Comment on "Methanol dimer formation drastically enhances hydrogen abstraction from methanol by OH at low temperature" by W. Siebrand, Z. Smedarchina, E. Martínez-Núñez and A. Fernández-Ramos, Phys. Chem. Chem. Phys., 2016, 18, 22712.

The article "Methanol dimer formation drastically enhances hydrogen abstraction from methanol by OH at low temperature" proposes a dimer mediated mechanism in order to explain the large low temperature rate coefficients for the OH + methanol reaction measured by several groups. It is demonstrated here theoretically that under the conditions of these low temperature experiments, there are insufficient dimers formed for the proposed new mechanism to apply. Experimental evidence is also presented to show that dimerization of the methanol reagent does not influence the rate coefficients reported under the conditions of methanol concentration used for the kinetics studies. It is also emphasised that the low temperature experiments have been performed using both the Laval nozzle expansion and flow-tube methods, with good agreement found for the rate coefficients measured using these two distinct techniques.

Reactivity of OH and CH3OH Between 22 and 64 K: Modelling the Gas Phase Production of CH3O in Barnard 1B.

In the last years, ultra-low temperature chemical kinetic experiments have demonstrated that some gas-phase reactions are much faster than previously thought. One example is the reaction between OH and CH3OH, which has been recently found to be accelerated at low temperatures yielding CH3O as main product. This finding opened the question of whether the CH3O observed in the dense core Barnard 1b could be formed by the gas-phase reaction of CH3OH and OH. Several chemical models including this reaction and grain-surface processes have been developed to explain the observed abundance of CH3O with little success. Here we report for the first time rate coefficients for the gas-phase reaction of OH and CH3OH down to a temperature of 22 K, very close to those in cold interstellar clouds. Two independent experimental set-ups based on the supersonic gas expansion technique coupled to the pulsed laser photolysis-laser induced fluorescence technique were used to determine rate coefficients in the temperature range 22-64 K. The temperature dependence obtained in this work can be expressed as k(22-64 K) = (3.6 ± 0.1) × 10-12(T/300 K)-(1.0±0.2) cm3 molecule-1 s-1. Implementing this expression in a chemical model of a cold dense cloud results in CH3O/CH3OH abundance ratios similar or slightly lower than the value of ∼ 3 × 10-3 observed in Barnard 1b. This finding confirms that the gas-phase reaction between OH and CH3OH is an important contributor to the formation of interstellar CH3O. The role of grain-surface processes in the formation of CH3O, although it cannot be fully neglected, remains controversial.

Kinetics and mechanism of the tropospheric reaction of 3-hydroxy-3-methyl-2-butanone with Cl atoms.

The relative rate coefficient for the gas-phase reaction of 3-hydroxy-3-methyl-2-butanone (3H3M2B) with Cl atoms was determined under atmospheric conditions (298 ± 2 K, 720 ± 2 Torr). The products of the reaction were identified and quantified. This work provides the first kinetic and mechanistic determinations of the gas-phase reaction of Cl atoms with 3H3M2B. The rate measurements and the products studies were performed in two simulation chambers coupled to the gas chromatography-mass spectrometer (GC-MS) and the Fourier transform infrared (FTIR) techniques, respectively. The obtained average rate coefficient was (1.13 ± 0.17) × 10(-10) cm(3) molecule(-1) s(-1) using propene and 1,3-butadiene as reference compounds. The major primary reaction products observed in this study were (with % molar yields): acetic acid (42.6 ± 4.8) and 2,3-butanedione (17.2 ± 2.3). Results and mechanism are discussed in terms of the structure-reactivity relationship and compared with the reported reactivity with the other atmospheric oxidants. The atmospheric implications derived from this study are discussed as well.

UV absorption cross-sections of a series of dimethylbenzaldehydes.

The ultraviolet absorption cross-sections of 2,4-, 2,5-, 2,6-, 3,4- and 3,5- dimethylbenzaldehydes are reported in the wavelength range 240-320 nm. The measurements were carried out in the temperature range 318-363 K using two different experimental systems (D 2 lamp-monochromator and D 2 lamp-diode array). The absorption spectra of the five aldehydes have been found to exhibit relatively high absorption cross-sections in the region of the tropospheric interest with maxima around 290 nm. This work provides the first UV cross-section measurements for these aromatic aldehydes. The obtained cross-section values enable us to estimate the tropospheric photolysis lifetimes of these compounds. The results suggest that photolysis could be an important removal process for these species in the troposphere.

Study of benzylperoxy radical using laser photolysis: ultraviolet spectrum, self-reaction, and reaction with HO2 kinetics.

The ultraviolet absorption spectrum of benzylperoxy radical and the kinetics of the reactions 2C(6)H(5)CH(2)O(2) --> products (I) and C(6)H(5)CH(2)O(2) + HO(2) --> products (II) are studied. Experiments are carried out using the laser photolysis technique with time-resolved UV-visible absorption spectroscopy over the temperature range 298-353 K and the pressure range 50-200 Torr. The UV spectrum is determined relative to the known cross section of the ethylperoxy radical C(2)H(5)O(2) at 250 nm. Using factor analysis, the spectrum obtained is refined and the concentrations of the main absorbing species are extracted. The kinetic parameters are determined by analyzing and simulating the temporal profiles of the species concentrations and the experimental optical densities in the spectral region 220-280 nm. These are obtained using the recent UV spectra of the absorbing species existing in our mechanism. The Arrhenius expressions for reactions I and II are (cm(3).molecule(-1).s(-1)) k(I) = 2.50 x 10(-14)e(1562/)(T) and k(II) = 5.70 x 10(-14)e(1649/)(T). Our results are discussed and compared to literature data.

