Evaluation of the separation characteristics of application-specific (pesticides and dioxins) open-tubular columns for gas chromatography

The solvation parameter model is used to characterize the retention properties of four application-specific open-tubular columns (Rtx-CLPesticides, Rtx-OPPesticides, Rtx-Dioxin and Rtx-Dioxin2) at five equally spaced temperatures over the range 60-140 degrees C. Cluster analysis is used to compare the system constants to a database of forty open-tubular columns characterized according to the same method. System constants differences and retention factor correlation plots are then used to determine selectivity differences between the application-specific columns and their nearest neighbors identified by cluster analysis. The Rtx-CLPesticides and Rtx-OPPesticides columns are shown to belong to the selectivity group containing poly(dimethylmethyltrifluoroprpylsiloxane) stationary phases with Rtx-OPPesticides having a similar selectivity to a poly(dimethylmethyltrifluoropropylsiloxane) stationary phase containing 20% methyltrifluoropropylsiloxane monomer (DB-200) and Rtx-CLPesticides separation properties for a stationary phase containing less than 20% methyltrifluoropropylsiloxane monomer. The Rtx-Dioxin and Rtx-Dioxin2 columns are located in the selectivity group dominated by the poly(dimethyldiphenylsiloxane) stationary phases containing less than 20% diphenylsiloxane monomer. The Rtx-Dioxin and Rtx-Dioxin2 columns are shown to be selectivity equivalent to a (5% phenyl) carborane-siloxane copolymer stationary phase (Stx-500) and a second generation silarylene-siloxane copolymer stationary phase containing dimethylsiloxane and diphenylsiloxane monomers (DB-XLB), respectively.     

Solvation molar enthalpies and heat capacities of n-alkanes and n-alkylbenzenes on stationary phases of wide-ranging polarity

A comparison of the most usual gas chromatographic methods for the calculation of partial molar enthalpies of solvation (Δ(sol)H(o)) has been carried out. Those methods based on the fitting of lnV(g) or ln(k/T) vs. 1/T and ln(k/T) vs. (1/T and the temperature arrangement, T(a)) are the most adequate ones for obtaining Δ(sol)H(o) values. However, the latter is the only reliable option for Δ(sol)H(o) estimation when commercial WCOT capillary columns are used, since in this case the estimation of some variables involved in the V(g) determination is less accurate or even impossible. Consequently, in this paper, Δ(sol)H(o) obtained from ln(k/T) vs. (1/T+T(a)) fitting at 373.15 and 298.15K for n-alkanes and n-alkylbenzenes on 12 commercial capillary columns coated with stationary phases covering the 203-3608 McReynolds polarity range are reported. Moreover, molar heat capacities of solvation at constant pressure (Δ(sol)C(p)(o)) have also been calculated using this method. A clear influence on Δ(sol)H(o) of the type and content of the substitution group in the stationary phase was observed. In addition, a linear relationship of Δ(sol)C(p)(o) with the van der Waals volume of the n-alkanes and the temperature gradient of density of the stationary phase was found. The effect of the size of the hydrocarbon on both thermodynamic variables was also investigated.     

Stationary phase optimized selectivity liquid chromatography: Basic possibilities of serially connected columns using the "PRISMA" principle

A new procedure (stationary phase optimized selectivity liquid chromatography: SOS-LC) is described for the optimization of the HPLC stationary phase, using serially connected columns and the principle of the "PRISMA" model. The retention factors (k) of the analytes were determined on three different stationary phases. By use of these data the k values were predicted applying theoretically combined stationary phases. These predictions resulted in numerous intermediate theoretical separations from among which only the optimal one was assembled and tested. The overall selectivity of this separation was better than that of any individual base stationary phase. SOS-LC is independent of the mechanism and the scale of separation.     

Evaluation of the separation characteristics of application-specific (volatile organic compounds) open-tubular columns for gas chromatography

The solvation parameter model is used to characterize the separation characteristics of two application-specific open-tubular columns (Rtx-Volatiles and Rtx-VGC) and a general purpose column for the separation of volatile organic compounds (DB-WAXetr) at five equally spaced temperatures over the range 60-140 degrees C. System constant differences and retention factor correlation plots are then used to determine selectivity differences between the above columns and their closest neighbors in a large database of system constants and retention factors for forty-four open-tubular columns. The Rtx-Volatiles column is shown to have separation characteristics predicted for a poly(dimethyldiphenylsiloxane) stationary phase containing about 16% diphenylsiloxane monomer. The Rtx-VGC column has separation properties similar to the poly(cyanopropylphenyldimethylsiloxane) stationary phase containing 14% cyanopropylphenylsiloxane monomer DB-1701 for non-polar and dipolar/polarizable compounds but significantly different characteristics for the separation of hydrogen-bond acids. For all practical purposes the DB-WAXetr column is shown to be selectivity equivalent to poly(ethylene glycol) columns prepared using different chemistries for bonding and immobilizing the stationary phase. Principal component analysis and cluster analysis are then used to classify the system constants for the above columns and a sub-database of eleven open-tubular columns (DB-1, HP-5, DB-VRX, Rtx-20, DB-35, Rtx-50, Rtx-65, DB-1301, DB-1701, DB-200, and DB-624) commonly used for the separation of volatile organic compounds. A rationale basis for column selection based on differences in intermolecular interactions is presented as an aid to method development for the separation of volatile organic compounds.     

