Development of sandwich HPLC microcolumns for analyte adsorption on the millisecond time scale

A new class of columns is reported that uses only microgram quantities of active support and that provides for the retention of biological compounds and other analytes on the millisecond time scale. This was accomplished by packing standard HPLC supports into layers as small as 60 microm in length and using only 90 microg of support material. This provided columns with effective residence times in the millisecond time range when routine HPLC flow rates and pressures were used. The retention of analytes by such columns was examined under both adsorption- and diffusion-limited conditions. The RPLC adsorption of hemoglobin (a system with diffusion-limited retention) was found to give 95% binding in as little as 4 ms. The adsorption of fluorescein by an anti-fluorescein antibody column (an adsorption-limited system) gave 95% retention in 100-120 ms. One application examined for these columns was their use in a chromatographic-based competitive binding immunoassay. This used bovine serum albumin (BSA) as the model analyte, and fluorescein-labeled BSA was used for detection. The resulting approach had a contact time of 180 ms between the sample and an anti-BSA immunoaffinity microcolumn and provided a signal within 5-25 s after sample injection. The columns developed in this work should also be useful in other situations that involve a small amount of a stationary phase or that require short column residence times.     

Wavelength Dependence of Backscatter by use of Aerosol Microphysics and Lidar Data Sets: Application to 2.1- mum Wavelength for Space-Based and Airborne Lidars

An aerosol microphysics dataset was used to model backscatter in the 0.35-11-mum wavelength range, with the results validated by comparison with measured cw and pulsed lidar backscatter obtained during two NASA-sponsored airborne field experiments. Different atmospheric features were encountered, with aerosol backscatter ranging over 4 orders of magnitude. Modeled conversion functions were used to convert existing lidar backscatter datasets to 2.1 mum. Resulting statistical distribution shows the midtropospheric aerosol backscatter background mode of beta(2.1) to be between ~3.0 x 10(-10) and ~1.3 x 10(-9) m(-1) sr(-1), ~10-20 times higher than that for beta(9.1); and a beta(2.1) boundary layer mode of ~1.0 x 10(-7) to ~1.3 x 10(-6) m(-1) sr(-1), ~3-5 times higher than beta(9.1).     

Young driver accidents in the UK: the influence of age, experience, and time of day

Young drivers, especially males, have relatively more accidents than other drivers. Young driver accidents also have somewhat different characteristics to those of other drivers; they include single vehicle accidents involving loss of control; excess speed for conditions; accidents during darkness; accidents on single carriageway rural roads; and accidents while making cross-flow turns (i.e. turning right in the UK, equivalent to a left turn in the US and continental Europe). A sample of over 3000 accident cases was considered from midland British police forces, involving drivers aged 17-25 years, and covering a two year period. Four types of accident were analysed: right-turns; rear-end shunts; loss of control on curves; and accidents in darkness. Loss of control on curves and accidents in darkness were found to be a particular problem for younger drivers. It was found that cross-flow turn accidents showed the quickest improvement with increasing driver experience, whereas accidents occurring in darkness with no street lighting showed the slowest rate of improvement. 'Time of day' analyses suggested that the problems of accidents in darkness are not a matter of visibility, but a consequence of the way young drivers use the roads at night. There appears to be a large number of accidents associated with voluntary risk-taking behaviours of young drivers in 'recreational' driving.     

An application of the theory of planned behaviour to truck driving behaviour and compliance with regulations

A questionnaire study was conducted with truck drivers to help understand driving and compliance behaviour using the theory of planned behaviour (TPB). Path analysis examined the ability of the TPB to explain the direct and indirect factors involved in self-reported driving behaviour and regulation compliance. Law abiding driving behaviour in trucks was related more to attitudes, subjective norms and intentions than perceived behavioural control. For compliance with UK truck regulations, perceived behavioural control had the largest direct effect. The differing results of the path analyses for driving behaviour and compliance behaviour suggest that any future interventions that may be targeted at improving either on-road behaviour or compliance with regulations would require different approaches.     

Light absorption from particulate impurities in snow and ice determined by spectrophotometric analysis of filters

Light absorption by particulate impurities in snow and ice can affect the surface albedo and is important for the climate. The absorption properties of these particles can be determined by collecting and melting snow samples and extracting the particulate material by filtration of the meltwater. This paper describes the optical design and testing of a new instrument to measure the absorption spectrum from 400 to 750 nm wavelength of the particles collected on filters using an "integrating-sandwich" configuration. The measured absorption is shown to be unaffected by scattering of light from the deposited particulates. A set of calibration standards is used to derive an upper limit for the concentration of black carbon (BC) in the snow. The wavelength dependence of the absorption spectra from 450 to 600 nm is used to calculate an absorption ?ngstrom exponent for the aerosol. This exponent is used to estimate the actual BC concentration in the snow samples as well as the relative contributions of BC and non-BC constituents to the absorption of solar radiation integrated over the wavelength band 300 to 750 nm.     

