Internal‐Rotation in Hydrogen Peroxide: The Far‐Infrared Spectrum and the Determination of the Hindering Potential

The torsional oscillation between the two OH groups of the hydrogen peroxide molecule is investigated through a study of the far‐infrared absorption spectrum of the molecule. A 1‐m‐focal‐length vacuum grating monochromator was used to scan the region from 15 to 700 cm−1 with an average resolution of 0.3 cm−1. The observed spectrum contains seven perpendicular‐type bands of which only the Q branches are resolved. The centers of the seven bands are at 11.43, 116.51, 198.57, 242.76, 370.70, 521.68, and 557.84 cm−1. These bands result from transitions between different states of the internal rotation and their identification makes it possible to construct the internal‐rotation energy level scheme through the first five excited states. Relative to the torsional ground state, these levels occur at 11.43, 254.2, 370.7, 569.3, and 775.9 cm−1.A theory of internal rotation in the hydrogen peroxide molecule is developed for use in the analysis of the far‐infrared spectra. In this theory, the Hamiltonian is constructed assuming all structural distances and angles fixed except the dihedral angle x defining the relative position of the two OH bars. By the use of a contact transformation the Hamiltonian is put in the form H (asymmetric top)+H(internal rotation) where the interaction between the internal and over‐all rotations arises through the x dependence of the inertial parameters of H(asymmetric top). It is assumed that the relative position of the two OH bars is governed by a potential‐energy function of the form V(x) = V1cosx+V2cos2x+V3cos3xV(x)=V1cosx+V2cos2x+V3cos3x. The internal‐rotation wave equation [αpx2+V(x)]M(x) = EM(x)[αpx2+V(x)]M(x)=EM(x) is solved numerically by an electronic‐computer and the potential function parameters V1=993 cm−1, V2=636 cm−1, and V3=44 cm−1 are chosen to fit the internal‐rotation energy‐level scheme. The trans and cis potential barrier heights are 386 and 2460 cm−1, respectively, and the potential‐function minima are located 111.5° from the cis configuration. Diagonalization of the matrix of the complete Hamiltonian to second order by the use of perturbation theory is sufficient to account for the observed Q‐branch shapes in the far infrared region.Two microwave frequencies observed by Massey and Bianco at 22 054.5 and 27 639.6 Mc/sec are identified from their Stark effects as the first excited‐state transitions J, K, n, τ=8, 6, 1, 1→7, 5, 1, 3 and J, K, n, τ=8, 5, 1, 3→9, 6, 1, 1, respectively, where the internal‐rotation quantum number n=1 denotes the first excited torsional state and where τ denotes trans symmetric (τ=1 and 2) or antisymmetric (τ=3 and 4) states. The form of the dipole moment operator is assumed to be μ0 cos(x/2) and μ0 is found to be 3.15 D in agreement with the value obtained from the torsional ground‐state transitions.Two J=0 microwave series observed by Massey, Beard, and Jen in a mixed sample of the deuterated species D2O2 and HOOD give confirmation of the potential function determined from the H2O2 analysis. The K=4→5 series is identified as the D2O2 first excited torsional state transition n=1→1, τ=4→2. The K=0→1 series is identified as the HOOD torsional ground‐state transition n=0→0, τ=4→2. Only very small changes in the trans barrier height are necessary to fit the constant terms of these series exactly. These changes, which are expected to arise from vibration‐internal rotation interactions, show a reasonable progression from H2O2 to D2O2: V (trans, HOOH) = 386 cm−1, V (trans, HOOD) = 381 cm−1 and V (trans, DOOD) = 378 cm−1.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/71115/2/JCPSA6-42-6-1931-1.pd

Iron(III)-catalyzed chlorination of activated arenes

A general and regioselective method for the chlorination of activated arenes has been developed. The transformation uses iron(III) triflimide as a powerful Lewis acid for the activation of N-chlorosuccinimide and the subsequent chlorination of a wide range of anisole, aniline, acetanilide and phenol derivatives. The reaction was utilized for the late-stage mono- and di-chlorination of a range of target compounds such as the natural product nitrofungin, the antibacterial agent chloroxylenol and the herbicide chloroxynil. The facile nature of this transformation was demonstrated with the development of one-pot tandem iron-catalyzed dihalogenation processes allowing highly regioselective formation of different carbon-halogen bonds. The synthetic utility of the resulting dihalogenated aryl compounds as building blocks was established with the synthesis of natural products and pharmaceutically relevant targets

Defining Prostatic Vascular Pedicle Recurrence and the Anatomy of Local Recurrence of Prostate Cancer on Prostate-specific Membrane Antigen Positron Emission Tomography/Computed Tomography.