Investigation of polar stationary phases for the separation of sympathomimetic drugs with nano-liquid chromatography in hydrophilic interaction liquid chromatography mode

In this study, the retention and selectivity of a mixture of basic polar drugs were investigated in hydrophilic interaction chromatographic conditions (HILIC) using nano-liquid chromatography (nano-LC). Six sympathomimetic drugs including ephedrine, norephedrine, synephrine, epinephrine, norepinephrine and norphenylephrine were separated by changing experimental parameters such as stationary phase, acetonitrile (ACN) content, buffer pH and concentration, column temperature. Four polar stationary phases (i.e. cyano-, diol-, aminopropyl-silica and Luna HILIC, a cross-linked diol phase) were selected and packed into fused silica capillary columns of 100 μm internal diameter (i.d.). Among the four stationary phases investigated a complete separation of the all studied compounds was achieved with aminopropyl silica and Luna HILIC stationary phases only. Best chromatographic results were obtained employing a mobile phase composed by ACN/water (92/8, v/v) containing 10 mM ammonium formate buffer pH 3. The influence of the capillary temperature on the resolution of the polar basic drugs was investigated in the range between 10 and 50 °C. Linear correlation of ln k vs. 1/T was observed for all the columns; ΔH° values were negative with Luna HILIC and positive with aminopropyl- and diol-silica stationary phases, demonstrating that different mechanisms were involved in the separation.To compare the chromatographic performance of the different columns, Van Deemter curves were also investigated.     

Packing procedures for high efficiency, short ion-exchange columns for rapid separation of inorganic anions

An optimised packing procedure for the production of high efficiency, short, particle-packed ion-exchange columns is reported. Slurry-packing techniques were applied to a series of interconnected short columns, with the columns situated intermediate between the inlet and outlet ends of the series being used for separations. The fast separation and determination of inorganic anions was achieved using short (4mm ID, 30mm long) columns packed with Dionex AS20 high-capacity anion-exchange stationary phase. Seven inorganic anions (bromate, chloride, chlorate, nitrate, sulfate, chromate and perchlorate) are separated in 2.6min using a hydroxide gradient and a flow-rate of 1.8mL/min (total analysis time including re-equilibration was 3.5min). Under isocratic conditions, the home-packed columns exhibited efficiency values of 43,000N/m for chloride at a flow-rate of 0.3mL/min, compared to 54,000N/m for a commercial 250mm AS20 column at the same flow-rate. However, the short columns gave approximately a threefold higher sample throughput. The short, home-packed columns could be produced reproducibly and gave consistent performance over extended periods of usage.     

Determination of void/dead volume of liquid chromatographic columns containing β-cyclodextrin as the stationary phase. Part II. A new graphical method

Summary A new graphical method is proposed for the determination of the dead/void volume of liquid chromatographic columns with -cyclodextrin stationary phase. Two different approaches are presented which lead to very similar dead volume values for the cyclodextrin columns. The validity of the proposed method is discussed on the basis of column porosity values, as well as the resulting linear relationship between the logarithm of the capacity factor and the number of carbon atoms in the n-alkanol homologs. The method was applied to study the influence of various experimental parameters on the dead volume of cyclodextrin columns.     

Comparison of normal-phase and reversed-phase gravity-flow column methods for provitamin A determination

Summary Considering the high cost of HPLC, the use of preparative C₁₈ packing material as stationary phase in classical gravity-flow columns is proposed as an alternative for developing countries. In the present study, three methods were compared, one utilizing a normal-phase MgO: HyfloSupercel column, developed with increasing concentration of acetone in petroleum ether and two utilizing C₁₈ reversed-phase columns developed with acetonitrile-methanol-chloroform (RP-C₁₈ method) or with decreasing concentration of water in acetone (modified RP-C₁₈ method). Percent recoveries of -carotene from the columns were 98, 96 and 98% and of the entire analysis (-carotene added to kale) 92, 89 and 92%, for the normal phase, RP-C₁₈ and modified RP-C₁₈ methods respectively. No significant difference was observed in the provitamin A contents (exclusively -carotene) of two leafy vegetables determined by the modified reversed-phase and normal-phase methods; however, significantly lower values were obtained by the RP-C₁₈ method. The situation became more complicated when samples containing other provitamins were analyzed. For squash both types of stationary phase could separate - and -carotene; however, for tomato and red-fleshed papaya, part of lycopene remained mixed with -carotene in both reversed-phase columns. Although -cryptoxanthin was separated in the modified RP column, it was also mixed with lycopene in the RP column. For all samples, the normal-phase column demonstrated much better separation.     