Applying the motorcyclist's perspective to improve car drivers' attitudes towards motorcyclists

This study sought to provide a first crucial step in the direction of developing an intervention program aimed at improving safe attitudes and skills among car drivers towards motorcycles. We intended to improve drivers’ attitudes towards motorcyclists by exposing them to demands that motorcyclists face on the road. Car drivers were exposed to hazard perception clips taken from a motorcyclist's perspective, and interactive hazards in a motorcycle simulator. Car hazard perception clips and a car simulator were used as control conditions. A questionnaire assessed participant knowledge and attitudes towards motorcyclists before and after the intervention. After the intervention participants had more empathic- and fewer negative-attitudes, as well as safer attitudes towards motorcyclists. Self-reported attitude-change suggested that the use of motorcycle hazard perception clips was more effective than the simulator, and the intervention was most effective for those car drivers who reported the most negative attitudes prior viewing the clips or riding the simulator. Providing car drivers with a perspective of the motorcyclist may prove to be a useful tool for promoting safer attitudes towards motorcyclists.     

Monolayer structures of alkyl aldehydes: Odd-membered homologues

Crystalline monolayers of three aldehydes with an odd number of carbon atoms in the alkyl chain (C₇, C₉ and C₁₁) at low coverages are observed by a combination of X-ray and neutron diffraction. Analysis of the diffraction data is discussed and possible monolayer crystal structures are proposed; although unique structures could not be ascertained for all molecules. We conclude that the structures are flat on the surface, with the molecules lying in the plane of the layer. The C₁₁ homologue is determined to have a plane group of either p2, pgb or pgg, and for the C₇ homologue the p2 plane group is preferred.     

The infrared properties of magnetron-sputtered diamond-like thin films

We have measured the infrared reflectance, R, and the transmittance, T, of several amorphous and diamond-like carbon films deposited on GaAs substrates by d.c. magnetron sputtering in an Argon atmosphere. The thickness, d, and the refractive index, n, were found from the fringes in the near-infrared reflectance, which were due to the interference in the film, using an appropriate model for the absorption. The mid-infrared absorption coefficient , obtained from 1-R-T, was then fitted to a model of the absorption involving both vibrations and electronic transitions, using d and n. The electronic absorption was found to decrease with increasing pressure, along with an increase in the intensity of the hydrogen vibrational features. We associate the transparency with the presence of hydrogen and present support for this view by measuring a film in which hydrogen was deliberately introduced.     

Urinary globotriaosylsphingosine-related biomarkers for Fabry disease targeted by metabolomics

Fabry disease is a lysosomal storage disorder caused by deficiency of α-galactosidase A, resulting in glycosphingolipid accumulation in organs and tissues, including plasma and urine. Two disease-specific Fabry biomarkers have been identified and quantified in plasma and urine: globotriaosylceramide (Gb(3)) and globotriaosylsphingosine (lyso-Gb(3)). The search continues for biomarkers that might be reliable indicators of disease severity and response to treatment. The main objective of this study was to target other urinary biomarkers using a time-of-flight mass spectrometry metabolomic approach. Urinary metabolites of 63 untreated Fabry patients and 59 controls were analyzed. A multivariate statistical analysis performed on a subset of male samples revealed seven novel Fabry biomarkers in urine, all lyso-Gb(3) analogues having modified sphingosine moieties. The empirical formulas of the sphingosine modifications were determined by exact mass measurements (- C(2)H(4), - C(2)H(4) + O, - H(2), - H(2) + O, + O, + H(2)O(2), + H(2)O(3)). We evaluated the relative concentration of lyso-Gb(3) and its seven analogues by measuring area counts for each analogue in all Fabry patients. All samples were normalized to creatinine. We found higher concentrations for males with Fabry disease compared to females. None of these biomarkers were detected in controls. To our knowledge, this is the first time that lyso-Gb(3)-related Fabry disease biomarkers are detected in urine.     

Differences in passenger car and large truck involved crash frequencies at urban signalized intersections: An exploratory analysis

The influence of intersection features on safety has been examined extensively because intersections experience a relatively large proportion of motor vehicle conflicts and crashes. Although there are distinct differences between passenger cars and large trucks-size, operating characteristics, dimensions, and weight-modeling crash counts across vehicle types is rarely addressed. This paper develops and presents a multivariate regression model of crash frequencies by collision vehicle type using crash data for urban signalized intersections in Tennessee. In addition, the performance of univariate Poisson-lognormal (UVPLN), multivariate Poisson (MVP), and multivariate Poisson-lognormal (MVPLN) regression models in establishing the relationship between crashes, traffic factors, and geometric design of roadway intersections is investigated. Bayesian methods are used to estimate the unknown parameters of these models. The evaluation results suggest that the MVPLN model possesses most of the desirable statistical properties in developing the relationships. Compared to the UVPLN and MVP models, the MVPLN model better identifies significant factors and predicts crash frequencies. The findings suggest that traffic volume, truck percentage, lighting condition, and intersection angle significantly affect intersection safety. Important differences in car, car–truck, and truck crash frequencies with respect to various risk factors were found to exist between models. The paper provides some new or more comprehensive observations that have not been covered in previous studies.