Development of an advanced on-line position-specific stable carbon isotope system and application to methyl tert-butyl ether

We present an advanced system for on-line position-specific carbon isotope analysis. The main limitation of on-line intramolecular isotope ratio measurements has been that optimal pyrolytic fragments are obtained mostly at temperatures where the analyte has not completely reacted. As a result of undetermined isotopic fractionation, the isotopic signatures of the pyrolysis products are not strictly equal to these of the equivalent moieties in the parent molecule. We designed a pyrolytic unit in which both temperature and reaction time are variable parameters, enabling determination of the enrichment factor of the pyrolysis at optimal temperature by construction of a Rayleigh plot. In the case of methyl tert-butyl ether (MTBE) presented here, a 'pre-pyrolysis' fractionation of MTBE leading to a depletion of 0.9 parts per thousand was discovered and the enrichment factor of the optimal pyrolysis reaction was determined at -1.7 parts per thousand. Absolute delta C-13 values of two functional groups of MTBE - the methoxy group and the 2-methylpropane group - could be determined with 95% confidence intervals of 0.4 parts per thousand and 0.5 parts per thousand, respectively

Development of free sugar white chocolate, suitable for diabetics, using Stevia and sucralose as sweeteners: study of the thermal degradation kinetic

The purpose of this study was the development of formulations of white chocolate for diabetics with replacement of sucrose by sucralose (Su) and Stevia (St) using a mixture experimental design. The kinetic studies of thermodegradation which showed that binary combinations of Stevia with sucrose had synergistic effects since the matrix presented a lower thermal sensitivity to the non-enzymatic browning reaction than the samples formulated from the individual components. The phenomena of blooming during storage were studied by a computer vision system and image analysis. The results of sensory analysis revealed that the sample 100%St was not acceptable; however, combining Stevia with sucrose and sucralose, acceptable sensory chocolates were obtained with no statistically significant differences, compared to control 100%S (P> 0.05). Our study provides a chocolate suitable for diabetics, with an appropriate combination of sensorially acceptable sweeteners with higher stability than control sample.Fil: Rodriguez Furlan, Laura Teresa. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Invest. En Tecnología Química; Argentina. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia; ArgentinaFil: Baracco, Yanina. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia; ArgentinaFil: Zaritzky, Noemi. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; ArgentinaFil: Campderrós, Mercedes. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia; Argentin

Determination of Equilibrium Constants for the Reaction between Acetone and HO_2 Using Infrared Kinetic Spectroscopy

The reaction between the hydroperoxy radical, HO_2, and acetone may play an important role in acetone removal and the budget of HO_x radicals in the upper troposphere. We measured the equilibrium constants of this reaction over the temperature range of 215–272 K at an overall pressure of 100 Torr using a flow tube apparatus and laser flash photolysis to produce HO_2. The HO_2 concentration was monitored as a function of time by near-IR diode laser wavelength modulation spectroscopy. The resulting [HO_2] decay curves in the presence of acetone are characterized by an immediate decrease in initial [HO_2] followed by subsequent decay. These curves are interpreted as a rapid (<100 μs) equilibrium reaction between acetone and the HO_2 radical that occurs on time scales faster than the time resolution of the apparatus, followed by subsequent reactions. This separation of time scales between the initial equilibrium and ensuing reactions enabled the determination of the equilibrium constant with values ranging from 4.0 × 10^(–16) to 7.7 × 10^(–1)8 cm^3 molecule^(–1) for T = 215–272 K. Thermodynamic parameters for the reaction determined from a second-law fit of our van’t Hoff plot were Δ_(r)H°_(245) = −35.4 ± 2.0 kJ mol^(–1) and Δ_(r)S°_(245) = −88.2 ± 8.5 J mol^(–1) K^(–1). Recent ab initio calculations predict that the reaction proceeds through a prereactive hydrogen-bonded molecular complex (HO_2–acetone) with subsequent isomerization to a hydroxy–peroxy radical, 2-hydroxyisopropylperoxy (2-HIPP). The calculations differ greatly in the energetics of the complex and the peroxy radical, as well as the transition state for isomerization, leading to significant differences in their predictions of the extent of this reaction at tropospheric temperatures. The current results are consistent with equilibrium formation of the hydrogen-bonded molecular complex on a short time scale (100 μs). Formation of the hydrogen-bonded complex will have a negligible impact on the atmosphere. However, the complex could subsequently isomerize to form the 2-HIPP radical on longer time scales. Further experimental studies are needed to assess the ultimate impact of the reaction of HO_2 and acetone on the atmosphere

