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.     

System constants for the bis(cyanopropylsiloxane)-co-methylsilarylene HP-88 and poly(siloxane) Rtx-440 stationary phases

The solvation parameter model is used to characterize the retention properties of the bis(cyanopropylsiloxane)-co-methylsilarylene, HP-88, and poly(siloxane), Rtx-440, stationary phases over the temperature range 60-140 degrees C. HP-88 is among the most cohesive, dipolar/polarizable and hydrogen-bond basic of stationary phases for open-tubular column gas chromatography. It has no hydrogen-bond acidity or capacity for electron lone pair interactions. It exhibits similar selectivity to the poly(cyanopropylsiloxane) stationary phase SP-2340. Rtx-440 is a low-polarity, low-cohesion stationary phase with a moderate capacity for dipolar/polarizable and hydrogen-bond base interactions. It has no hydrogen-bond acidity and possesses weak electron lone pair interactions. It has unique selectivity when compared against a system constants database for 28 common stationary phase compositions. Cluster analysis indicated that the poly(cyanopropylphenyldimethylsiloxane) stationary phase containing 6% cyanopropylphenylsiloxane monomer, DB-1301, the poly(dimethyldiphenylsiloxane) stationary phase containing 20% diphenylsiloxane monomer, Rtx-20, the poly(siloxane) stationary phase of unknown composition, DB-624, and DX-1 [a mixture of poly(dimethylsiloxane) and poly(ethylene glycol) 9:1] are the closest selectivity matches in the database. The selectivity of DB-1301 and Rtx-440 are very similar for solutes with weak hydrogen-bond acidity allowing one stationary phase to be substituted for the other with likely success. For strong hydrogen-bond acids, such as phenols, DB-1301 and Rtx-440 exhibit different selectivity.     

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.     

Assessment of the selectivity equivalence of DB-608 and DB-624 open-tubular columns for gas chromatography

The solvation parameter model is used to characterize the selectivity of DB-608 and DB-624 open-tubular columns at five equally spaced temperatures over the range 60 to 140 degrees C. The system constants for the DB-608 and DB-624 columns were used as selectivity parameters to search a database of open-tubular columns to identify columns with similar selectivity. The search was refined using the absolute deviation of the system constants and retention factor regression models for varied compounds. For method development it is shown that the selectivity of the poly(cyanopropylphenyldimethylsiloxane) stationary phase containing 6% cyanopropylphenylsiloxane monomer (DB-1301) is equivalent to DB-624 and the poly(dimethyldiphenylsiloxane) stationary phases containing either 50 or 65% diphenylsiloxane monomer (Rtx-50 and Rtx-65) are suitable choices for DB-608.     

Selectivity assessment of popular stationary phases for open-tubular column gas chromatography

The solvation parameter model is used to study the influence of temperature and composition on the selectivity of nine poly(siloxane) and two poly(ethylene glycol) stationary phase chemistries for open-tubular column gas chromatography. A database of system constants for the temperature range 60-140 degrees C was constructed from literature values with additional results determined for HP-50+, DB-210, DB-1701, DB-225 and SP-2340 columns. The general contribution of monomer composition (methyl, phenyl, cyanopropyl, and trifluoropropyl substituents) on the capacity of poly(siloxane) stationary phases for dispersion, electron lone pair, dipole-type and hydrogen-bond interactions is described. The selectivity coverage of the open-tubular column stationary phases is compared with a larger database for packed column stationary phases at a reference temperature of 120 degrees C. The open-tubular column stationary phases provide reasonable coverage of the range of dipole-type and hydrogen-bond base interactions for non-ionic packed column stationary phases. Deficiencies are noted in the coverage of electron lone pair interactions. None of the open-tubular column stationary phases are hydrogen-bond acids. The system constants are shown to change approximately linearly with temperature over the range 60-140 degrees C. The intercepts and slopes of these plots are used to discuss the influence of temperature on stationary phase selectivity.     

