A study of the atmospherically relevant reaction between molecular chlorine and dimethylsulfide (DMS): establishing the reaction intermediate and measurement of absolute photoionization cross-sections

In a study using UV photoelectron spectroscopy (PES) of the atmospherically relevant reaction CH3SCH3 + Cl2 → CH3SCH2Cl + HCl bands associated with a reaction intermediate have been observed. These have been assigned to ionization of the covalently bound molecule (CH3)2SCl2 on the basis of the intensity of the observed bands as a function of reaction time, molecular orbital calculations of vertical ionization energies and evidence from infrared spectroscopy. A method has also been developed, with the flow-tube/PE spectrometer combination used, to measure photoionization cross-sections of the reagents and products at the photon energy utilized and this has allowed the photoionization cross-section of the intermediate to be estimated. This work augments an earlier study in which the rate constant of the reaction between CH3SCH3 (DMS) and Cl2 has been measured at room temperature.

Unusual isotope effect in the reaction of chlorosilylene with trimethylsilane-1-d: Absolute rate studies and quantum chemical and Rice–Ramsperger–Kassel–Marcus calculations provide strong evidence for the involvement of an intermediate complex

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1- silacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with trimethylsilane-1-d, Me3SiD, in the gas phase. The reaction was studied at total pressures up to 100 Torr (with and without added SF6) over the temperature range of 295−407 K. The rate constants were found to be pressure independent and gave the following Arrhenius equation: log[(k/(cm3 molecule−1 s−1)] = (−13.22 ± 0.15) + [(13.20 ± 1.00) kJ mol−1]/(RT ln 10). When compared with previously published kinetic data for the reaction of ClSiH with Me3SiH, kinetic isotope effects, kD/kH, in the range from 7.4 (297 K) to 6.4 (407 K) were obtained. These far exceed values of 0.4−0.5 estimated for a single-step insertion process. Quantum chemical calculations (G3MP2B3 level) confirm not only the involvement of an intermediate complex, but also the existence of a low-energy internal isomerization pathway which can scramble the D and H atom labels. By means of Rice−Ramsperger−Kassel−Marcus modeling and a necessary (but small) refinement of the energy surface, we have shown that this mechanism can reproduce closely the experimental isotope effects. These findings provide the first experimental evidence for the isomerization pathway and thereby offer the most concrete evidence to date for the existence of intermediate complexes in the insertion reactions of silylenes.

Trevor Griffiths' 'Absolute Beginners': socialist humanism and the television studio

This article examines how conventional studio production strategies were active in the construction of political meaning in the 1974 television play 'Absolute Beginners' written by Trevor Griffiths. Produced for the BBC anthology series Fall of Eagles, the play dramatises Lenin's involvement with the Russian Social Democratic Workers Party (RSDWP) and explores the contradictions between personal ethics and political necessity. Through close textual analysis and contextual discussion of other plays in the series, this piece demonstrates how shot patterns and spatial and performative devices in 'Absolute Beginners' supported the drama's socialist-humanist themes. Drawing on existing writing about the studio mode, it argues that the qualities of intimacy and presentational distance that it engendered were highly appropriate for the personal and the political dialectic in 'Absolute Beginners'. While using authorship as a convenient category for referring to the coherence of Griffiths' thematic concerns and dramatic structure during this period, the article complicates notions of the television dramatist as author by arguing for the importance of visual style and showing how 'ordinary' studio form was operational in the play's political meanings.

Determination of the absolute accuracy of UK chamber facilities used in measuring methane emissions from livestock

Respiration chambers are one of the primary sources of data on methane emissions from livestock. This paper describes the results from a coordinated set of chamber validation experiments which establishes the absolute accuracy of the methane emission rates measured by the chambers, and for the first time provides metrological traceability to international standards, assesses the impact of both analyser and chamber response times on measurement uncertainty and establishes direct comparability between measurements made across different facilities with a wide range of chamber designs. As a result of the validation exercise the estimated combined uncertainty associated with the overall capability across all facilities reduced from 25.7% (k = 2, 95% confidence) before the validation to 2.1% (k = 2, 95% confidence) when the validation results are applied to the facilities’ data.

A Lateglacial archaeological site in the far north-west of Europe at Rubha Port an t-Seilich, Isle of Islay, western Scotland: Ahrensburgian-style artefacts, absolute dating and geoarchaeology

The exact pattern, process and timing of the human re-colonization of northern Europe after the end of the last Ice Age remain controversial. Recent research has provided increasingly early dates for at least pioneer explorations of latitudes above 54°N in many regions, yet the far north-west of the European landmass, Scotland, has remained an unexplained exception to this pattern. Although the recently described Hamburgian artefacts from Howburn and an assemblage belonging to the arch-backed point complex from Kilmelfort Cave have established at least a sporadic human presence during earlier stages of the Lateglacial Interstadial, we currently lack evidence for Younger Dryas/Greenland Stadial 1 (GS-1) activity other than rare stray finds that have been claimed to be of Ahrensburgian affiliation but are difficult to interpret in isolation. We here report the discovery of chipped stone artefacts with technological and typological characteristics similar to those of the continental Ahrensburgian at a locality in western Scotland. A preliminary analysis of associated tephra, pollen and phytoliths, along with microstratigraphic analysis, suggest the artefacts represent one or more episodes of human activity that fall within the second half of GS-1 and the Preboreal period

Absolute Thellier paleointensities from Ponta Grossa dikes (southern Brazil) and the early Cretaceous geomagnetic field strength

