Alkylpolysiloxane glass capillary columns combining high temperature stability of the stationary liquid and deactivation of the surface

Summary A new method of making alkylpolysiloxane (OV 1, OV 101, OV 17, Dexsil 400, SE 52, SE 54) columns with high stability at temperatures above 300°C of both the stationary liquid itself (low bleeding) and of the surface deactivation (no tailing of polar solutes with extended use at temperatures beyond 250°C) is described. The best results were achieved on dealkalinized alkali glass but also on borosilicate surfaces which have been additionally HF treated before coating in both cases. The procedure can also be applied to leached alkali and borosilicate surfaces successfully. The best deactivations of the glass surface are attained in a two step procedure: firstly by treatment with gaseous HF/N₂ mixture and secondly by simple heating of the coated and closed column at temperatures between 350° and 450°C for several hours. The tailing behaviour of such columns for polar solutes is considerably improved by this procedure as shown by test chromatograms. The procedure can also be applied to leached alkali and borosilicate surfaces successfully.Extract also presented at the 8th National Meeting on Analytical Chemistry of the Swedish Chemical Society, Lund, June 1979 and at the 10th International Symposium on Chromatography and Electrophoresis, Venice, Italy, June 1979.     

New developments and experiences with glass capillary column production and sampling techniques

Summary An introductory discussion is given on the manufacture of glass capillary columns, including details of the methods of column testing and of the properties of the inner surfaces of glass capillaries. As a result a simple method for the testing of various kinds of support surfaces is presented which allows stepwise control of the column making procedure. A new kind of pretreatment of soft glass surfaces with HCl and HF at 450°C is described which allows the production of non-polar columns with much improved tailing behaviour for strongly polar solutes. Concerning capillary column sampling a new technique of direct sampling without previous vaporisation of the sample outside the column is presented together with a double column system for selective sampling of complex mixtures.     

Contribution of adsorption to rentension data in capillary gas chromatography part II. Non-polar stationary phases

Summary The influence of adsorption on the dependence of retention data upon film thickness of the non-polar stationary phases OV-101 and Apiezon L coated on glass (series of capillary columns with non-deactivated and Carbowax 20 M deactivated surface) and fused silica has been studied. Limiting values of Kovats indices, I, of solutes which exhibit tendency to hydrogen bonding are calculated for each series of columns.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Crosslinking of alkylpolysiloxane filsm on various types of glass surfaces including fused silica using γ-radiation of a60cobalt-source. Comparison to crosslinking by thermal peroxid treatment

Summary Crosslinking of alkylpolysiloxane stationary phases, especially in thick film capillary columns, is useful for the homogenous coating of fused silica and pretreated alkaliglass surfaces. The films of the stationary liquid are immobilized against solvent rinsing using CH₂Cl₂, pentane, and acetone, and maintain homogenity even at high temperature. Various doses of -radiation from a⁶⁰Co. source were used for the crosslinking instead of the thermal peroxid treatment recently described by other authors. The effect of the -radiation crosslinking-procedure was investigated in comparison to the peroxid method in regard of: decrease of stationary phase content by solvent rinsing, separation efficiency, tailing behaviour, and bleeding of the columns obtained. Similar results as with the cumylperoxid-treatment were achieved using the -radiation-method. By -radiation no polar functional groups or moleculs are introduced into the stationary phase, however, as with the peroxid method. Less than 20% of the various stationary liquids are usually removed from the columns by solvent rising after crosslinking using both methods depending on the doses of radiation and the cumylperoxid concentration applied respectively.Dedicated to Dr. L. S. Ettre on the occasion of his 60th birthday.     

