Biomedical subjects

Alan G Ryder

Publications and source records attributed to Alan G Ryder.

10 recordsLinked to original sources

PubMed2006

Comparison of derivative preprocessing and automated polynomial baseline correction method for classification and quantification of narcotics in solid mixtures.

This work offers a real-world comparison of derivative preprocessing and a new polynomial method described by Lieber and Mahadevan-Jansen (LMJ) for baseline correction of Raman spectra with widely varying backgrounds. This comparison is based on their outcomes in factor analysis, analyte discrimination, and quantification. Both correction methods are applied to a Raman spectra data set taken from 85 solid samples of illegal narcotics diluted with various materials. It is found that neither approach outperforms the other, as they give similar principal component analysis (PCA) models and quantification errors: cocaine and heroin show cross-validation errors of approximately 8%, while MDMA is quantified to a cross-validation error of approximately 3-4%. The LMJ method does offer several other advantages, the most significant being the retention of original peak shapes after the correction, which simplifies the interpretation of the preprocessed spectra. The LMJ method is therefore recommended for use as a baseline correction method in future research with Raman spectroscopy.

Algorithms↗

PubMed2005

Time-resolved fluorescence studies on bovine serum albumin denaturation process.

The denaturation of Bovine Serum Albumin (BSA) by a chaotropic agent, guanidinium hydrochloride (GuH+Cl-) was studied by fluorescence lifetime analysis. The BSA was labelled with 1-anilino-8-naphthalene sulfonate (ANS) at two different molar ratios (1:1) and (1:10). The non-exponential fluorescence kinetics of the BSA-ANS complex at different stages of denaturation is analysed using three different models: a discrete tri-exponential sum, stretched exponential, and Gaussian lifetime distribution. In all cases, the fluorescence decay times decreased with protein denaturation. The results from the models show that there are at least two different binding sites located in the BSA protein with different water accessibility.

Anilino Naphthalenesulfonates↗

PubMed2005

Surface enhanced Raman scattering for narcotic detection and applications to chemical biology.

Raman spectroscopy is rapidly finding favour for applications in the life science because of the ease with which it can be used to extract significant data from tissue and cells. However, the Raman effect is an inherently weak effect, which hinders the analysis of low concentration analytes. Raman sensitivity can be improved via the surface enhanced Raman scattering (SERS) effect. In SERS, Raman spectra are dramatically amplified when a molecule is adsorbed onto nano-roughened noble metal surfaces such as silver and gold. The degree of enhancement enables single-molecule detection, which offers the potential for the unambiguous identification of analytes at concentrations that are useful in both a forensic and a chemical biology context. Here we discuss some of the practical applications of SERS to both low-level narcotic detection, and how this can be applied to chemical biology.

Bacteria↗

PubMed2004

The use of chloroaluminium phthalocyanine tetrasulfonate (AlPcTS) for time-delayed fluorescence imaging.

Phthalocyanine derivatives are currently under investigation for use in photodynamic therapy, which is a promising cancer treatment. These materials, which display preferential uptake in cancerous cells, also exhibit high fluorescence yields and can be used for tumour detection. Problems with steady-state fluorescence techniques such as excitation scatter and background autofluorescence can be eliminated by using time-resolved imaging techniques without the need for filters. A tissue phantom was assembled to test a constructed time-gated imaging system by drilling 36 wells of varying diameter and depth (10 mm to 1 mm) into a block of polymethyl methacrylate (PMMA). The system was used to record images of chloroaluminium phthalocyanine tetrasulfonate (AlPcTS) at differing concentrations in neat aqueous solvent and cell suspensions within the wells. A mixture of Intralipid (to mimic tissue scatter) and Evan's blue (to mimic tissue absorption) of depths ranging from 1 mm to 10 mm was placed on top of the PMMA block. The ensuing images were analysed using signal-to-noise ratios and contrast-detail curves. The results indicate that the time-gated imaging system can prevent background excitation scatter from distorting the fluorescence signal from a longer-lived photosensitizer without the need for filters.

Equipment Failure Analysis↗

PubMed2004

Assessing the maturity of crude petroleum oils using total synchronous fluorescence scan spectra.

