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R Andrew Shalliker

Publications and source records attributed to R Andrew Shalliker.

At least 19 recordsLinked to original sources
PubMed2006

Visualising viscous fingering in chromatography columns: high viscosity solute plug.

The interface between two fluids that have different viscosities and are percolating through a porous bed is unstable. Sooner or later, a flow instability termed viscous fingering (VF) develops. This phenomenon is important in chromatography because the solute plug does not have the same viscosity as the mobile phase. Because the sample is often much more viscous than the mobile phase, it is the interface at the rear of the sample band that is usually unstable. This situation is frequent in many modes of chromatography, e.g., in preparative and in multidimensional chromatography, in size exclusion chromatography, in frontal analysis, and in other physicochemical measurements (e.g., determination of adsorption isotherms and of mass transfer parameters). When the solute plug is more viscous than the mobile phase, we observed that the solute band compressed. When the viscosity contrast increased up to 0.30 cP, fingers appeared to trail behind the solute plug. The development of fingers then became more substantial as the viscosity contrast increased. To avoid effects associated with VF, the mobile phase and the solute plug should have nearly the same viscosity.

Adsorption↗
PubMed2006

An assessment of the retention behaviour of polycyclic aromatic hydrocarbons on reversed phase stationary phases: selectivity and retention on C18 and phenyl-type surfaces.

In this manuscript the retention and selectivity of a set of linear and non-linear PAHs were evaluated on five different reversed-phase columns. These phases included C18 and C18 Aqua stationary phases, as well as three phenyl phases: Propyl-phenyl, Synergi polar-RP and Cosmosil 5PBB phase. Overall, the results revealed that the phenyl-type columns offered better separation performance for the linear PAHs, while the separation of the structural isomer PAHs was enhanced on the C18 columns. The Propyl-phenyl column was found to have the highest molecular-stationary phase interactions, as evidenced by the greatest rate of change in 'S' (0.71) as a function of the molecular weight in the PAH homologous series, despite having the lowest surface coverage (3% carbon load) (where S is the slope of a plot of logk versus the solvent composition). In contrast, the C18 Aqua column, having the highest surface coverage (15% carbon load) was found to have the second lowest molecular-stationary phase interactions (rate of change in S=0.61). Interestingly, the Synergi polar-RP column, which also is a phenyl stationary phase behaved more 'C18-like' than 'phenyl-like' in many of the tests undertaken. This is probably not unexpected since all five phases were reversed phase.

Benzene Derivatives↗
PubMed2006

Visualising the onset of viscous fingering in chromatography columns.

Viscous fingering is an important fluid transport phenomenon that manifests itself when two fluids having different viscosities move in the same direction. Their interface is unstable and a complex fingering pattern may arise. This phenomenon is important in chromatography because it may lead to a decrease or even a failure in separations. The onset of viscous fingering was visually observed by packing a glass column with particles having the same refractive index as the mobile phase and injecting plugs of dye solutions having viscosities different from that of the mobile phase. Severe fingering effects are observed if the viscosity difference exceeds 0.17 cP. However, for smaller viscosity differences, band distortions are observed that may affect retention data, band efficiency, and band resolution. Careful attention should be paid to matching the mobile phase viscosity and that of the injection plug when accurate chromatographic information is required.

Chromatography, High Pressure Liquid↗
PubMed2006

Multidimensional liquid chromatography for sample characterisation.

While LC finds enormously widespread use in almost all areas of chemical science, the technique is limited as a means of identification because compounds do not elute with unique retention times. This limitation spurred the growth of hyphenated instrumental methods of analysis, such as LC-MS/MS, which because of the MS/ MS detection became a method of identification. However, techniques like LC-MS/ MS are specialised and require high initial purchase and running costs, inhibiting the more widespread growth of the technique. In an attempt to increase the separation power of LC, multi-dimensional LC was developed. This expanded the separation space and subsequently has allowed the development of methods with fingerprinting ability due to the lower probability of component overlap. The work in this study illustrates the application of 2-D LC as a means of chemical fingerprinting. We employed a sample base of various low molecular weight oligostyrenes and their diastereomers that represent a population of compounds whose selectivities in a one-dimensional separation are almost unity and hence essentially impossible to separate. Yet in a 2-D domain almost all individual components occupy unique 2-D retention times.

Journal Article↗
PubMed2005

Study of the selectivity of reversed-phase columns for the separation of polycarboxylic acids and polyphenol compounds.

