An NMR study of hydrogen exchange in p-hydroxybenzoic acid

The compound has been used over a temperature range in dimethylsulfoxide, with trichloroacetic acid and triethylamine as catalysts. The rate constant for uncatalyzed bimolecular exchange at 25 C is k_N=131 M^–1 sec^–1; the constant for acid-catalyzed exchange is k_A=0.9 · 10⁴ M^–1 sec^–1; and that for base-catalyzed exchange is k_B=0.5 · 10⁴ M^–1 sec^–1. The activation energy for uncatalyzed exchange is 5.75 kcal/mole. The exchange rates in dimethylformamide and acetone are higher, on account of differences in the hydrogen bond. The exchange rates of the isomers fall in the sequence ortho > para > meta, which is due to conjugation and intramolecular hydrogen bonding. The exchange mechanism is discussed. Simple relationships in dimensionless parameters are given for calculating the exchange rate from the shape of the NMR signal.     

1-diphenylphosphinyl-2,2-dimethylaziridine - a new precursor of α,α-dimethylarylalkylamines

The new synthesis of α,α-dimethylarylalkylamines from 1-diphenylphosphinyl-2,2-dimethylaziridine is described.     

Constructing orthogonal pandiagonal Latin squares and panmagic squares from modular n‐queens solutions

In this article, we show how to construct pairs of orthogonal pandiagonal Latin squares and panmagic squares from certain types of modular n‐queens solutions. We prove that when these modular n‐queens solutions are symmetric, the panmagic squares thus constructed will be associative, where for an n × n associative magic square A = (a_ij), for all i and j it holds that a_ij + an?i?1,n?j?1 = c for a fixed c. We further show how to construct orthogonal Latin squares whose modular difference diagonals are Latin from any modular n‐queens solution. As well, we analyze constructing orthogonal pandiagonal Latin squares from particular classes of non‐linear modular n‐queens solutions. These pandiagonal Latin squares are not row cyclic, giving a partial solution to a problem of Hedayat. © 2007 Wiley Periodicals, Inc. J Combin Designs 15: 221–234, 2007     

Local-global principles for representations of quadratic forms

We prove a local-global principle for the problem of representations of quadratic forms by quadratic forms over ℤ, in codimension ≥5. The proof uses the ergodic theory of p-adic groups, together with a fairly general observation on the structure of orbits of an arithmetic group acting on integral points of a variety.     

Permeability of pure and mixed gases in silicone rubber at elevated pressures

The transport properties of silicone rubber are reported at 35°C for a series of pure gases (He, N₂, CH₄, CO₂, and C₂H₄) and gas mixtures (CO₂/CH₄ and N₂/CO₂) for pressures up to 60 atm. The effects of pressure and concentration on the permeability of various gases have been analyzed to consider plasticization and hydrostatic compression effects. Over an extended pressure and concentration range, both compression of free volume and eventual plasticization phenomena were observed for the various penetrants. In pure component studies, plasticization effects tended to dominate hydrostatic compression effects for the more condensible penetrants (C₂H₄ and CO₂) while the reverse was true for the low sorbing N₂ and He. These issues are discussed in terms of penetrant diffusion coefficients versus pressure to clarify the interplay between the opposing effects for the penetrants of markedly different solubilities. Additional insight into the somewhat complex interplay of the plasticization and hydrostatic compression effects are given by mixed gas permeation results. It was found that the permeability of nitrogen in a 10/90 CO₂/N₂ and a 50/50 CO₂/N₂ mixture was increased by the presence of CO₂ because the plasticizing nature of CO₂ is able to overcome nitrogen's compression effect.     

