Electrosynthesis of 2,3-dimethyltartaric acid from pyruvic acid in acid medium

This study reports the electrohydrodimerization of pyruvic acid to 2,3-dimethyltartaric acid in sulphuric acid medium (0.5 M H₂SO₄) on a lead cathode. The main products detected were lactic acid and 2,3-dimethyltartaric acid. The selectivity towards the formation of 2,3-dimethyltartaric acid was studied vs. pyruvic acid concentration in sulphuric acid solution, at −1.1 V vs. MSE. The best selectivity of 2,3-dimethyltartaric acid reached 69% for an initial concentration of 1.7 M pyruvic acid. The yield of pyruvic acid was 84%.     

Wall to fluid heat transfer in liquid fluidised beds: Part 2

Wall to fluid heat transfer coefficients and radial temperature profiles have been obtained for beds of hydrodynamically similar spheres fluidized with water in a 2.058 inch pipe at a constant heat flux. From packed bed to open pipe conditions, heat transport occurs mainly by turbulent mixing, although conduction through the particles and possibly particle convection have some effect at low porosities. This result contradicts a previously published prediction based on model calculations using erroneous temperature profiles⁽²⁴⁾. The model predicts a minor role for particle convection when appropriate temperature profiles are used. A series model based on the observed shift of thermal resistance from the wall region to the bulk of the bed with decreasing porosity is used to correlate heat transfer coefficients. The shift in resistance largely accounts for the maximum in heat transfer coefficient plots.     

A priori evaluation of dynamic subgrid models of turbulence in square duct flow

A priori tests of two dynamic subgrid-scale (SGS) turbulence models have been performed using a highly resolved direct numerical simulation database for the case of turbulent incompressible flow in a straight duct of square cross-section. The model testing is applied only to the homogeneous flow direction where grid filtering can be applied without the introduction of commutation errors. The first SGS model is the dynamic (Smagorinsky/eddy viscosity) SGS model (DSM) developed by Germano et al. [1] while the second is the dynamic two parameter (mixed) model (DTM) developed by Salvetti and Banerjee [2]. For the Smagorinsky model we have used both the Fourier cut-off filter and a modified Gaussian filter which has the property that it removes aliasing errors in consistent a priori model-testing for spectral-based datasets. Results largely consistent with those found for plane channel flow are observed but with some slight differences in the corner regions. As found in prior studies of this sort, there is a very poor correlation of the modelled and exact subgrid-scale dissipation in the case of the DSM. The DSM over-predicts subgrid-scale dissipation on average. Instantaneously, the model provides an inaccurate representation of subgrid-scale dissipation, in general underestimating the magnitude by approximately one order of magnitude. On the other hand, the DTM shows excellent agreement with the exact SGS dissipation over most of the duct cross-section with a correlation coefficient of approximately 09.     

Contaminants, diet, plasma fatty acids and smoking in Greenland 1999-2005

OBJECTIVES: The purpose of this study is to monitor and assess human exposure to pollution in the Arctic which presents a potential future health risk for the local populations. Epidemiological studies in Greenland have shown that human blood levels of several organic contaminants are very high, especially in the North where people depend on local food. In East Greenland (Ittoqqortoormiit (Scoresbysund)) the population shows the highest blood levels of several persistent organic pollutants found in Arctic countries, especially PCB, the levels of which exceed Canadian guideline levels. As in other Arctic countries, the predominant source of these contaminants is the local diet. However, other factors such as smoking may influence the metabolism and thereby the accumulation of toxic substances. STUDY DESIGN: This project is part of the human health program of the ongoing circumpolar "Artic Monitoring and Assessment Programme". Lifestyle, anthropometric factors, and dietary survey results covering 500 men and women from 6 Greenlandic districts were analyzed along with other factors blood lipids, fatty acid profiles, heavy metals and concentrations of persistent organic pollutants (POPs). RESULTS: The dietary survey showed that the traditional food on the average provided 20-30% of the total energy intake. However, the relative monthly meal intake of seal, whale, polar bear, fish and game, and the composition of imported food, varied between districts. Seal and polar bear intake, and, in particular all the plasma n-3 fatty acids, were significantly correlated with organic contaminant concentrations, (betaHCH, chlordanes, DDTs, Hexachlorobenzene, Mirex, PCBs, and toxaphenes) p<0.01(). After adjusting for age, district, dietary factors or plasma n-3 fatty acids, smoking was significantly correlated with high levels of all the above mentioned POPs. CONCLUSION: The main predictors of high contaminant levels in Greenland were age, district, male gender, smoking and high plasma n-3/n-6 ratio as a marker of high dietary intake of local marine mammals.     

Raman spectroscopic analysis of biochemical changes in individual triglyceride-rich lipoproteins in the pre- and postprandial state

Individual triglyceride-rich lipoprotein (TGRL) particles derived from human volunteers are nondestructively analyzed by laser tweezers Raman microspectroscopy, and information on their composition and distribution is obtained. The Raman signature of single optically trapped very low-density lipoproteins (VLDL), a subclass of TGRL, which play an important role in cardiovascular disease, exhibits distinct peaks associated with molecular vibrations of fatty acids, proteins, lipids, and structural rearrangements of lipids. Our analysis of pre- and postprandial VLDL exhibits the signature of biochemical changes in individual lipoprotein particles following the consumption of meals. Interaction of VLDL with endothelium leads to the breakdown of complex triacylglycerols and the formation of a highly ordered core of free saturated fatty acids in the particle. A particle distribution analysis reveals trends in the degree to which this process has occurred in particles at different times during the postprandial period. Differences in particle distributions based on the different ratios of polyunsaturated to saturated fats in the consumed meals are also easily discerned. Individual lipoprotein particles hydrolyzed in vitro through addition of lipoprotein lipase (LpL) exhibit strikingly similar changes in their Raman spectra. These results demonstrate the feasibility of monitoring the dynamics of lipid metabolism of individual TGRL particles as they interact with LpL in the endothelial cell wall using Raman spectroscopy.     

Surface-enhanced Raman scattering from individual au nanoparticles and nanoparticle dimer substrates

Surface-enhanced Raman scattering (SERS) intensities for individual Au nanospheres, nanoshells, and nanosphere and nanoshell dimers coated with nonresonant molecules are measured, where the precise nanoscale geometry of each monomer and dimer is identified through in situ atomic force microscopy. The observed intensities correlate with the integrated quartic local electromagnetic field calculated for each specific nanostructure geometry. In this study, we find that suitably fabricated nanoshells can provide SERS enhancements comparable to nanosphere dimers.     

Plasmon transmissivity and reflectivity of narrow grooves in a silver film

Surface plasmon (SP) reflectivity and transmissivity of narrow grooves in silver films are studied. The SP source is the probe of a scanning near-field optical microscope. Locally detected leakage radiation from the SP provides detailed information on the paths of SP propagation, in particular the influence of perturbations. Global detection provides representative average data on the SP properties of a given metal film and its structures. A groove of 200 nm width, for instance, reflects/transmits about 15%/80% of 'blue-green' SP radiation at normal incidence.