Electron spin relaxation times and rapid scan EPR imaging of pH‐sensitive amino‐substituted trityl radicals

Carboxy‐substituted trityl (triarylmethyl) radicals are valuable in vivo probes because of their stability, narrow lines, and sensitivity of their spectroscopic properties to oxygen. Amino‐substituted trityl radicals have the potential to monitor pH in vivo, and the suitability for this application depends on spectral properties. Electron spin relaxation times T₁ and T₂ were measured at X‐band for the protonated and deprotonated forms of two amino‐substituted triarylmethyl radicals. Comparison with relaxation times for carboxy‐substituted triarylmethyl radicals shows that T₁ exhibits little dependence on protonation or the nature of the substituent, which makes it useful for measuring O₂ concentration, independent of pH. Insensitivity of T₁ to changes in substituents is consistent with the assignment of the dominant contribution to spin lattice relaxation as a local mode that involves primarily atoms in the carbon and sulfur core. Values of T₂ vary substantially with pH and the nature of the aryl group substituent, reflecting a range of dynamic processes. The narrow spectral widths for the amino‐substituted triarylmethyl radicals facilitate spectral‐spatial rapid scan electron paramagnetic resonance imaging, which was demonstrated with a phantom. The dependence of hyperfine splittings patterns on pH is revealed in spectral slices through the image. Copyright © 2014 John Wiley & Sons, Ltd.     

Azidocarbonyl-substituted cubanoureas

Despite the angular strain associated with the assembly of small rings, 1,2-diisocyanatocubane reacts with trimethylsilyl azide under mild conditions to form a hexacyclic ring assembly that contains an imidazolidone ring fused to one edge of cubane. This compound was identified as an azidocarbonyl-substituted cubanourea by means of X-ray crystal structure analysis of the nitro-derivative, the energetic compound N-azidocarbonyl-N¹-nitrocubanourea.     

Electron spin echo and CW perspective in 3D EPR imaging

Three-dimensional spectral-spatial-spatial images are presented for a sample containing six different species in seven compartments. EPR spectra used to construct these images were obtained by the normal CW methods and by electron spin echo detection. Images of the sample when viewed from these two different perspectives are contrasted.     

Longitudinal muon spin relaxation in organic radicals in the vapour phase

The aim of this work is the study of longitudinal field relaxation for organic radicals in the gas or vapour phase, for which the technique of Muon Spin Relaxation proves to be uniquely suitable. Following on from the first such study of the muonium substituted ethyl radical in gaseous ethene [1], the present work represents the beginning of a systematic study of species of various molecular symmetries and still higher molecular weight, with a view to investigating their collisional dynamics. Preliminary data for the muonium substituted cyclohexadienyl radical in benzene vapour, and the results of tests for radical formation in acetylene and carbon monoxide, are presented.     

Alkynes as Linchpins for the Additive Annulation of Biphenyls: Convergent Construction of Functionalized Fused Helicenes

A new approach to fused helicenes is reported, where varied substituents are readily incorporated in the extended aromatic frame. From the alkynyl precursor, the final helical compounds are obtained under mild conditions in a two‐step process, in which the final C?C bond is formed via a photochemical cyclization/ dehydroiodination sequence. The distortion of the π‐system from planarity leads to unusual packing in the solid state. Computational analysis reveals that substituent incorporation perturbs geometries and electronic structures of these nonplanar aromatics.     

Simplified method for microlitre deuterium measurements in water and urine by gas chromatography-high-temperature conversion-isotope ratio mass spectrometry