Quantification of sirolimus by liquid chromatography-tandem mass spectrometry using on-line solid-phase extraction

Quantification of the new immunosuppressant sirolimus (syn. rapamycin; Rapamune((R))) in whole blood by chromatography is essential for its clinical use since no immunoassay is available although monitoring is mandatory. Here we report on a rapid and convenient liquid chromatography (LC)-tandem mass spectrometry method and describe our practical experience with its routine use. Whole blood samples were hemolyzed and deproteinized using an equal volume (150 mul) of a mixture of methanol/zinc sulfate solution containing the internal standard desmethoxy-rapamycin. After centrifugation, the clear supernatants were submitted to an on-line solid-phase extraction procedure using the polymeric Waters Oasis HLB(R) material, with elution of the extracts onto the analytical column in the back-flush mode by column switching. For analytical chromatography a RP-C18 column was used with 90/10 methanol/2 mM ammonium acetate as the mobile phase. A 1:10 split was used for the transfer to the mass spectrometer, a Micromass Quattro LC-tandem mass spectrometry system equipped with a Z-spray((R)) source and used in the positive electrospray ionization mode. The following transitions were recorded: sirolimus, 931&gt;864 m/z, and desmethoxy-rapamycin (I.S.), 901&gt;834 m/z. The analytical running time was 5 min, including on-line extraction. The method has a linear calibration curve (r&gt;0.99; range 1.6-50 mug/l) and is rugged and precise with monthly CVs &lt;7% at a sirolimus concentration of 13.1 mug/l in routine use; the instrumentation proved to be reliable and required minimal maintenance

Evaluation of a bulk calorimeter and heat balance for determination of supersonic combustor efficiency

Results are presented from the shakedown and evaluation test of a bulk calorimeter. The calorimeter is designed to quench the combustion at the exit of a direct-connect, hydrogen fueled, scramjet combustor model, and to provide the measurements necessary to perform an analysis of combustion efficiency. Results indicate that the calorimeter quenches reaction, that reasonable response times are obtained, and that the calculated combustion efficiency is repeatable within + or -3 percent and varies in a regular way with combustor model parameters such as injected fuel equivalence ratio

Hydrocarbon ratios during PEM-WEST A: A model perspective

A useful application of the hydrocarbon measurements collected during the Pacific Exploratory Mission (PEM-West A) is as markers or indices of atmospheric processing. Traditionally, ratios of particular hydrocarbons have been interpreted as photochemical indices, since much of the effect due to atmospheric transport is assumed to cancel by using ratios. However, an ever increasing body of observatonial and theoretical evidence suggests that turbulent mixing associated with atmospheric transport influences certain hydrocarbon ratios significantly. In this study a three-dimensional mesoscale photochemical model is used to study the interaction of photochemistry and atmospheric mixing on select hydrocarbons. In terms of correlations and functional relationships between various alkanes the model results and PEM-West A hydrocarbon observations share many similar characteristics as well as explainable differences. When the three-dimensional model is applied to inert tracers, hydrocarbon ratios and other relationships exactly follow those expected by simple dilution with model-imposed "background air," and the three-dimensional results for reactive hydrocarbons are quite consistent with a combined influence of photochemistry and simple dilution. Analogous to these model results, relationships between various hydrocarbons collected during the PEM-West A experiment appear to be consistent with this simplified picture of photochemistry and dilution affecting individual air masses. When hydrocarbons are chosen that have negligeble contributions to clean background air, unambiguous determinations of the relative contributions to photochemistry and dilution can be estimated from the hydrocarbon samples. Both the three-dimensional model results and the observations imply an average characteristic lifetime for dilution with background air roughly equivalent to the photochemical lifetime of butane for the western Pacific lower troposphere. Moreover, the dominance of OH as the primary photochemical oxidant downwind of anthropogenic source regions can be inferred from correlations between the highly reactive alkane ratios. By incorporating back-trajectory information within the three-dimensional model analysis, a correspondence between time and a particular hydrocarbon or hydrocarbon ratio can be determined, and the influence of atmospheric mixing or photochemistry can be quantified. Results of the three-dimensional model study are compared and applied to the PEM-West A hydrocarbon dataset, yielding a practical methodology for determining average OH concentrations and atmospheric mixing rates from the hydrocarbon measurements. Aircraft data taken below 2 km during wall flights east of Japan imply a diurnal average OH concentration of ∼3 × 106 cm-3. The characteristic time for dilution with background air is estimated to be ∼2.5 days for the two study areas examined in this work. Copyright 1996 by the American Geophysical Union

