Biomedical subjects

Colin F Poole

Publications and source records attributed to Colin F Poole.

At least 19 recordsLinked to original sources

PubMed2006

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.

Chromatography, Gas↗

PubMed2006

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.

Chromatography, Gas↗

PubMed2006

Insights into the retention mechanism on an octadecylsiloxane-bonded silica stationary phase (HyPURITY C18) in reversed-phase liquid chromatography.

Plots of the retention factor against mobile phase composition were used to organize a varied group of solutes into three categories according to their retention mechanism on an octadecylsiloxane-bonded silica stationary phase HyPURITY C18 with methanol-water and acetonitrile-water mobile phase compositions containing 10-70% (v/v) organic solvent. The solutes in category 1 could be fit to a general retention model, Eq. (2), and exhibited normal retention behavior for the full composition range. The solutes in category 2 exhibited normal retention behavior at high organic solvent composition with a discontinuity at low organic solvent compositions. The solutes in category 3 exhibited a pronounced step or plateau in the middle region of the retention plots with a retention mechanism similar to category 1 solutes at mobile phase compositions after the discontinuity and a different retention mechanism before the discontinuity. Selecting solutes and appropriate composition ranges from the three categories where a single retention mechanism was operative allowed modeling of the experimental retention factors using the solvation parameter model. These models were then used to predict retention factors for solutes not included in the models. The overwhelming number of residual values [log k (experimental) - log k (model predicted)] were negative and could be explained by contributions from steric repulsion, defined as the inability of the solute to insert itself fully into the stationary phase because of its bulkiness (i.e., volume and/or shape). Steric repulsion is shown to strongly depend on the mobile phase composition and was more significant for mobile phases with a low volume fraction of organic solvent in general and for mobile phases containing methanol rather than acetonitrile. For mobile phases containing less than about 20 % (v/v) organic solvent the mobile phase was unable to completely wet the stationary phase resulting in a significant change in the phase ratio and for acetonitrile (but less so methanol) changes in the solvation environment indicated by a discontinuity in the system maps.

Acetonitriles↗

PubMed2006

Separation characteristics of phenyl-containing stationary phases for gas chromatography based on silarylene-siloxane copolymer chemistries.

The solvation parameter model is used to characterize the retention properties of five open-tubular column stationary phases (ZB-5 ms, DB-5 ms, DB-XLB, DB-17 ms, and DB-35 ms) based on silarylene-siloxane copolymer chemistries at five equally spaced temperatures over the range 60-140 degrees C. System constant differences and regression models for varied compounds are used to establish the selectivity equivalence of the silarylene-siloxane copolymer stationary phases and to compare their separation characteristics with poly(dimethyldiphenylsiloxane) stationary phases containing a nominally similar concentration of phenyl groups. These studies demonstrate that ZB-5 ms and DB-5 ms are selectivity equivalent. DB-XLB is significantly more dipolar and polarizable than DB-5 ms. In general terms, the silarylenesiloxane copolymer stationary phases are slightly less cohesive and more dipolar and polarizable with similar hydrogen-bond basicity to the poly(dimethyldiphenylsiloxane) stationary phases they were designed to replace. None of the silarylenesiloxane copolymer or poly(dimethyldiphenylsiloxane) stationary phases are hydrogen-bond acidic. Selectivity differences between the two types of stationary phase are temperature dependent and tend to be smaller at higher temperatures within the temperature range studied. Consequently, selectivity differences cannot be globalized without reference to the temperature for the comparison.

Journal Article↗

PubMed2006

Distribution of neutral organic compounds between n-heptane and methanol or N,N-dimethylformamide.

Partition coefficients for a number of varied compounds were determined for the n-heptane-methanol and n-heptane-DMF partition systems and used to derive a general model for the distribution of neutral compounds in the biphasic systems. The partition coefficient, log Kp, was correlated through the solvation parameter model giving log Kp = -0.056 + 0.164E-0.620S-1.337A-0.957B + 0.507V for the n-heptane-methanol system with a multiple correlation coefficient of 0.986, standard error of the estimate 0.086, and Fischer statistic 413 for 65 compounds. For n-heptane-DMF, the model is log Kp = 0.065 + 0.030E-1.405S-2.039A-0.806B + 0.721V with a multiple correlation coefficient of 0.991, standard error of the estimate 0.080, and Fischer statistic 560 for 59 compounds. In the models the solute descriptors are excess molar refraction E, dipolarity/polarizability S, overall hydrogen bond acidity, and basicity A and B, respectively, and McGowan's characteristic volume V. Either model is expected to be able to estimate further values of the partition coefficient to about 0.08 log units and is applicable to a wide range of compounds. Applications include the choice of partitioning systems for sample clean-up, countercurrent chromatography, and estimation of solute descriptors for water insoluble or unstable compounds.

