Evaluation of nonlinear chromatographic performance by frontal analysis using a simple multi-plate mathematical model

A multi-plate (NIP) mathematical model was proposed by frontal analysis to evaluate nonlinear chromatographic performance. One of its advantages is that the parameters may be easily calculated from experimental data. Moreover, there is a good correlation between it and the equilibrium-dispersive (E-D) or Thomas models. This shows that it can well accommodate both types of band broadening that is comprised of either diffusion-dominated processes or kinetic sorption processes. The MP model can well describe experimental breakthrough curves that were obtained from membrane affinity chromatography and column reversed-phase liquid chromatography. Furthermore, the coefficients of mass transfer may be calculated according to the relationship between the MP model and the E-D or Thomas models. (C) 2004 Elsevier B.V. All rights reserved.

Silica bonded stationary phases: Innovative functionalization methods and novel chromatographic separations based on molecular recognition

The research work included in this thesis examines the synthesis, characterization and chromatographic evaluation of novel bonded silica stationary phases. Innovative methods of preparation of silica hydride intermediates and octadecylsilica using a “green chemistry” approach eliminate the use of toxic organic solvents and exploit the solvating power and enhanced diffusivity of supercritical carbon dioxide to produce phases with a surface coverage of bonded ligands which is comparable to, or exceeds, that achieved using traditional organic solvent-based methods. A new stationary phase is also discussed which displays chromatographic selectivity based on molecular recognition. Chapter 1 introduces the chemistry of silica stationary phases, the retention mechanisms and theories on which reversed-phase liquid chromatography and hydrophilic interaction chromatograpy are based, the art and science of achieving a well packed liquid chromatography column, the properties of supercritical carbon dioxide and molecular recognition chemistry. Chapter 2 compares the properties of silica hydride materials prepared using supercritical carbon dioxide as the reaction medium with those synthesized in an organic solvent. A higher coverage of hydride groups on the silica surface is seen when a monofunctional silane is reacted in supercritical carbon dioxide while trifunctional silanes result in a phase which exhibits different properties depending on the reaction medium used. The differing chromatographic behaviour of these silica hydride materials prepared using supercritical carbon dioxide and using organic solvent are explored in chapter 3. Chapter 4 focusses on the preparation of octadecylsilica using mono-, di- and trifunctional alkoxysilanes in supercritical carbon dioxide and in anhydrous toluene. The surface coverage of octadecyl groups, as calculated using thermogravimetric analysis and elemental analysis, is highest when a trifunctional alkoxysilane is reacted with silica in supercritical carbon dioxide. A novel silica stationary phase is discussed in chapter 5 which displays selectivity for analytes based on their hydrogen bonding capabilities. The phase is also highly selective for barbituric acid and may have a future application in the solid phase extraction of barbiturates from biological samples.

Validation of Thin Layer Chromatographic Methods

Thin-layer and high-performance thin-layer chromatography (TLC/HPTLC) methods for assaying compound(s) in a sample must be validated to ensure that they are fit for their intended purpose and, where applicable, meet the strict regulatory requirements for controlled products. Two validation approaches are identified in the literature, i.e. the classic and the alternative, which is using accuracy profiles.Detailed procedures of the two approaches are discussed based on the validation of methods for pharmaceutical analysis, which is an area considered having more strict requirements. Estimation of the measurement uncertainty from the validation approach using accuracy profiles is also described.Examples of HPTLC methods, developed and validated to assay sulfamethoxazole and trimethoprim on the one hand and lamivudine, stavudine, and nevirapine on the other, in their fixed-dose combination tablets, are further elaborated.

Low molecular weight halocarbons in the Humber and Rhine estuaries determined using a new purge-and-trap gas chromatographic method

A number of chlorinated and brominated low molecular weight hydrocarbons (halocarbons) have been measured in and adjacent to the North Sea estuaries of the Humber and the Rhine. The measurements have been carried out using a newly constructed purge-and-trap sample work-up system coupled to megabore gas chromatography with electron capture detection. The results show that whereas the Humber is a pronounced source of the anthropogenic halocarbons carbon tetrachloride and perchloroethylene, the input from the Rhine into the North Sea of these compounds is more modest. Some halocarbons normally considered as mainly or even exclusively of natural origin are released from the two investigated estuaries into the North Sea. A distinct patch of high concentrations of the naturally produced compound bromoform was observed in the southwestern North Sea. The results have also been used to examine some of the halocarbons for common sources.

Development and application of a high resolution liquid chromatographic method for the analysis of complex pigment distributions

Ternary and binary gradient systems have been developed for the high-performance liquid chromatographic analysis of complex pigment distributions typical of natural samples. Improved chromatographic resolution reveals significantly more pigment components in extracts from a sediment (Priest Pot, Cumbria, UK), a microbial mat (les Salines de la Trinital, South Catalonia, Spain) and a culture (C. phaeobacteroides) including novel bacteriochlorophyll derivatives. The methods developed are directly suited to LC–MS analysis and the automated acquisition of MS/MS data for pigments.

Wind generation output during cold weather-driven electricity demand peaks in Ireland

Recent cold winters and prolonged periods of low wind speeds have prompted concerns about the increasing penetration of wind generation in the Irish and other northern European power systems. On the combined Republic of Ireland and Northern Ireland system there was in excess of 1.5 GW of installed wind power in January 2010. As the penetration of these variable, non-dispatchable generators increases, power systems are becoming more sensitive to weather events on the supply side as well as on the demand side. In the temperate climate of Ireland, sensitivity of supply to weather is mainly due to wind variability while demand sensitivity is driven by space heating or cooling loads. The interplay of these two weather-driven effects is of particular concern if demand spikes driven by low temperatures coincide with periods of low winds. In December 2009 and January 2010 Ireland experienced a prolonged spell of unusually cold conditions. During much of this time, wind generation output was low due to low wind speeds. The impacts of this event are presented as a case study of the effects of weather extremes on power systems with high penetrations of variable renewable generation.

CHROMATOGRAPHIC AND IMMUNOLOGICAL CHARACTERIZATION OF NEUROPEPTIDE Y-LIKE AND PANCREATIC POLYPEPTIDE-LIKE PEPTIDES FROM THE NEMATODE ASCARIS-SUUM

1. Immunoreactivity (IR) towards neuropeptide Y (NPY) and pancreatic polypeptide (PP) has previously been demonstrated in nematodes by immunocytochemistry (ICC).

IMMUNOCHEMICAL AND CHROMATOGRAPHIC ANALYSES OF A NEUROPEPTIDE FROM THE MONOGENEAN PARASITE, DICLIDOPHORA-MERLANGI - EVOLUTIONARY ASPECTS OF THE NEUROPEPTIDE-Y SUPERFAMILY

1. A neuropeptide exhibiting pancreatic polypeptide-immunoreactivity (PP-IR) has been isolated and characterised from the parasitic platyhelminth, Diclidophora merlangi.