Biomedical subjects

Michael J Ford

Publications and source records attributed to Michael J Ford.

15 recordsLinked to original sources

PubMed2006

Optimization of plasmonic heating by gold nanospheres and nanoshells.

Gold nanoparticles have strong and tunable absorption peaks in their optical extinction spectra, a phenomenon that has recently been exploited to generate localized heating in the vicinity of these particles. However the optimum particle geometry and illumination regime to maximize these effects appears not to have been previously examined in any detail. Here we show that the interplay between the particles' absorption cross-sections, volume, and surface area lead to there being specific conditions that can maximize particle temperature and surface heat flux. Optical absorption efficiencies were calculated from the formulation of Mie, and radiative, convective, and conductive heat transfer models were used to model the thermal performance of particles in different situations. Two technologically relevant scenarios for illumination, namely, irradiation by sunlight at 800 W/m2 and by a monochromatic laser source of 50 kW/m2 tuned to the peak absorption wavelength, were considered. For irradiation by sunlight, the resultant heat flux is optimized for an 80 nm diameter nanoshell with an aspect ratio of 0.8, while for irradiation by laser the maximum heat flux is found for 50 nm nanoshells, with an aspect ratio of 0.9.

Journal Article↗

PubMed2006

Evaluation of a surface-sampling probe electrospray mass spectrometry system for the analysis of surface-deposited and affinity-captured proteins.

A combined self-aspirating electrospray emitter/surfacing-sampling probe coupled with an ion trap mass spectrometer was used to sample and mass analyze proteins from surfaces. The sampling probe mass spectrometer system was used to sample and detect lysozyme that had been deposited onto a glass slide using a piezoelectric spotter or murine gamma-interferon affinity captured on a glass slide using surface-immobilized anti-gamma-interferon antibody. The detection level for surface-deposited lysozyme (spot size < or =200 microm) was approximately 1.0 fmol (approximately 100 fmol/mm2) as determined from the ability to measure accurately the protein molecular mass from the mass spectrum acquired by sampling the deposit. These detection limits may be sufficient for certain applications in which protein fractions from a separation method are collected onto a surface. Radiolabeled proteins were used to quantify the surface density of immobilized antibody and the efficiency of capture of the gamma-interferon on glass and higher surface area ceramic supports. The capture density of gamma-interferon at surface saturation ranged from about 23 to 50 fmol/mm2 depending on the capture surface. Nonetheless, mass spectrometric detection of affinity capture protein was successful in some cases, but the results were not reproducible. Thus, improvement of the sampling system, ionization efficiency and/or capture density will be necessary for practical sampling of affinity-captured proteins. The means to accomplish improved sampling system detection limits and to increase the absolute amounts of protein captured per unit area are discussed.

Affinity Labels↗

PubMed2006

Symptom interpretation and quality of life in patients with irritable bowel syndrome.

BACKGROUND: Patients with irritable bowel syndrome (IBS) are often believed to attribute unexplained symptoms to physical disorders. We tested this hypothesis by assessing symptom interpretation, symptom severity, and quality of life in patients attending hospital gastroenterology clinics. AIM: The main aims of this study were: to assess the symptom attributional styles of hospital gastroenterological outpatients with IBS and non-IBS disorders in comparison with unselected patients attending their GP; to establish the relationships between attributional style, quality of life, and IBS severity score in hospital gastroenterology outpatients; and to test the hypothesis that the IBS severity score correlates with a somatising style of symptom attribution. DESIGN OF STUDY: Systematic quantitative analysis. SETTING: General practice and gastroenterology outpatient clincs. METHOD: Patients attending hospital gastroenterology clinics were recruited prospectively and completed validated questionnaires. These were the Medical Outcome Survey (MOS SF-36), the IBS Severity Score, and the Symptom Interpretation Questionnaire (SIQ). The latter measures the tendency to interpret somatic symptoms in three ways: as a physical disorder (somatising attributional style), as an emotional response to stress (psychologising attributional style), or as a normal experience (normalising attributional style). The diagnosis of IBS was based on the Rome II criteria; the control groups comprised gastroenterology outpatients with non-IBS diagnoses and unselected patients attending general practice. RESULTS: Quality of life in IBS patients attending hospital outpatients (n = 32, male:female ratio 9:23) was not significantly different from that of non-IBS patients (n = 70, male:female ratio 32:38). In all patient groups, the normalising style of symptom interpretation predominated; psychologising styles correlated with impaired quality of life in the mental health domains. In IBS patients, the tendency to seek a psychological explanation for physical symptoms correlated significantly with the severity of the abdominal pain. CONCLUSIONS: Symptom interpretation does not differ between IBS and non-IBS patients referred to hospital gastroenterology clinics. The tendency to attribute somatic symptoms to a physical disorder does not explain why only a minority of IBS subjects seek medical attention. The idea that most IBS patients are committed to a somatic explanation of symptoms appears to be a myth.