A systematic investigation was undertaken into the relative separation performance of five reversed-phase chromatography columns including some commercially new hybrid packed columns for a series of polycarboxylic acids and polyphenol compounds. Information theory (IT) and factor analysis (FA), together with a basic evaluation of retention information (band shape, retention factor and elution order) were used to compare four columns to a conventional C18 column. The results revealed very little difference in retention behaviour between the Phenomenex Aqua C18 column, the Waters XTerra RP C18 column, and the conventional Phenomenex Luna C18 column. However, there were notable differences in the retention processes between the Phenomenex Synergi polar-RP column, which is an ether-linked phenyl base with polar endcapping, and the Luna C18 column. The most significant differences were observed between the Luna C18 column and a Phenomenex Luna Cyano column. However, the limited degree of retention of the polycarboxylic acids and polyphenol compounds on the Luna Cyano column permits only limited use for the separation of these types of compounds. Overall, the Phenomenex Synergi polar-RP column exhibited the best performance for the separation of the test solutes compared to that of the conventional C18 column, with IT yielding an Informational Similarity of 0.99 and FA a moderate correlation coefficient of 0.70. The Phenomenex Synergi polar-RP column gave the best peak shape and offered substantial selectivity differences thereby providing a good alternative over the conventional C18 column for separating polycarboxylic acids and polyphenols.

Adsorption↗
PubMed2005

Viscous fingering induced flow instability in multidimensional liquid chromatography.

Viscous fingering is a flow instability phenomenon that results in the destabilisation of the interface between two fluids of differing viscosities. The destabilised interface results in a complex mixing of the two fluids in a pattern that resembles fingers. The conditions that enhance this type of flow instability can be found in coupled chromatographic separation systems, even when the solvents used in each of the separation stages have seemingly similar chemical and physical properties (other than viscosity). For example, the viscosities of acetonitrile and methanol are sufficiently different that instability at the interface between these two solvents can be established and viscous fingering results. In coupled chromatographic systems, the volume of solvent transported from one separation dimension to the second often exceeds the injection volume by two or more orders of magnitude. As a consequence, viscous fingering may occur, when otherwise following the injection of normal analytical size injection plugs viscous fingering would not occur. The findings in this study illustrate the onset of viscous fingering in emulated coupled chromatographic systems and show the importance of correct solvent selection for optimum separation performance.

Acetonitriles↗
PubMed2005

Molecular differences between deuterated and protonated polystyrenes using reversed-phase high-performance liquid chromatography.

Isotopic substitution is a technique used to highlight particular bonds within a molecule for kinetic, spectroscopic and structure analysis. It is presumed that although some properties such as stretching frequencies will not be the same for substituted analogues, the chemical interactions will not vary appreciably as a function of labelling. Reversed-phase liquid chromatography has been used to demonstrate that there are significant differences between the chromatographic behaviour of a sequence of deuterated and protonated oligomeric polystyrenes. Two-dimensional reversed-phase liquid chromatography was used to show that even the diasteromers of the oligomers (n = 5) have retention mechanisms that are dependent on the subtle changes to the molecular conformation and electronic structure, which are a consequence of deuteration.

Chromatography, High Pressure Liquid↗
PubMed2005

Utilising retention correlation for the separation of oligostyrenes by coupled-column liquid chromatography.

The separation of n = 2-5 n-butyloligostyrenes has been illustrated by reversed-phase reversed-phase (RP-RP) coupled-column liquid chromatography. The coupled-column separation has been achieved by use of a C18 column with methanol as the mobile phase followed by a DiamondBond C18 column with acetonitrile (ACN) mobile phase. The DiamondBond C18 is a hybrid carbon clad zirconia (CCZ)-C18 stationary phase. Unlike a C18-carbon clad zirconia two-dimensional liquid chromatographic system, which is orthogonal, the C18 and DiamondBond C18 columns combination exhibit correlations based upon the molecular weight of n-butyloligostyrenes. Using an alternative strategy to two-dimensional liquid chromatography, the molecular weight dependence displayed by both the C18 column and DiamondBond C18 has been used to increase throughput or decrease analysis time in the analysis of the n-butyloligostyrenes. However, this is at the expense of a portion of the two-dimensional peak capacity displayed by the C18-carbon clad zirconia system.

Chromatography, Liquid↗
PubMed2004

Comprehensive two-dimensional separations of complex mixtures using reversed-phase reversed-phase liquid chromatography.