Selectivity equivalence of poly(ethylene glycol) stationary phases for gas chromatography

The solvation parameter model is used to study differences in selectivity for poly(ethylene glycol) stationary phases for packed column (Carbowax 20M) and fused-silica, open-tubular column (HP-20M, AT-Wax, HP-INNOWax and DB-FFAP) gas chromatography. All phases are dipolar, strongly hydrogen-bond basic with no hydrogen-bond acidity and of moderate cohesion. No two phases are exactly alike, however, and selectivity differences identified with cavity formation and dispersion interactions, n- and pi-electron pair interactions, dipole-type interactions and hydrogen-bond interactions are quantified by differences in the system constants at a fixed temperature where retention occurs solely by gas-liquid partitioning. The system constants vary linearly with temperature over the range 60-140 degrees C (except for n- and pi-electron pair interactions which are temperature invariant) facilitating a general comparison of the importance of temperature on selectivity differences for compared phases. From a mechanistic point of view it is demonstrated that selectivity differences can result from chemical differences between the poly(ethylene glycol) stationary phases and from differences in the relative contribution of interfacial adsorption to the retention mechanism. The latter depends on both system properties and solute characteristics.     

Selectivity equivalence of two poly(methylphenylsiloxane) open-tubular columns prepared with different deactivation techniques for gas chromatography

The solvation parameter model is used to characterize the retention properties of a poly(methylphenylsiloxane) column Rxi-50 over the temperature range 60-240 degrees C. The smooth variation of the system constants with temperature affords a general picture of how the relative importance of the different intermolecular interactions change with temperature. The system constants and retention factors for varied compounds are compared with those for Rtx-50 prepared with a similar stationary phase but using a different surface deactivation technique. The two columns are shown to be nearly selectivity equivalent. The Rtx-50 column is slightly more cohesive, dipolar/polarizable and hydrogen-bond basic than Rxi-50, while Rxi-50 is slightly more electron lone pair attractive and hydrogen-bond acidic. Only the difference in hydrogen-bond acidity can be identified with some certainty as related to the difference in deactivation processes. For compounds with a separation greater than 0.2 retention factor units on Rtx-50, it should be relatively straightforward to achieve an acceptable separation for the same compounds on Rxi-50.     

Insights into the Retention Mechanism on a Pentafluorophenylpropylsiloxane-Bonded Silica Stationary Phase (Discovery HS F5) in RP-LC

The solvation parameter model is used to elucidate the retention mechanism of neutral compounds on the pentafluorophenylpropylsiloxane-bonded silica stationary phase (Discovery HS F5) with methanol-water and acetonitrile-water mobile phases containing from 10 to 70% (v/v) organic solvent. The dominant factors that increase retention are solute size and electron lone pair interactions while polar interactions reduce retention. A comparison of the retention mechanism with an octadecylsiloxane-bonded silica stationary phase based on the same silica substrate and with a similar bonding density (Discovery HS C18) provides additional insights into selectivity differences for the two types of stationary phase. The methanol-water solvated pentafluorophenylpropylsiloxane-bonded silica stationary phase is more cohesive and/or has weaker dispersion interactions and is more dipolar/polarizable than the octadecylsiloxane-bonded silica stationary phase. Differences in hydrogen-bonding interactions contribute little to relative retention differences. For mobile phases containing more than 30% (v/v) acetonitrile selectivity differences for the pentafluorophenylpropylsiloxane-bonded and octadecylsiloxane-bonded silica stationary phases are no more than modest with differences in hydrogen-bond acidity of greater importance than observed for methanol-water. Below 30% (v/v) acetonitrile selectivity differences are more marked owing to incomplete wetting of the octadecylsiloxane-bonded silica stationary phase at low volume fractions of acetonitrile that are not apparent for the pentafluorophenylpropylsiloxane-bonded silica stationary phase. Steric repulsion affects a wider range of compounds on the octadecylsiloxane-bonded than pentafluorophenylpropylsiloxane-bonded silica stationary phase with methanol mobile phases resulting in additional selectivity differences than predicted by the solvation parameter model. Electrostatic interactions with weak bases were unimportant for methanol-water mobile phase compositions in contrast to acetonitrile-water where ion-exchange behavior is enhanced, especially for the pentafluorophenylpropylsiloxane-bonded silica stationary phase. The above results are compatible with a phenomenological interpretation of stationary phase conformations using the haystack, surface accessibility, and hydro-linked proton conduit models.     