Adult↗

PubMed2005

Automation of a surface sampling probe/electrospray mass spectrometry system.

An image analysis automation concept and the associated software (HandsFree TLC/MS) were developed to control the surface sampling probe-to-surface distance during operation of a surface sampling electrospray system. This automation system enables both "hands-free" formation of the liquid microjunction used to sample material from the surface and hands-free reoptimization of the microjunction thickness during a surface scan to achieve a fully automated surface sampling system. The image analysis concept and the practical implementation of the monitoring and automated adjustment of the sampling probe-to-surface distance (i.e., liquid microjunction thickness) are presented. The added capabilities for the preexisting surface sampling electrospray system afforded through this software control are illustrated by an example of automated scanning of multiple development lanes on a reversed-phase C8 TLC plate and by imaging inked lettering on a paper surface. The post data acquisition processing and data display aspects of the software package are also discussed.

Chromatography, Thin Layer↗

PubMed2005

Quantitative thin-layer chromatography/mass spectrometry analysis of caffeine using a surface sampling probe electrospray ionization tandem mass spectrometry system.

Quantitative determination of caffeine on reversed-phase C8 thin-layer chromatography plates using a surface sampling electrospray ionization system with tandem mass spectrometry detection is reported. The thin-layer chromatography/electrospray tandem mass spectrometry method employed a deuterium-labeled caffeine internal standard and selected reaction monitoring detection. Up to nine parallel caffeine bands on a single plate were sampled in a single surface scanning experiment requiring 35 min at a surface scan rate of 44 mum/s. A reversed-phase HPLC/UV caffeine assay was developed in parallel to assess the mass spectrometry method performance. Limits of detection for the HPLC/UV and thin-layer chromatography/electrospray tandem mass spectrometry methods determined from the calibration curve statistics were 0.20 ng injected (0.50 muL) and 1.0 ng spotted on the plate, respectively. Spike recoveries with standards and real samples ranged between 97 and 106% for both methods. The caffeine content of three diet soft drinks (Diet Coke, Diet Cherry Coke, Diet Pepsi) and three diet sport drinks (Diet Turbo Tea, Speed Stack Grape, Speed Stack Fruit Punch) was measured. The HPLC/UV and mass spectrometry determinations were in general agreement, and these values were consistent with the quoted values for two of the three diet colas. In the case of Diet Cherry Coke and the diet sports drinks, the determined caffeine amounts using both methods were consistently higher (by approximately 8% or more) than the literature values.

Caffeine↗

PubMed2005

Thin-layer chromatography and mass spectrometry coupled using desorption electrospray ionization.

Desorption electrospray ionization (DESI) was demonstrated as a means to couple thin-layer chromatography (TLC) with mass spectrometry. The experimental setup and its optimization are described. Development lanes were scanned by moving the TLC plate under computer control while directing the stationary DESI emitter charged droplet plume at the TLC plate surface. Mass spectral data were recorded in either selected reaction monitoring mode or in full scan ion trap mode using a hybrid triple quadrupole linear ion trap mass spectrometer. Fundamentals and practical applications of the technique were demonstrated in positive ion mode using selected reaction monitoring detection of rhodamine dyes separated on hydrophobic reversed-phase C8 plates and reversed-phase C2 plates, in negative ion full scan mode using a selection of FD&C dyes separated on a wettable reversed-phase C18 plate, and in positive ion full scan mode using a mixture of aspirin, acetaminophen, and caffeine from an over-the-counter pain medication separated on a normal-phase silica gel plate.

Acetaminophen↗

PubMed2005

Thin-layer chromatography/electrospray ionization triple-quadrupole linear ion trap mass spectrometry system: analysis of rhodamine dyes separated on reversed-phase C8 plates.

