Reaction kinetics of muonium with the halogen gases (F2, Cl2, and Br2)

Copyright @ 1989 American Institute of PhysicsBimolecular rate constants for the thermal chemical reactions of muonium (Mu) with the halogen gases—Mu+X2→MuX+X—are reported over the temperature ranges from 500 down to 100, 160, and 200 K for X2=F2,Cl2, and Br2, respectively. The Arrhenius plots for both the chlorine and fluorine reactions show positive activation energies Ea over the whole temperature ranges studied, but which decrease to near zero at low temperature, indicative of the dominant role played by quantum tunneling of the ultralight muonium atom. In the case of Mu+F2, the bimolecular rate constant k(T) is essentially independent of temperature below 150 K, likely the first observation of Wigner threshold tunneling in gas phase (H atom) kinetics. A similar trend is seen in the Mu+Cl2 reaction. The Br2 data exhibit an apparent negative activation energy [Ea=(−0.095±0.020) kcal mol−1], constant over the temperature range of ∼200–400 K, but which decreases at higher temperatures, indicative of a highly attractive potential energy surface. This result is consistent with the energy dependence in the reactive cross section found some years ago in the atomic beam data of Hepburn et al. [J. Chem. Phys. 69, 4311 (1978)]. In comparing the present Mu data with the corresponding H atom kinetic data, it is found that Mu invariably reacts considerably faster than H at all temperatures, but particularly so at low temperatures in the cases of F2 and Cl2. The current transition state calculations of Steckler, Garrett, and Truhlar [Hyperfine Interact. 32, 779 (986)] for Mu+X2 account reasonably well for the rate constants for F2 and Cl2 near room temperature, but their calculated value for Mu+Br2 is much too high. Moreover, these calculations seemingly fail to account for the trend in the Mu+F2 and Mu+Cl2 data toward pronounced quantum tunneling at low temperatures. It is noted that the Mu kinetics provide a crucial test of the accuracy of transition state treatments of tunneling on these early barrier HX2 potential energy surfaces.NSERC (Canada), Donors of the Petroleum Research Fund, administered by the American Chemical Society, for their partial support of this research and the Canada Council

Recoil effects of photoelectrons in a solid

High energy resolution C 1$s$ photoelectron spectra of graphite were measured at the excitation energy of 340, 870, 5950 and 7940eV using synchrotron radiation. On increasing the excitation energy, i.e., increasing kinetic energy of the photoelectron, the bulk origin C 1$s$ peak position shifts to higher binding energies. This systematic shift is due to the kinetic energy loss of the high-energy photoelectron by kicking the atom, and is clear evidence of the recoil effect in photoelectron emission. It is also observed that the asymmetric broadening increases for the higher energy photoelectrons. All these recoil effects can be quantified in the same manner as the M\"ossbauer effect for $\gamma$-ray emission from nuclei embedded in crystals.Comment: 4 pages, 2 figure

Particle approximation of the one dimensional Keller-Segel equation, stability and rigidity of the blow-up

We investigate a particle system which is a discrete and deterministic approximation of the one-dimensional Keller-Segel equation with a logarithmic potential. The particle system is derived from the gradient flow of the homogeneous free energy written in Lagrangian coordinates. We focus on the description of the blow-up of the particle system, namely: the number of particles involved in the first aggregate, and the limiting profile of the rescaled system. We exhibit basins of stability for which the number of particles is critical, and we prove a weak rigidity result concerning the rescaled dynamics. This work is complemented with a detailed analysis of the case where only three particles interact

HPV infection and immunochemical detection of cell-cycle markers in verrucous carcinoma of the penis

