Calculation of pressure using the virtual-volume-variation method and the virial method from chain conformations obtained by Monte Carlo simulations on the second nearest neighbor diamond lattice

For a model system of polyethylene of chain lengths 40 and 100 carbon atoms, we calculated the pressure at different densities and compared them with the experimental values. The simulation was conducted on the second nearest neighbor diamond lattice, and the pressure was calculated using the virtual-volume-variation method after the system was reverse mapped to its fully atomistic form in continuous space and energy minimized. In addition, the pressure was also calculated from the virial route by conducting a short molecular dynamics simulation starting from the energy minimized structure. We show that the pressure obtained from our simulations is quite reasonable in the length of simulation time (in Monte Carlo steps) normally employed in our group. These results provide additional evidence for the equilibration of our model systems, and methodology to calculate the pressure in our lattice models.     

Effect of adding glycols to the micellar properties of Tween: small-angle neutron scattering and turbidity measurements

Small-angle neutron scattering (SANS) and turbidity measurements have been carried out on the nonionic surfactants Tween 20 and Tween 80, in the presence of diethyleneglycol (DEG), triethyleneglycol (TEG), ethylene glycol monoethyl ether (EGMEE), and ethyleneglycol mono butyl ether (EGMBE). SANS measurements show that the shapes of the Tween 20 and Tween 80 micelles are oblate ellipsoidal, which do not change predominantly in the presence of DEG and TEG. However, the presence of EGMBE and EGMEE reduces the aggregation number of Tween. This has been attributed to the solubilization of EGMBE and EGMEE in the Tween micelles, providing them with additional hydrophobicity.     

Determination of Gentian Violet in human urine and poultry feed by high performance liquid chromatography with electrochemical detection using a carbon fibre microelectrode flow cell

A sensitive and relatively selective high performance liquid chromatographic method for the determination of Gentian Violet (GV) in human urine and chicken feed is described. The method is based on solid-phase extraction, with subsequent reversed-phase chromatographic separation on a cyano column and amperometric detection using a carbon fibre microelectrode flow cell operated at + 1.3 V. The peak currents were directly proportional to GV concentration over the concentration range 1-30 ppb (for urine samples analysis) and 1-20 ppm for poultry feed analysis. Using this method, the minimum detectable concentration was estimated to be 0.5 ppb. The method was applied successfully to the determination of GV in human urine and in chicken feed, and it was concluded that the method could be applied to the quantitative analysis of GV in the presence of its major metabolite, leuco GV. In the proposed procedure, the occurrence of matrix effects during urine analysis was significant. The electrochemical pretreatment regime described in this paper was used to overcome these effects. Recovery studies were performed on both the human urine and chicken feed samples. The recovery of GV ranged from 92 to 96% in both matrices, with a relative standard deviation of less than 5.5%.     

Determination of micro amounts of uranium by a molybdenum blue method

A new and highly sensitive spectrophotometric method has been developed for the determination of micro amounts of uranium by a molybdenum blue method. The method is based on the observation that at low acidities uranium(IV) reduces ammonium molybdate to molybdenum blue, the absorbance of which is proportional to the amount of uranium present. The variables affecting development of the colour have been investigated and the conditions optimized. Beer's law is found to hold good for uranium concentrations between 1 and 20 ppm, with a precision of 2%. The effect of diverse ions has been studied. The method is useful for the determination of uranium present as an impurity (down to 0.1%) in plutonium, neptunium or thorium.     

Joint effects of elevated levels of ultraviolet-B radiation, carbon dioxide and ozone on plants

There is growing interest regarding the joint effects of elevated levels of surface ultraviolet B (UV-B) radiation, carbon dioxide (CO2) and ozone (O3) on plants. Our current knowledge of this subject is too limited to draw any specific conclusions, although one might state that such effects are likely to be highly species dependent and may be more than additive, additive or less than additive. There are a number of uncertainties associated with the experimental protocols used and the conclusions reached in many studies. Nevertheless, in North America, there appear to be genotypes of three monocot crop species (Avena sativa L., Oryza sativa L. and Sorghum vulgare L.); six dicot crops (Cucumis sativus L., Lactuca sativa L., Lycopersicon esculentum Mill., Phaseolus vulgaris L., Pisum sativum L. and Solanum tuberosum L.) and two conifer species (Pinus ponderosa Dougl. and Pinus taeda L.) that may be considered sensitive to the joint effects of elevated levels of UV-B, CO2 and O3. However, to provide a more reliable assessment or validation of the predictions, future research must consider the concept of plant response surfaces and describe them more fully in numerical terms. Achieving that objective will require close cooperation among a number of scientists representing geographic locations with known spatial and temporal differences in UV-B, CO2 and O3 to conduct experiments under their site-specific conditions, using common plant materials and experimental protocols.     

