A sensitive semi-micro column HPLC method with peroxyoxalate chemiluminescence detection and column switching for determination of MDMA-related compounds in hair

A sensitive semi-micro column HPLC method with peroxyoxalate chemiluminescence (POCL) detection and column switching has been developed for simultaneous determination of 3,4-methylenedioxymethamphetamine (MDMA) and related compounds, for example 3,4-methylenedioxyamphetamine, methamphetamine, and amphetamine, in hair. After digestion of the hair with 1 mol L⁻¹ sodium hydroxide the compounds were extracted with n-heptane and derivatized with 4-(N,N-dimethylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole. A mixture of hydrogen peroxide and bis(2,4,5-trichloro-6-carbopentoxyphenyl)oxalate in acetonitrile was used as post-column CL reagent. Calibration plots showed linearity was good (r = 0.999); detection limits were 0.02–0.16 ng mg⁻¹ hair at a signal-to-noise ratio of 3. The precision of the method, as RSD (n = 5), in intra-day and inter-day assays was better than 5.0 and 6.9%, respectively. The proposed method was sufficiently sensitive to detect low ng mg⁻¹ levels of MDMA and related compounds in hair, and could be used for quantification of the compounds in hair samples from patients treated in a chemical dependency unit.     

Effects of Hydrogen for Different Stereospecific Active Sites on Ultra Low TiCl3 Loading Supported Catalyst

The relationship between the stereospecificity of active sites and hydrogen effects on propylene polymerization was investigated for MgCl₂‐supported TiCl₃ catalysts at ultra‐low Ti contents. Hydrogen had no effect on the catalyst activities for isospecific sites and for aspecific sites. The efficiency of hydrogen as a chain‐transfer agent was found to depend on the stereospecificity of the active sites. Hydrogen was effective for isospecific sites but was not effective for aspecific sites. From the viewpoint of hydrogen dissociation, isospecific sites should have hydrogen dissociation sites in their surroundings. Therefore, isospecific sites may be in the island to be affected by hydrogen and isolated sites may be aspecific or have low isospecificity.

     

Dynamics of 15N natural abundance in wood-decomposing fungi and their ecophysiological implications

Nine species of basidiomycota and one species of ascomycota were grown in an ammonium sulphate media and on beech wood; and the general (15)N dynamic patterns of the hyphae were examined. The fungal body initially became depleted in (15)N in both the types of incubation. However, the underlying mechanisms were quite different, that is, significant fungal (15)N drop on the beech wood is associated with the fungal N reallocation and the uptake of atmospheric ammonia and/or NO(x), in addition to isotope fractionation during assimilation. Although the (15)N values of the wood-decomposing basidiocarps were generally close to the (15)N values of the wood, it does not always indicate that the wood derived N was the sole N source for the fungi throughout the growth periods as shown in our wood-decomposing experiment.     

Optimum speech level to minimize listening difficulty in public spaces

For ideal speech communication in public spaces, it is important to determine the optimum speech level for various background noise levels. However, speech intelligibility scores, which is conventionally used as the subjective listening test to measure the quality of speech communication, is near perfect in most everyday situations. For this reason, it is proposed to determine optimum speech levels for speech communication in public spaces by using listening difficulty ratings. Two kinds of listening test were carried out in this work. The results of the tests and our previous work [M. Morimoto, H. Sato, and M. Kobayashi, J. Acoust. Soc. Am. 116, 1607-1613 (2004)] are jointly discussed for suggesting the relation between the optimum speech level and background noise level. The results demonstrate that: (1) optimum speech level is constant when background noise level is lower than 40 dBA, (2) optimum speech level appears to be the level, which maintains around 15 dBA of SN ratio when the background noise level is more than 40 dBA, and (3) listening difficulty increases as speech level increases under the condition where SN ratio is good enough to keep intelligibility near perfect.     

Electrospray droplet impact/secondary ion mass spectrometry (EDI/SIMS) using NaF and AgF as cationization matrices

In our previous paper, it was suggested that metal fluorides may be useful as cationization matrices in Electrospray droplet impact/SIMS. In this work, NaF and AgF were used as the cationization matrices for cyclodextrin (CD), polyethylene glycol (PEG), polystyrene (PS), garlic juice, and sliced raw rice. EDI mass spectra were measured without and with the use of matrices. Enhancement of ion abundances of [M + Na]⁺ for CD and PEG with NaF matrix and that of [M + Ag]⁺ for PS with AgF matrix were observed. However, the addition of matrices was not effective for the cationization of garlic juice and sliced raw rice samples. This may be due to the Coulombic repulsion of the reagent ions of Na⁺ or Ag⁺ with the preformed K⁺ adducts of oligosaccharides already present in the samples. Copyright © 2015 John Wiley & Sons, Ltd.     