Penile verrucous carcinoma is a rare disease and little is known of its aetiology or pathogenesis. In this study we examined cell-cycle proteins expression and correlation with human papillomavirus infection in a series of 15 pure penile verrucous carcinomas from a single centre. Of 148 penile tumours, 15 (10%) were diagnosed as pure verrucous carcinomas. The expression of the cell-cycle-associated proteins p53, p21, RB, p16INK4A and Ki67 were examined by immunohistochemistry. Human papillomavirus infection was determined by polymerase chain reaction to identify a wide range of virus types. The expression of p16INK4A and Ki67 was significantly lower in verrucous carcinoma than in usual type squamous cell carcinoma, whereas the expression of p53, p21 and RB was not significantly different. p53 showed basal expression in contrast to usual type squamous cell carcinoma. Human papillomavirus infection was present in only 3 out of 13 verrucous carcinomas. Unique low-risk, high-risk and mixed viral infections were observed in each of the three cases. In conclusion, lower levels of p16INK4A and Ki67 expressions differentiate penile verrucous carcinoma from usual type squamous cell carcinoma. The low Ki67 index reflects the slow-growing nature of verrucous tumours. The low level of p16INK4A expression and human papillomavirus detection suggests that penile verrucous carcinoma pathogenesis is unrelated to human papillomavirus infection and the oncogenes and tumour suppressor genes classically altered by virus infection.Peer reviewedFinal Accepted Versio

Stress-induced c-Fos expression is differentially modulated by dexamethasone, diazepam and imipramine

Immobilization stress upregulates c-Fos expression in several CNS areas. Repeated stress or the use of drugs can modulate stress-induced c-Fos expression. Here, we investigated in 40 different areas of the rat brain the effects of dexamethasone (SDX, a synthetic glucocorticoid), diazepam (SBDZ, a benzodiazepine), and imipramine (IMI, an antidepressant) on the c-Fos expression induced by restraint stress. Wistar rats were divided into four groups and submitted to 20 days of daily injection of saline (three first groups) or imipramine, 15 mg/kg, i.p. On day 21, animals were submitted to injections of saline (somatosensory, SS), SDX (1 mg/kg, i.p.), SBDZ (5 mg/kg, i.p.), or IMI (15 mg/kg, i.p.) before being submitted to restraint. Immediately after stress, the animals were perfused and their brains processed with immunohistochemistry for c-Fos (Ab-5 Oncogene Science). Dexamethasone reduced stress- induced c-Fos expression in SS cortex, hippocampus, paraventricular nucleus of the hypothalamus (PVH), and locus coeruleus (LC), whereas diazepam reduced c-Fos staining in the SS cortex, hippocampus, bed nucleus of stria terminalis, septal area, and hypothalamus (preoptic area and supramammillary nucleus). Chronic administration of imipramine decreased staining in the hippocampus, PVH, and LC, while increasing it in the nucleus raphe pallidus. We conclude that dexamethasone, diazepam and imipramine differentially modulate stress-induced Fos expression. the present study provides an important comparative background that may help in the further understanding of the effects of these compounds and on the brain activation as well as on the behavioral, neuroendocrine, and autonomic responses to stress.UFRRJ, Dept Physiol Sci, BR-23890000 Rio de Janeiro, BrazilUniversidade Federal de São Paulo, Dept Physiol, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Psychobiol, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Physiol, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Psychobiol, São Paulo, BrazilWeb of Scienc

SPring-8 BL36XU: Catalytic Reaction Dynamics for Fuel Cells

A tapered undulator beamline BL36XU was constructed at SPring-8 to conduct structural and electronic analysis of dynamic events on polymer electrolyte fuel cell (PEFC) cathode catalysts for the development of next-generation PEFCs. BL36XU provides various time and spatially resolved XAFS techniques in an energy range from 4.5 to 35 keV for investigating PEFCs under the operating conditions. In addition, we developed in-situ complementary measurement systems, such as in-situ time-resolved XAFS/XRD and ambient pressure HAXPES systems. This report describes the performance and present status of the BL36XU

Molecular deformation in the O 1s[-1] 2πu excited states of CO2 probed by the triple-differential measurement of fragment ions

