Insight into Solvent Coordination of an Iron Porphyrin Hydroxylamine Complex from Spectroscopy and DFT Calculations

The reduction of Fe(OEP)(NO) in the presence of substituted phenols leads to a three‐electron reduction to form Fe(OEP)(NH2OH), which has been characterized by visible spectroscopy and electron stoichiometry. In this work, we have further characterized this species using infrared and 1H NMR spectroscopy, along with DFT calculations. The infrared bands in the 3400–3600 cm–1 region, due to hydroxylamine, were significantly downshifted to the 2500–2700 cm–1 region when 4‐[D1]chlorophenol replaced the normal abundance acid. Using 1H NMR spectroscopy, the hydroxylamine and the meso‐protons were identified. From DFT calculations, the 1H NMR spectra were most consistent with a six‐coordinate complex, Fe(OEP)(NH2OH)(THF)

A Probablistic Origin for a New Class of Bivariate Polynomials

We present here a probabilistic approach to the generation of new polynomials in two discrete variables. This extends our earlier work on the 'classical' orthogonal polynomials in a previously unexplored direction, resulting in the discovery of an exactly soluble eigenvalue problem corresponding to a bivariate Markov chain with a transition kernel formed by a convolution of simple binomial and trinomial distributions. The solution of the relevant eigenfunction problem, giving the spectral resolution of the kernel, leads to what we believe to be a new class of orthogonal polynomials in two discrete variables. Possibilities for the extension of this approach are discussed.Comment: This is a contribution to the Special Issue on Dunkl Operators and Related Topics, published in SIGMA (Symmetry, Integrability and Geometry: Methods and Applications) at http://www.emis.de/journals/SIGMA

Attitudes to English as a language for international development in rural Bangladesh

The high status of English within a global economy of languages has meant that English-language education is increasingly being promoted in international development initiatives. This is despite the fact that it may seem more valuable for the estimated 1.4 billion people living in poverty in the world to focus development initiatives on the lowering of infant mortality rates, clean water supply, access to electricity, and the provision of basic education, for example. A reason for the promotion of English-language education in development contexts is in part a response to a growing conviction that English-language education can play an important role in helping people gain the resources to lift themselves out of poverty and increase their ability to participate in the world economic systems from which they have previously been excluded. Despite the strong associations often made between the English language and development, there is, however, only limited evidence showing a relationship between the two. A first step in understanding this impact is an understanding of perceptions and expectations of English learning for personal and national development, and this research project investigates these in two rural communities in Bangladesh. Through the use of an ethnographic survey of two rural areas, it studies the needs and aspirations of the local community in order to better understand perceptions of whether and if so how English-language education could productively contribute to development as part of a wider programme of social and economic support

Redox and Spectroscopic Properties of Iron Porphyrin Nitroxyl in the Presence of Weak Acids

The spectroelectrochemistry and voltammetry of Fe(OEP) (NO) in the presence of substituted phenols was studied. Cyclic voltammetry showed that two closely spaced waves were observed for the reduction of Fe(OEP) (NO) in the presence of substituted phenols. The first wave was a single electron reduction under voltammetric conditions. The second wave was kinetically controlled, multielectron process. Visible spectroelectrochemistry of Fe(OEP) (NO) in the presence of substituted phenols showed that three species were present during the electrolysis. Additional spectroscopic studies indicated that the two reduction species were Fe(OEP) (HNO) and Fe(OEP)(H2NOH). The Fe(OEP) (HNO) species, which can be generated chemically, was stable over a period of hours. Additional acid did not lead to further protonation. Proton NMR spectroscopy confirmed the Fe(OEP) (HNO) species could be deprotonated under basic conditions. The third species, Fe(OEP)(H2NOH), was generated by the further reduction of the chemically generated Fe(OEP) (HNO) complex. Both the Fe(OEP) (HNO) and Fe(OEP)(H2NOH) complexes could be slowly oxidized back to Fe(OEP) (NO). At millimolar concentrations of Fe(OEP) (HNO), there was no evidence for the disproportionation of Fe(OEP) (HNO) to Fe(OEP) (NO) and H2 in the presence of substituted phenols. Nor was there evidence for the generation of N2O. The FTIR spectroelectrochemistry showed changes in the infrared spectra in the presence of substituted phenols, but no isotopic sensitive bands were observed for the reduced species between 1450 and 1200 cm–1. This may be because the νNO band shifted into a region (1500–1450 cm–1) where it would be difficult to observe

