A magnetic resonance imaging-based articulatory and acoustic study of "retroflex" and "bunched" American English /r/

Speakers of rhotic dialects of North American English show a range of different tongue configurations for /r/. These variants produce acoustic profiles that are indistinguishable for the first three formants [Delattre, P., and Freeman, D. C., (1968). "A dialect study of American English r's by x-ray motion picture," Linguistics 44, 28-69; Westbury, J. R. et al. (1998), "Differences among speakers in lingual articulation for American English /r/," Speech Commun. 26, 203-206]. It is puzzling why this should be so, given the very different vocal tract configurations involved. In this paper, two subjects whose productions of "retroflex" /r/ and "bunched" /r/ show similar patterns of F1-F3 but very different spacing between F4 and F5 are contrasted. Using finite element analysis and area functions based on magnetic resonance images of the vocal tract for sustained productions, the results of computer vocal tract models are compared to actual speech recordings. In particular, formant-cavity affiliations are explored using formant sensitivity functions and vocal tract simple-tube models. The difference in F4/F5 patterns between the subjects is confirmed for several additional subjects with retroflex and bunched vocal tract configurations. The results suggest that the F4/F5 differences between the variants can be largely explained by differences in whether the long cavity behind the palatal constriction acts as a half- or a quarter-wavelength resonator.     

Perturbation of Spin Crossover Behavior by Covalent Post‐Synthetic Modification of a Porous Metal–Organic Framework

Covalent post‐synthetic modification is a versatile method for gaining high‐level synthetic control over functionality within porous metal–organic frameworks and for generating new materials not accessible through one‐step framework syntheses. Here we apply this topotactic synthetic approach to a porous spin crossover framework and show through detailed comparison of the structures and properties of the as‐synthesised and covalently modified phases that the modification reaction proceeds quantitatively by a thermally activated single‐crystal‐to‐single‐crystal transformation to yield a material with lowered spin‐switching temperature, decreased lattice cooperativity, and altered color. Structure–function relationships to emerge from this comparison show that the approach provides a new route for tuning spin crossover through control over both outer‐sphere and steric interactions.     

The use of Raman microscopy and laser desorption ionization mass spectrometry in the examination of synthetic organic pigments in modern works of art

Synthetic organic pigments are widely used in modern and contemporary works of art. They have been examined by a variety of techniques including spectroscopic methods such as Fourier transform infrared spectroscopy, Raman, and X‐ray powder diffraction as well as chromatographic or mass spectrometric techniques such as pyrolysis‐gas chromatography/mass spectrometry and laser desorption ionization mass spectrometry (LDI–MS). Often, a combination of techniques has been used to examine these pigments. This paper describes use of Raman spectroscopy to create a database of colorants including two pigments not previously reported, PO1 and PO2. Then, using Raman spectroscopy in combination with LDI–MS, samples from modern works of art by artists including Mark Rothko, Barnett Newman, and José de Rivera were examined in order to identify the pigments present. One finding was that Rothko used a variety of red pigments over the course of his career including PR11 which has not been previously reported in artwork, and PO2 found with its positional isomer PR1. Knowledge of the colorants serves to inform conservators about display and treatment decisions. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.     

A new lot sizing and scheduling heuristic for multi-site biopharmaceutical production

Biopharmaceutical manufacturing requires high investments and long-term production planning. For large biopharmaceutical companies, planning typically involves multiple products and several production facilities. Production is usually done in batches with a substantial set-up cost and time for switching between products. The goal is to satisfy demand while minimising manufacturing, set-up and inventory costs. The resulting production planning problem is thus a variant of the capacitated lot-sizing and scheduling problem, and a complex combinatorial optimisation problem. Inspired by genetic algorithm approaches to job shop scheduling, this paper proposes a tailored construction heuristic that schedules demands of multiple products sequentially across several facilities to build a multi-year production plan (solution). The sequence in which the construction heuristic schedules the different demands is optimised by a genetic algorithm. We demonstrate the effectiveness of the approach on a biopharmaceutical lot sizing problem and compare it with a mathematical programming model from the literature. We show that the genetic algorithm can outperform the mathematical programming model for certain scenarios because the discretisation of time in mathematical programming artificially restricts the solution space.     

