Gary R. Dennis

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.

Surface pressure measurements of human tears and individual tear film components indicate that proteins are major contributors to the surface pressure

Purpose: Tear film stability has been associated with a low surface tension (high surface pressure), which has been attributed to a variety of tear film components. In this study, we examined the contribution of various tear proteins, mucin, and meibomian lipids to the surface pressure of human tears. Methods: A Langmuir trough was used to measure and compare the surface activities of albumin, lipocalin, β-lactoglobulin, lactoferrin, lysozyme, secretory IgA, mucin, meibomian lipid, and tears. Results: All proteins exhibited surface activity. The surface pressure-area (Π-A) profiles of most protein films at equilibrium surface pressure (Πeq) were sigmoidal and showed hysteresis between the expansion and compression phases of the cycle. Πeq of most proteins took 4-9 hours to occur. By contrast, the Π-A profiles for meibomian lipid films were hyperbolic rather than sigmoidal and had little hysteresis, and Πeq was attained within 1 hour. The Π-A profiles of mucin films showed mostly hyperbolic characteristics with small hysteresis. The Π-A profiles of films of tears were sigmoidal, showed strong hysteresis, and reached Πeq at about 5 hours. Partitioning of the proteins and whole tears into the subphase also occurred. Conclusion: Comparison between the dynamic Π-A profiles of tears and those of individual tear film components shows that tear film proteins not only are capable of surface activity but also are major contributors to the surface activity of the tear film.

The surface activity of purified ocular mucin at the air-liquid interface and interactions with meibomian lipids

Purpose: Ocular mucins are thought to contribute to the stability of the tear film by reducing surface tension. The purpose of this study was to compare the effect of different mucins and hyaluronic acid (HA) alone and mixed with meibomian lipids on the surface pressure at an air-liquid interface. Methods: A Langmuir trough and Wilhelmy balance were used to measure and compare the surface activity of bovine submaxillary gland mucin (BSM), purified BSM, purified bovine ocular mucin and HA, and mixtures of these with meibomian lipids, phosphatidylcholine, and phosphatidylglycerol. Their appearance at the surface of an air-buffer interface was examined using epifluorescence microscopy. Results: Purified ocular mucin had no surface activity even at concentrations that were 100 times more than normally occur in tears. By contrast, commercial BSM caused changes to surface pressure that were concentration dependent. The surface pressure-area profiles showed surface activity with maximum surface pressures of 12.3-22.5 mN/m depending on the concentration. Purified BSM showed no surface activity at low concentrations, whereas higher concentrations reached a maximum surface pressure of 25 mN/m. HA showed no surface activity, at low or high concentrations. Epifluorescence showed that the mucins were located at the air-buffer interface and changed the appearance of lipid films. Conclusion: Purified bovine ocular mucin and HA have no surface activity. However, despite having no surface activity in their own right, ocular mucins are likely to be present at the surface of the tear film, where they cause an increase in surface pressure by causing a compression of the lipids (a reorganization of the lipids) and alter the viscoelastic properties at the surface.

Effects of coupling agent on the physical properties of wood-polymer composites

Abstract Wood-polymer composites based on two Australian commercial timbers, radiata pine (pinus radiata) a soft wood and fast growing plantation timber, and blackbutt (eucalyptus piluliaris), a hard wood which is also a plantation timber, were prepared using the vinyl monomer, methyl methacrylate (MMA). It has been established that polymethyl methacrylate does not form bonds with the hydroxyl groups of the cellulose fibres but simply bulks the void spaces within the wood structure. Coupling agents have been known to increase adhesion of wood fibre to polymer matrix. In this study wood samples were pretreated with the coupling agent, vinyltriacetoxysilane, before impregnation with MMA in order to evaluate the effects of the silane coupling agent on the physical properties of wood-polymer composites. These composites were prepared using a catalyst-accelerator method and the polymerisation process was initiated at room temperature. This method involves the impregnation of wood samples using MMA containing benzoyl peroxide (1%), lauroyl peroxide (0.5%) and the accelerator: N,N-dimethylaniline (0.5%). In contrast to the conventional catalyst-heat method, this method requires no heating in the initiation process and thus results in virtually no loss of monomer. In general, there were improvements in dimensional stabilities (positive effects in both anti-shrink and anti-absorption efficiencies), compressive strength and hardness of silane treated wood-polymer composites. The morphology of the composites was examined using scanning electron microscopy and improved adhesion was evident for composites treated with the coupling agent. Since WPC find greatest use in medium to high unit cost products such as flooring and secondary construction items, improvements in both physical and mechanical properties of WPC would have important implications for the wood industry.