Background The term local recurrence in prostate cancer is considered to mean persistent local disease in the prostatic bed, most commonly at the site of the vesicourethral anastomosis (VUA). Since the introduction of prostate-specific membrane antigen (PSMA) positron emission tomography/computed tomography (PET/CT) and magnetic resonance imaging for assessment of early biochemical recurrence (BCR), we have found histologically confirmed prostate cancer in the prostatic vascular pedicle (PVP). If a significant proportion of local recurrences are distant to the VUA, it may be possible to alter adjuvant and salvage radiation fields in order to reduce the potential morbidity of radiation in selected patients. Objective To describe PVP local recurrence and to map the anatomic pattern of prostate bed recurrence on PSMA PET/CT. Design setting and participants This was a retrospective multicentre study of 185 patients imaged with PSMA PET/CT following radical prostatectomy (RP) between January 2016 and November 2018. All patient data and clinical outcomes were prospectively collected. Recurrences were documented according to anatomic location. For patients presenting with local recurrence, the precise location of the recurrence within the prostate bed was documented. Intervention PSMA PET/CT for BCR following RP. Results and limitations A total of 43 local recurrences in 41/185 patients (22%) were identified. Tumour recurrence at the PVP was found in 26 (63%), VUA in 15 (37%), and within a retained seminal vesicle and along the anterior rectal wall in the region of the neurovascular bundle in one (2.4%) each. Histological and surgical evidence of PVP recurrence was acquired in two patients. The study is limited by its retrospective nature with inherent selection bias. This is an observational study reporting on the anatomy of local recurrence and does not include follow-up for patient outcomes. Conclusions Our study showed that prostate cancer can recur in the PVP and is distant to the VUA more commonly than previously thought. This may have implications for RP technique and for the treatment of selected patients in the local recurrence setting. Patient summary We investigated more precise identification of the location of tumour recurrence after removal of the prostate for prostate cancer. We describe a new definition of local recurrence in an area called the prostatic vascular pedicle. This new concept may alter the treatment recommended for recurrent disease

Descriptive Topological Spaces for Performing Visual Search

Accepted versionThis article presents an approach to performing the task of visual search in the context of descriptive topological spaces. The presented algorithm forms the basis of a descriptive visual search system (DVSS) that is based on the guided search model (GSM) that is motivated by human visual search. This model, in turn, consists of the bottom-up and top-down attention models and is implemented within the DVSS in three distinct stages. First, the bottom-up activation process is used to generate saliency maps and to identify salient objects. Second, perceptual objects, defined in the context of descriptive topological spaces, are identified and associated with feature vectors obtained from a VGG deep learning convolutional neural network. Lastly, the top-down activation process makes decisions on whether the object of interest is present in a given image through the use of descriptive patterns within the context of a descriptive topological space. The presented approach is tested with images from the ImageNet ILSVRC2012 and SIMPLIcity datasets. The contribution of this article is a descriptive pattern-based visual search algorithm."This research has been supported by the Natural Sciences and Engineering Research Council of Canada (NSERC) Discovery Grant 418413, and the Faculty of Graduate Studies at the University of Winnipeg."https://link.springer.com/chapter/10.1007/978-3-662-58768-3_

Measurement of the muon anti-neutrino double-differential cross section for quasi-elastic scattering on hydrocarbon at~Eν∼3.5E_\nu \sim 3.5 GeV

We present double-differential measurements of anti-neutrino quasi-elastic scattering in the MINERvA detector. This study improves on a previous single differential measurement by using updated reconstruction algorithms and interaction models, and provides a complete description of observed muon kinematics in the form of a double-differential cross section with respect to muon transverse and longitudinal momentum. We include in our signal definition zero-meson final states arising from multi-nucleon interactions and from resonant pion production followed by pion absorption in the primary nucleus. We find that model agreement is considerably improved by a model tuned to MINERvA inclusive neutrino scattering data that incorporates nuclear effects such as weak nuclear screening and two-particle, two-hole enhancements.Comment: 47 pages, 31 figure

Genetic variation in the MBL2 gene is associated with Chlamydia trachomatis infection and host humoral response to Chlamydia trachomatis infection