A comprehensive two-dimensional reversed-phase reversed-phase liquid chromatographic system for the separation of a complex mixture of oligostyrenes was developed using results from a previous theoretical assessment of the informational similarity, percent synentropy, orthogonality and peak capacity of hypothetically coupled systems. The degree of sample attribute order in the first separation dimension was also used in the development of the experimental two-dimensional system. A C18(methanol)/CCZ(acetonitrile) two-dimensional system was chosen for the comprehensive analysis of the oligostyrene mixtures because this system had the lowest solute crowding, highest orthogonality and was observed to have order with respect to a sample attribute in the first separation dimension. The separations achieved were in full agreement with the results from information theory and (a geometric approach to) factor analysis assessments. High sampling rates in the first liquid chromatographic dimension were shown to be impossible or inefficient when the peak capacity and separation time of the second dimension was high or when the aim of the exercise was to isolate individual sample constituents in high yield.

Chromatography, Liquid↗
PubMed2004

Evaluation of the uniformity of analytical-size chromatography columns prepared by the downward packing of particulate slurries.

The axial heterogeneity of downward slurry-packed chromatography columns was evaluated. A series of columns were prepared that varied in total length from 5 to 30 cm. Each column was packed in stainless steel tubing that was sectioned to allow the column to be divided into 5-cm sections after packing. Each 5-cm section of these columns was then tested for chromatographic performance. In total, 22 such column sections were tested. The results of the study show that the consolidation of the packed bed is a very complex problem, yet systematic variations of the column performance were observed, depending on the location of the section tested from within the entire column. For example, when columns longer than 20 cm were packed, the most homogeneous and best performing section of the column was the lower midsection. Whereas for columns shorter than 20 cm in length, the best sectioned region of the bed was the lower and outlet region. In all cases, the most poorly packed region of the bed was the column inlet section, irrespective of the bed length. The phenomenon associated with this axial heterogeneity undoubtedly results from a complex interplay between wall friction, particle momentum, and the pressure pulsations resulting from the packing process.

Journal Article↗
PubMed2004

Separation of oligostyrene isomers in a complex mixture using two-dimensional heart-cutting reversed-phased liquid chromatography.

The development of a two-dimensional liquid chromatographic system requires a process of assessment that can yield an optimum performing system with minimal experimental evaluation. Information Theory and a geometric approach to Factor Analysis are two techniques that when used in combination, provide important information on the expected two-dimensional performance. In the present study, we compare the predicted separation performance of two-dimensional systems that have been subjected to analysis by Information Theory and Factor Analysis to that of actual chromatographic separation performance. Our test separation comprised a mixture of 32 oligostyrene structural isomers and stereoisomers. The optimal combination as determined by Information Theory and Factor Analysis consisted of a C18 column with a methanol mobile phase in the first dimension and a carbon clad zirconia column with an acetonitrile mobile phase in the second dimension. This system was also shown to be the most successful practical system when a heart-cutting approach was employed. The practical results were in total agreement with the results from Information Theory and Factor Analysis. The number of isomers resolved using this system was 27. A second system, namely one comprising of a C18 column and methanol mobile phase in the first dimension and a carbon clad zirconia column with a methanol mobile phase in the second dimension was also predicted to be a system with high separation potential. However, practical assessment of this system did not realise the theoretical predictions, largely due to the long separation times required in the second dimension. Furthermore, all combinations that employed a C18 column with an acetonitrile mobile phase in the first dimension failed to realise the theoretical separation potential due to high solute crowding, low orthogonality and a disordered arrangement of bands along the first separation axis. This was also predicted by the theoretical assessment.

Chromatography, High Pressure Liquid↗
PubMed2004

Using analytical multidimensional isocratic HPLC methods of separation to isolate active constituents in natural products.

Multidimensional reversed-phase HPLC was employed to isolate the active constituents from a crude extract of Clerodendrum floribundum R. Br. These active constituents were known to have bioactivity against the enzyme xanthine oxidase and potentially could be employed in the treatment of gout. Using a multidimensional separation approach, rapid isolation of the active constituents was achieved from a complex sample matrix. As each separation dimension was isocratic, no equilibration time was required and consequently the technique shows promise in the scale up to preparative levels where high throughput is important.

Biological Products↗
PubMed2003

Evaluation of the two-dimensional reversed-phase-reversed-phase separations of low-molecular mass polystyrenes.