Insights into the retention mechanism of neutral organic compounds on polar chemically bonded stationary phases in reversed-phase liquid chromatography

The solvation parameter model is used to characterize the retention properties of a 3-aminopropylsiloxane-bonded (Alltima amino), three 3-cyanopropylsiloxane-bonded (Ultrasphere CN, Ultremex-CN and Zorbax SB-CN), a spacer bonded propanediol (LiChrospher DIOL) and a multifunctional macrocyclic glycopeptide (Chirobiotic T) silica-based stationary phases with mobile phases containing 10 and 20% (v/v) methanol-water. The low retention on the polar chemically bonded stationary phases compared with alkylsiloxane-bonded silica stationary phases arises from the higher cohesion of the polar chemically bonded phases and an unfavorable phase ratio. The solvated polar chemically bonded stationary phases are considerably more hydrogen-bond acidic and dipolar/polarizable than solvated alkylsiloxane-bonded silica stationary phases. Selectivity differences are not as great among the polar chemically bonded stationary phases as they are between the polar chemically bonded phases and alkylsiloxane-bonded silica stationary phases.     

Comparison of a variety of gas chromatographic columns with different polarities for the separation of chlorinated dibenzo-p-dioxins and dibenzofurans by high-resolution mass spectrometry

The applicability of 13 different GC columns (Agilent HP-5MS, Restek Rtx-5MS, Rtx-Dioxin2, Supelco Equity 5, SP-2331, Varian VF-5MS, CP-Sil 8 CB LowBleed/MS, J&W Scientific DB-5, DB-225, DB-XLB, DB-5MS, Phenomenex ZB-5MS, and ZB-5UMS) for US Environmental Protection Agency (EPA) methods 1613b, 8290 and European Standard Method EN 1948 for measurement of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) has been evaluated for the separation of all International Toxic Equivalent Factor (I-TEF) isomers (tetra- through octachlorinated at 2,3,7,8 positions) from closely eluting isomers using high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The relative performance data are compared based on mass chromatograms using a "visualization approach", absolute retention times, 2,3,7,8-substituted, total dioxins and furans concentrations, as well as TEQ comparisons. None of the columns tested were able to separate all 17 I-TEFs from other co-eluted isomers. Our data indicate that all I-TEFs isomers can be fully differentiated from closely eluting isomers using either of two sets of non-polar and polar stationary phase combinations. One set consists of DB-5 (HP-5MS, Rtx-5MS, Equity-5) and DB-225 GC columns and another set would have a combination of DB-5MS (ZB-5MS, VF-5MS, CP-Sil 8 CB LowBleed/MS) with SP-2331. However, depending on the source of PCDDs/PCDFs a laboratory could choose a single GC column that separates the 2,3,7,8-substituted congeners that contribute most significantly to the overall TEQ. These data are the most comprehensive to date, provide a valuable addition to operational criteria for the standard EPA methods 1613b, 8290, European Standard Method EN 1948 and will allow researches to compare data generated according to the different compliance analytical procedures.     

System constants of synthesized poly(methyl-3,3,3-trifluoropropyl) siloxanes

The method of solvation model has been applied to five poly (methyl-trifluoropropyl) siloxanes (TFPSXX) prepared in our laboratories, at five trifluoropropyl (TFP) group contents, XX = 0, 11.5, 26.3, 35.5 and 50.0%, at 80, 100, 120 and 140 degrees C. Previously, specific retention volumes of 60-odd solutes of varied polarities were measured upon each of these stationary phases within the above temperature range. Constant s prevails over all other constants, TFPSXX stationary phases showing strong dipole/induced dipole forces with the solutes, moderate acidity and no basicity at all. Constant e is zero in the stationary phase without TFP groups, but has negative low-medium values for the other fluorine contents, XX from 11.5 to 50.0%, hinting at repulsive forces, as expected. Normal values for constant l, decreasing from the less cohesive TFPS00 to the more cohesive TFPS50, were found. For each TFP content constants s, a and l show a negative temperature dependence, while constant e increases as temperature increases. Constant c also decreases with increasing temperature. At each temperature, constants s and a increase with increasing %TFP (or increasing stationary phase polarity), whereas constants e and l show the opposite trend, diminishing with increasing polarity of the stationary phase. Principal component analysis shows that the five stationary phases presented in this work conform a group with other earlier synthesized trifluoropropyl siloxanes and other fluorinated stationary phases taken from literature: VB-210, QF-1, DB-200, DB-210 and PFS6, showing the same selectivity which only the fluorine atom confers. A dendrogram of 38 stationary phases supports these results.     