The efficiency of open tubular gas chromatographic columns part II. A comparison of theoretical equations for the efficiency of support coated open tubular columns

Summary A detailed comparison is given of the various equations derived by Golay and that derived by Hawkes for assessing the theoretical efficiency of SCOT columns.The terms in these equations which describe the resistance to mass transfer in both the gas phase and in the liquid phase are given in a form which permits the equations to be compared directly.A numerical comparison is then made of the potential efficiency predicted by the different equations for five partition ratio values for a set of nine idealized SCOT columns with a wide range of porous layer thickness and liquid loading. The potential column efficiencies are expressed in terms of the maximum theoretical mean specific plate number.It is shown that appreciable differences occur between the theoretical efficiencies given by the different equations when the porous layer thickness and liquid loading are high, but these differences are small for most of the columns used in practice.     

Prediction of retention data from stationary phase constants in gas chromatography

Summary Specific retention volumes and retention indices for selected compounds can be predicted from different sets of stationary phase constants by multiple regression. Errors in the corresponding calculated retention times are between 5 and 15%. Intercept (A) and slope (B) values are given for 72 McReynolds stationary phases. The A value can be predicted from the retention index of benzene with a standard deviation of 9%.     

利用HCI程序确定儿茶酚化合物的反相高效液相色谱最佳分离条件

有效地确定了反相高效液相色谱分离儿茶酚化合物的最佳条件。在水和甲醇的二元流动相里分别加入乙酸缓冲液,利用基于ln k=ln kw +SF, k=A+B/F, ln k=L+MF+NF2 (F是流动相中有机物甲醇的体积分数)等保留因子的一次或二次方程式的塔板理论得到色谱分离结果;利用保留原理得到等度和梯度洗脱的最佳条件。得出最佳初始流动相是含0.1%乙酸的水和含0.1%乙酸的甲醇(体积比为75∶25)的混合溶液;梯度洗脱条件：初始流动相保持15 min,然后用10 min的时间将上述二元流动相的体积比线性变换成50∶50,直到完成全部分离。通过实验证实该计算结果与实验值相近。     

The orthogonal character of stationary phases for gas chromatography

A database of system constants for 32 open-tubular columns at 100 degrees C is used to identify stationary phases for obtaining a wide selectivity space in comprehensive GC. Three parameters based on the Euclidean distance (D-parameter) or vectors (d-parameter and costheta) in hyperspace are used to establish the chemical similarity and retention correlation as an inverse scale of selectivity differences. It is shown that the poly(methyloctylsiloxane) stationary phase is the best candidate for a low-selectivity stationary phase and affords a wider selectivity space when combined with a selective polar stationary phase than poly(dimethylsiloxanes). The most suitable polar stationary phases are poly(ethylene glycols) or bis(cyanopropylsiloxane-co-silarylenes and to a lesser extent poly(methyltrifluoropropylsiloxanes). No systems are truly orthogonal but angles between individual stationary phase vectors of about 75 degrees are possible by choosing the correct combination of stationary phases.     

Porous polymers coated with stationary phases. Contribution of the support to retention behaviour in gas chromatography

Summary The gas chromatographic behaviour of a series of compounds of different polarity on columns of Ethofat 60/25 on Chromosorb P HMDS (an inactive support) and Chromosorb 101 (an active support) was investigated. To observe how the support influences the chromatographic process, we separated the contribution to the retention volume of the interaction phenomena associated with the stationary phase, the solid support and the corresponding interfaces. In some cases the Chromosorb 101 exerts an influence on the process even with high percentages (>10%) of stationary phase. The values of the experimental partition constants of a series of compounds and the factors that contribute to adsorption on these columns are calculated.     

Effect of the carrier gas pressure on the dynamic and separation characteristics of divinylbenzene-based monolithic capillary columns for gas chromatography

The efficiency and dynamic characteristics of divinylbenzene-based monolithic capillary columns for gas chromatography were analyzed using a test mixture composed of five light hydrocarbons. The chromatographic properties of these columns were evaluated within the framework of two varieties of the van Deemter equation, the classical one and that proposed by Giddings (with consideration given to the pressure drop across the column). An analysis of the van Deemter curves demonstrated that the main contribution to peak smearing comes from the diffusion processes in the mobile phase. The contribution from the resistance to mass transfer between the mobile and stationary phases is less important. Negative values obtained for A in the van Deemter equation and for C _s in the Giddings model, parameters that characterize the stationary phase structure and mass transfer kinetics in the stationary phase, have no physical meaning, a result calling for further studies of this type of monolithic capillary columns since the classical theory supposed these parameters to be strictly positive. Under optimal conditions, the HETP of the monolithic columns was found to be 3 to 4 times smaller than that typical of open capillary columns of the same diameter.     

