages[1，2]等制备了涂渍型5A和13X型分子筛的毛细管柱，对低碳烃类化合物显示了良好的分离能力，分析柱温较填充柱降低约100℃．邹乃忠等[3～5]也先后制备了分子筛层的毛细管柱用来作直馏汽油的分析．由于通…     

In situ synthesis of molecularly imprinted polymers on glass microspheres in a column

A facile method to fabricate molecularly imprinted polymers (MIPs) on glass microspheres in a column was developed. The column was prepacked with glass microspheres, and then the prepolymerization mixture was injected into the interstitial volume of the column. The polymerization took place in situ and the column could be directly used for high-performance liquid chromatography after the template had been removed. The template consumption was reduced greatly because the prepolymerization mixture just filled the interstitial volume between the glass microspheres in the column. The MIPs obtained exhibited better kinetic properties, higher efficiency, and low back pressure of the column. Emodin imprinted polymers were prepared by this method and were used for solid-phase extraction.     

Effect of stationary phase hydrophobicity and mobile phase composition on the separation of carboxylic acids in ion chromatography

In a previous work, we studied the retention behavior of monovalent and divalent carboxylic acids on a highly cross-linked polystryene-divinylbenzene anion-exchange column (IonPac AS4A-SC) using a carbonate-based buffer, and a retention model was applied to the chromatographic data obtained. In this work we characterized the retention of carboxylates (formic, acetic, propionic, lactic, pyruvic, oxalic, malonic, succinic, fumaric, maleic, tartaric, glutaric, adipic, malic, mucic, trans-beta-hydromuconic, trans,trans-muconic acids) on a column with higher hydrophilicity (IonPac AS11) according to analyte and stationary phase properties, using previously investigated eluent compositions and comparing the retention data obtained. Moreover, the effect of organic modifiers (CH3OH and CH3CN) in the eluent on the retention factors was also evaluated. The chromatographic data obtained on the IonPac AS11 column were fitted by the retention model and allowed one to obtain and to compare ion-specific selectivity constants (parameters of the model) with the ones obtained with the previous column.     

On-line simultaneous removal of human serum albumin and enrichment of doxazosin using a weak cation-exchange monolithic column

A weak cation-exchange monolithic column was prepared by modifying the GMA-EDMA (glycidyl methacrylate-co-ethylene glycol dimethacrylate) monoliths with ethylenediamine and monochloracetic acid. The properties of the column were investigated; the column exhibited the ability of low backpressure and fast analysis. Using this monolithic column, trace doxazosin in human serum albumin (HSA) solution and plasma samples has been on-line tested, the extraction efficiency and the maximum loading capacity of the monolithic column were obtained. The results showed that the monolithic column could realize deproteinization and trace drug enrichment simultaneously in the HSA solution and human plasma, which provided a simple, cheap, effective and friendly to environment method for assaying drugs in the blood.