Evaluation of the annoyance due to helicopter rotor noise

A program was conducted in which 25 test subjects adjusted the levels of various helicopter rotor spectra until the combination of the harmonic noise and a broadband background noise was judged equally annoying as a higher level of the same broadband noise spectrum. The subjective measure of added harmonic noise was equated to the difference in the two levels of broadband noise. The test participants also made subjective evaluations of the rotor noise signatures which they created. The test stimuli consisted of three degrees of rotor impulsiveness, each presented at four blade passage rates. Each of these 12 harmonic sounds was combined with three broadband spectra and was adjusted to match the annoyance of three different sound pressure levels of broadband noise. Analysis of variance indicated that the important variables were level and impulsiveness. Regression analyses indicated that inclusion of crest factor improved correlation between the subjective measures and various objective or physical measures

Subjective response to seated fore-and-aft direction whole-body vibration

Subjective response to seated, fore-and-aft direction, whole-body vibration of the type experienced in automobiles was investigated. Fore-and-aft acceleration was measured at the seat guide of a small automobile when driving over two representative road surfaces, and was replicated in a laboratory setting using a whole-body vibration test rig and rigid seat. A single 15-second section of each of the two acceleration time histories was band-pass filtered to the frequency interval from 0.5 to 50.5 Hz, and was used as a base stimulus. Thirteen test stimuli were then constructed for each base stimulus by rescaling to BS 6841 Wd frequency-weighted r.m.s. amplitudes from 0.01 to 0.86 m/s2. Two groups of 16 participants (8 male and 8 female in each case) rated the discomfort of the test stimuli. The first group was asked to use the psychophysical method of magnitude estimation while the second used a Borg CR-10 scale. The order of presentation of the test stimuli was fully randomised and each was repeated 3 times. For each group of participants, regression analysis was used to determine both the individual and the group mean Stevens’Power Law exponent describing the relationship between stimulus amplitude and subjective response. All mean power exponents were found to be less than unity, with the CR-10 scale having produced smaller exponents than magnitude estimation. The power exponents ranged from 0.66 to 0.91, corroborating the value of 0.84 obtainable from the guidelines of standard BS 6841.The results suggest that the numerical response scale provided in the BS 6841 guidelines is appropriate for use in the case of automobile fore-andaft vibration, but that the semantic labels under-represent the actual human subjective response in this direction. Psychophysical test method, vibration stimulus range and test participant gender were all found to affect the Stevens’ Power Law exponent achieved from subjective testing. Each factor may therefore require control when attempting to compare human responses to vibration originating from different automobiles

Radiation-induced growth and isothermal decay of infrared-stimulated luminescence from feldspar

Optically stimulated luminescence (OSL) ages can determine a wide range of geological events or processes, such as the timing of sediment deposition, the exposure duration of a rock surface, or the cooling rate of bedrock. The accuracy of OSL dating critically depends on our capability to describe the growth and decay of laboratory-regenerated luminescence signals. Here we review a selection of common models describing the response of infrared stimulated luminescence (IRSL) of feldspar to constant radiation and temperature as administered in the laboratory. We use this opportunity to introduce a general-order kinetic model that successfully captures the behaviour of different materials and experimental conditions with a minimum of model parameters, and thus appears suitable for future application and validation in natural environments. Finally, we evaluate all the presented models by their ability to accurately describe a recently published feldspar multi-elevated temperature post-IR IRSL (MET-pIRIR) dataset, and highlight each model's strengths and shortfalls