The direct analysis of separated rhodamine dyes on reversed-phase C(8) thin-layer chromatography plates using a surface sampling/electrospray emitter probe coupled with a triple-quadrupole linear ion trap mass spectrometer is presented. This report represents continuing work to advance the performance metrics and utility of this basic surface sampling electrospray mass spectrometry system for the analysis of thin-layer chromatography plates. Experimental results examining the role of sampling probe spray end configuration on liquid aspiration rate and gas-phase ion signal generated are discussed. The detection figures-of-merit afforded by full-scan, automated product ion and selected reaction monitoring modes of operation were examined. The effect of different eluting solvents on mass spectrum signal levels with the reversed-phase C(8) plate was investigated. The combined effect of eluting solvent flow-rate and development lane surface scan rate on preservation of chromatographic resolution was also studied. Analysis of chromatographically separated red pen ink extracts from eight different pens using selected reaction monitoring demonstrated the potential of this surface sampling electrospray mass spectrometry system for targeted compound analysis with real samples.

Journal Article↗

PubMed2005

Self-aspirating atmospheric pressure chemical ionization source for direct sampling of analytes on surfaces and in liquid solutions.

A self-aspirating heated nebulizer probe is described and demonstrated for use in the direct analysis of analytes on surfaces and in liquid samples by atmospheric pressure chemical ionization (APCI) mass spectrometry. Functionality and performance of the probe as a self-aspirating APCI source is demonstrated using reserpine and progesterone as test compounds. The utility of the probe to sample analytes directly from surfaces was demonstrated first by scanning development lanes of a reversed-phase thin-layer chromatography plate in which a three-component dye mixture, viz., Fat Red 7B, Solvent Green 3, and Solvent Blue 35, was spotted and the components were separated. Development lanes were scanned by the sampling probe operated under computer control (x, y plane) while full-scan mass spectra were recorded using a quadrupole ion trap mass spectrometer. In addition, the ability to sample the surface of pharmaceutical tablets (viz., Extra Strength Tylenol and Evista tablets) and to detect the active ingredients (acetaminophen and raloxifene, respectively) selectively was demonstrated using tandem mass spectrometry (MS/MS). Finally, the capability to sample analyte solutions from the wells of a 384-well microtiter plate and to perform quantitative analyses using MS/MS detection was illustrated with cotinine standards spiked with cotinine-d3 as an internal standard.

Atmospheric Pressure↗

PubMed2005

Characterisation of derivatised monomeric and prepolymeric isocyanates by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry and structural elucidation by tandem mass spectrometry.

Isocyanates are an important class of compounds in occupational hygiene monitoring due mainly to their behaviour as respiratory sensitisers. Here, we demonstrate the application of matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS) and MALDI tandem mass spectrometry (MS-MS) to the analysis of derivatised isocyanate monomers and prepolymers. The aim of the work has been to gauge the selectivity obtainable from the direct analysis of isocyanate mixtures without prior separation. Monomeric and prepolymeric isocyanate mixtures were analysed as their 1-(2-methoxyphenyl) piperazine derivatives and the potential of MALDI time-of-flight (ToF)-MS for an NCO monitoring program was assessed. The results obtained demonstrated the possibility of direct mixture analysis by this method. MALDI-MS-MS was used for the elucidation of fragment structures in the prepolymer samples. The developed methodology was then applied to the analysis of swabs from an occupational hygiene monitoring scheme and enabled the identification of the isocyanate species detected.

Air Pollutants, Occupational↗

PubMed2004

Trends in the band structures of the group-I and -II oxides.

Measured and calculated band structures for the six lightest group-I and -II oxides are reported. Band structures have been measured using electron momentum spectroscopy, a technique that maps the ground-state occupied orbitals resolved both in energy and momentum. Measurements are compared with first-principles calculations carried out within the linear combination of atomic orbitals approximation using both Hartree-Fock (HF) and density functional (DFT) methods. Three DFT functionals are used representative of the local density approximation, the generalized gradient approximation, and a hybrid method incorporating exact exchange. The calculated O 2p bandwidths and O 2p-2s band gaps generally scale linearly with the inverse of the oxygen-oxygen separation squared, but consistently show an anomaly at Li(2)O. These trends, including the anomaly, are also observed in the experimental data. HF calculations consistently overestimate the oxygen 2p-2s band gap by almost a factor of two. Measured band gaps lie within the range of the three DFT functionals employed, with evidence that the description of exchange becomes more important as the cation size increases. Both HF and DFT calculations overestimate the oxygen valence bandwidths, with DFT giving more accurate predictions. Both observed and calculated bandwidths converge as the cation size increases, indicating that exchange-correlation effects become less important as the metallic ion becomes larger.

Journal Article↗

PubMed2004

Rotation planar chromatography coupled on-line with atmospheric pressure chemical ionization mass spectrometry.