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.

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.

Effects of π‐π Interactions on the Separation of PAHs on Phenyl‐Type Stationary Phases

Abstract Phenyl‐type stationary phase surfaces are useful for the separation of highly aromatic compounds because of the extensive intermolecular forces between the π‐electron systems. For this reason, we studied the retention behaviour and selectivity of polycyclic aromatic hydrocarbons (PAHs) on Synergi polar‐RP and Cosmosil 5PBB chromatography columns using methanol/water, acetonitrile/water, benzene spiked (0.5%) methanol/water, and benzene spiked (0.5%) acetonitrile/water mobile phases. These four solvent systems were employed because π‐π. interactions between the aromatic solute (i.e., PAH) and the aromatic stationary phase should be inhibited in mobile phases that are also π electron rich, and hence a competitor for the analyte. Our results showed that the acetonitrile mobile phases were substantially stronger eluents than the methanol mobile phases, which was consistent with the premise that retention of aromatic compounds is sensitive to π‐π. interactions. Aside from changes in absolute retention, selectivity of the PAHs was also generally greater in methanol rather than acetonitrile mobile phases because the methanol did not attenuate the π‐π. bonding interactions between the PAH and the stationary phase; but, despite this, the retention behaviour of the Synergi polar‐RP column was similar to that observed on C18 columns. The excessive retention times of the Cosmosil 5PBB column were decreased dramatically when acetonitrile was used as the mobile phase; however, selectivity between structural isomers was lost.

Implications to stormwater management as a result of lot scale rainwater tank systems : a case study in Western Sydney, Australia

Rainwater tanks are increasingly adopted in Australia to reduce potable water demand and are perceived to reduce the volume of stormwater discharge from developments. This paper investigates the water balance of rainwater tanks, in particular the possible impacts these tanks could have in controlling the stormwater discharge volume. The study collected water quantity data from two sites in the Hawkesbury City Council area, New South Wales, Australia and utilised the collected data in a simple water balance model to assess the effectiveness of rainwater tanks in reducing the stormwater discharge volume. The results indicate that a significant reduction in discharge volume from a lot scale development can be achieved if the rainwater tank is connected to multiple end-uses, but is minimal when using irrigation alone. In addition, the commonly used volumetric runoff coefficient of 0.9 was found to over-estimate the runoff from the roof areas and to thereby under-estimate the available volume within the rainwater tanks for retention or detention. Also, sole reliance on the water in the rainwater tanks can make the users aware of their water use pattern and water availability, resulting in significant reductions in water use as the supply dwindles, through self-imposed water restrictions.

π-Selective stationary phases: (III) Influence of the propyl phenyl ligand density on the aromatic and methylene selectivity of aromatic compounds in reversed phase liquid chromatography

The retention characteristics of phenyl type stationary phases for reversed phase high performance liquid chromatography are still largely unknown. This paper explores the retention process of these types of stationary phases by examining the retention behaviour of linear PAHs and n-alkylbenzenes on a series of propyl phenyl stationary phases that have changes in their ligand density (1.23, 1.31, 1.97, 2.50 micromol m(-2)). The aromatic and methylene selectivities increased with increasing ligand density until a point where a plateau was observed, overall the propyl phenyl phases had a higher degree of aromatic selectivity than methylene selectivity indicating that these columns are suitable for separations involving aromatic compounds. Also, retention characteristics relating to the size of the solute molecule were observed to be influenced by the ligand density. It is likely that the changing retention characteristics are caused by the different topologies of the stationary phases at different ligand densities. At high ligand densities, the partition coefficient became constant.

Enhancing the separation performance of the first-generation silica monolith using active flow technology: parallel segmented flow mode of operation.

Active flow technology (AFT) columns are designed to minimise inefficient flow processes associated with the column wall and radial heterogeneity of the stationary phase bed. This study is the first to investigate AFT on an analytical scale 4.6mm internal diameter first-generation silica monolith. The performance was compared to a conventional first-generation silica monolith and it was observed that the AFT monolith had an increase in efficiency values that ranged from 15 to 111%; the trend demonstrating efficiency gains increasing as the volumetric flow to the detector was decreased, but with no loss in sensitivity.