X-ray absorptiometry of bone in obese and eutrophic children from Valparaiso, Chile.

OBJECTIVE: To assess and compare bone mineral content (BMC) and bone mineral density (BMD) by dual X-ray absorptiometry (DEXA) measurement in obese and eutrophic children. METHODS: In a cross sectional, case control study 16 obese children (8 male, 8 female) aged 5 to 13 years were recruited from the outpatient nutrition clinic of Carlos van Buren Hospital, Valparaiso, Chile, during 1997. Sixteen healthy eutrophic children matched for sex, chronological age, height, and pubertal stage were enrolled as controls. The mean dietary calcium intake was 580 +/- 100 mg/day. All obese patients had more than 2 standard deviation (SD) of height/weight ratio. Lumbar spine (L2-L4) BMD, femoral neck BMD, total body BMD, and total body BMC were measured by posteroanterior dual photon DEXA. The results were expressed as mean +/- SD. Comparison of the data was determined by Wilcoxon and Student t test. RESULTS: Mean BMC was 1684.1 +/- 492.38 g in obese children and 1418.2 +/- 483.48 g in controls (p < 0.001, Student t test; p = 0.001, Wilcoxon test). Mean total BMD was 817.5 +/- 99.37 g/cm2 in obese children and 771.62 +/- 105.62 g/cm2 in controls. (p = 0.041 by Wilcoxon). Mean hip BMD was 784.4 +/- 117.05 g/cm2 in obese children and 801.67 +/- 150.34 g/cm2 in controls. Mean spine BMD was 724.87 +/- 171.75 g/cm2 in obese children and 686 +/- 137.08 g/cm2 in controls (not significant). CONCLUSION: Obese children have more total body BMC than eutrophic children. There was no significant difference in regional hip BMD and lumbar spine BMD among obese and normal children. Obese children may have larger bones.

MR imaging of intramedullary and intradural-extramedullary spinal cysticercosis.

OBJECTIVE: The purpose of our study was to retrospectively review the MR imaging findings in a group of patients with clinically proven cysticercosis involving the spinal cord, the spinal subarachnoid space, or both. MATERIALS AND METHODS: We retrospectively reviewed images of 16 patients with clinically diagnosed spinal cysticercosis to summarize the imaging characteristics. All patients underwent T1- and T2-weighted sagittal, axial, or both sagittal and axial MR imaging before i.v. administration of paramagnetic contrast media. Thirteen patients also underwent sagittal, axial, or both sagittal and axial T1-weighted MR imaging after i.v. gadolinium administration. In addition, all patients underwent cranial CT, MR imaging, or both to reveal possible evidence of cranial cysticercosis. RESULTS: MR imaging revealed isolated intradural-extramedullary involvement (n = 9), isolated intramedullary involvement (n = 3), combined intradural-extramedullary and intramedullary involvement (n = 3), and/or syringomyelia caused by infection and associated with chronic spinal arachnoiditis (n = 2). Evidence of intradural-extramedullary disease included cystic structures within the subarachnoid space or homogeneous sheetlike enhancement within the subarachnoid space over the surface of the spinal cord. Evidence of intramedullary disease included focal cystic lesions or syringomyelic cavitation of the spinal cord. All patients had evidence of simultaneous intracranial cysticercosis as shown on cranial CT, MR imaging, or both. CONCLUSION: In the absence of scolex visualization, cysticercotic involvement of the spinal cord or spinal subarachnoid space has a nonspecific appearance on MR imaging. On the basis of the findings in this group of patients, we believe that spinal cysticercosis is most often accompanied by intracranial disease.

Systemic reactions to the Samsum ant: an IgE-mediated hypersensitivity.

BACKGROUND: In the United Arab Emirates the sting of the Pachycondyla sennaarensis ant (PSA) causes allergic reactions in certain persons. It is a common problem and is becoming a public health hazard. Up to now the diagnosis has been based only on the history, because the mechanism of the reaction was not yet established. OBJECTIVE: The aim of our study was to prepare an allergenic extract that would be used for skin tests and to prepare a reagent for specific IgE titration. Results of both skin tests and specific IgE were to be compared with the clinical history. METHODS: We studied 31 patients with anaphylactic reactions and performed clinical examinations, skin tests, and specific IgE antibody titrations. A control group of 22 subjects were also studied. RESULTS: In 30 of 31 patients (97%) findings of PSA skin tests and/or specific IgE were positive. In the control groups PSA skin test results were negative in 86% and negative for specific IgE in 68%. CONCLUSION: The study shows that the mechanism of the reaction to the sting of the PSA is a type I IgE-mediated hypersensitivity and that the diagnosis can now be confirmed by skin tests and specific IgE determination.

Migration and naturalization laws in Egypt, Lebanon, Syria, Jordan, Kuwait, and the United Arab Emirates. Part II: naturalization laws.

PIP: For Part 1 of this paper, see 46: Title 3840. In Part 2, the author reviews the laws pertaining to naturalization in selected countries of the Middle East and examines the different naturalization requirements in each country. The effect of naturalization on members of the naturalized citizen's family is discussed. The ability to exercise fundamental rights is studied with respect to native and naturalized citizens. Divestiture of citizenship and its effects on dependent relations are also examined^ieng