Electron- and photon-impact ionization of furfural.

The He(i) photoelectron spectrum of furfural has been investigated, with its vibrational structure assigned for the first time. The ground and excited ionized states are assigned through ab initio calculations performed at the outer-valence Green's function level. Triple differential cross sections (TDCSs) for electron-impact ionization of the unresolved combination of the 4a″ + 21a' highest and next-highest occupied molecular orbitals have also been obtained. Experimental TDCSs are recorded in a combination of asymmetric coplanar and doubly symmetric coplanar kinematics. The experimental TDCSs are compared to theoretical calculations, obtained within a molecular 3-body distorted wave framework that employed either an orientation average or proper TDCS average. The proper average calculations suggest that they may resolve some of the discrepancies regarding the angular distributions of the TDCS, when compared to calculations employing the orbital average.

Electronic excitation of carbonyl sulphide (COS) by high-resolution vacuum ultraviolet photoabsorption and electron-impact spectroscopy in the energy region from 4 to 11 eV.

The electronic state spectroscopy of carbonyl sulphide, COS, has been investigated using high resolution vacuum ultraviolet photoabsorption spectroscopy and electron energy loss spectroscopy in the energy range of 4.0-10.8 eV. The spectrum reveals several new features not previously reported in the literature. Vibronic structure has been observed, notably in the low energy absorption dipole forbidden band assigned to the (4π←3π) ((1)Δ←(1)Σ(+)) transition, with a new weak transition assigned to ((1)Σ(-)←(1)Σ(+)) reported here for the first time. The absolute optical oscillator strengths are determined for ground state to (1)Σ(+) and (1)Π transitions. Based on our recent measurements of differential cross sections for the optically allowed ((1)Σ(+) and (1)Π) transitions of COS by electron impact, the optical oscillator strength f0 value and integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis. Subsequently, ICSs predicted by the scaling are confirmed down to 60 eV in the intermediate energy region. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of carbonyl sulphide in the upper stratosphere (20-50 km).

Electronic excitation of furfural as probed by high-resolution vacuum ultraviolet spectroscopy, electron energy loss spectroscopy, and ab initio calculations.

The electronic spectroscopy of isolated furfural (2-furaldehyde) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 3.5-10.8 eV energy-range, with absolute cross section measurements derived. Electron energy loss spectra are also measured over a range of kinematical conditions. Those energy loss spectra are used to derive differential cross sections and in turn generalised oscillator strengths. These experiments are supported by ab initio calculations in order to assign the excited states of the neutral molecule. The good agreement between the theoretical results and the measurements allows us to provide the first quantitative assignment of the electronic state spectroscopy of furfural over an extended energy range.

Electronic states of tetrahydrofurfuryl alcohol (THFA) as studied by VUV spectroscopy and ab initio calculations.

The electronic spectroscopy of isolated tetrahydrofurfuryl alcohol (THFA) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 5.0-10.8 eV energy-range, with absolute cross-section measurements derived. The He(I) photoelectron spectrum was also collected to quantify ionization energies in the 9-16 eV spectral region. These experiments are supported by the first high-level ab initio calculations performed on the excited states of the neutral molecule and on the ground and excited state of the positive ion. The good agreement between the theoretical results and the measurements allows us to quantify for the first time the electronic-state spectroscopy of THFA. The present work also considers the question of the lowest energy conformers of the molecule and its population distribution at room temperature.

Valence and ionic lowest-lying electronic states of ethyl formate as studied by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy, and ab initio calculations.

The highest resolution vacuum ultraviolet photoabsorption spectrum of ethyl formate, C2H5OCHO, yet reported is presented over the wavelength range 115.0-275.5 nm (10.75-4.5 eV) revealing several new spectral features. Valence and Rydberg transitions and their associated vibronic series, observed in the photoabsorption spectrum, have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. Calculations have also been carried out to determine the ionization energies and fine structure of the lowest ionic state of ethyl formate and are compared with a newly recorded He(I) photoelectron spectrum (from 10.1 to 16.1 eV). New vibrational structure is observed in the first photoelectron band. The photoabsorption cross sections have been used to calculate the photolysis lifetime of ethyl formate in the upper stratosphere (20-50 km).

Differential cross sections for intermediate-energy electron scattering from α-tetrahydrofurfuryl alcohol: excitation of electronic-states.