Measurement of mass-, energy-, and angle-resolved fragment ions reveals that the β value for C+ with kinetic energy ≥~3 eV is ∼0.9 in the region of the O 1s→2πu excitation and that the β value for O+ with kinetic energy ≥~4 eV varies from -0.23 to -0.57 across the O 1s→2πu resonance. These findings postulate that the CO2 molecule excited to the lower branch of the vibronically split O 1s[-1]2πu excited states deforms into a bent geometry while the molecule excited to the higher branch remains in a linear geometry

Non-existence and uniqueness results for supercritical semilinear elliptic equations

Non-existence and uniqueness results are proved for several local and non-local supercritical bifurcation problems involving a semilinear elliptic equation depending on a parameter. The domain is star-shaped but no other symmetry assumption is required. Uniqueness holds when the bifurcation parameter is in a certain range. Our approach can be seen, in some cases, as an extension of non-existence results for non-trivial solutions. It is based on Rellich-Pohozaev type estimates. Semilinear elliptic equations naturally arise in many applications, for instance in astrophysics, hydrodynamics or thermodynamics. We simplify the proof of earlier results by K. Schmitt and R. Schaaf in the so-called local multiplicative case, extend them to the case of a non-local dependence on the bifurcation parameter and to the additive case, both in local and non-local settings.Comment: Annales Henri Poincar\'e (2009) to appea

Direct binding of gangliosides to Helicobacter pylori vacuolating cytotoxin (VacA) neutralizes its toxin activity.

Gangliosides are target receptors for bacterial entry, yet those present in human milk exhibit a protective role against bacterial infection. Here, we show that treatment with ganglioside mixture at a concentration of 100 microg/mL resulted in significant inhibition of the vacuole formation activity of Helicobacter pylori vacuolating cytotoxin (VacA) in gastric epithelial cancer AZ-521 cells. All gangliosides (GM1, GM2, GM3, GD1a, GD1b, GD3 and GT1b) examined showed good neutralizing capacity against VacA. A pull-down assay was performed using lyso-GM1 coupled to Sepharose as the tagged polysaccharide polymer to capture VacA from H. pylori culture supernatant. GM1-VacA complexes were successfully precipitated, suggesting that GM1 binds directly to VacA. The hydrodynamic binding of lyso-GM1 and VacA measured by fluorescence correlation spectroscopy had a K(d) value of 190 nM. VacA also bound to lyso-GM1 at pH 2 corresponding to the physiological pH of human stomach. Collectively, these results showed that direct binding of H. pylori VacA to free gangliosides neutralizes the toxin activity of VacA. These findings offer an alternative insight into the role of gangliosides in VacA toxicity and the pathogenesis of H. pylori

Strong HLA-DR expression in microsatellite stable carcinomas of the large bowel is associated with good prognosis

Progression of colorectal cancer may follow either of two main genetic routes: the chromosome- or microsatellite-instability pathways. Association between the patients' prognosis and microsatellite instability has been questioned. Improved survival has previously been found in patients with expression of HLA-DR antigens on their tumour cells. In this study, the expression of HLA-DR antigen was investigated by immunohistochemistry in 357 large bowel carcinomas stratified by microsatellite instability status. Sixteen per cent of the tumours showed strong HLA-DR expression and 35% had weak DR expression. We confirmed that patients with strong positive HLA-DR staining had improved survival (P<0.001) compared to patients with no HLA-DR expression. Strong epithelial HLA-DR staining was significantly associated with high level of microsatellite instability (P<0.001). In the subgroup of tumours with characteristics typical of the chromosomal instability phenotype, i.e. in microsatellite-stable tumours, the patients positive for the HLA-DR determinants showed better survival than those without HLA-DR expression. The protective effect of HLA-DR expression on survival was confirmed by multivariate analysis, both in the whole patient group and in the microsatellite-stable/microsatellite instability-low group. This might be explained by enhanced T-cell mediated anti-tumour immune responses against tumour cells in the HLA-DR positive tumours. The finding of better patient survival in the subgroup of strong HLA-DR positive microsatellite-stable tumours may have clinical implications for these patients