Studies on the recovery of233U from phosphate containing aqueous waste using DBDECMP as extractant

A method for the recovery and purification of²³³U from phosphate containing analytical waste is developed. Extraction studies with DBDECMP (Di-butyl, N, N-diethylcarbamoyl-methyl phosphonate) in xylene were carried out to explore the feasibility of separation and purification of²³³U from such wastes. Based on the data obtained, optimum conditions for the recovery of²³³U are suggested.     

Nano-Impact Single-Entity Electrochemistry Enables Plasmon-Enhanced Electrocatalysis**

Plasmon-enhanced electrocatalysis (PEEC), based on a combination of localized surface plasmon resonance excitation and an electrochemical bias applied to a plasmonic material, can result in improved electrical-to-chemical energy conversion compared to conventional electrocatalysis. Here, we demonstrate the advantages of nano-impact single-entity electrochemistry (SEE) for investigating the intrinsic activity of plasmonic catalysts at the single-particle level using glucose electrooxidation and oxygen reduction on gold nanoparticles as model reactions. We show that in conventional ensemble measurements, plasmonic effects have minimal impact on photocurrents. We suggest that this is due to the continuous equilibration of the Fermi level (E_F) of the deposited gold nanoparticles with the E_F of the working electrode, leading to fast neutralization of hot carriers by the measuring circuit. The photocurrents detected in the ensemble measurements are primarily caused by photo-induced heating of the supporting electrode material. In SEE, the E_F of suspended gold nanoparticles is unaffected by the working electrode potential. As a result, plasmonic effects are the dominant source of photocurrents under SEE experimental conditions.     

Cholesterol packing around lipids with saturated and unsaturated chains: a simulation study

The fundamental role of cholesterol in the regulation of eukaryotic membrane structure is well-established. However the manner in which atomic level interactions between cholesterol and lipids, with varying degrees of chain unsaturation and polar groups, affect the overall structure and organization of the bilayer is only beginning to be understood. In this paper we describe a series of Molecular Dynamics simulations designed to provide new insights into lipid-cholesterol interactions as a function of chain unsaturation. We have run simulations of varying concentrations of cholesterol in dipalmitoyl phosphatidylcholine (DPPC), palmitoyl-oleyol phosphatidylcholine (POPC), and dioleyol phosphatidylcholine (DOPC) bilayers. Structural analysis of the simulations reveals both atomistic and systemic details of the interactions and are presented here. In particular, we find that the minimum partial molecular area of cholesterol occurs in POPC-Chol mixtures implying the most favorable packing. Physically, this appears to be related to the fact that the two faces of the cholesterol molecule are different from each other and that the steric cross section of cholesterol molecules drops sharply near the small chain tails.     

Estimation of berberine in ayurvedic formulations containing Berberis aristata

A sensitive, simple, rapid, and efficient high-performance thin-layer chromatographic (HPTLC) method has been developed and validated for the analysis of berberine in marketed Ayurvedic formulations containing Berberis aristata DC for regulatory purposes. Chromatography of methanolic extracts of these formulations was performed on silica gel 60 F254 aluminum-backed TLC plates of 0.2 mm layer thickness. The plate was developed up to 66 mm with the ternary-mobile phase butanol-acetic acid-water (8 + 1 + 1, v/v/v) at 33 +/- 5 degrees C with 5 min of tank saturation. The marker, berberine, was quantified at its maximum absorbance of 350 nm. The limit of detection and limit of quantitation values were found to be 5 and 10 ng/spot. The linear regression analysis data for the calibration plot showed a good linear relationship with correlation coefficient = 0.9994 in the concentration range of 10 to 50 ng/spot for berberine with respect to peak area. The instrumental precision was found to be 0.49% coefficient of variation (CV), and repeatability of the method was 0.73% CV. Recovery values from 98.27 to 99.11% indicate excellent accuracy of the method. The developed HPTLC method is very accurate, precise, and cost-effective, and it has been successfully applied to the assay of marketed formulations containing B. aristata for determination of berberine.