Rapid, quantitative analysis of ppm/ppb nicotine using surface-enhanced Raman scattering from polymer-encapsulated Ag nanoparticles (gel-colls)

Rapid, quantitative SERS analysis of nicotine at ppm/ppb levels has been carried out using stable and inexpensive polymer-encapsulated Ag nanoparticles (gel-colls). The strongest nicotine band (1030 cm(-1)) was measured against d(5)-pyridine internal standard (974 cm(-1)) which was introduced during preparation of the stock gel-colls. Calibration plots of I-nic/I-pyr against the concentration of nicotine were non-linear but plotting I-nic/I-pyr against [nicotine](x) (x = 0.6-0.75, depending on the exact experimental conditions) gave linear calibrations over the range (0.1-10 ppm) with R-2 typically ca. 0.998. The RMS prediction error was found to be 0.10 ppm when the gel-colls were used for quantitative determination of unknown nicotine samples in 1-5 ppm level. The main advantages of the method are that the gel-colls constitute a highly stable and reproducible SERS medium that allows high throughput (50 sample h(-1)) measurements.

Measurement of Quenching Coefficients and Developement of Calibration Methods for Quantitative Spectroscopy of Plasma at Elevated Pressures

Measurements of collisional de-excitation (quenching) coefficients required for the interpretation of emission and fluorescence spectroscopic measurements are reported. Particular attention is turned on argon transitions which are of interest for actinometric determinations of atomic ground state populations and on fluorescence lines originating from excited atoms and noble gases in connection with two-photon excitation (TALIF) of atomic radicals. A novel method is described which allows to infer quenching coefficients for collisions with molecular hydrogen of noble gas states in the energy range up to 24 eV. The excitation is performed in these experiments by collisions of energetic electrons in the sheath of an RF excited hydrogen plasma during the field reversal phase which lasts about 10 ns. We describe in addition a calibration method - including quenching effects - for the determination by TALIF of absolute atomic radical densities of hydrogen, nitrogen and oxygen using two-photon resonances in noble gases close by the resonances of the species mentioned. The paper closes with first ideas on a novel technique to bypass quenching effects in TALIF by introducing an additional, controllable loss by photoionization that will allow quenching-free determination of absolute atomic densities with prevalent nanosecond laser systems in situations where collisional de-excitation dominates over spontaneous emission.

Testing the reliability of the JEOL FEGSEM 6500F electron microprobe for quantitative major element analysis of glass shards from rhyolitic tephra.

Electronprobe microanalysis is now widely adopted in tephra studies as a technique for determining the major element geochemistry of individual glass shards. Accurate geochemical characterization is crucial for enabling robust tephra-based correlations; such information may also be used to link the tephra to a specific source and often to a particular eruption. In this article, we present major element analyses for rhyolitic natural glass standards analysed on three different microprobes and the new JEOL FEGSEM 6500F microprobe at Queen’s University Belfast. Despite the scatter in some elements, good comparability is demonstrated among data yielded from this new system, the previous Belfast JEOL-733 Superprobe, the JEOL-8200 Superprobe (Copenhagen) and the existing long-established microprobe facility in Edinburgh. Importantly, our results show that major elements analysed using different microprobes and variable operating conditions allow two high-silica glasses to be discriminated accurately.

Fast, quantitative nucleoside protection under solvent-free conditions

Persilylation of nucleoside hydroxyls was effected in quantitative yields under solvent-free conditions using a ball mill. In addition, one-pot persilylation and acylation of cytidine was performed as an exemplar reaction demonstrating the utility of solvent-free approaches to nucleoside chemistry.

Were last glacial climate events simultaneous between Greenland and France? A quantitative comparison using non-tuned chronologies

Several large abrupt climate fluctuations during the last glacial have been recorded in Greenland ice cores and archives from other regions. Often these Dansgaard-Oeschger events are assumed to have been synchronous over wide areas, and then used as tie-points to link chronologies between the proxy archives. However, it has not yet been tested independently whether or not these events were indeed synchronous over large areas. Here, we compare Dansgaard-Oeschger-type events in a well-dated record from southeastern France with those in Greenland ice cores. Instead of assuming simultaneous climate events between both archives, we keep their age models independent. Even these well-dated archives possess large chronological uncertainties that prevent us from inferring synchronous climate events at decadal to multi-centennial time scales. If possible, comparisons between proxy archives should be based on independent, non-tuned time-scales. Copyright (C) 2009 John Wiley & Sons, Ltd.

Quantitative mapping of aqueous microfluidic temperature with sub-degree resolution using fluorescence lifetime imaging microscopy

The use of a water-soluble, thermo-responsive polymer as a highly sensitive fluorescence-lifetime probe of microfluidic temperature is demonstrated. The fluorescence lifetime of poly(N-isopropylacrylamide) labelled with a benzofurazan fluorophore is shown to have a steep dependence on temperature around the polymer phase transition and the photophysical origin of this response is established. The use of this unusual fluorescent probe in conjunction with fluorescence lifetime imaging microscopy (FLIM) enables the spatial variation of temperature in a microfluidic device to be mapped, on the micron scale, with a resolution of less than 0.1 degrees C. This represents an increase in temperature resolution of an order of magnitude over that achieved previously by FLIM of temperature-sensitive dyes

A meta-analysis of latitudinal variations in life-history traits of roach, Rutilus rutilus, over its geographical range: linear or non-linear relationships?

1. We collated information from the literature on life history traits of the roach (a generalist freshwater fish), and analysed variation in absolute fecundity, von Bertalanffy parameters, and reproductive lifespan in relation to latitude, using both linear and non-linear regression models. We hypothesized that because most life history traits are dependent on growth rate, and growth rate is non-linearly related with temperature, it was likely that when analysed over the whole distribution range of roach, variation in key life history traits would show non-linear patterns with latitude.

A critical review of some recent developments in quantitative research on gender and achievement in the United Kingdom

Over recent years the findings of a number of quantitative research studies have been published in the UK on gender and achievement. Much of this work has emanated from Stephen Gorard and his colleagues and has not only been highly critical of existing approaches to handling quantitative data but has also suggested a number of alternative and, what they claim to be, more valid ways of measuring differential patterns of achievement and underachievement between groups. This article shows how much of this work has been based upon rather under-developed measures of achievement and underachievement that tend, in turn, to generate a number of misleading findings that have questionable implications for practice. It will be argued that this body of work provides a useful case study in the problems of quantitative research that fails to engage adequately with the substantive theoretical and empirical literature and considers some of the implications of this for future research in this area.