New Explanation for Ligand Bending in Transition Metal Tris(dithiolate) Complexes

The results of Fenske-Hall molecular orbital calculations are reported for the trigonal prismatic complexes Mo(S(2)C(2)H(2))(3) and Mo(S(2)C(6)H(4))(3). Both complexes exhibit a bend of the S-C-C-S ligand plane away from the S-Mo-S plane. A series of calculations which systematically follow the changes in electronic structure as the bend angle alpha is varied between 0 and 30 degrees indicates that the bend can be attributed to a second order Jahn-Teller distortion. The driving force for this distortion, which allows mixing between a set of ligand pi orbitals and the metal d(z)()()2 orbital, should be greatest for d(0) systems. In these systems the bent geometry leads to the stabilization of the doubly occupied HOMO. The driving force for ligand bending should be lower in systems having more or fewer electrons (e.g. Re(S(2)C(2)Ph(2))(3) or V(S(2)C(2)Ph(2))(3), respectively). While the steric bulk of the dithiolate ligands in the latter complexes may also influence the degree of ligand bending, this is probably a secondary effect.     

Hypericin-Induced Phototoxicity in Cultured Fibroblasts and Swine Erythrocytes

Hypericin is a naturally occurring photosensitizer, whose presence in plants has been responsible for cutaneous phototoxicity in grazing animals. The photosensitizing properties of this agent have recently been exploited in models for anti-tumor and anti-viral activity. The cytotoxicity of hypericin and light was assessed in 3T3 mouse fibroblasts using the MTT [3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide)] assay and the lactate dehydrogenase (LDH) leakage assay. Membrane damage was assessed in swine erythrocytes using hemolysis, potassium (K⁺) leakage and formation of lipid hydroperoxides. Concentration- and light-dependent decreases in fibroblast viability were seen starting at hypericin concentrations of 1.25 μM and light power flux levels of 24 J/cm² using a visible light source and at 0.417 μM hypericin and a similar light dose using a solar simulator, No LDH leakage was observed at hypericin concentrations up to 30 μM and visible light up to 144 J/cm². Light-and/or concentration-dependent increases in hemolysis, K⁺ leakage and formation of lipid hydroperoxides in red blood cell (RBC) membranes were observed, but at concentrations and light doses much greater than those required to induce cytotoxicity in fibroblasts. Lipid peroxidation and hemolysis occurred at 15 μM hypericin and 24 J/cm² (visible light source). Potassium ion leakage occurred at concentrations and light levels as low as 5 μM and 12 J/cm² or 15 μM and 4.8 J/cm² (visible light source) but was still a less sensitive indicator than fibroblast cytotoxicity. Evidence for both type I and type II reactions was shown in RBC membranes by TLC analysis of cholesterol products. In the absence of light, hypericin appears to be relatively nontoxic in the models tested.     

Synthesis of some isomeric 4,11-dihydro-5H-[1]benzoxocino[4,3-d] or [3,4-c]isoxazol-5-ones and isomeric 4,5,10,11-tetrahydrobenzo[5,6]-cycloocta[2,1-d] or [1,2-c]isoxazol-5-ones

The title compounds were prepared by acid-catalyzed cyclization of aryloxymethyl- or (2-arylethyl)-4-carboxymethylisoxazoles which in turn were synthesized from aryloxymethyl- or (2-arylethyl)isoxazole-4-carboxylic acids by Arndt-Eistert homologation.     

Proton and carbon-13 nuclear magnetic resonance spectroscopy and conformational aspects of 5,6,7,8-tetrahydro-4-chromanone derivatives

The 25 MHz ¹³C and 350 MHz ¹H-nmr spectra of the title compounds are reported. Conformational equilibria in variously substituted 5,6,7,8-tetrahydrochromanones are discussed. Compounds bearing a t-butyl group at the 6 position appear to be conformationally homogenous.     

Synthesis of some 3-alkenyl-4-oxo-6,7-dihydro-4H-pyrano[3,4-d]isoxazoles

A series of 3-alkenyl-4-oxo-6,7-dihydro-4H-pyrano[3,4-d]isoxazole derivatives was prepared by reaction of hydroxylamine with 4,5-dioxo-2,3,7,8-tetrahydro-4H,5H-pyrano[4,3-b]pyran derivatives.