Flexible soft glass capillary columns vs. flexible fused silica capillary columns for gas chromatography-a critique

The gas chromatographic use of flexible thin walled soft glass capillary columns coated with non-polar stationary phases is compared to similar columns made of fused silica glass. With non-polar soft glass columns, the use of surface roughening viagaseous HCI followed by a Carbowax 20 M pretreatment gave adsorptive phenomena, and thermal instability. With very polar soft glass columns where a variety of cyanopropyl silicone phases were coated directly onto the NaCI crystal matrix, adsorptive effects were again prominent and frequent break-down in film stability with time, was also observed. These undesirable effects were due to the presence of metal oxides in the soft glass. Attempts to remove these materials from the thin walled soft glass surface by means of acid leaching produced significant brittleness. This deleterious result was further increased by attempts at high temperature silylation or polysiloxane deactivation. In sharp contrast, the fused silica surface was essentially free of metal oxides and the surface silanol groups are easily neutralized by silylation or polysiloxane deactivation techniques. No brittleness was observed following these procedures. An increasing series of high molecular weight, viscous, polymeric vinyl containing non-polar and highly polar stationary phases have been produced which readily wet the surface of the fused silica and are easily crosslinked in the presence of free radical generators. These columns are essentially free of all the problems noted with flexible thin walled soft glass. When all of the parameters involved in the fabrication of a glass capillary column are assessed, it appears at this time, that the flexible fused silica glass column with cross linked phases approaches the “ideal” capillary column.     

Surface treatment,deactivation and coating in (GC)2 (glass capillary gas chromatography)

Summary The surface treatment, deactivation and coating of glass capillaries is discussed. Several techniques described in the literature are compared and for some critical points, new improved methods are advanced. Full details are given of optimised procedures yielding good results with every possible stationary phase. As an example, Table II mentions efficiencies of 3800 plates m^–1 for OV-17 and of 1850 plates m^–1 for OF-1, which hitherto was an impossible phase in (GC)² (proposed abbreviation for glass capillary gas chromatography).     

Characterization of glass,quartz, and fused silica capillary column surfaces from contact-angle measurements

Summary This paper describes the systematic characterization of glass and the newly introduced fused silica and quartz capillary columns from surface wettability measurements. Common gas chromatographic stationary phases were used in capillary-rise measurements at temperatures up to 300°C. By construction of Zisman plots and using the Cassie equation, the relative surface concentrations of wettable and non-wettable groups were determined. By application of the Fowkes equation, the dispersion force component of the surface energy was investigated. The influence of various surface treatments such as leaching, silylation, and polymeric film formation are discussed. Wettability measurements were also used to evaluate the thermostability of various treated surfaces and to compare the surface properties of glass, quartz, and fused silica. The wettability of the surfaces with selected stationary phases as a function of temperature is also discussed.     

Deactivation of fused silica capillary columns with cyanopropylhydrosiloxanes

A method is described for surface deactivation and modification of fused silica capillary columns with a cyanopropyl-containing reagent. The deactivation procedure involved a dehydrocondensation reaction between a bis(cyanopropyl)methylhydropolysiloxane reagent and surface silanol groups at an optimum temperature of only 250°C. Actual critical surface tension measurements were made using the capillary rise method. Excellent deactivation for acidic and basic compounds at the low ng level, and wettability for nonpolar and polar polysiloxane stationary phases were obtained. A procedure was developed to remove acidic impurities that are present in polar stationary phases.     

Characterization,evaluation and in-situ cross-linking of new polar phases in capillary gas chromatography

Summary The possibilities of OV-1701 and RSL-310, two new stationary phases, have been evaluated for capillary gas chromatography in fused silica columns. OV-1701 is a cyanopropylphenyldimethyl polysiloxane of moderate polarity possessing excellent chromatographic characteristics. The phase exhibits high coating and chromatographic efficiencies, high temperature stability and is suitable for cross-linking. RSL-310 is a polar liquid stationary phase yet to be permanently bonded in a capillary column. The selectivity of both phases extends the applicability of fused silica columns.Presented at the 14th International Symposium on Chromatography London, September, 1982     

The preparation of immobilized stationary phase fused silica capillary columns with OV-1701-vinyl deactivation

A new simplified method was developed for the preparation of immobilized stationary phase fused silica capillary columns coated with OV-1-vinyl, SE-54, and OV-1701-vinyl. This methodology includes the application of the moderately polar stationary phase OV-1701-vinyl as a surface deactivation agent that may also participate in the dicumyl peroxide initiated free radical immobilization process. Practical details of the procedure are presented and applications of the laboratory-produced columns are illustrated with capillary gas chromatographic separations of standard mixtures. Possible contributions of the OV-1701-vinyl deactivation layer to both crosslinking and surface bonding in the immobilization process are discussed.     