Analysis of isomeric tropane alkaloids from Schizanthus grahamii by very fast gas chromatography

This study presents a very fast GC analysis applied for the baseline separation of isomeric tropane alkaloids extracted from the stem-bark of Schizanthus grahamii (Solanaceae). The work provided a challenging application where isothermal analysis in conjunction with very short narrow bore columns (3 m x 100 microm ID and 1.5 m x 50 microm ID) was particularly suited for the speeding up. Experimental parameters were used in the optimisation steps, including selection of stationary phase, temperature, internal column diameter and optimal practicable gas velocity. Some considerations about sample injection in fast isothermal analysis are also briefly presented. Finally, the investigated approach allowed a very fast baseline separation of four positional and configurational isomers in less than 9 s.     

Investigations of a new field in gas chromatography: capillary columns with a super-thick layer of stationary liquid phase

Basic characteristics (efficiency, selectivity, non-equilibrium) of capillary columns with a super-thick layer of stationary liquid phase are investigated. In contrast to traditionally used capillary columns with standard stationary phase thickness of 0.1-0.5 um, some new variables are now established. Firstly, the values of relative retention depend on carrier gas linear velocity. Secondly, the asymmetry of chromatographic peaks increased in accordance with the increase in carrier gas velocity. Thirdly, it was theoretically and experimentally shown that dependence of the height equivalent to a theoretical plate (HETP) on carrier gas velocity is linear. The above noted variables are evidences that the new type of GC is realized under these conditions. The use of capillary columns with super-thick layer of stationary liquid phase is practical when the following problems have to be solved: (1) Separation of highly volatile substances; (2) Preliminary concentration of trace compounds from strong diluted samples; (3) Improvements in measurement and accuracy due to the advantages of splitless injection into wide bore columns with super-thick films. Solutions to some analytical tasks while using super-thick stationary liquid phase are shown: (1) Large volume injection into capillary column with sample transfer speed up to 100 microL min(-1); (2) Isothermal splitless injection; (3) Separation of low boiling compounds; (4) Separation of polar substances (alcohols).     

Novel stationary phases based on asphaltenes for gas chromatography

We present the results of investigations on the possibility of the application of the asphaltene fraction isolated from the oxidized residue from vacuum distillation of crude oil as a stationary phase for gas chromatography. The results of the investigation revealed that the asphaltene stationary phases can find use for the separation of a wide range of volatile organic compounds. The experimental values of Rohrschneider/McReynolds constants characterize the asphaltenes as stationary phases of medium polarity and selectivity similar to commercially available phases based on alkyl phthalates. Isolation of asphaltenes from the material obtained under controlled process conditions allows the production of a stationary phase having reproducible sorption properties and chromatographic columns having the same selectivity. Unique selectivity and high thermal stability make asphaltenes attractive as a material for stationary phases for gas chromatography. A low production cost from a readily available raw material (oxidized petroleum bitumens) is an important economic factor in case of application of the asphaltene stationary phases for preparative and process separations.     

Effect of viscosity on stationary phase stability in capillary column gas chromatography

With recent advances in column technology it is now possible to prepare highly efficient, very inert, and thermally stable capillary columns coated with nonpolar polysiloxane stationary phases. Unfortunately, the same degree of success has not been achieved for some of the more polar polysiloxane phases. A parameter that has been studied little in the past in relation to stationary phase film stability is the viscosity of the stationary phase. In this paper the efficiency and stability of coated columns are correlated to the viscosity of the phase. Due to their structure, the viscosity of the phenyl-containing polysiloxanes change rapidly with temperature and hence, thin-film coatings are not stable at elevated temperatures. By using high viscosity phenyl-containing methylphenylpolysiloxanes which were recently synthesized, efficient and stable columns have been prepared.     

A crosslinked chiral stationary phase for the separation of enantiomers by gas and supercritical fluid chromatography

Crosslinking experiments for the chiral stationary phase OV-225-L-Val-t-butylamide within both fused silica and glass capillary columns have been carried out. Amino acid enantiomers were separated on crosslinked columns by both GC and SFC methods. In SFC, the a values of amino acid enantiomers are independent of the density of the mobile phase, and they are hig her than those obtained by GC for the tested enantiomers with the same column due to the lower column temperature used in SFC.