Thomas J. Glynn

Quantitative analysis of cocaine in solid mixtures using Raman spectroscopy and chemometric methods

Near-infrared (785 nm) excitation was used to obtain Raman spectra from a series of 33 solid mixtures containing cocaine, caffeine and glucose (9.8–80.6% by weight cocaine), which were then analysed using chemometric methods. Principal component analysis of the data was employed to ascertain what factors influenced the spectral variation across the concentration range. It was found that 98% of the spectral variation was accounted for by three principal components. Analysis of the score and loadings plots for these components showed that the samples can be clearly classified on the basis of cocaine concentration. Discrimination on the basis of caffeine and glucose concentrations was also possible. Quantitative calibration models were generated using partial least-squares algorithms which predicted the concentration of cocaine in the solid mixtures containing caffeine and glucose from the Raman spectrum with a root mean standard error of prediction (RMSEP) of 4.1%. Caffeine and glucose concentrations were estimated with RMSEPs of 5.2 and 6.6%, respectively. These measurements demonstrate the feasibility of using near-IR Raman spectroscopy for rapid quantitative characterization of illegal narcotics. Copyright

Temperature dependence of the photoluminescence intensity of ordered and disordered In0.48Ga0.52P

The integrated photoluminescence (PL) intensities of both ordered and disordered epilayers of InGaP grown on GaAs have been measured as a function of temperature. The highest PL efficiency occurs in the most disordered sample. We find that the PL intensities can drop from 2 to almost 4 orders of magnitude between 12 and 280 K. The samples show an Arrhenius behavior characterized by two activation energies. Below 100 K the activation energies lie in the region of 10–20 meV. Above 100 K the activation energy is approximately 50 meV except in the most disordered sample where it increases to 260 meV. We conclude that the low‐temperature PL efficiency is most likely controlled by carrier thermalization from spatial fluctuations of the band edges followed by nonradiative recombination. At higher temperatures the PL efficiency is dominated by a nonradiative path whose characteristic activation energy and transition probability depend upon the degree of sublattice ordering.

Identifications and quantitative measurements of narcotics in solid mixtures using near-IR Raman spectroscopy and multivariate analysis

Raman spectroscopy offers the potential for the identification of illegal narcotics in seconds by inelastic scattering of light from molecular vibrations. In this study cocaine, heroin, and MDMA were analyzed using near-IR (785 nm excitation) micro-Raman spectroscopy. Narcotics were dispersed in solid dilutants of different concentrations by weight. The dilutants investigated were foodstuffs (flour, baby milk formula), sugars (glucose, lactose, maltose, mannitol), and inorganic materials (Talc powder, NaHCO3, MgSO4·7H2O). In most cases it was possible to detect the presence of drugs at levels down to ∼10% by weight. The detection sensitivity of the Raman technique was found to be dependent on a number of factors such as the scattering cross-sections of drug and dilutant, fluorescence of matrix or drug, complexity of dilutant Raman spectrum, and spectrometer resolution. Raman spectra from a series of 20 mixtures of cocaine and glucose (0–100% by weight cocaine) were collected and analyzed using multivariate analysis methods. An accurate prediction model was generated using a Partial Least Squares (PLS) algorithm that can predict the concentration of cocaine in solid glucose from a single Raman spectrum with a root mean standard error of prediction of 2.3%.

Characterization of crude oils using fluorescence lifetime data

The average fluorescence lifetimes of nine North Sea crude oils with API gravities of between 20 and 51 were measured using a modular, filter based, instrument developed in-house. Two pulsed light emitting diode (LED) excitation sources (460 and 510 nm) were used to excite fluorescence, the lifetime of which was measured at a range of emission wavelengths. Fluorescence lifetimes were found to vary from 1.8 to 8.2 ns with confidence intervals of +/- 0.11 ns. The average lifetimes at all emission wavelengths were linearly correlated with API gravity and with aromatic concentration with the best results being obtained with the 460 nm excitation source. Predictive models with an accuracy of +/- 7.6 API degrees were generated using partial least-squares methods from average fluorescence lifetimes measured at an emission wavelength of 500 nm using 460 nm excitation. A better correlation was found between the aromatic concentration of the oils and the ratio of the average fluorescence lifetimes at measured at 550 and 650 nm using 460 nm excitation. This led to a quantitative model with an accuracy of +/- 5.4% for aromatic concentration.