There have been many applications of fluorescence methods for the analysis of crude petroleum oils down through the years. However, none of these studies has yielded a robust qualitative or quantitative method for quantifying the chemical composition, or assessing the maturity of crude oils. Simple fluorescence parameters such as lifetime, intensity, and intensity ratios do not correlate well with chemical composition particularly for medium weight crude oils [A. G. Ryder, T. J. Glynn, and M. Feely (2003). Proc. SPIE-Int. Soc. Opt. Eng. 4876, 1188-1195.]. A better approach may be to use the Total Synchronous Fluorescence Scan (TSFS) method to fully interrogate the complex chemical composition of the oils [D. Patra and A. K. Mishra (2002). Anal. Bioanal. Chem. 373, 304-309.]. We present TSFS spectra from 18 crude petroleum oils of varying composition, sourced from around the world. The TSFS plots of these oils are very complex, with the contours being spread over the full 250-700 nm wavelength range (lambda(ex)) and 40-200 nm wavelength interval (delta lambda) sampled. The 3-D contour maps tend to two contour concentrations one at lambda(em) < 300 nm, delta lambda = 120-200 nm, and a second near lambda(ex) approximately 380-400 nm, delta lambda = 40-60 nm. The first feature represents fluorescence emission originating mainly from energy transfer processes with the second, longer wavelength feature originating from fluorescence emission generated by a higher proportion of direct excitation as opposed to emission resulting from energy transfer. The topography of the 3D contour plots is therefore influenced by the balance between energy transfer and direct fluorescence emission, which is governed by the chemical composition of the crude oils. We discuss how the gross chemical composition affects TSFS spectra and how TSFS can be used to assess oil maturity with a view to developing quantitative methods.

Journal Article↗

PubMed2004

Time-resolved fluorescence microspectroscopy for characterizing crude oils in bulk and hydrocarbon-bearing fluid inclusions.

Time-resolved fluorescence data was collected from a series of 23 bulk crude petroleum oils and six microscopic hydrocarbon-bearing fluid inclusions (HCFI). The data was collected using a diode laser fluorescence lifetime microscope (DLFLM) over the 460-700 nm spectral range using a 405 nm excitation source. The correlation between intensity averaged lifetimes (tau) and chemical and physical parameters was examined with a view to developing a quantitative model for predicting the gross chemical composition of hydrocarbon liquids trapped in HCFI. It was found that tau is nonlinearly correlated with the measured polar and corrected alkane concentrations and that oils can be classified on this basis. However, these correlations all show a large degree of scatter, preventing accurate quantitative prediction of gross chemical composition of the oils. Other parameters such as API gravity and asphaltene, aromatic, and sulfur concentrations do not correlate well with tau measurements. Individual HCFI were analyzed using the DLFLM, and time-resolved fluorescence measurements were compared with tau data from the bulk oils. This enabled the fluid within the inclusions to be classified as either low alkane/high polar or high alkane/low polar. Within the high alkane/low polar group, it was possible to clearly discriminate HCFI from different locales and to see differences in the trapped hydrocarbon fluids from a single geological source. This methodology offers an alternative method for classifying the hydrocarbon content of HCFI and observing small variations in the trapped fluid composition that is less sensitive to fluctuations in the measurement method than fluorescence intensity based methods.

Colloids↗

PubMed2004

Time-resolved fluorescence spectroscopic study of crude petroleum oils: influence of chemical composition.

The fluorescence of crude petroleum oils is sensitive to changes in chemical composition and many different fluorescence methods have been used to characterize crude oils. The use of fluorescence lifetimes to quantitatively characterize oil composition has practical advantages over steady-state measurements, but there have been comparatively few studies in which the lifetime behavior is correlated with gross chemical compositional data. In this study, the fluorescence lifetimes for a series of 23 crude petroleum oils with American Petroleum Institute (API) gravities of between 10 and 50 were measured at several emission wavelengths (450-785 nm) using a 380 nm light emitting diode (LED) excitation source. It was found that the intensity average fluorescence lifetime (tau) at any emission wave-length does not correlate well with either API gravity or aromatic concentration. However, it was found that tau is strongly negatively correlated with both the polar and sulfur concentrations and positively correlated with the corrected alkane concentration. This indicates that the fluorescence behavior of crude petroleum oils is governed primarily by the concentration of quenching species. All the strong lifetime-concentration correlations are nonlinear and show a high degree of scatter, especially for medium to light oils with API gravities of between 25 and 40. The degree of scatter is greatest for oils where the concentrations (wt %) of the polar fraction is approximately 10 +/- 4%, the asphaltene component is approximately 1 +/- 0.5%, and sulfur is 0.5 +/- 0.4%. This large degree of scatter precludes the use of average fluorescence lifetime data obtained with 380 nm excitation for the accurate prediction of the common chemical compositional parameters of crude petroleum oils.