English for economic development: a case study of migrant workers from Bangladesh

This report investigates the relationship between English language learning and economic development among workers from rural Bangladesh who emigrated to the Middle East in search of employment. It provides first-hand accounts of language and other needs of those living and working in contexts of this sort, and provides valuable insights which can feed into the design and implementation of English language education policies and programmes

Catalytic Reduction of Bisulfite by Myoglobin/Surfactant Films

The voltammetry of bisulfite at a film formed with myoglobin was studied in aqueous solutions. A broad wave was observed for the reduction of bisulfite. Using controlled potential electrolysis, the reduction at potentials positive of the FeII/FeIwave formed dithionite exclusively. As the potential approached the region for the FeII/FeI reduction, bisulfite was reduced primarily to HS−. Even at the negative potentials, some dithionite was still formed, which could then be electrochemically reduced to thiosulfate. Analysis of the formation of HS−, dithionite and thiosulfate during the electrolysis was consistent with the parallel formation of HS−and dithionite, the latter of which was reduced to thiosulfate. Thiosulfate was verified by chemical analysis of the products from controlled potential electrolysis of the solution, and dithionite was observed spectroscopically using spectroelectro−chemistry

A Mechanical Analog of the Two-bounce Resonance of Solitary Waves: Modeling and Experiment

We describe a simple mechanical system, a ball rolling along a specially-designed landscape, that mimics the dynamics of a well known phenomenon, the two-bounce resonance of solitary wave collisions, that has been seen in countless numerical simulations but never in the laboratory. We provide a brief history of the solitary wave problem, stressing the fundamental role collective-coordinate models played in understanding this phenomenon. We derive the equations governing the motion of a point particle confined to such a surface and then design a surface on which to roll the ball, such that its motion will evolve under the same equations that approximately govern solitary wave collisions. We report on physical experiments, carried out in an undergraduate applied mathematics course, that seem to verify one aspect of chaotic scattering, the so-called two-bounce resonance.Comment: 9 pages, 8 figures, link to one youtube vide

X-ray Structure and Properties of the Ferrous Octaethylporphyrin Nitroxyl Complex

The preparation and characterization of the iron octaethylporphyrin nitroxyl ion, [Fe(OEP)(NO)−], is reported. The complex was synthesized by the one-electron reduction of Fe(OEP)(NO) using anthracenide as the reducing agent. The compound was isolated as the potassium (2.2.2)cryptand salt. The anion was characterized using X-ray analysis with visible and infrared spectroscopy. The spectral features of the iron nitroxyl complex were consistent with previous literature reports. The important structural changes upon reduction were a significant decrease in the Fe–N–O bond angle from 142° to 127° and an increase in the N–O bond length from that in the starting nitrosyl moiety. The porphyrin ring became significantly less planar upon reduction, but the displacement of the iron atom from the 24-atom plane was essentially unchanged. In spite of the attempt to encapsulate the potassium ion with the (2.2.2)cryptand, significant interaction between K+ and the oxygen of the nitroxyl were observed, indicating a contact ion pair in the crystal structure. Comparison between the experimental structure and the DFT-calculated parameters were reported. The results are consistent with the Fe–N–O moiety being the site of the reduction, with little evidence for the reduction of the iron itself or the porphyrin ring. The proton NMR spectrum was also obtained, and the chemical shifts were significantly different from other S = 0 metalloporphyrin complexes. These shifts, though, were consistent with the DFT calculations

Challenges in Partially-Automated Roadway Feature Mapping Using Mobile Laser Scanning and Vehicle Trajectory Data

Connected vehicle and driver's assistance applications are greatly facilitated by Enhanced Digital Maps (EDMs) that represent roadway features (e.g., lane edges or centerlines, stop bars). Due to the large number of signalized intersections and miles of roadway, manual development of EDMs on a global basis is not feasible. Mobile Terrestrial Laser Scanning (MTLS) is the preferred data acquisition method to provide data for automated EDM development. Such systems provide an MTLS trajectory and a point cloud for the roadway environment. The challenge is to automatically convert these data into an EDM. This article presents a new processing and feature extraction method, experimental demonstration providing SAE-J2735 map messages for eleven example intersections, and a discussion of the results that points out remaining challenges and suggests directions for future research.Comment: 6 pages, 5 figure