Journal Article↗

PubMed2005

Revised solute descriptors for characterizing retention properties of open-tubular columns in gas chromatography and their application to a carborane-siloxane copolymer stationary phase.

An iteration procedure is used to calculate revised solute descriptors for 103 varied compounds suitable for characterizing the retention properties of stationary phases for gas chromatography using the solvation parameter model. The iteration procedure utilizes a database of retention factors obtained on up to 39 open-tubular columns and up to five temperatures in the range 60-140 degrees C for the 103 solutes. The average of the standard deviation [Sigma(logk(exp)-logk(calc))(2)/(n(c)-1)](0.5) where logk(exp) is the experimental retention factor, logk(calc) the model predicted retention factor, and n(c) the total number of retention factors) on all columns is 0.018 for the revised solute descriptors compared with 0.045 for the original values. When used to characterize the retention properties of six open-tubular columns selected to represent different selectivity groups the revised solute descriptors afford improved values for the multiple correlation coefficient and standard deviations of the system constants, and about a three-fold improvement in the standard error of the estimate compared with the original solute descriptors. The revised solute descriptors were used to model retention on the carborane-siloxane copolymer stationary phase Stx-500. This phase has low cohesion, is weakly electron lone pair repulsive, weakly dipolar/polarizable, and weakly hydrogen-bond basic. It has no hydrogen-bond acidity. Its separation properties are similar to those of the poly(diphenyldimethylsiloxane) stationary phases containing 5% diphenylsiloxane monomer, but it is not selectivity equivalent to these phases, being more dipolar/polarizable and a weaker hydrogen-bond base.

Chromatography, Gas↗

PubMed2005

Model for the distribution of neutral organic compounds between n-hexane and acetonitrile.

Partition coefficients for 69 varied compounds were determined for the n-hexane-acetonitrile partition system and combined with 74 partition coefficients for (largely) terpenes, esters and alkylaromatic compounds determined by Isidorov and coworkers and 27 extraction p-values determined by Bowman and Beroza to derive a general model for the distribution of neutral compounds in the biphasic system. The partition coefficients, logK(p), were correlated through the solvation parameter model giving logK(p) = 0.097(+/- 0.049) + 0.189(+/-0.041)E - 1.332(+/-0.056)S - 1.649(+/-0.055)A - 0.966(+/-0.074)B + 0.773(+/-0.040)V with a multiple correlation coefficient of 0.985, standard error of the estimate 0.114, and Fischer statistic 1087. The solute descriptor E is the excess molar refraction, S is the dipolarity/polarizability, A and B are the overall hydrogen-bond acidity and basicity, respectively, and V is McGowan's characteristic volume. The model is expected to be able to estimate further values of the partition coefficient to about 0.1 log units and is applicable to a wide range of compounds except for n-alkylcarboxylic acids, which have higher partition coefficients than predicted, most likely due to the formation of oligomers (e.g. dimers) in the n-hexane layer.

Acetonitriles↗

PubMed2005

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.

Chromatography, Gas↗

PubMed2005

Models for the adsorption of organic compounds at gas-water interfaces.

The solvation parameter model is used to characterize interactions responsible for adsorption at the gas-water interface for bulk water at 15 and 25 degrees C, snow at -6.8 degrees C, mineral-supported water films (alumina, calcium carbonate and quartz) at 15 degrees C, and dry soil at 15 degrees C. The mineral-supported water films and dry soil adsorption data are modeled at different relative humidities in the range 40-99%. The models produce satisfactory results with standard errors of the estimate of 0.12 to 0.17 for regression of the model predicted adsorption equilibrium constants against the experimental values (range for equilibrium constants -2 to -7 log units). The water surface is polar with a significant capacity for dipole-type and hydrogen-bonding interactions. In addition, it is strongly electron lone pair repulsive. Dispersion interactions favor adsorption at the water surface. Mineral-supported water films at relative humidities greater than 40% demonstrate adsorption properties similar to bulk water. The adsorption characteristics, however, depend on the relative humidity and the nature of the support. In the case of dry soil the adsorption properties at different relative humidities cannot simply be explained by adsorption of a water film covering the soil surface and the changes in adsorption characteristics with relative humidity are more complex than the mineral-supported water films.

Adsorption↗

PubMed2004

Effect of solvent strength and temperature on retention for a polar-endcapped, octadecylsiloxane-bonded silica stationary phase with methanol-water mobile phases.

