Cross Sections and Asymmetry Parameters for Formic Acid in the Vacuum-Ultraviolet Energy Range.

We present an experimental and theoretical investigation of the photon interaction with formic acid in the vacuum-ultraviolet energy range. The absolute absorption cross sections and ionization efficiencies were measured in the 11.2-21.4 and 13.5-21.4 eV ranges, respectively, using a double-ion chamber technique. Photoionization and neutral-decay cross sections were derived from these results. From the present ionization cross sections and previously reported ionic dissociative branching ratios, the partial cross sections for dissociating processes were obtained. Theoretically, the photoionization cross sections and the asymmetry parameters of the photoelectron angular distributions for ionization out of the six outermost valence orbitals (10a', 2a″, 9a', 1a″, 8a', and 7a') were obtained in the energy range from near-threshold to 35 eV. For that, the Padé approximant technique along with the single-center partial-wave expansion method was applied to solve the Lippmann-Schwinger equation in the static-exchange-polarization level of approximation. This is the first theoretical investigation concerning the determination of the asymmetry parameters and photoionization cross sections of formic acid in the vacuum-ultraviolet energy range. Comparison is made between our results and the previous ones.

Photoabsorption and Photoionization Cross Sections of Pyridine in the Vacuum-Ultraviolet Energy Range.

We have performed an experimental investigation into the interaction of vacuum-ultraviolet synchrotron radiation with pyridine molecules in the gas phase. Specifically, a double-ion chamber spectrometer was used to measure the absolute photoabsorption cross sections and the photoionization quantum yields from the ionization threshold to 21.5 eV. Moreover, photoionization and neutral-decay cross sections in absolute scale were derived from these data. In addition, the fragmentation pattern was investigated as a function of the photon energy by using a time-of-flight mass spectrometer and the photoelectron-photoion coincidence technique. Thus, the absolute partial ionization cross sections for each ionic fragment were obtained. Comparisons are made with experimental data available in the literature.

Fragmentation of Valence and Carbon Core Excited and Ionized CH2FCF3 Molecule.

The photofragmentation dynamics of 1,1,1,2-tetrafluoroethane (R134a) with photon energies from 12 eV up to 320 eV, surrounding the C 1s edge is discussed. The ionic moieties were measured in coincidence with the ejected electrons (PEPICO mode), and detected as a function of the photon energy. Around the C K core edge, the fragmentation profiles are examined regarding the site specific excitation of the CH2FCF3 molecule. In the present case, site-selectivity is favored by the distinct chemical environments surrounding both C atoms. NEXAFS spectrum at the C 1s edge simulation has been obtained at the TDDFT level and excited state geometry optimization calculations have been performed at the inner-shell multiconfigurational self-consistent field level. Our observations indicate that the C(H2F) 1s excitation to a highly repulsive potential expels a fluorine atom leaving the heavier radical fragment C2F3H2* which relaxes to the fundamental state of the ion C2F3H2+. On the other hand, the excitation from the C(F3) 1s carbon to a repulsive state in the C-C bond, leads to a C-C bond cleavage, explaining the observed site specific fragmentation.

Anti-inflammatory and cicatrizing activities of thymol, a monoterpene of the essential oil from Lippia gracilis, in rodents.

ETHNOPHARMACOLOGICAL RELEVANCE: Lippia gracilis Schauer (Verbenaceae) has long been recognized in folk medicine as a medicinal plant. The essential oil of Lippia gracilis has antimicrobial activity and is used externally to treat cutaneous diseases, burns, wounds, and ulcers. Recently, our research group demonstrated that the essential oil of Lippia gracilis leaves possesses antinociceptive and anti-inflammatory actions and its major component identified was thymol. The objective of this study was to assess the anti-inflammatory and wound healing activities of thymol in rodents. MATERIALS AND METHODS: For the anti-inflammatory analysis the paw oedema and peritonitis models were used, followed by the assessment of the mieloperoxidase (MPO) activity, total cell counting, and histological analysis. The animals were treated (i.p., n=6/group) with thymol (10, 30, and 100 mg/kg), dexamethasone (2 mg/kg), or vehicle (1% Tween 80). In order to assess the wound healing potential, thymol was vehiculated into collagen-based dressing films and a biological wound healing test was conducted. The retraction index of the wounds and histological analysis were performed on the 3rd, 7th, 14th, and 21th days, split into three groups: undressed wounds (CTR), dressed with collagen-based films (COL), and dressed with collagen-based containing thymol (COLTHY) films. RESULTS: Thymol reduced significantly the oedema (100 mg/kg, P<0.001) and, besides, diminished the influx of leukocytes to the injured area (10, 30, and 100 mg/kg), according to the assessment of MPO activity (P<0.001), total cell count (P<0.05), and histological analysis. Wounds dressed with COLTHY films showed significantly bigger wound retraction rates (7 and 14 day, P<0.05) and improved the granulation reaction, as well provided better collagenization density and arrangement during wound healing. CONCLUSIONS: This study suggests that thymol is a promising compound to be used in treatment of inflammatory processes as well as wound healing. The pharmacological actions of Lippia gracilis in popular medicine practices may be related, at least in part, to the presence of thymol in the essential oil.

Two size regimes of methanol clusters produced by adiabatic expansion.

Free neutral methanol clusters produced by adiabatic expansion have been studied by photoelectron spectroscopy and line shape modeling. The results show that clusters belonging to two distinct size regimes can be produced by changing the expansion conditions. While the larger size regime can be well described by line shapes calculated for clusters consisting of hundreds of molecules, the smaller size regime corresponds to methanol oligomers, predominantly of cyclic structure. There is little contribution from dimers to the spectra.

The electronic structure of free water clusters probed by Auger electron spectroscopy.

(H2O)(N) clusters generated in a supersonic expansion source with N approximately 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these final states and give rise to their intensity in the AES. Density-functional investigations of model systems for the doubly ionized final states--the water dimer and a 20-molecule water cluster--were performed to analyze the localization of the two valence holes in the electronic ground states. Whereas these holes are preferentially located at the same water molecule in the dimer, they are delocalized in the cluster showing a preference of the holes for surface molecules. The calculated double-ionization potential of the cluster (22.1 eV) is in reasonable agreement with the low-energy limit of the delocalized hole shoulder in the AES.

The size of neutral free clusters as manifested in the relative bulk-to-surface intensity in core level photoelectron spectroscopy.

A new approach for obtaining an estimate of the effective size of the free neutral clusters is proposed. The approach relies on an experimental measure of the surface and interior or "bulk" cluster atoms provided by the x-ray photoelectron spectroscopy and on a model for the attenuation of photoelectrons ejected from the bulk of the cluster as the result of the ionizing irradiation. The experimental part gives the ratio of the electron signal from the bulk cluster atoms to that from the cluster surface atoms for a wide range of cluster sizes and electron kinetic energies. The attenuated response of the bulk atoms is modeled using an exponential law with the cluster size and kinetic-energy-dependent electron escape depth as parameters. For the experimental size range, model-based calculations for Ar, Kr, and Xe clusters are presented. The cluster size estimates obtained from comparison of the model calculations and experimental results agree well with those determined from the parameters of the cluster creation process. The combination of experiment and modeling also makes it possible to estimate the effective escape depth for electron propagation in free clusters. For Ar, Kr, and Xe clusters of varying mean size, absolute determination of the surface and bulk electron binding energies of the core levels used in the experiments has also been made.