Asymmetric hydroamination of aminoallenes catalyzed by titanium and tantalum complexes of chiral sulfonamide alcohol ligands

A series of bidentate sulfonamide alcohol ligands with varying steric and electronic properties was synthesized. The titanium and tantalum complexes of these ligands, prepared in situ from either Ti(NMe₂)₄ or Ta(NMe₂)₅, were used as catalysts for the asymmetric hydroamination of 6-methyl-hepta-4,5-dienylamine, giving exclusively the α-vinylpyrrolidine product. The titanium derived catalysts gave products with low stereoselectivity, up to 11%ee favoring (+)-2-(2-methyl-propenyl)-pyrrolidine, while the tantalum derived catalysts gave products with higher and opposite stereoselectivity, up to 34%ee favoring (−)-2-(2-methyl-propenyl)-pyrrolidine.     

Correlating the scattered intensities of P3HT and PCBM to the current densities of polymer solar cells

Grazing-incidence X-ray diffraction and rocking scans have quantified the structure of poly(3-hexylthiophene) and [6,6]-phenyl-C(61)-butyric acid methyl ester in the active layers of organic solar cells. Our study reveals that the device J(SC) correlates with the local structural development of pure PCBM and, to second order, the extent of out-of-plane P3HT π-stacking.     

Endolaryngeal contact pressures

In this work, we present a new method for in vivo endolaryngeal contactpressure measurement with a miniature pressure transducer. Using this methodology, contact pressures can be measured during videoendoscopy at different locations between the artyenoids and also at various locations along the membranous vocal folds. Twenty adults with organic and functional voice disorders and two vocally healthy adults participated as subjects. Endolaryngeal contact pressure measures were made during a series of phonatory tasks varying pitch, loudness, and phonatory onset and offset. Measures were also made during nonphonatory tasks, including throat clearing, coughing, Valsalva maneuvres, and gagging. The most remarkable findings were: (1) interarytenoid contact pressures were considerably greater than intraglottal contact pressures; (2) interarytenoid contact pressures were greater for lower than higher pitches; (3) both interarytenoid and intraglottal contact pressures were remarkably large during hard glottal attack; and (4) overall, the largest endolaryngeal pressures were recorded between the arytenoids, during a thoracic fixation maneuver and during gag reflex.This work was supported in part by Deutsche Forschungsgemeinschaft (He 2869/1-1), by a grant from the “Verein zur Förderung hör-, sprach- und stimmgestörter Patienten an der FU Berlin e.V.” (nonprofit organization), Berlin, Germany, and by Grant No. K08 DC00139 from the National Institute on Deafness and Other Communication Disorders.     

Progressive ganglion cell loss and optic nerve degeneration in DBA/2J mice is variable and asymmetric

Background  

Glaucoma is a chronic neurodegenerative disease of the retina, characterized by the degeneration of axons in the optic nerve and retinal ganglion cell apoptosis. DBA/2J inbred mice develop chronic hereditary glaucoma and are an important model system to study the molecular mechanisms underlying this disease and novel therapeutic interventions designed to attenuate the loss of retinal ganglion cells. Although the genetics of this disease in these mice are well characterized, the etiology of its progression, particularly with respect to retinal degeneration, is not. We have used two separate labeling techniques, post-mortem DiI labeling of axons and ganglion cell-specific expression of the βGeo reporter gene, to evaluate the time course of optic nerve degeneration and ganglion cell loss, respectively, in aging mice.     

Time-dependent strength parameters for tungsten carbides containing 6 or 16% cobalt at room and elevated temperatures

The time-dependent and statistical variations in strength for two grades of tungsten carbide have been studied at room and elevated temperatures. At room temperature, the effect of time under stress was found to be small, about l % decrease in strength being obtained for each decade increase in time for the material containing 6 % cobalt. However, at elevated temperatures, the strength degradation was found to be about 28 % for each decade increase in time. This is of interest in the engineering application of these materials, since the test temperatures employed are frequently obtained in metal-cutting tools.     

Nonspecific laryngeal granuloma: A case study of a professional singer

A professional singer with laryngeal granuloma underwent surgery following failed response to conservative treatments. Two primary findings emerged. First, although a sizable lesion was present initially, presurgical voice measures were largely normal or superior. The exception was elevated phonatory effort during singing. Second, postsurgical voice functions were entirely normal or superior (including phonatory effort), despite demanding singing performances a few weeks following surgery. The results add to the limited corpus of quantitative, normative-referenced data on voice in patients with granulomas and are inconsistent with previous reports of voice abnormalities in such patients and poor functional response to surgery.     

Methotrexate analogs. 7. Synthesis of two higher homologs and a positional isomer of methotrexate diethyl ester as potential antitumor agents

Analogs of methotrexate diethyl ester ( 1 ) were prepared, in which the distances separating the ester functions from each other and from the carboxamide function of the p-aminobenzoate moiety were varied via the use of methylene groups as “spacers”. The diethyl esters 3 and 4 , with D,L-α-aminoadipate and D,L-α-aminopimelate side chains in place of L-glutamate, displayed approximately the same order of activity as compound 1 against bacterial and mammalian cells in culture, and were inhibitors of the enzyme dihydrofolate reductase. When given intraperitoneally to L1210 1eukemic mice at a dose of 120 mg./kg. q3d 1,4,7, compound 4 produced a 67% increase in survival and no evidence of toxicity, whereas methotrexate diethyl ester ( 1 ) gave a 44% increase in survival at a dose of 45 mg./kg. q3d 1,4,7 but was toxic at higher doses. The positional isomer 2 was inactive.     

Surface and aggregation behavior of aqueous solutions of Ru(II) metallosurfactants. 3. Effect of chain number and orientation on the structure of adsorbed films of [Ru(bipy)2(bipy')]Cl2 complexes

The surface behavior of a range of surfactant [Ru(bipy)(2)(p,p'-dialkyl-2,2'-bipy)]Cl(2) complexes, which we express as Ru(q)(p)C(n) where n is the alkyl chain length, p refers to the substitution position on the bipyridine ligand (=4 or 5), and q (=1 or 2) is the number of substituted alkyl chains, has been examined using neutron reflectometry. The adsorption of the single-chain Ru(1)(4)C(19) and Ru(1)(5)C(19) surfactants is strongly time-dependent, taking in excess of 10 h to form an equilibrium film. It is suggested that the slow adsorption rate is related to the alkyl chain length rather than the low monomer concentration present in the solutions. At concentrations below the critical micelle concentration (cmc) of Ru(1)(4)C(19), the film of Ru(1)(5)C(19) is denser than that of Ru(1)(4)C(19) at comparable concentration, consistent with the mass densities of the bulk solids, whereas at concentrations close to and greater than this cmc the converse pertains. Close to the cmc, the adsorbed films possess an average area per molecule significantly less than the nominal headgroup area of the surfactants (approximately 30 angstroms(2) compared with approximately 100 angstroms(2)). This fact together with consideration of the thickness and density of the adsorbed films leads to the conjecture that surface aggregates may be the adsorbing units. The adsorption of the double-chain surfactant Ru(1)(p)C(19), in contrast to the behavior of the Ru(1)(p)C(19) surfactants, is weak and independent of time. This behavior is attributed to the alkyl chain orientation. The adsorption behavior of a racemic mixture of the Delta and Lambda isomers of Ru(2)(4)C(19) has been compared with that of the Delta isomer. It is found that the film of racemic material is more closely packed than that of the resolved complex.