Crosslinked methylphenylsilicones as stationary phases for capillary gas chromatography

Summary Methyl(phenyl)silicones offer useful selectivities when used as stationary phases in gas chromatography (GC). Such phases have, however, hitherto been of restricted importance in capillary GC due to the lack of phases having a viscosity high enough to ensure stationary phase film stability. Further, to utilize fully the possibilities of a methyl(phenyl)silicone capillary column, it must also possess high efficiency and a high degree of deactivation.In this work, the preparation of soda-glass capillary columns coated within situ cured methyl(phenyl) and methyl(tolyl)-silicones is presented. Vulcanization was made possible by the introduction of some vinyl substitution in the gum to be cured: tolyl-containing gums could be cured without the presence of vinyl groups. In addition, fused silica capillary columns coated with OV-1701 were prepared.The columns show a coating efficiency of above 80%, a thermal stability up to 320 °C and a high degree of deactivation. Their utility is demonstrated by the separation of samples containing polynuclear aromatics, antidepressants and some potent mutagens.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Gas Chromatographic Separation of Enantiomers on Cyclodextrin Derivatives

In investigations concerned with the phenomenon of molecular chirality, the use of gas chromatography for the enantiomeric analysis of stable, volatile compounds is a technique of steadily growing importance. ^[1] In the last three years an important breakthrough in gas-chro-matographic separation of enantiomers has been achieved by using alkylated cyclodextrins (α, β, and γ) as chiral stationary phases in high-resolution capillary columns. In academic and commercial practice two different and complementary strategies have been adopted up to now. In the first, alkylated cyclodextrins are diluted with polysiloxanes and coated on glass or fused silica capillary columns. In the second, lipophilic per-n-pentylcyclodextrins and hydrophilic di-n-pentyl- and hydroxyalkylpermethylcyclodextrins are coated directly in the form of liquid phases onto suitably pretreated glass or fused silica surfaces. These techniques permit enantiomer separations not only for polar diols and alcohols, derivatized hydroxycarboxylic acids, amino acids, sugars, and alkyl halides, but also for nonpolar alkenes, cyclic saturated hydrocarbons, and metal π complexes. An important aspect for practical applications is that in many cases the enantiomers can be separated without previous derivatization. Whereas the resolution of racemates of unfunctionalized hydrocarbons is attributed to an enantioselective host–guest inclusion complex, some observations indicate that for polar guest molecules additional enantioselective interactions are also involved. The new chiral stationary phases can be used over a wide range of temperatures (25 to 250°C). The technique described is likely to become widely adopted as a simple, accurate and highly sensitive method for the enantiomeric analysis of chiral compounds that can be vaporized without decomposition. It will also stimulate future research aimed at finding universal cyclodextrin phases and elucidating the mechanisms of enantioselectivity.     

Deactivation of small-diameter fused-silica capillary columns for gas and supercritical fluid chromatography

Summary In order to prevent plugging during deactivation of small diameter (50 m i.d.) capillary columns for gas and supercritical fluid chromatography, various high temperature deactivation methods were employed. Pure hexamethyldisilazane and hexamethyldisiloxane (a substitute for D₄) were dynamically coated on the column, while a film (0.05 m) of OV-101 was statically coated, before high temperature (450°C) treatment. Excellent deactivated columns were obtained, and no significant difference in column activity was observed using any of these three methods.Dedicated to Professor S. R. Lipsky on the occasion of his 60th birthday.     