We report on measurements of differential cross sections (DCSs) for electron impact excitation of a series of Rydberg electronic-states in α-tetrahydrofurfuryl alcohol (THFA). The energy range of these experiments was 20-50 eV, while the scattered electron was detected in the 10°-90° angular range. There are currently no other experimental data or theoretical computations against which we can directly compare the present measured results. Nonetheless, we are able to compare our THFA DCSs with earlier cross section measurements for Rydberg-state electronic excitation for tetrahydrofuran, a similar cyclic ether, from Do et al. [J. Chem. Phys. 134, 144302 (2011)]. In addition, "rotationally averaged" elastic DCSs, calculated using our independent atom model with screened additivity rule correction approach are also reported. Those latter results give integral cross sections consistent with the optical theorem, and supercede those from the only previous study of Milosavljevic et al. [Eur. Phys. J. D 40, 107 (2006)].

Limonene: electronic state spectroscopy by high-resolution vacuum ultraviolet photoabsorption, electron scattering, He(I) photoelectron spectroscopy and ab initio calculations.

Electronic state spectroscopy of limonene has been investigated using vacuum ultraviolet photoabsorption spectroscopy in the energy range 5.0-10.8 eV. The availability of a high resolution photon beam (~0.075 nm) enabled detailed analysis of the vibrational progressions and allowed us to propose, for the first time, new assignments for several Rydberg series. Excited states located in the 7.5-8.4 eV region have been studied for the first time. A He(I) photoelectron spectrum has also been recorded from 8.2 to 9.5 eV and compared to previous low resolution works. A new value of 8.521 ± 0.002 eV for the ground ionic state adiabatic ionisation energy is proposed. Absolute photoabsorption cross sections were derived in the 10-26 eV range from electron scattering data. All spectra presented in this paper represent the highest resolution data yet reported for limonene. These experiments are complemented by new ab initio calculations performed for the three most abundant conformational isomers of limonene, which we then used in the assignment of the spectral bands.

Electronic state spectroscopy of methyl formate probed by high resolution VUV photoabsorption, He(i) photoelectron spectroscopy and ab initio calculations.

The first ab initio calculations of the vertical excitation energies and oscillator strengths are presented for the neutral electronic transitions of methyl formate, C(2)H(4)O(2). The highest resolution VUV photoabsorption spectrum of the molecule yet reported is presented over the wavelength range 115 to 310 nm (10.8 to 4.0 eV) revealing several new spectral features. Valence and Rydberg transitions and their associated vibronic series, observed in the photoabsorption spectrum, have been assigned in accordance with new theoretical results. The calculations have been carried out to determine the excitation energies of the lowest energy ionic states of methyl formate and are compared with a newly recorded He(i) photoelectron spectrum (10.4 to 17.0 eV). New vibrational structure is observed in the first photoelectron band. The photoabsorption cross-sections have been used to calculate the photolysis lifetime of methyl formate in the upper stratosphere (20-50 km).

Valence shell electronic spectroscopy of isoprene studied by theoretical calculations and by electron scattering, photoelectron, and absolute photoabsorption measurements.

The first ab initio calculations (vertical energies and oscillator strengths) are reported for the neutral electronic transitions of isoprene (2-methyl-1,3-butadiene), CH(2)CHC(CH(3))CH(2). The VUV photoabsorption spectroscopy of the molecule is presented in the energy range 4.6 to 10.8 eV (270-125 nm) with the highest resolution yet reported above 6.05 eV, revealing new spectral features. Valence and Rydberg transitions have been assigned in accordance with the theoretical results and the associated vibronic series have been analysed. The absolute photoabsorption cross sections at energies below 6.89 eV have been used to calculate the photolysis lifetime of isoprene in the upper stratosphere (20-50 km). Electron energy loss spectroscopy (EELS) measurements have enabled further photoabsorption cross sections to be derived in the range 9-28 eV. The first ab initio calculations have been carried out to determine excitation energies to the lowest energy ionic states of isoprene. The calculations are compared with the He(i) photoelectron spectrum (8 to 17 eV) and new vibrational structure is observed in the first photoelectron band.

Electronic state spectroscopy of c-C5F8 explored by photoabsorption, electron impact, photoelectron spectroscopies and ab initio calculations.

The electronic transitions and resonance-enhanced vibrational excitations of octafluorocyclopentene (c-C5F8) have been investigated using high-resolution photoabsorption spectroscopy in the energy range 6-11 eV. In addition, the high-resolution electron energy loss spectrum (HREELS) was recorded under the electric dipolar excitation conditions (100 eV incident energy, approximately 0 degrees scattering angle) over the 5-14 eV energy loss range. A He(I) photoelectron spectrum (PES) has also been recorded between 11 and 20 eV, allowing us to derive a more precise value of (11.288 +/- 0.002) eV for the ground neutral state adiabatic ionization energy. All spectra presented in this paper represent the first and highest resolution data yet reported for octafluorocyclopentene. Ab initio calculations have been performed for helping in the assignment of the spectral bands for both neutral excited states and ionic states.