Synergi Hydro-RP is a new type of polar-endcapped, octadecylsiloxane-bonded silica packing for reversed-phase liquid chromatography. Its retention properties as a function of solvent strength and temperature are evaluated from the change in retention factors over the composition range (0-70% v/v methanol) and temperature range (25-65 degrees C) using the solvation parameter model and response surface methodologies. The main factors that affect retention are solute size and hydrogen-bond basicity, with minor contributions from solute hydrogen-bond acidity, dipole-type and electron lone pair interactions. Within the easily accessible range for both temperature and solvent strength, the ability to change selectivity is much greater for solvent strength than temperature. Also, a significant portion of the effect of increasing temperature is to reduce retention without changing selectivity. Response surfaces for the system constants are smooth and non-linear, except for cavity formation and dispersion interactions (v system constant), which is linear. Modeling of the response surfaces suggests that solvent strength and temperature are not independent factors for the b, s and e system constants and for the model intercept (c term).

Hydrogen Bonding↗

PubMed2004

Chromatographic and spectroscopic methods for the determination of solvent properties of room temperature ionic liquids.

Room temperature ionic liquids are novel solvents with favorable environmental and technical features. Synthetic routes to over 200 room temperature ionic liquids are known but for most ionic liquids physicochemical data are generally lacking or incomplete. Chromatographic and spectroscopic methods afford suitable tools for the study of solvation properties under conditions that approximate infinite dilution. Gas-liquid chromatography is suitable for the determination of gas-liquid partition coefficients and activity coefficients as well as thermodynamic constants derived from either of these parameters and their variation with temperature. The solvation parameter model can be used to define the contribution from individual intermolecular interactions to the gas-liquid partition coefficient. Application of chemometric procedures to a large database of system constants for ionic liquids indicates their unique solvent properties: low cohesion for ionic liquids with weakly associated ions compared with non-ionic liquids of similar polarity; greater hydrogen-bond basicity than typical polar non-ionic solvents; and a range of dipolarity/polarizability that encompasses the same range as occupied by the most polar non-ionic liquids. These properties can be crudely related to ion structures but further work is required to develop a comprehensive approach for the design of ionic liquids for specific applications. Data for liquid-liquid partition coefficients is scarce by comparison with gas-liquid partition coefficients. Preliminary studies indicate the possibility of using the solvation parameter model for interpretation of liquid-liquid partition coefficients determined by shake-flask procedures as well as the feasibility of using liquid-liquid chromatography for the convenient and rapid determination of liquid-liquid partition coefficients. Spectroscopic measurements of solvatochromic and fluorescent probe molecules in room temperature ionic liquids provide insights into solvent intermolecular interactions although interpretation of the different and generally uncorrelated "polarity" scales is sometimes ambiguous. All evidence points to the ionic liquids as a unique class of polar solvents suitable for technical development. In terms of designer solvents, however, further work is needed to fill the gaps in our knowledge of the relationship between ion structures and physicochemical properties.

Chemical Phenomena↗

PubMed2004

Determination of acid dissociation constants by capillary electrophoresis.

Capillary electrophoresis affords a simple, automated approach for the measurement of pKa values in the range 2-11 at a throughput of less than 1 h per sample per instrument. Agreement with literature values is usually within 0.20 log units with a precision better than 0.07 log units. The attractive features of capillary electrophoresis for pKa measurements are: (1) conventional instrumentation with a high level of automation are suitable for all measurements; (2) because it is a separation method samples need not be of high purity; (3) samples of low water solubility with suitable chromophores are easily handled (detection limits in the microM range); (4) sample consumption per measurement is in the microgram range; and (5) since only mobilities are measured, exact knowledge of concentrations is not needed. The general approach can be extended to pKa measurements in aqueous-organic solvent mixtures and non-aqueous solvents with suitable calibration. The widespread use of absorbance detection in capillary electrophoresis means that the sample must have a suitable chromophore for detection. The main source of controllable error is the accuracy of buffer standardization and their stability in use, and uncontrollable error, the retentive interactions of the sample with the column wall. The latter seems to be a rare problem in practice for typical operating conditions.

Acids↗

PubMed2004

Evaluation of a structure-driven retention model for temperature-programmed gas chromatography.

The solvation parameter model is suitable for describing the retention properties of compounds of varied structure in temperature-programmed gas chromatography. An empirical second-order model provides a good account of the change in system constants as a function of program rate. These relationships codify the reduction in retention time at higher program rates and changes in elution order (selectivity) with program rate. The prediction of retention times from structure, while quite good, is probably adversely affected by descriptor quality and the possibility of a mixed retention mechanism on polar stationary phases. Plots of experimental against predicted temperature-programmed retention times for varied compounds are linear but generally contain a small bias from an ideal model (slope of one and an intercept of zero). The average absolute deviation in temperature-programmed retention times on three columns (DB-210, DB-1701 and EC-Wax) varied from 0.15 to 0.89 min with the best results obtained at higher program rates on the columns of lower polarity.