The resolving power of four reversed-phase-reversed-phase two-dimensional (2D) chromatographic systems was evaluated using information theory (IT) and a geometric approach to factor analysis. The first separation dimension employed a C18 column, while the second separation dimension employed a carbon clad zirconia column. Mobile phases in each dimension were either methanol or acetonitrile. The sample matrix that was employed in this study contained a mixture of 58 components, comprised of stereoisomers and structural isomers of a systematic variation in molecular weight. Each of the components were oligostyrenes, with between two and five configurational repeating units having either n-butyl, sec-butyl or tert-butyl end groups. In the two-dimensional systems employed in this study, between 46 and 49 of the 58 components could be separated, depending on the mobile phase combinations--with apparent resolution that could not possibly be achieved in a single one-dimensional separation. The results from this study indicate that in order to fully evaluate the resolving power of a 2D system multiple methods of analysis that evaluate the separation potential are most appropriate. This becomes increasingly important when the sample contains components that are very closely related and the retention of solutes displays a high degree of solute crowding.

Molecular Weight↗
PubMed2003

Axial and radial diffusion coefficients in a liquid chromatography column and bed heterogeneity.

The axial and transverse diffusion coefficients of a band of iodine in a chromatographic column were measured optically as a function of time. It was found that the axial diffusion coefficient remains constant even when the edges of the sample band get close to the wall. By contrast, the radial diffusion coefficient decreases progressively with increasing time when the edges of the sample band leave the core region and begin to diffuse inside the wall region. The local axial and transverse diffusion coefficients of the band decrease from the column center toward the wall. Hence, the increase in local height equivalent to a theoretical plate observed in the region close to the wall must be explained by increasing mass transfer resistances and degree of heterogeneity of the bed.

Chromatography, Liquid↗
PubMed2003

Comprehensive coupled reversed-phase reversed-phase separations of a complex isomeric mixture.

Using predictions based on results obtained from Information Theory and Factor Analysis for the two-dimensional separation of a complex isomeric mixture, a practical experimental comprehensive coupled reversed phase-reversed phase chromatographic system was developed. In total four reversed phase-reversed phase systems were studied, each of which theory predicted would be able to resolve essentially equal numbers of components. However, in practice only one of these coupled systems realised the theoretical potential. This system employed as the first dimension, a C18 stationary phase with methanol as the mobile phase and as the second dimension, carbon clad zirconia as the stationary phase and acetonitrile as the mobile phase. In this system, 27 of the 32 isomers of a mixture of oligostyrenes were resolved. Failure of the remaining coupled systems to achieve the theoretical potential was attributed to high solute crowding, low efficiency of separation space utilisation and long analysis times in the second dimension.

Journal Article↗
PubMed2002

Two dimensional reversed-phase-reversed-phase separations isomeric separations incorporating C18 and carbon clad zirconia stationary phases.

Informational theory and a geometric approach to factor analysis were employed to evaluate the degree of orthogonality of a two-dimensional reversed-phase-reversed-phase chromatographic system. The system incorporated a C18 column as one dimension and a carbon clad zirconia column as the second dimension. In order to study the resolving power of this system, the separation of a sample matrix containing an artificial mix of 32 isomers (structural and diastereoisomers) was evaluated. Using this system, between 25 and 28 of the 32 isomers could be separated, depending on the mobile phase combinations--with resolution that could not possibly be achieved in a single one dimensional separation. The results from this study indicate that in order to fully evaluate the resolving power of a 2D system multiple methods of analysis are most appropriate. This becomes increasingly important when the sample contains components that are very closely related and the retention of solutes is clustered in one quadrant of the 2D space. Ultimately, the usefulness of the 2D separation is determined by the goals of analyst.

Carbon↗
PubMed2002

Development of a two-dimensional liquid chromatography system with trapping and sample enrichment capabilities.

A two-dimensional HPLC system was developed where "heart-cutting" chromatography, in conjunction with cold temperature trapping, was used to isolate and concentrate specific sample analytes. Low molecular mass polystyrene oligomers were used as model compounds to illustrate the operation of the instrument and evaluate the performance of the trapping system. A critical factor in the operation of the trapping system was the relative degree of retention between the first column and the trapping column. The results of this study showed that up to 32 consecutive heart-cut fractions from the first separation dimension could be stored in a trapping column with good analyte recovery and without significant loss in resolution upon elution on the second separation dimension.

Chromatography, High Pressure Liquid↗