Sensitive and selective determination of peptides,PG and PGP,using a novel fluorogenic reagent 4-chlorobenzene-1,2-diol

A novel fluorometric method was developed for the sensitive and selective detection of Pro-Gly (PG) and Pro-Gly-Pro (PGP) using 4-chlorobenzene-1,2-diol (4-CBD) as a fluorogenic reagent. The reaction was performed at 37°C for 30 min in the presence of a borate buffer (pH 7.0) and sodium periodate. The resulting fluorescence intensity was measured using a spectrofluorometer with excitation and emission wavelengths of 450 nm and 535 nm. To obtain a stable fluorescent signal and maximise its intensity, different reaction conditions such as the concentrations of the reagents, the reaction time, and the pH were optimised. Under the optimised conditions, a linear relationship was obtained between fluorescence intensity and peptide concentrations from 1.0–40.0 µmol L^?1 with a limit of detection of 1.0 µmol L^?1 (S/N = 3). Both PG and PGP generated a strong signal out of all the peptides tested and no other biogenic substances such as amino acids or proteins produced any fluorescence. The reaction thus developed is simple, rapid, selective, and sensitive. It can be applied to the determination of peptides as biomarkers or substrates.     

Estimation of absolute sound pressure in a small-sized sonochemical reactor

A small-sized sonochemical reactor in which the absolute value of the sound pressure amplitude can be estimated from the vibration velocity of the transducer was investigated. The sound pressure distribution in the reactor and the relationship between the vibration velocity and the sound pressure amplitude were derived through Helmholtz wave equation. The reactor consists of a bolt-clamped Langevin transducer and a rectangular cell with a tungsten reflector. A 3λ/4-standing-wave-field was generated in the reactor to simplify the sound pressure distribution. The sound pressure distribution was measured from the optical refractive index change of water using a laser interferometer. The experimental and theoretical results showed a good agreement in the absolute value of the sound pressure amplitude, and it was confirmed that the sound pressure in the sonochemical reactor can be estimated from the input current of the vibrator.     

Analysis of first stage ignition delay times of dimethyl ether in a laminar flow reactor

The combustion chemistry of the first stage ignition and chemistry/flow interactions are studied for dimethyl ether (DME) with a mathematical analysis of two systems: a plug flow reactor study is used to reduce the reaction chemistry systematically. A skeletal reaction mechanism for the low temperature chemistry of DME until the onset of ignition is derived on the basis of the detailed DME mechanism of the Lawrence Livermore National Laboratory – see Curran, Fischer and Dryer, Int. J. Chem. Kinetics, Vol. 32 (2000). It is shown that reasonably good results for ignition delay times can be reached using a simple system of three ordinary differential equations and that the resulting analytical solution depends only on two reaction rates and the initial fuel concentration. The stepwise reduction of the system based on assumptions yields an understanding on why these reactions are so important. Furthermore, the validation of the assumptions yields insight into the influence of the fuel and the oxygen concentration on the temperature during the induction phase. To investigate the influence of chemistry/flow interactions, a 2D model with a laminar Hagen–Poiseuille flow and 2D-polynomial profiles for the radial species concentration is considered. For the 2D model, it is found that only the diffusion coefficients and the reactor radius need to be taken into consideration additionally to describe the system sufficiently. Also, the coupling of flow and chemistry is clarified in the mathematical analysis. The insight obtained from the comparison of the 2D model and the plug flow model is used to establish an average velocity for the conversion of ignition locations to ignition delay times in a laminar flow reactor. Finally, the 2D analytical solution is compared against new experimental data, obtained in such a laminar flow reactor for an undiluted DME/air mixture with an equivalence ratio of φ = 0.835 and a temperature range of 555 to 585 K at atmospheric pressure.     

The Global Methane Cycle: Isotopes and Mixing Ratios,Sources and Sinks

Abstract

A review of the global cycle of methane is presented with emphasis on its isotopic composition. The history of methane mixing ratios, reconstructed from measurements of air trapped in ice-cores is described. The methane record now extends back to 420 kyr ago in the case of the Vostok ice cores from Antarctica. The trends in mixing ratios and in δ¹³C values are reported for the two Hemispheres. The increase of the atmospheric methane concentration over the past 200 years, and by 1% per year since 1978, reaching 1.7 ppmv in 1990 is underlined.

The various methane sources are presented. Indeed the authors describe the methane emissions by bacterial activity under anaerobic conditions in wet environments (wetlands, bogs, tundra, rice paddies), in ruminant stomachs and termite guts, and that originating from fossil carbon sources, such as biomass burning, coal mining, industrial losses, automobile exhaust, sea floor vent, and volcanic emissions. Furthermore, the main sinks of methane in the troposphere, soils or waters via oxidation are also reported, and the corresponding kinetic isotope effects.     

An optimal odd unimodular lattice in dimension 72

It is shown that if there is an extremal even unimodular lattice in dimension 72, then there is an optimal odd unimodular lattice in that dimension. Hence, the first example of an optimal odd unimodular lattice in dimension 72 is constructed from the extremal even unimodular lattice which has been recently found by G. Nebe.