Chromatography, Gas↗

PubMed2004

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.

Journal Article↗

PubMed2003

Separation methods for estimating octanol-water partition coefficients.

Separation methods for the indirect estimation of the octanol-water partition coefficient (logP) are reviewed with an emphasis on high throughput methods with a wide application range. The solvation parameter model is used to identify suitable separation systems for estimating logP in an efficient manner that negates the need for empirical trial and error experiments. With a few exceptions, systems based on reversed-phase chromatography employing chemically bonded phases are shown to be unsuitable for estimating logP for compounds of diverse structure. This is because the fundamental properties responsible for chromatographic retention tend to be different to those responsible for partition between octanol and water, especially the contribution from hydrogen bonding interactions. On the other hand, retention in several micellar and microemulsion electrokinetic chromatography systems is shown to be highly correlated with the octanol-water partition coefficient. These systems are suitable for the rapid, high throughput determination of logP for neutral, weakly acidic, and weakly basic compounds. For compounds with a permanent charge, electrophoretic migration and electrostatic interactions with the stationary phase results in inaccurate estimation of partition coefficients. The experimental determination of solute descriptors offers an alternative approach for estimating logP, and other biopartitioning properties. A distinct advantage of this approach is that once the solute descriptors are known, solute properties can be estimated for any distribution or transport system for which a solvation parameter model has been established.

Chromatography, Liquid↗

PubMed2003

System maps for retention of neutral organic compounds under isocratic conditions on a reversed-phase monolithic column.

The solvation parameter model is used to create systems maps for the separation of neutral organic compounds on a Chromolith Performance RP-18e octadecylsiloxane-bonded silica-based monolithic column for water-acetonitrile and water-methanol mobile phase compositions from 10 to 70% (v/v) organic solvent. These results demonstrate that the retention properties of the monolithic column are similar to those of conventional octadecylsiloxane-bonded silica particle-packed columns. It is further shown that the selectivity for the monolithic column falls within the selectivity range for typical particle-packed columns at two mobile phase compositions for which a direct comparison is possible.

Acetonitriles↗

PubMed2003

Thin-layer chromatography: challenges and opportunities.

The purpose of this article is to identify core technologies with the potential to influence the development of thin-layer chromatography over the next decade or so. Core technologies are identified as: (i) methods to provide a constant and optimum mobile phase velocity (forced flow and electroosmotically-driven flow), (ii) video densitometry for recording multidimensional chromatograms, (iii) in situ scanning mass spectrometry, and (iv) bioactivity monitoring for selective detection. In combination with two-dimensional, multiple development and coupled column-layer separation techniques these core technologies could dramatically increase the use of thin-layer chromatography for the characterization of complex mixtures. It is also demonstrated that thin-layer chromatography has strong potential as a surrogate chromatographic model for estimating biopartitioning properties. To convert these opportunities into practice the current state-of-the-art of the core technologies is described and the principle obstacles to progress identified.

Chromatography, Thin Layer↗

PubMed2003

Evaluation of a reversed-phase column (supelcosil LC-ABZ) under isocratic and gradient elution conditions for estimating octanol-water partition coefficients.

The solvation parameter model is used to identify suitable chromatographic models for estimating the octanol-water partition coefficient for neutral compounds of varied structure by reversed-phase liquid chromatography. The stationary phase Supelcosil LC-ABZ with methanol-water mobile phases affords a series of suitable correlation models for estimating the octanol-water partition coefficient (log KOW) under isocratic and gradient elution conditions. Isocratic separations with mobile phase compositions containing from about 25 to 40% (v/v) methanol provide the most accurate results for log KOW values in the range -0.1 to 4.0. Gradient separations programmed from 5 to 100% (v/v) methanol are suitable for faster separations of compounds with large log KOW values. The standard error in the estimate for the regression models of the predicted log KOW values against literature values are 0.135 log units for the 30% (v/v) methanol-water isocratic system and 0.263 log units for the methanol-water gradient system. Isocratic retention factors predicted from two gradient separations with gradient times of 15 and 45 min afford a poorer fit for the correlation models between log KOW and the estimated retention factors than that of either the above isocratic and gradient models. Plots of the retention factor (log k) as a function of mobile phase composition are generally non-linear. Values of log kw obtained by non-linear extrapolation to a volume fraction of 0% (v/v) methanol do not afford a useful model for estimating log KOW.

Journal Article↗