Identifying the radiating core of Lighthill’s source term

A decomposition of the Lighthill source term is effected which yields ten sub-terms comprising velocity, vorticity, dilatation and density fields. An analysis methodology is then developed, aimed at understanding the respective roles played by these sub-terms in the production of sound. By Direct Numerical Simulation of a temporal mixing-layer—chosen both for its simplicity and its amenability to analysis in wavenumber space—the radiating components of the different sub-terms are isolated and studied. Interesting identities are observed between specific events in the evolution of the flow and the various sub-terms of the source, and the essence of the sound production mechanism is found to comprise subtle imbalances which disrupt inherent space–time symmetries which exist between the various sub-terms.      

A cationic hydro­xo-bridged dinuclear gallium complex

The crystal structure of μ-hydro­xo-bis{[N-iso­propyl-2-(isopropyl­amino)­tropon­imino-N,N′](methyl)gallium(II)} tetrakis(pentafluorophenyl)borate (troponimine is 2,4,6-cycloheptatrien-1-imine), [Ga₂(C₁₄H₂₂N₂)₂(OH)]B(C₆H₅)₄, is discussed. The two (ⁱPr₂-ATI)GaMe (ATI is aminotroponimime) units of the dinuclear cation are linked by a bridging hydro­xo group and are both slightly twisted from planarity.     

Some criteria for the applicability of synthetic standards for laser spectral analysis of refractories

Summary The applicability of a series of synthetic standards for laser local analysis of refractories has been determined on the basis of 4 criteria: homogeneity, equality of the form and size of the craters formed by the laser beam, densities and plasma clouds. The validity of these criteria has been checked by comparison of the results received by electrone microprobe area scanning and by shooting the same places with a laser beam and reading the results with the help of synthetic standards.

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Kriterien zur Anwendbarkeit synthetischer Standards für die Laser-Spektralanalyse von feuerfesten Materialien

Zusammenfassung Die Anwendbarkeit von synthetischen Standards für die Laser-Lokalanalyse von feuerfesten Materialien wurde auf Grund von 4 Kriterien beurteilt: Homogenität, Gleichheit von Form und Größe der vom Laserstrahl verursachten Krater, Dichten und Plasmawolken. Die Gültigkeit dieser Kriterien wurde durch Vergleich der erhaltenen Ergebnisse mit den mit Hilfe der Elektronenmikrosonde erzielten Resultaten geprüft.

     

Comparing nanoparticle risk perceptions to other known EHS risks

Over the last decade social scientific researchers have examined how the public perceives risks associated with nanotechnology. The body of literature that has emerged has been methodologically diverse. The findings have confirmed that some publics perceive nanotechnology as riskier than others, experts feel nanotechnology is less risky than the public does, and despite risks the public is optimistic about nanotechnology development. However, the extant literature on nanotechnology and risk suffers from sometimes widely divergent findings and has failed to provide a detailed picture of how the public actually feels about nanotechnology risks when compared to other risks. This study addresses the deficiencies in the literature by providing a comparative approach to gauging nanotechnology risks. The findings show that the public does not fear nanotechnology compared to other risks. Out of 24 risks presented to the participants, nanotechnology ranked 19th in terms of overall risk and 20th in terms of “high risk.”     

Coaxial fiber-optic chemical-sensing excitation-emission matrix fluorometer

Great reductions in the overall size and complexity of high throughput multichannel UV-visible fluorometers were achieved by coupling a compact optical fiber array to compact dispersive transmission optics. The coaxial configuration centers on the insertion of a silica/silica optical fiber into the hollow region of a UV-fused silica capillary waveguide. The outer core delivers the maximum power of the narrow wavelength region of the excitation spectrum created by coupling a xenon arc discharge lamp to a compact spectrometer. The molecular fluorescence resulting from the interaction of light emitted at the distal end of the hollow waveguide and the sample matrix is received and transmitted to a CCD via a compact dispersive grating-prism (grism) optical assembly. A linear array of the coaxial optical fibers permits a full excitation-emission matrix spectrum of the analyte matrix to be projected onto the face of the CCD. The in situ identification and monitoring of polycyclic aromatic hydrocarbons was carried out for the initial application testing for this prototype.