Impact of flavor attributes on consumer liking of Swiss cheese.

Although Swiss cheese is growing in popularity, no research has examined what flavor characteristics consumers desire in Swiss cheese, which was the main objective of this study. To this end, a large group of commercially available Swiss-type cheeses (10 domestic Swiss cheeses, 4 domestic Baby Swiss cheeses, and one imported Swiss Emmenthal) were assessed both by 12 trained panelists for flavor and feeling factors and by 101 consumers for overall liking. In addition, a separate panel of 24 consumers rated the same cheeses for dissimilarity. On the basis of liking ratings, the 101 consumers were segmented by cluster analysis into 2 groups: nondistinguishers (n = 40) and varying responders (n = 61). Partial least squares regression, a statistical modeling technique that relates 2 data sets (in this case, a set of descriptive analysis data and a set of consumer liking data), was used to determine which flavor attributes assessed by the trained panel were important variables in overall liking of the cheeses for the varying responders. The model explained 93% of the liking variance on 3 normally distributed components and had 49% predictability. Diacetyl, whey, milk fat, and umami were found to be drivers of liking, whereas cabbage, cooked, and vinegar were drivers of disliking. Nutty flavor was not particularly important to liking and it was present in only 2 of the cheeses. The dissimilarity ratings were combined with the liking ratings of both segments and analyzed by probabilistic multidimensional scaling. The ideals of each segment completely overlapped, with the variance of the varying responders being smaller than the variance of the non-distinguishers. This model indicated that the Baby Swiss cheeses were closer to the consumers' ideals than were the other cheeses. Taken together, the 2 models suggest that the partial least squares regression failed to capture one or more attributes that contribute to consumer acceptance, although the descriptive analysis of flavor and feeling factors was able to account for 93% of the variance in the liking ratings. These findings indicate the flavor characteristics Swiss cheese producers should optimize, and minimize, to create cheeses that best match consumer desires.

Does negative expiratory pressure (NEP) during spontaneous breathing predict respiratory impairment in elderly?

OBJECTIVE: The purpose of this study is to assess whether expiratory flow limitation (FL), as measured by applying a negative pressure at the mouth during tidal expiration, can evaluate the respiratory impairment in elderly patients. METHODS: The study was carried out in 67 consecutive elderly inpatients (24 men and 43 women). Negative expiratory pressure (NEP) of -5 (NEP 5) and -10 (NEP 10) cm H2O were applied during spontaneous tidal expiration. According to the results of the NEP technique, the patients were stratified in two categories: not flow limited and flow limited. We realized then classic forced expiratory manoeuvres (FEV1, FVC) and clinical evaluation of dyspnea (NYHA). According to the values of the lung function data, elderly patients were then divided in 3 groups (normal, obstructive, restrictive). RESULTS: The sensitivity, the specificity, the positive and negative predictive values for the diagnosis of obstructive syndrome by the presence of flow limitation during NEP 5 were 53, 74, 45, 79% respectively and 58, 83, 58, 83% respectively during NEP 10. These findings show that the correlation between FL obtained by the NEP technique during spontaneous breathing and spirometry is not very good despite the fact that both were well correlated with dyspnea score. CONCLUSIONS: In clinical practice, faced with an elderly dyspneic patient unable to perform maximal expiratory manoeuvres, the evaluation of flow limitation by NEP technique seems nor to be reliable to predict an obstructive functional impairment nor to be able to explain the origin of his dyspnea.

Changes in secreted salivary sodium are sufficient to alter salt taste sensitivity: use of signal detection measures with continuous monitoring of the oral environment.

A signal detection measure of NaCl taste sensitivity was developed with continuous monitoring of the Na+ concentration of the oral environment. Taste sensitivity was reduced when saliva was stimulated by chewing to secrete with elevated Na+ levels. Monitoring of the oral environment for Na+ allowed a computation of physical signal strengths for NaCl and water stimuli; changes in these strengths, brought about by variations in secreted salivary sodium, furnish an explanation for alterations in NaCl taste sensitivity.

Relationship of papillae number to bitter intensity of quinine and PROP within and between individuals.