Alkanes↗

PubMed2003

Evaluation of acridine in Nafion as a fluorescence-lifetime-based pH sensor.

We report a novel fluorescence-lifetime-based pH sensing method that utilizes acridine incorporated into Nafion (AcNaf) as the fluorescent indicator. The AcNaf sensor is excited using a 380 nm light emitting diode (LED) and the fluorescence lifetimes are measured at 450 and 500 nm. The fluorescence behavior of acridine as a function of pH in aqueous phosphate buffers and incorporated into the Nafion membrane has been investigated. The results show that incorporating acridine into Nafion changes the apparent ground-state pKa from -5.45 to -9, while the apparent excited-state pKa* is only slightly changed (approximately 9.4 in 0.1 M phosphate buffer). The AcNaf film shows a good pH response with a change in average lifetime of approximately 19 ns (at an emission wavelength of 450 nm) over the pH 8 to 10 range. We also show that excited-state protonation does not occur in the AcNaf sensor film and that chloride quenching cannot occur because of the permselective nature of Nafion. We also discuss how the unique structure of Nafion affects the fluorescence behavior of acridine at various pH values and examine the impact of buffer concentration on apparent pKa and pH sensing ability.

Acridines↗

PubMed2002

Classification of narcotics in solid mixtures using principal component analysis and Raman spectroscopy.

Eighty-five solid samples consisting of illegal narcotics diluted with several different materials were analyzed by near-infrared (785 nm excitation) Raman spectroscopy. Principal Component Analysis (PCA) was employed to classify the samples according to narcotic type. The best sample discrimination was obtained by using the first derivative of the Raman spectra. Furthermore, restricting the spectral variables for PCA to 2 or 3% of the original spectral data according to the most intense peaks in the Raman spectrum of the pure narcotic resulted in a rapid discrimination method for classifying samples according to narcotic type. This method allows for the easy discrimination between cocaine, heroin, and MDMA mixtures even when the Raman spectra are complex or very similar. This approach of restricting the spectral variables also decreases the computational time by a factor of 30 (compared to the complete spectrum), making the methodology attractive for rapid automatic classification and identification of suspect materials.

Cocaine↗

PubMedDate not supplied

Determination of the modulation transfer function for a time-gated fluorescence imaging system.

The use of fluorescence for cancer detection is currently under investigation. Presently, steady-state fluorescence detection methods are in use, but have limitations due to poor contrast between the fluorescence of the tumor and background autofluorescence. Improved contrast can be obtained with time-resolved techniques because of the differing lifetimes between autofluorescence and exogenous photosensitizers that selectively accumulate within tumor tissue. An imaging system is constructed using a fast-gated (200-ps) charge-coupled device (CCD) camera and a pulsed 635-nm laser diode. To characterize the ability of the system to transfer object contrast to an image, the modulation transfer function (MTF) of the system is acquired by employing an extended knife-edge technique. A knife-edge target is assembled by drilling a rectangular well into a block of polymethyl methacrylate (PMMA). The imaging system records images of the photosensitizer, chloroaluminum phthalocyanine tetrasulfonate (AlPcTS), within the well. AlPcTS was chosen to test the system because of its strong absorption of 635-nm, high fluorescence yield, and relatively long fluorescence lifetime (approximately 7.5 ns). The results show that the system is capable of resolving 10(-4) M AlPcTS fluorescence as small as 1 mm. The findings of this study contribute to the development of a time-gated imaging system using fluorescence lifetimes.

Algorithms↗