An experimental method for testing the solvophobic theory by using graphitized carbon black in GC and LC

Summary The net solvent effect for several solute-solvent pairs has been calculated by using the solvophobic approach for describing the liquid chromatographic process. For the same solutes and solvents the net solvent effect has been experimentally measured by using graphitized carbon black columns in GC and HPLC. A comparison between the measured and calculated values made in terms of normalized free energy changes, indicates that the solvophobic theory is fairly adequate for predicting the sequence of solvent strength and provides a comprehensive explanation of the various interactions occurring in reversed-phase LC. A critical discussion of the deviations of the theory from the experimental data is also presented.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Effect of the Measurement Temperature on the Dispersive Component of the Surface Free Energy of a Heat Treated SiO2 Xerogel

The surface free energy of a monolithic silica xerogel treated at 1000°C has been measured by inverse gas chromatography in the temperature range 25–150°C using n-alkanes. Values of the dispersive component, _S ^D, vary from 49.07 mJ·m^–2 at 25°C to 17.20 mJ·m^–2 at 150°C. The _S ^D value obtained at 25°C is lower than that found for amorphous and crystalline silicas but higher than that found for glass fibres meaning that the heat treatment at 1000°C changes drastically the structure of the silica xerogel showing a surface similar to a glass. However, the higher value of _S ^D in comparison to glass fibres can be attributed to the mesoporous structure present in the silica xerogel. In the temperature range of 60–90°C there exists an abrupt change of the _S ^D values as well as in the dispersive component of the surface enthalpy, h _S ^D. Such abrupt change can be attributed to an entropic contribution of the surface free energy.     

Wide-bore glass capillary columns for gas chromatography. Their preparation and application

Summary Methods for the preparation of wide-bore glass capillary columns for gas chromatography are presented. The pretreatment of the columns (etching, carbonization, deactivation and/or surface-coating with porous materials), and the coating of them with polar or apolar phases (preferably by the static method) is described. The performance of the columns prepared is evaluated and a number of applications are given, such as analysis of volatile compounds, pesticides, lipids and GC/MS analysis. In some respects, the wide-bore glass capillaries have advantages over the narrow-bore types. They can be installed very easily in GC-instruments, and permit the analysis of larger samples. A system of collecting separated sub-g fractions in glass capillary traps, which makes direc re-injection from these traps possible, completes the methods presented.     

Sol-Gel Fabrication and Properties of Silica Cores of Optical Fibers Doped with Yb3+, Er3+, Al2 O3 or TiO2

Optical cores of preforms for drawing optical fibers doped with Er3+ and Yb3+ were fabricated by the sol-gel method with the aim of increasing the thickness of glass layers coated in a single coating cycle and to determine the relation between the preparation conditions and optical properties of the fibers. Al2O3-P2O5-SiO2 and TiO2-P2O5-SiO2 glasses have been studied as matrices for entrapping the rare-earth elements. Input sols have been prepared from silicon and titanium alkoxides, AlCl3, ErCl3, YbCl3, POCl3, water and a modifier under acidic catalysis of HCl. The sols were coated on the inner wall of a silica substrate tube and the gel layers were sintered at high temperatures up to 2000°C after which the tube was collapsed into the preform. Continuous and homogenous glass films with the maximum thickness of about 8 m were fabricated. The influence of high-temperature heat treatment of the layers on their composition and optical attenuation was observed. The amplified stimulated emission of Er3+ around 1.55 m was measured under the excitation of the fibers by an Nd : YAG laser at 1.064 m.     

High Temperature Behavior of a Gel-Derived SiOC Glass: Elasticity and Viscosity

The high temperature behavior of a sol-gel derived silicon oxycarbide glass containing 12 at.% carbon has been characterized by means of creep and in-situ ultrasonic echography measurements. Temperature induced changes include structural relaxation and densification from 1000 to 1200°C, and crystallization to form a fine and homogeneous -SiC/glass-matrix nanocomposite with 2.5 nm large crystals above 1200°C. Young's modulus measurements clearly reveal a consolidation of the material upon annealing below 1200°C. Crystallization is almost complete after few hours at 1300°C and results in a significant increase in Young's modulus. The viscosity of the oxycarbide glass is much higher than that of fused silica, with two orders of magnitude difference at 1200°C, and the glass transition temperature ranges from 1320 to 1370°C.     

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.     

Radiochromatographic studies of isobutylene oxidation over SnO2

Radiochromatographic studies of isobutylene oxidation over SnO₂ confirm the formation of carbon dioxide from the products of oxidative olefin condensation.

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