We report a detailed rock magnetic and Thellier paleointensity study from similar to 130.5 Ma Ponta Grossa Dike Swarms in Southern Brazil. Twenty-nine samples from seven cooling units were pre-selected for paleointensity experiments based on their low viscosity index, stable remanent magnetization and close to reversible continuous thermomagnetic curves. 19 samples characterized by negative pTRM tests, Arai concave- up curves or positive pTRM tests with NRM loss uncorrelated with TRM acquisition were rejected. High quality reliable paleointensity determinations are determined from detailed evaluation criteria, with 10 samples belonging to three dikes passing the tests. The site-mean paleointensity values obtained in this study range from 25.6 +/- 4.3 to 11.3 +/- 2.1 mu T and the corresponding VDM`s range from 5.7 +/- 0.9 to 2.5 +/- 0.5 (10(22) Am(2)). These data yield a VDM mean value of 4.1 +/- 1.6 x 10(22) Am(2). Significant variability of Earth`s magnetic field strength is observed for Ponta Grossa Dikes with the mean value being significantly lower as compared to the mean VDM obtained from the nearby Parana Magmatic Province. The paleointensities for the Ponta Grossa Dikes are in agreement with absolute paleointensities retrieved from the submarine basaltic glasses from 130 to 120 Ma. It seems that a relatively low field prevailed just before the Cretaceous Normal Superchron.

Absolute normalization for uncorrelated background with the event mixing technique

We present a method to determine the magnitude of the uncorrelated background distribution obtained with the event mixing technique, through the simultaneous observation of the projectile elastic scattering in different detectors, which correspond to random coincidences. The procedure is tested with alpha-d angular correlation data from the (6)Li + (59)Co reaction at E(lab) = 29.6 MeV. We also show that the method can be applied using the product of singles events, when singles measurements are available. (C) 2009 Elsevier B.V. All rights reserved.

ON THE MINIMUM ABSOLUTE VALUE of THE DISCRIMINANT of ABELIAN FIELDS of DEGREE p(2)

Let p be a prime number. A formula for the minimum absolute value of the discriminant of all Abelian extensions of Q of degree p(2) is given in terms of p.

Ratios of dijet production cross sections as a function of the absolute difference in rapidity between jets in proton-proton collisions at root s=7 TeV

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Further monoterpene chromane esters from Peperomia obtusifolia: VCD determination of the absolute configuration of a new diastereomeric mixture

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Potentialities and practical limitations of absolute neutron dosimetry using thin films of uranium and thorium applied to the fission track dating

Neutron dosimetry using natural uranium and thorium thin films makes possible that mineral dating by the fission-track method can be accomplished, even when poor thermalized neutron facilities are employed. In this case, the contributions of the fissions of (235)U, (238)U and (232)Th induced by thermal, epithermal and fast neutrons to the population of tracks produced during irradiation are quantified through the combined use of natural uranium and thorium films.If the Th/U ratio of the sample is known, only one irradiation (where the sample and the films of uranium and thorium are present) is necessary to perform the dating. However, if that ratio is unknown, it can be determined through another irradiation where the mineral to be dated and both films are placed inside a cadmium box.Problems related with film manufacturing and calibration are discussed. Special attention is given to the utilization of thin films having very low uranium content. The problems faced suggest that it may be better to substitute these films by uranium doped standard glasses calibrated with thicker uranium films (thickness greater than 1.5 x 10(13) mu m).

The absolute configuration of 1-(3 ',4 '-dihydroxycinnamoyl)cyclopentane-2,3-diol from the Amazonian tree Chimarrhis turbinata

An antioxidant, 1-(3',4'-dihydroxycinnamoyl) cyclopentane-2,3-diol [ or ( E)-2,3-dihydroxycyclopentyl-3-(3',4'-dihydroxyphenyl) acrylate ( 1)], and two known trans- and cis-chlorogenic acid methyl esters were isolated from the ethanolic extract of the leaves of Chimarrhis turbinata. The relative configuration of 1 was determined by NMR and by comparison of the circular dichroic spectrum ( CD) with those of the enantiomers of synthetic 3', 4'-dimethoxycinnamoyl analogues. The absolute configuration of one of the synthetic enantiomers was determined using the CD exciton chirality method. This established the structure of naturally occurring 1 as (E)- 2,3-dihydroxycyclopentyl- 3-(3', 4'-dihydroxyphenyl) acrylate.

Determination of absolute configuration of 1,3-diols by the modified Mosher's method using their di-MTPA esters

1,3-Diols are frequently involved in biologically important compounds and, therefore, determination of the stereochemistry of these structural elements, in particular those in acyclic systems, has been one of the focuses of attention in natural products chemistry. The modified Mosher's method, commonly used for the determination of the absolute configuration of secondary alcohols, was applied to determine the absolute configuration of 1,3-diols with their di-MTPA esters. Several epimeric pairs of syn- and anti-1,3-diols with known absolute configurations were converted to the corresponding di-MTPA esters and the Delta delta values were then calculated. For the acyclic syn-1,3-diols, the Delta delta values were systematically arranged as predicted from the basic concept of the modified Mosher's method, demonstrating that the method is valid for these compounds. In contrast, the Delta delta values were irregularly arranged for the acyclic anti-1,3-diols and, accordingly, this method is not valid for these cases. These results are complementary to those of the previously reported CD exciton chirality method and, hence, the combined use of the modified Mosher's method and the CD exciton chirality method can determine the absolute configuration of the acyclic 1,3-diols. Also, this method is successfully applicable to cyclic 1,3-diols irrespective of their relative stereochemistry. (C) 2002 Wiley-lass, Inc.