Signs of l-doubling constants in NF3

Computed infrared band contours are presented for the two degenerate fundamentals of the NF3 molecule, using the l-resonance band contour program described by Cartwright and Mills, with values of the vibration-rotation constants determined from the microwave spectrum by Morino and co-workers. Computed contours are presented for both possible signs of the l-doubling constant, and comparison with the observed band contours leads to the conclusion that q3 = −121.4 MHz and q4 = +51.4 MHz.

ASYM20: a program for force constant and normal coordinate calculations, with a critical review of the theory involved

The theory of harmonic force constant refinement calculations is reviewed, and a general-purpose program for force constant and normal coordinate calculations is described. The program, called ASYM20. is available through Quantum Chemistry Program Exchange. It will work on molecules of any symmetry containing up to 20 atoms and will produce results on a series of isotopomers as desired. The vibrational secular equations are solved in either nonredundant valence internal coordinates or symmetry coordinates. As well as calculating the (harmonic) vibrational wavenumbers and normal coordinates, the program will calculate centrifugal distortion constants, Coriolis zeta constants, harmonic contributions to the α′s. root-mean-square amplitudes of vibration, and other quantities related to gas electron-diffraction studies and thermodynamic properties. The program will work in either a predict mode, in which it calculates results from an input force field, or in a refine mode, in which it refines an input force field by least squares to fit observed data on the quantities mentioned above. Predicate values of the force constants may be included in the data set for a least-squares refinement. The program is written in FORTRAN for use on a PC or a mainframe computer. Operation is mainly controlled by steering indices in the input data file, but some interactive control is also implemented.

The high-resolution infrared spectrum of HOF near 2700 cm-1: the ground and 2v2 states

The a/b hybrid-type ν1 fundamental and 2ν2 overtone bands of HOF were investigated by FTIR spectroscopy with a resolution close to 0.008 cm−1. Improved ground state parameters of HOF were determined from a merge of more than 3000 ground state combination differences formed from ν1 and previously measured ν2 transitions with the reported pure rotational lines. Excited state parameters of the v2 = 2 state, ν0 = 2686.924 6(1) and χ22 = −9.942 4(1) cm−1, were determined employing Watson's A-reduced Hamiltonian up to sixth order in I′ representation. The 2ν2 state was found to be unperturbed, the excited state parameters being closely related to those of ν2.

Calibration and use of a cesium-iodide prism in the infrared

With a cesium-iodide prism the long wavelength range of an infrared spectrometer may be extended to 55µ The use of such a prism, the choice of optical system, and the problems of stray radiation are all discussed. Accurate data are assembled for calibration in this region, and sample calibration traces are shown. A simple gas absorption cell is described for use at long wavelengths.

Developments in near infrared spectroscopy

Vibrational spectroscopy at high excitation is an important research frontier for two reasons. Firstly, the near infrared is proving to be an important area for the analytical applications of spectroscopy, and we would therefore like to understand how the spectra we observe relate to the molecular structure of the absorbing species. Secondly, there is a fundamental interest in understanding molecular dynamics and energy flow within a polyatomic molecule at high excitation, because this is the boundary between spectroscopy and chemistry through which we try to understand the details of a chemical reaction. In this presentation I shall survey recent progress in this field.

Remote gas detection and quantitative analysis from infrared emission spectra obtained by Fourier transform infrared spectroscopy

Techniques for obtaining quantitative values of the temperatures and concentrations of remote hot gaseous effluents from their measured passive emission spectra have been examined in laboratory experiments. The high sensitivity of the spectrometer in the vicinity of the 2397 cm-1 band head region of CO2 has allowed the gas temperature to be calculated from the relative intensity of the observed rotational lines. The spatial distribution of the CO2 in a methane flame has been reconstructed tomographically using a matrix inversion technique. The spectrometer has been calibrated against a black body source at different temperatures and a self absorption correction has been applied to the data avoiding the need to measure the transmission directly. Reconstruction artifacts have been reduced by applying a smoothing routine to the inversion matrix.

Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111)

Temperature-programmed reaction measurements supported by scanning tunneling microscopy have shown that phenylacetylene and iodobenzene react on smooth Au(111) under vacuum conditions to yield biphenyl and diphenyldiacetylene, the result of homocoupling of the reactant molecules. They also produce diphenylacetylene, the result of Sonogashira cross-coupling, prototypical of a class of reactions that are of paramount importance in synthetic organic chemistry and whose mechanism remains controversial. Roughened Au(111) is completely inert toward all three reactions, indicating that the availability of crystallographically well-defined adsorption sites is crucially important. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy show that the reactants are initially present as intact, essentially flat-lying molecules and that the temperature threshold for Sonogashira coupling coincides with that for C−I bond scission in the iodobenzene reactant. The fractional-order kinetics and low temperature associated with desorption of the Sonogashira product suggest that the reaction occurs at the boundaries of islands of adsorbed reactants and that its appearance in the gas phase is rate-limited by the surface reaction. These findings demonstrate unambiguously and for the first time that this heterogeneous cross-coupling chemistry is an intrinsic property of extended, metallic pure gold surfaces: no other species, including solvent molecules, basic or charged (ionic) species are necessary to mediate the process.

Whole crop cereals 2. Prediction of apparent digestibility and energy value from in vitro digestion techniques and near infrared reflectance spectroscopy and of chemical composition by near infrared reflectance spectroscopy

Samples of whole crop wheat (WCW, n = 134) and whole crop barley (WCB, n = 16) were collected from commercial farms in the UK over a 2-year period (2003/2004 and 2004/2005). Near infrared reflectance spectroscopy (NIRS) was compared with laboratory and in vitro digestibility measures to predict digestible organic matter in the dry matter (DOMD) and metabolisable energy (ME) contents measured in vivo using sheep. Spectral models using the mean spectra of two scans were compared with those using individual spectra (duplicate spectra). Overall NIRS accurately predicted the concentration of chemical components in whole crop cereals apart from crude protein. ammonia-nitrogen, water-soluble carbohydrates, fermentation acids and solubility values. In addition. the spectral models had higher prediction power for in vivo DOMD and ME than chemical components or in vitro digestion methods. Overall there Was a benefit from the use of duplicate spectra rather than mean spectra and this was especially so for predicting in vivo DOMD and ME where the sample population size was smaller. The spectral models derived deal equally well with WCW and WCB and Would he of considerable practical value allowing rapid determination of nutritive value of these forages before their use in diets of productive animals. (C) 2008 Elsevier B.V. All rights reserved.

Change in the effect of constant photoperiods on the rate of sexual maturation in modern genotypes of domestic pullet

1. Data for modern egg-type hybrids reared on constant daylengths show that, as expected, they mature more quickly than earlier genotypes. However, the constant photoperiod which gives earliest sexual maturity has not changed as a result of selection and is 10 h for both early and modern genotypes. 2. Further analysis showed that the rate of delay in sexual maturity for constant photoperiods above 10 h is similar for modern and for early hybrids ( +0.29 d for each incremental one hour of photoperiod), the response of modern hybrids below 10 h ( +4.22 d for each one-hour reduction in photoperiod) is more than double that of early hybrids ( +1.71 d/h).

Near infrared reflectance spectroscopy (NIRS) to predict biological parameters of maize silage: effects of particle comminution, oven drying temperature and the presence of residual moisture

Maize silage nutritive quality is routinely determined by near infrared reflectance spectroscopy (NIRS). However, little is known about the impact of sample preparation on the accuracy of the calibration to predict biological traits. A sample population of 48 maize silages representing a wide range of physiological maturities was used in a study to determine the impact of different sample preparation procedures (i.e., drying regimes; the presence or absence of residual moisture; the degree of particle comminution) on resultant NIR prediction statistics. All silages were scanned using a total of 12 combinations of sample pre-treatments. Each sample preparation combination was subjected to three multivariate regression techniques to give a total of 36 predictions per biological trait. Increased sample preparations procedure, relative to scanning the unprocessed whole plant (WP) material, always resulted in a numerical minimisation of model statistics. However, the ability of each of the treatments to significantly minimise the model statistics differed. Particle comminution was the most important factor, oven-drying regime was intermediate, and residual moisture presence was the least important. Models to predict various biological parameters of maize silage will be improved if material is subjected to a high degree of particle comminution (i.e., having been passed through a 1 mm screen) and developed on plant material previously dried at 60 degrees C. The extra effort in terms of time and cost required to remove sample residual moisture cannot be justified. (c) 2005 Elsevier B.V. All rights reserved.