Evaluation of the separation characteristics of application-specific (fatty acid methyl esters) open-tubular columns for gas chromatography

The solvation parameter model is used to characterize the separation properties of the polar stationary phases EC-Wax and PAG with a poly(ethylene oxide) backbone (substituted with propylene oxide in the case of PAG) and the cyanopropyl-substituted polysilphenylene-siloxane stationary phase BPX90 at five equally spaced temperatures between 60 and 140 degrees C. The separation characteristics of these stationary phases are compared to four PEG and two poly(cyanopropylsiloxane) stationary phases (HP-20M, HP-Innowax, SolGel-Wax, DB-WAXetr, HP-88, and SP-2340) characterized in the same way. The database of system constants for these polar stationary phases is used to provide insight into the separation mechanism for fatty acid methyl esters and to determine selectivity differences that can be expected for generically similar stationary phase types. The discussion is not structured to indicate which stationary phase should be used for a particular separation but to provide a general framework to demonstrate the relationship between the retention mechanism and stationary phase chemistry.     

Comparison of the Separation Characteristics of the Organic–Inorganic Hybrid Octadecyl Stationary Phases XTerra MS C18 and XBridge C18 and Shield RP18 in RPLC

Differences in the system constants of the solvation parameter model, discontinuities in retention factor plots (log k against volume fraction of organic solvent) and retention factor correlation plots are used to study the retention mechanism on XTerra MS C₁₈, XBridge C₁₈ and XBridge Shield RP₁₈ stationary phases with acetonitrile–water and methanol–water mobile phases containing from 10 to 70% (v/v) organic solvent. Wetting of XBridge C₁₈ at 10 and 20% (v/v) acetonitrile is incomplete and is responsible for small changes in the retention mechanism. The intermolecular interactions responsible for retention on XTerra MS C₁₈ and XBridge C₁₈ are similar with minor differences in cavity formation and hydrogen-bonding interactions responsible for small selectivity differences. On the other hand, for bulky solutes there are large changes in retention at low volume fractions of organic solvent (<40% v/v) associated with steric repulsion on the XTerra MS C₁₈ stationary phases that is absent for XBridge C₁₈. Selectivity differences are more apparent for XBridge C₁₈ and XBridge Shield RP₁₈. For acetonitrile-water mobile phases cavity formation in the solvated XBridge Shield RP₁₈ is slightly more difficult and hydrogen-bond acid and base interactions are more important than for XBridge C₁₈. With methanol–water mobile phases it becomes slightly easier to form a cavity in the solvated XBridge RP₁₈ compared with XBridge C₁₈. In addition, the methanol-water solvated XBridge RP₁₈ is a stronger hydrogen-bond base and more dipolar/polarizable than XBridge C₁₈. These variations in selectivity justify the use of XBridge C₁₈ and XBridge Shield RP₁₈ as complementary stationary phases for method development.     

Comparison of series 5 gas chromatography column performances from a variety of manufacturers for separation of chlorinated dibenzo-p-dioxins and dibenzofurans using high-resolution mass spectrometry

An extended study of seven fused silica capillary gas chromatographic (GC) columns has been conducted with regard to separation of international toxic equivalent factor (I-TEF) isomers (tetra- through octa-chlorinated at 2,3,7,8 positions) of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) from closely co-eluted other isomers using high-resolution gas chromatography-high-resolution mass spectrometry (HRGC-HRMS). The data are explicated in mass chromatograms of Series 5 GC columns from a variety of manufacturers (Varian CP-Sil 8 CB LowBleed/MS, Phenomenex ZB-5UMS, Agilent HP-5MS, Restek Rtx-5MS, Supelco Equity-5, J&W Scientific DB-5 and DB-5MS), according to relative retention times, and 2,3,7,8-substituted isomer concentrations for each of the columns tested. Results showed differences between 5% phenyl methyl silicone and 5% silphenylene (Si-arylene) silicone polymer type GC stationary phases in separation of 2,3,7,8-substituted PCDDs/PCDFs from closely co-eluted isomers. The separation differences for Si-arylene type columns resulted in lower toxic equivalence (TEQ) values compared to the siloxane-based columns. Because of differences in product nomenclature and manufacturing practices by various manufacturers, incorrect assumptions and comparisons may be made regarding the interchangeability of these columns for PCCD/PCDF separations. The data presented are the most comprehensive to date and provide a valuable addition to operational criteria for the standard US Environmental Protection Agency methods 1613b and 8290.     