The coupling of a rotation planar preparative thin-layer chromatography system on-line with mass spectrometry is demonstrated using a simple plumbing scheme and a self-aspirating heated nebulizer probe of a corona discharge atmospheric pressure chemical ionization source. The self-aspiration of the heated nebulizer delivers approximately 20 microL/min of the 3.0 mL/min eluate stream to the mass spectrometer, eliminating the need for an external pump in the system. The viability of the coupling is demonstrated with a three-dye mixture composed of fat red 7B, solvent green 3, and solvent blue 35 separated and eluted from a silica gel-coated rotor using toluene. The real-time characterization of the dyes eluting from the rotor is illustrated in positive ion full-scan mode. Other self-aspirating ion source systems including atmospheric pressure photoionization, electrospray ionization, and inductively coupled plasma ionization, for example, might be configured and used in a similar manner coupled to the chromatograph to expand the types of analytes that could be ionized, detected, and characterized effectively.

Journal Article↗

PubMed2004

An improved thin-layer chromatography/mass spectrometry coupling using a surface sampling probe electrospray ion trap system.

A combined surface sampling probe/electrospray emitter coupled with an ion trap mass spectrometer was used for the direct read out of unmodified reversed-phase C18 thin-layer chromatography (TLC) plates. The operation of the surface sampling electrospray ionization interface in positive and negative ionization modes was demonstrated through the direct analysis of TLC plates on which a commercial test mix comprised of four dye compounds viz., rhodamine B, fluorescein, naphthol blue black, and fast green FCF, and an extract of the caffeine-containing plant Ilex vomitoria, were spotted and developed. Acquisition of full-scan mass spectra and automated collection of MS/MS product ion spectra while scanning a development lane along the surface of a TLC plate demonstrated the advantages of using an ion trap in this combination. Details of the sampling system, benefits of analyzing a developed lane in both positive ion and negative ion modes, levels of detection while surface scanning, surface scan speed effects, and the utility of three-dimensional data display, are also discussed.

Amido Black↗

PubMed2004

Efficient analyte oxidation in an electrospray ion source using a porous flow-through electrode emitter.

This article describes the components, operation, and use of a porous flow-through electrode emitter in an electrospray ion source. This emitter electrode geometry provided enhanced mass transport to the electrode surface to exploit the inherent electrochemistry of the electrospray process for efficient analyte oxidation at flow rates up to 800 microL/min. An upstream current loop in the electrospray source circuit, formed by a grounded contact to solution upstream of the emitter electrode, was utilized to increase the magnitude of the total current at the emitter electrode to overcome current limits to efficient oxidation. The resistance in this upstream current loop was altered to control the current and "dial-in" the extent of analyte oxidation, and thus, the abundance and nature of the oxidized analyte ions observed in the mass spectrum. The oxidation of reserpine to form a variety of products by multiple electron transfer reactions and oxidation of the ferroceneboronate derivative of pinacol to form the ES active radical cation were used to study and to illustrate the performance of this new emitter electrode design. Flow injection, continuous infusion, and on-line HPLC experiments were performed.

Borates↗

PubMed2002

Determination of alkyl benzyl and dialkyl dimethyl quaternary ammonium biocides in occupational hygiene and environmental media by liquid chromatography with electrospray ionisation mass spectrometry and tandem mass spectrometry.

A new method for the simultaneous qualitative and quantitative determination of alkyl benzyl and dialkyl quaternary ammonium compounds (QACs) has been developed. Analysis is by reversed-phase high-performance liquid chromatography coupled with electrospray ionisation mass spectrometry. QACs are extremely amenable to the electrospray ionisation technique (limit of detection of BAC C12 homologue 3 ng ml(-1)). The selectivity of mass spectrometric detection allows simultaneous determination of benzyl and dialkyl dimethyl ammonium compounds. The method was successfully applied to the analysis of real samples (occupational hygiene sampling devices, products and swimming pool water). Structural information was obtained by MS-MS and cone voltage ion dissociation techniques. Ion dissociation enabled the structural elucidation of an unknown quaternary ammonium compound present in a commercial formulation.

Chromatography, High Pressure Liquid↗

PubMed2002

Applications of selective neutrality tests to molecular ecology.

This paper reviews how statistical tests of neutrality have been used to address questions in molecular ecology are reviewed. The work consists of four major parts: a brief review of the current status of the neutral theory; a review of several particularly interesting examples of how statistical tests of neutrality have led to insight into ecological problems; a brief discussion of the pitfalls of assuming a strictly neutral model if it is false; and a discussion of some of the opportunities and problems that molecular ecologists face when using neutrality tests to study natural selection.

Animals↗