Deuterium (2H) in water and urine can be measured by off-line and, more recently, on-line techniques using isotope ratio mass spectrometry (IRMS). We describe a new simple on-line pyrolysis method for the analysis of 2H/1H in water and urine samples by continuous flow IRMS, normally used for 2H/1H measurements in organic compounds. A deactivated column connected the split injector to a high-temperature conversion reactor (TC HD), and 0.5 microL of sample was injected. Accuracy and precision were determined with Vienna Standard Mean Ocean Water (VSMOW), Standard Light Antarctic Precipitation (SLAP), and Greenland Ice Sheet Precipitation (GISP). The range of linearity was measured with a calibration curve of enriched water from 0 up to 0.1 atom percent excess (APE) (i.e. -72 up to 6323 delta per mil (deltaD per thousand)) with a precision of <5 per thousand and accuracy ranging between 1 and 55 per thousand. Blinded reanalysis of urine samples by an equilibration device (Gas Bench) and by a dedicated pyrolysis system (TC/EA) was performed and results compared by the Bland-Altman test. Enrichments ranged between 600 and 2400 per thousand deltaD(VSMOW) with a precision of +/-5 per thousand. Urine enrichments described by our method were strongly correlated with values obtained by Gas Bench and TC/EA (p < 0.0001). There was a significant memory effect that was reduced by injecting the sample 15 times and discarding the first 10 injections, together with accurate furnace conditioning and appropriate cleaning of the syringe. Data indicate that the method is accurate, and that it can be used for water and urine deuterium determination when a Gas Bench or TC/EA instrument is not available and the amount of sample is limited.     

On perturbations of strongly admissible prior distributions

Consider a parametric statistical model, P(dx|θ), and an improper prior distribution, ν(dθ), that together yield a (proper) formal posterior distribution, Q(dθ|x). The prior is called strongly admissible if the generalized Bayes estimator of every bounded function of θ is admissible under squared error loss. Eaton [M.L. Eaton, A statistical diptych: Admissible inferences-recurrence of symmetric Markov chains, Annals of Statistics 20 (1992) 1147–1179] used the Blyth–Stein Lemma to develop a sufficient condition, call it , for strong admissibility of ν. Our main result says that, under mild regularity conditions, if ν satisfies and g(θ) is a bounded, non-negative function, then the perturbed prior distribution g(θ)ν(dθ) also satisfies and is therefore strongly admissible. Our proof has three basic components: (i) Eaton's [M.L. Eaton, A statistical diptych: Admissible inferences-recurrence of symmetric Markov chains, Annals of Statistics 20 (1992) 1147–1179] result that the condition is equivalent to the local recurrence of the Markov chain whose transition function is R(dθ|η)=∫Q(dθ|x)P(dx|η); (ii) a new result for general state space Markov chains giving conditions under which local recurrence is equivalent to recurrence; and (iii) a new generalization of Hobert and Robert's [J.P. Hobert, C.P. Robert, Eaton's Markov chain, its conjugate partner and -admissibility, Annals of Statistics 27 (1999) 361–373] result that says Eaton's Markov chain is recurrent if and only if the chain with transition function is recurrent. One important application of our results involves the construction of strongly admissible prior distributions for estimation problems with restricted parameter spaces.     

Full-field measurements of flow through a scaled metal foam replica

Open-celled foam geometries show great promise in heat/mass transfer, chemical treatment, and enhanced mixing applications. Flow measurements on these geometries have consisted primarily of observations of the upstream and downstream effects the foam has on the velocity field. Unfortunately, these observations give little insight into the flow inside the foam. We have performed quantitative flow measurements inside a scaled replica of a metal foam, ϕ = 0.921, D _Cell = 2.5 mm, by Magnetic Resonance Velocimetry to better understand the fluid motion inside the foam and give an alternative method to determine the foam cell and pore sizes. Through these 3-D, spatially resolved measurements of the flow field for a cell Reynolds number of 840, we have shown that the transverse motion of the fluid has velocities 20–30% of the superficial velocity passing through the foam. This strong transverse motion creates and dissipates streamwise jets with peak velocities 2–3 times the superficial velocity and whose coherence length is strongly correlated to the cell size of the foam. This complex fluid motion is described as “mechanical mixing” and is attributed to the geometry of the foam. A mechanical dispersion coefficient, D _M, was formed which demonstrates the transverse dispersion of this geometry to be 14 times the kinematic viscosity and 10 times the thermal diffusivity of air at 20°C and 1 atm.