This study aims to assess the potential association of MBL2 gene single nucleotide polymorphisms (SNPs) to Chlamydia trachomatis infection. We analysed a selected sample of 492 DNA and serum specimens from Dutch Caucasian women. Women were categorized into four groups of infection status based on the results of DNA and antibody tests for C. trachomatis: Ct-DNA+/IgG+, CtDNA+/IgG−, Ct-DNA−/IgG+, and Ct-DNA−/IgG−. We compared six MBL2 SNPs (−619G > C (H/L), −290G > C (Y/X), −66C > T (P/Q), +154C > T (A/D), +161A > G (A/B), and +170A > G (A/C)) and their respective haplotypes in relation to these different subgroups. The −619C (L) allele was less present within the Ct-DNA−/IgG+ group compared with the Ct-DNA−/IgG− group (OR = 0.49; 95% CI: 0.28–0.83), while the +170G (C) allele was observed more in the Ct-DNA+/IgG+ group as compared with the Ct-DNA−/IgG− group (OR = 2.4; 95% CI: 1.1–5.4). The HYA/HYA haplotype was more often present in the Ct-DNA−/IgG− group compared with the Ct-DNA+/IgG+ group (OR = 0.37; 95% CI: 0.16–0.87). The +170G (C) allele was associated with increased IgG production (p = 0.048) in C. trachomatis PCR-positive women. This study shows associations for MBL in immune reactions to C. trachomatis. We showed clear associations between MBL2 genotypes, haplotypes, and individuals’ stages of C. trachomatis DNA and IgG positivity.NGI Life Sciences Pre-Seed and a EuroTransBio grant.https://www.mdpi.com/journal/ijerphMedical Microbiolog

The X-ray emission of the gamma Cassiopeiae stars

Long considered as the "odd man out" among X-ray emitting Be stars, \gamma Cas (B0.5e IV) is now recognized as the prototype of a class of stars that emit hard thermal X-rays. Our classification differs from the historical use of the term "gamma Cas stars" defined from optical properties alone. The luminosity output of this class contributes significantly to the hard X-ray production in massive stars in the Galaxy. The gamma Cas stars have light curves showing variability on a few broadly-defined timescales and spectra indicative of an optically thin plasma consisting of one or more hot thermal components. By now 9--13 Galactic \approx B0-1.5e main sequence stars are judged to be members or candidate members of the \gamma Cas class. Conservative criteria for this designation are for a \approxB0-1.5e III-V star to have an X-ray luminosity of 10^{32}--10^{33} ergs s^{-1}, a hot thermal spectrum containing the short wavelength Ly \alpha FeXXV and FeXXVI lines and the fluorescence FeK feature all in emission. If thermality cannot be demonstrated, for example from either the presence of these Ly \alpha lines or curvature of the hard continuum; these are the gamma Cas candidates. We discuss the history of the discovery of the complicated characteristics of the variability in the optical, UV, and X-ray domains, leading to suggestions for the physical cause of the production of hard X-rays. These include scenarios in which matter from the Be star accretes onto a degenerate secondary star and interactions between magnetic fields on the Be star and its decretion disk. The greatest aid to the choice of the causal mechanism is the temporal correlations of X-ray light curves and spectra with diagnostics in the optical and UV wavebands. We show why the magnetic star-disk interaction scenario is the most tenable explanation for the creation of hard X-rays on these stars.Comment: Review paper for "X-ray Emissions from Hot Stars and their Winds" compendium to be published by Advances in Space Research in mid-2016. Paper is comprised of 66 pages, 15 figure

Advances in Improving Tolerance to Waterlogging in \u3cem\u3eBrachiaria\u3c/em\u3e Grasses

Poor drainage is found on about 11.3% of agricultural land in Latin America where physiography promotes flooding, high groundwater tables, or stagnant surface water (waterlogging). Waterlogging drastically reduces oxygen diffusion into the soil causing hypoxia which is the main limitation that reduces root aerobic respiration and the absorption of minerals and water. Under waterlogging conditions plants can adapt with traits and mechanisms that improve root aeration such as production of aerenchyma and development of adventitious roots. During the rainy season Brachiaria pastures are exposed to waterlogging conditions that can severely limit pasture productivity and hence animal production. The main objective of an inter-institutional and multidisciplinary project was to identify Brachiaria hybrids combining waterlogging tolerance with high forage yield and quality to improve meat and milk production and mitigate the impacts of climate change in the humid areas of Latin America. Researchers at the Centro Internacional de Agricultura Tropical (CIAT) have developed a screening method to evaluate waterlogging tolerance in Brachiaria. Using this method, 71 promising hybrids derived from three Brachiaria species (B. ruziziensis, B. brizantha, and B. decumbens) were evaluated. Four hybrids were identified as superior in waterlogging tolerance. Their superiority was based on greater green leaf biomass production, a greater proportion of green leaf to total leaf biomass, greater green leaf area, leaf chlorophyll content, and photosynthetic efficiency, and reduced dead leaf biomass. These hybrids together with previously selected hybrids and germplasm accessions are being field-tested for waterlogging tolerance in collaboration with National Agricultural Research Institutions and farmers from Colombia, Nicaragua, and Panama