On the quantum efficiency of chromium-doped glasses

Abstract It is argued that in chromium-doped glasses the environment about the chromium ion can undergo a much greater deformation, when the electronic state of the ion changes from 4 A 2 to 4 T 2 , than is the case for most crystalline materials. An increased deformation enhances the probability for multiphonon relaxation. The case of Cr 3+ ions in low field sites in oxide glasses is considered. The large deformation shows up as a large Stokes shift of the 4 T 2 ↔ 4 A 2 transitions, and it is argued that the enhanced multiphonon relaxation is responsible for the low quantum efficiency of broadband-emitting chromium-doped glasses.

Nanocrystalline structure of nanobump generated by localized photoexcitation of metal film

The extreme cooling rates in material processing can be achieved in a number of current and emerging femtosecond laser techniques capable of highly localized energy deposition. The mechanisms of rapid solidification of a nanoscale region of a metal film transiently melted by a localized photoexcitation are investigated in a large-scale atomistic simulation. The small size of the melted region, steep temperature gradients, and fast two-dimensional electron heat conduction result in the cooling rate exceeding 1013 K/s and create conditions for deep undercooling of the melt. The velocity of the liquid/crystal interface rises up to the maximum value of ∼80 m/s during the initial stage of the cooling process and stays approximately constant as the temperature of the melted region continues to decrease. When the temperature drops down to the level of ∼0.6Tm, a massive homogeneous nucleation of the crystal phase inside the undercooled liquid region takes place and prevents the undercooled liquid from reaching th...

Time-domain measurement of fluorescence lifetime variation with pH

Advances in the design and miniaturization of the lasers and electronics required for Time Correlated Single Photon Counting (TCSPC) measurement of fluorescence lifetime have simplified the use of the time domain method. We have assembled a compact portable system that is capable of measuring lifetimes down to approximately 200 ps (with deconvolution) and that can operate at a range of excitation and emission wavelengths. The excitation sources are pulsed LEDs and laser diodes with a maximum pulse rate of 40 MHz and are easily interchanged. Furthermore, the development of violet and blue GaN LEDs and laser diodes is expanding the range of fluorophores available for fluorescence lifetime measurement of ion concentrations. pH sensitive fluorophores have a wide range of biological and clinical applications. The use of fluorescence lifetime rather than intensity to measure pH has a number of advantages including the reduction of effects due to the photobleaching, scattering, and intensity variations in the excitation source. Using our compact TCSPC instrumentation we have measured the dependence of fluorescence lifetimes on pH for a range of dyes in phosphate buffer over the physiologically important range of 6.0 to 8.0. Most dyes exhibit only a small variation in lifetime (<1.0ns) over the 6.0 to 8.0 pH range; however, acridine exhibits a large variation in lifetime and hence shows promise as a pH indicator.

Luminescence study of LiGa5−xFexO8

Abstract Absorption, excitation, and luminescence measurements are presented for LiGa5−xFexO8 with concentrations x from 0.015 to 0.26. The emission and excitation data indicate that the red luminescence observed is due to the 6A1(6S)←4T1(4G) transition in the d5 configuration for Fe3+ in tetrahedral sites. Single-crystal samples allow direct absorption measurements for the first time and these indicate that most of the Fe3+ substitutes for Ga3+ in octahedral sites. Fine structure in the zero-phonon line and in the sideband is reported.

Luminescence from β-Ga2O3: Cr3+

Abstract Cr3+ substitutes readily for Ga3 + in β-Ga2O3 and the luminescence at room temperature from this material is broadband and originates mainly on the 4T2 level. We have examined this luminescence over a wide range of temperature to determine the radiative efficiency of the material and the relative positions of the 2E and 4T2 emitting levels.

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 (τ̄) 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 τ̄ 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 τ̄ measurements. Individual HCFI were analyzed using the DLFLM, and time-resolved fluorescence measurements were compared with τ̄ 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.