Kinetics and mechanism of the reactions of CH3CO and CH3C(O)CH2 radicals with O2. Low-pressure discharge flow experiments and quantum chemical computations

The reactions CH(3)CO + O(2)--> products (1), CH(3)CO + O(2)--> OH +other products (1b) and CH(3)C(O)CH(2) + O(2)--> products (2) have been studied in isothermal discharge flow reactors with laser induced fluorescence monitoring of OH and CH(3)C(O)CH(2) radicals. The experiments have been performed at overall pressures between 1.33 and 10.91 mbar of helium and 298 +/- 1 K reaction temperature. OH formation has been found to be the dominant reaction channel for CH(3)CO + O(2): the branching ratio, Gamma(1b) = k(1b)/k(1), is close to unity at around 1 mbar, but decreases rapidly with increasing pressure. The rate constant of the overall reaction, k(2), has been found to be pressure dependent: the fall-off behaviour has been analysed in comparison with reported data. Electronic structure calculations have confirmed that at room temperature the reaction of CH(3)C(O)CH(2) with O(2) is essentially a recombination-type process. At high temperatures, the further reactions of the acetonyl-peroxyl adduct may yield OH radicals, but the most probable channel seems to be the O(2)-catalysed keto-enol transformation of acetonyl. Implications of the results for atmospheric modelling studies have been discussed.     

Bounds for modular L-functions in the level aspect

Let f be a primitive (holomorphic or Maaß) cusp form of level q and non-trivial nebentypus. Then for the associated L-function satisfies , where the implied constant depends polynomially on s and the Archimedean parameters of f (weight or Laplacian eigenvalue).     

Extremal mean width when covering the 1-skeleton

For a given convex body K in ^d, let D_n be the compact convexset of maximal mean width whose 1-skeleton can be covered byn congruent copies of K. Based on the fact that the mean widthis proportional to the average perimeter of two-dimensionalprojections, it is proved that D_n is close to being a segmentfor large n.     

Popular distances in 3-space

Let m(n) denote the smallest integer m with the property that any set of n points in Euclidean 3-space has an element such that at most m other elements are equidistant from it. We have that cn^1/3 log log n m(n) n^3/5 β(n), where c> 0 is a constant and β(n) is an extremely slowly growing function, related to the inverse of the Ackermann function.     

Hypoxia-induced transcription of dopamine D3 and D4 receptors in human neuroblastoma and astrocytoma cells

Background

The aim of this study is to examine the influence of the catechol-O-methyltranferase (COMT) gene (polymorphism Val158 Met) as a risk factor for Alzheimer's disease (AD) and mild cognitive impairment of amnesic type (MCI), and its synergistic effect with the apolipoprotein E gene (APOE). A total of 223 MCI patients, 345 AD and 253 healthy controls were analyzed. Clinical criteria and neuropsychological tests were used to establish diagnostic groups. The DNA Bank of the University of the Basque Country (UPV-EHU) (Spain) determined COMT Val158 Met and APOE genotypes using real time polymerase chain reaction (rtPCR) and polymerase chain reaction (PCR), and restriction fragment length polymorphism (RFLPs), respectively. Multinomial logistic regression models were used to determine the risk of AD and MCI.

Results

Neither COMT alleles nor genotypes were independent risk factors for AD or MCI. The high activity genotypes (GG and AG) showed a synergistic effect with APOE ε4 allele, increasing the risk of AD (OR = 5.96, 95%CI 2.74-12.94, p < 0.001 and OR = 6.71, 95%CI 3.36-13.41, p < 0.001 respectivily). In AD patients this effect was greater in women. In MCI patients such as synergistic effect was only found between AG and APOE ε4 allele (OR = 3.21 95%CI 1.56-6.63, p = 0.02) and was greater in men (OR = 5.88 95%CI 1.69-20.42, p < 0.01).

Conclusion

COMT (Val158 Met) polymorphism is not an independent risk factor for AD or MCI, but shows a synergistic effect with APOE ε4 allele that proves greater in women with AD.     

Modeling the influence of a laser pulse on the potential energy surface in optimal molecular control theory

Understanding and modeling the interaction between light and matter is essential to the theory of optical molecular control. While the effect of the electric field on a molecule's electronic structure is often not included in control theory, it can be modeled in an optimal control algorithm by a set or toolkit of potential energy surfaces indexed by discrete values of the electric field strength where the surfaces are generated by Born-Oppenheimer electronic structure calculations that directly include the electric field. Using a new optimal control algorithm with a trigonometric mapping to limit the maximum field strength explicitly, we apply the surface-toolkit method to control the hydrogen fluoride molecule. Potential energy surfaces in the presence and absence of the electric field are created with two-electron reduced-density-matrix techniques. The population dynamics show that adjusting for changes in the electronic structure of the molecule beyond the static dipole approximation can be significant for designing a field that drives a realistic quantum system to its target observable.     

The diminishing segment process

Let Ξ₀=[−1,1], and define the segments Ξ_n recursively in the following manner: for every n=0,1,…, let Ξ_n+1=Ξ_n∩[a_n+1−1,a_n+1+1], where the point a_n+1 is chosen randomly on the segment Ξ_n with uniform distribution. For the radius ρ_n of Ξ_n, we prove that n(ρ_n−1/2) converges in distribution to an exponential law, and we show that the centre of the limiting unit interval has arcsine distribution.     

Isolation and Characterization of Novel Capsorubin‐Like Carotenoids from the Red Mamey (Pouteria sapota)

From the ripe fruits of red mamey (Pouteria sapota), two new carotenoids, 3′‐deoxycapsorubin and 3,3′‐dideoxycapsorubin, were isolated and identified based on their UV/VIS, CD, ¹H‐NMR, and mass spectral data.     

Location tracking in mobile ad hoc networks using particle filters

Mobile ad hoc networks (MANETs) are dynamic networks formed on-the-fly as mobile nodes move in and out of each others' transmission ranges. In general, the mobile ad hoc networking model makes no assumption that nodes know their own locations. However, recent research shows that location-awareness can be beneficial to fundamental tasks such as routing and energy-conservation. On the other hand, the cost and limited energy resources associated with common, low-cost mobile nodes prohibits them from carrying relatively expensive and power-hungry location-sensing devices such as GPS. This paper proposes a mechanism that allows non-GPS-equipped nodes in the network to derive their approximated locations from a limited number of GPS-equipped nodes. In our method, all nodes periodically broadcast their estimated location, in terms of a compressed particle filter distribution. Non-GPS nodes estimate the distance to their neighbors by measuring the received signal strength of incoming messages. A particle filter is then used to estimate the approximated location, along with a measure of confidence, from the sequence of distance estimates. Simulation studies show that our solution is capable of producing good estimates equal or better than the existing localization methods such as APS-Euclidean for the more difficult scenario when the network connectivity is low.