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 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 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).

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)].

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.

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.

Photoabsorption measurements and theoretical calculations of the electronic state spectroscopy of propionic, butyric, and valeric acids.

Absolute photoabsorption cross sections of propionic (C2H5COOH), butyric (C3H7COOH), and valeric (C4H9COOH) acids have been measured from the dissociative pi* <-- n(o) transition (beginning around 5.0 eV) up to 10.7 eV. This constitutes the first study of the neutral electronic states of propionic and butyric acids at energies above the pi* <-- n(o) band, while no previous spectroscopic data is available for valeric acid in the present range. The present assignments are supported by the first theoretical calculations of electronic transition energies and oscillator strengths for these organic acids. In addition, the excitation energies of the vibrational modes of propionic acid in its neutral electronic ground state and the vertical ionisation energies of all three molecules have been calculated for the first time. The He(I) photoelectron spectroscopy of propionic acid has been measured from 10 to 16 eV, revealing new fine structure in the first ionic 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.

On the valence shell electronic spectroscopy of 2-vinyl furan.

The vacuum ultraviolet (VUV) absorption spectrum (3.50-10.33 eV, 350-120 nm) of gaseous 2-vinyl furan has been measured for the first time using both synchrotron radiation source and electron energy loss spectroscopies with absolute cross section determinations. The He I photoelectron spectrum obtained at higher resolution than previously has been interpreted with the aid of semiempirical molecular orbital calculations. Three excited states of type (1)pipi(*) are found responsible for an intense and structured first band observed between 4.2 and 5.8 eV (295-214 nm). Three triplet states were detected for the first time at about 2.46, 3.35, and 3.8 eV (477, 370, and 328 nm) which are, from the calculations, assigned as (3)pipi(*). Some partial Rydberg series, linked to IE(1) and IE(2) are identified. The VUV absorption spectrum bears little resemblance to that of the parent compound, furan. The electronically excited molecule is found akin to a linear polyene.

Comparison of FEV1 and specific airway conductance in assessing airway response to occupational agents.

BACKGROUND: There is theoretical evidence that specific airway conductance (SGaw) could be more reliable than forced expiratory volume in 1 s (FEV1) for assessing changes in airway calibre. We investigated the changes in FEV1 and SGaw when assessing bronchial responses to occupational agents. METHODS: SGaw and FEV1 were measured during inhalation challenges with various occupational agents in 174 consecutive subjects investigated for possible occupational asthma. RESULTS: A decline in SGaw of 50% or greater was documented in 77 of 90 subjects (86%) who showed a >/=20% fall in FEV1 and in 11 of 84 subjects (13%) who failed to demonstrate such a fall in FEV1. Among subjects who developed a >/=20% fall in FEV1, those who failed to develop a >/=50% decline in SGaw had a lower baseline SGaw than those who did. Among the group without a >/=20% fall in FEV1, a >/=50% decrease in SGaw was associated with either an 'intermediate' fall in FEV1 (between 15 and 17% from baseline value) (n = 4), a significant postchallenge increase in nonspecific bronchial hyper-responsiveness to histamine (n = 2), or both features (n = 3). CONCLUSIONS: A decline in SGaw of 50% or greater may provide useful complementary evidence of a bronchial response during challenges that produce equivocal results in FEV1.

Effects of the form of glasses on the perception of wine flavors: a study in untrained subjects.

Many wine connoisseur claim that the glass shape has a direct impact on wine aroma. This hypothesis was investigated in healthy volunteers (85 m, 96 f; age 19-73 years); 89 subjects received red wine, 92 subjects white wine. Subjects compared three glasses with a white wine and three glasses with a red. Glasses were of different shape but of the same height and of comparable opening diameter. All glasses had elegant stems; two glasses of 'tulip' and 'beaker'-like shapes were used in sessions with red and white wines. Different bulbous glasses were used in either red or white wine sessions. Subjects were blinded whether they received one or more wines. Intensity, hedonic tone, and quality of the wines were rated repeatedly before and after drinking. Ratings of wine odors from different glasses were influenced by glass shape. Importantly, this appeared not to relate to the esthetic impression the glasses made. Thus, the present data indicate that the shape of glasses seems to influence the perception of wine odors.

Does negative expiratory pressure influence performances of spirometry in older patients?

The aim of this study is to assess the influence of the negative expiratory pressure (NEP) technique on the performance of maximal expiratory manoeuvre in elderly patients. Firstly, the authors studied how NEP (at 5 and 10 cmH2O, NEP5 and NEP10) influences forced vital capacity (FVC) and forced expiratory volume in one second (FEV1) in 60 young healthy volunteers, in order to assess the fluctuations of the method. In the second part of the study, 65 successive elderly inpatients (>70 yrs old) were examined. In this group, 15 elderly patients were unable to perform the manoeuvre, 27 had a normal function, 14 had a lung function with obstructive pattern and nine with restrictive pattern. In young subjects, FVC during NEP5 and NEP10 compared to baseline values was 101+/-5%, and 103+/-5%, respectively, and FEV1 was 100+/-4% and 101+/-5%, respectively. In elderly patients with normal function, FVC during NEP5 and NEP10 compared to baseline values was 99+/-14% and 109+/-23%, respectively, and FEV1 was 97+/-9% and 104+/-13%, respectively. There were no relevant effects of the NEP application on FVC or FEV1 values in elderly patients with an obstructive or restrictive pattern. In elderly patients, the use of the negative expiratory pressure technique during maximal expiratory manoeuvres provides little complementary information compared to a classical manoeuvre. The negative expiratory pressure technique did not modify the initial diagnosis when compared with the classical manoeuvre.

[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.

Socioeconomic outcome of subjects experiencing asthma symptoms at work.

The aim of this study was to investigate the socioeconomic outcomes of subjects who experienced work-related asthma symptoms in the absence of demonstrable occupational asthma (OA) and to compare these outcomes with those found in subjects with documented OA. Subjects (n=157) who were being investigated for work-related asthma, were surveyed. Of these 86 had OA, ascertained by a positive specific inhalation challenge (SIC), and 71 subjects had a negative SIC response. After a median interval of 43 months (range 12-85 months), the subjects were interviewed to collect information on employment status, income changes, and asthma-related work disability. Rates of work disruption and income loss at follow-up were similar in subjects with negative SIC (46% and 59%, respectively) and in those with OA (38% and 62%). The median loss as a percentage of initial income was 23% in subjects with negative SIC and 22% in subjects with OA. Asthma-related work disability, defined as any job change or work loss due to asthma, was slightly more common in subjects with OA (72%) than in those with negative SIC (54%). This study shows that, even in the absence of demonstrable occupational asthma, work-related asthma symptoms are associated with considerable socioeconomic consequences.