Subjects were asked to assess the bitterness of one 6-n-propyl-2-thiouracil (PROP) and two quinine HCl (QHCl) concentrations presented via filter papers of varying sizes. The number of taste papillae stimulated by these filter papers was counted in each individual. Whole mouth sensitivity to PROP was determined in a separate session. In support of other demonstrations of spatial summation, these data indicated that perceived bitterness intensity increased as a function of area of stimulation within subjects. Between subjects, there was a significant trend for the perceived bitterness of PROP to increase with the lingual density of fungiform papillae, although this trend was highly variable and was only demonstrable among those who showed at least moderate sensitivity to PROP. On the other hand, the number of stimulated fungiform papillae failed to account for individual differences in perceived bitterness of QHCl.

Anion size of sodium salts and simple taste reaction times.

Simple taste reaction times (RT) and taste intensities were measured in adult humans for 100-mM aqueous solutions of sodium chloride, acetate, glutamate, ascorbate, and gluconate flowed over the anterodorsal tongue with a closed liquid delivery system. Results from 12 subjects showed a significant increase in RT with molecular weight of the tastant, and a correlation of 0.941 between RT and the square roots of anionic weights. A multiple regression analysis controlling for perceived taste intensity indicated that RT increased linearly with the square root of the anionic weight. These findings support a model that includes both the permeability of ions through the tight junctions between the taste receptor cells of fungiform papillae taste buds and the effects of ions at apical portions of the receptor cells. They also suggest that gustatory transduction of sodium salts in humans normally involves intercellular spaces of taste buds as part of the functional sensory structures, in addition to individual taste receptor cells.

Atherosclerosis and cerebral ischemic attacks: intakes of cerebrography with xenon133 inhaled and platelet tests in the diagnosis, clinical and therapeutic monitoring; the preventive role of dipyridamole.

A study of patients to develop the significance of the role of the blood platelets in the recurrence of transient cerebral ischemic attacks in patients with cerebral atheromatous, develop the effectiveness of dipyridamole in the prophylactic therapeutic regimen. In the group treated with dipyridamole, a 76.3% clinical improvement was recorded (mean increases of 11.2 ml/min. and 11.4 ml/min. of the cerebral hemispheric flows), 15.8% of cases stabilized (mean increases of 1.7 ml/min. and 1.2 ml/min.) and 7.9% failures (mean decreases of 10.4 ml/min. and 14.3 ml/min.) of these same flows. The cerebrography with xenon133 inhaled as well as the platelet tests used, constitute unfailing means of diagnosing and monitoring the clinical development.

Lung function and cardiac surgery.

In a series of 145 patients submitted to cardiac surgery, lung function data were correlated with the kind of heart disease, mitral or oartic or coronary stenosis; the post-operative evolution was evaluated. Patients with valvular diseases (VD) have a significant lower transfer capacity (TL) than coronary patients; mitral VD show a lower forced vital capacity (FVC) than aortic VD. All the patients present an important restrictive pattern in the early post-operative period. The long-term follow-up (greater than 6 months) objectivates the highly significant decrease of FVC and FEV1 in all categories of patients, while the total lung capacity remains low only in aortic VD. The transfer coefficient (TL/VA) improves significantly after mitral valve replacement, but it does not change in the other cases.

Adriamycin cardiotoxicity. Prognostic value of the systolic time intervals.

The aim of this study was to detect the cardiotoxicity of Adriamycin (ADM) by the evolution of the systolic time intervals (STI). The PEP/LVET ratio represents an easy and reproducible index of myocardial function. The more important this increase, the greater the risk of developing heart failure. A significant correlation exists between the variation of this ratio and the total administered dose, but the correlation coefficient is low. A heart failure may appear for doses of ADM under 500 mg/m2 but it is preceded by an increase of the index. In the absence of a significant modification, the generally admitted maximum dose of 550 mg/m2 may be exceeded. In case of a ratio increase in excess of 0.08 it will be necessary to balance the potential benefits of treatment with the hazards of cardiac failure. The PEP/LVET ratio allows proceeding with the cytostatic treatment in increased security by selecting the patients at high risk for cardiac failure.

[Diagnostic approach occupational asthma]. / Approches diagnostiques de l'asthme professionnel.

Occupational asthma is associated with significant medical and socioeconomic consequences. Therefore, the diagnosis should be based on objective and accurate evidence. Available diagnostic procedures include the clinical history, measurement of non-specific bronchial hyperresponsiveness, monitoring of expiratory peak flows at work, and specific inhalation challenges in the laboratory. Advantages and limitations of these tests are discussed in order to propose a pragmatic diagnostic approach where specific inhalation challenges play a central role.