Using near infrared reflectance spectroscopy (NIRS) to predict the biological parameters of maize silage

The microbial fermentability, ruminal degradability and digestibility of 48 maize silages were determined using in vitro gas production (GP), in situ degradability and in vitro digestibility procedures. The silages were produced from forage maize harvested throughout the summer of 1998, and represent a wide range of physiological maturities. Large variations among samples were observed for all biological parameters, with the exception of in vitro digestibility and the asymptote of in vitro GP. The potential of near infrared reflectance spectroscopy (NIRS) to predict the biological parameters measured was determined by regression of the biological data against the respective spectral profile. NIRS demonstrated only a moderate ability (R-2 > 0.60-0.80) to predict in vitro digestibility, modelled kinetics of gas production (excluding the asymptote of gas production) and the modelled ruminally soluble dry matter (DM) fraction. Calibration statistics for remaining biological parameters were unacceptably poor (R-2 = 0.60). (C) 2004 Elsevier B.V. All rights reserved.

The effect of environment on endosperm cell-wall development in Triticum aestivum during grain filling: an infrared spectroscopic imaging study

One of the major factors contributing to the failure of new wheat varieties is seasonal variability in end-use quality. Consequently, it is important to produce varieties which are robust and stable over a range of environmental conditions. Recently developed sample preparation methods have allowed the application of FT-IR spectroscopic imaging methods to the analysis of wheat endosperm cell wall composition, allowing the spatial distribution of structural components to be determined without the limitations of conventional chemical analysis. The advantages of the methods, described in this paper, are that they determine the composition of endosperm cell walls in situ and with minimal modification during preparation. Two bread-making wheat cultivars, Spark and Rialto, were selected to determine the impact of environmental conditions on the cell-wall composition of the starchy endosperm of the developing and mature grain, focusing on the period of grain filling (starting at about 14 days after anthesis). Studies carried out over two successive seasons show that the structure of the arabinoxylans in the endosperm cell walls changes from a highly branched form to a less branched form. Furthermore, during development the rate of restructuring was faster when the plants were grown at higher temperature with restricted water availability from 14 days after anthesis with differences in the rate of restructuring occurring between the two cultivars.

Functional coupling of the human dopamine D-2 receptor with G alpha(i1), G alpha(i2), G alpha(i3) and G alpha(o) G proteins: evidence for agonist regulation of G protein selectivity

1 The human dopamine D-2long (D-2L) receptor was expressed with four different G proteins in Sf9 cells using the baculovirus expression system. When co-expressed with G(i)/G(o) G proteins (G(i1)alpha, G(i2)alpha, G(i3)alpha, or G(o)alpha, plus Gbeta(1) and Ggamma(2)) the receptor displayed a high-affinity binding site for the agonists (dopamine and NPA), which was sensitive to GTP (100 mum), demonstrating interaction between the receptor and the different G proteins. 2 The receptor to G protein ratio (R: G ratio) was evaluated using [H-3]-spiperone saturation binding (R) and [S-35]-GTPgammaS saturation binding (G). R: G ratios of 1: 12, 1: 3, 1: 14 and 1: 5 were found for G(i1), G(i2), G(i3), and Go preparations, respectively. However, when R:G ratios of 1:2 and 1: 12 were compared for G(i2) and G(o), no difference was found for the stimulation of [S-35]-GTPgammaS binding. 3 Several agonists were tested for their ability to stimulate [S-35]-GTPgammaS binding to membranes co-expressing the receptor and various G proteins. All the compounds tested showed agonist activity in preparations expressing G(i3) and G(o). However, for G(i2) and G(i1) preparations, compounds such as S-(-)-3-PPP and p-tyramine were unable to stimulate [S-35]-GTPyS binding. 4 Most of the compounds showed higher relative efficacies (compared to dopamine) and higher potencies in the preparation expressing G(o). Comparison of the effects of different agonists in the different preparations showed that each agonist differentially activates the four G proteins. 5 We conclude that the degree of selectivity of G protein activation by the D-2L receptor can depend on the conformation of the receptor stabilised by an agonist.