Selectivity differences between sol-gel coated and immobilized liquid film open-tubular columns for gas chromatography

The solvation parameter model is used to determine the system constants for two sol-gel coated open-tubular columns at five equally spaced temperatures in the range 60-140 degrees C. Differences in the system constants as a function of temperature are used to determine the affect of sol-gel structure on the selectivity of SolGel-l and SolGel-Wax columns compared with conventionally coated and immobilized poly(dimethylsiloxane) and poly(ethylene glycol) stationary phases. The sol-gel columns should be suitable for similar separations to those presently performed on conventional immobilized liquid film columns of the same type but selectivity differences for polar compounds, which depend on temperature, should be anticipated.     

Insights into the Retention Mechanisms on Perfluorohexylpropylsiloxane-Bonded (Fluophase-RP) and Octadecylsiloxane-Bonded (Betasil C18) Stationary Phases Based on the Same Silica Substrate in RP-LC

The solvation parameter model is used to elucidate the retention mechanism on a perfluorohexylpropylsiloxane-bonded (Fluophase RP) and octadecylsiloxane-bonded (Betasil C18) stationary phases based on the same silica substrate with acetonitrile–water and methanol–water mobile phase compositions. Dewetting affects the retention properties of Fluophase RP at mobile phase compositions containing less than 20% (v/v) acetonitrile or 40% (v/v) methanol. It results in a loss of retention due to an unfavorable change in the phase ratio as well as changes in specific intermolecular interactions. Steric repulsion reduces retention of bulky solutes on fully solvated Betasil C18 with methanol–water (but not acetonitrile–water) mobile phase compositions but is not important for Fluophase RP. The retention of weak bases is affected by ion-exchange interactions on Fluophase RP with acetonitrile–water, and to a lesser extent, methanol-water mobile phases but these are weak at best for Betasil C18. The system constants of the solvation parameter model and retention factor scatter plots are used to compare selectivity differences for Fluophase RP, Betasil C18 and a perfluorophenylpropylsiloxane-bonded silica stationary phase Discovery HS F5 for conditions where incomplete solvation, steric repulsion and ion-exchange do not significantly contribute to the retention mechanism. Lower retention on Fluophase RP results from weaker dispersion and/or higher cohesion moderated to different extents by polar interactions since solvated Fluophase RP is a stronger hydrogen-bond acid and more dipolar/polarizable than Betasil C18. Retention factors for acetonitrile–water mobile phases are highly correlated for Fluophase RP and Betasil C18 except for compounds with a large excess molar refraction and weak hydrogen-bonding capability. Selectivity differences are more significant for methanol–water mobile phases. Retention factors on Fluophase RP are strongly correlated with those on Discovery HSF5 for acetonitrile–water mobile phases while methanol–water mobile phases retention on Fluophase RP is a poor predictor of the retention order on Discovery HS F5.     

Retention properties of acetone-water mobile phases on a biphenylsiloxane-bonded silica stationary phase in reversed-phase liquid chromatography

The solvation parameter model system constants and retention factors were used to interpret retention properties of 39 calibration compounds on a biphenylsiloxane-bonded stationary phase (Kinetex biphenyl) for acetone-water binary mobile phase systems containing 30–70% v/v. Variation in system constants, phase ratios, and retention factors of acetone-water binary mobile phases systems were compared with more commonly used acetonitrile and methanol mobile phase systems. Retention properties of acetone mobile phases on a Kinetex biphenyl column were more similar to that of acetonitrile than methanol mobile phases except with respect to selectivity equivalency. Importantly, selectivity differences arising between acetone and acetonitrile systems (the lower hydrogen-bond basicity of acetone-water mobile phases and differences in hydrogen-bond acidity, cavity formation and dispersion interactions) could be exploited in reversed-phase liquid chromatography method development on a Kinetex biphenyl stationary phase.