Two-step, one-pot Ni-catalyzed neopentylglycolborylation and complementary Pd/Ni-catalyzed cross-coupling with aryl halides, mesylates, and tosylates

Two-step, one-pot neopentylglycolborylation of aryl iodides and bromides catalyzed by NiCl2(dppe) and NiCl2(dppp) is reported. Electron-rich and electron-deficient aryl neopentylglycolboronates were efficiently cross-coupled with aryl iodides, bromides, chlorides, mesylates, and tosylates by exploiting complementary Pd/Ni and Ni/Ni catalysis. The borylation route was further extended to a three-step, one-pot synthesis of biaryls via in situ Ni-catalyzed borylation and Pd-mediated cross-coupling.     

Raney-Co mediated reductive cyclization of an alpha,beta-unsaturated nitrile

An expedient, five step synthesis of caprolactam 1 is reported starting from natural L-homoserine. The key step is a chemoselective reductive cyclization of alpha,beta-unsaturated nitrile 10 mediated by Raney-Co type metals. This hydrogenation is extensively investigated in order to account for the observed product distribution and yields.     

Identification of conformational structures of 2-phenylethanol and its singly hydrated complex by mass selective high-resolution spectroscopy and ab initio calculations

The flexible prototype molecule 2-phenylethanol (2-PE) and its singly hydrated complex have been investigated in a cold supersonic beam by a combination of high-resolution two-color R2PI spectroscopy and quantum chemistry ab initio calculations. The existence of two monomer structures separated by a high potential energy barrier, gauche and anti ones, was proven. Higher energy conformers are supposed to relax to the observed ones during the jet expansion process. We have identified the conformational structure of the complex between 2-PE and water, which corresponds to water binding to the most stable gauche conformer. No detectable structural changes of the host 2-PE molecule have been observed upon attachment of a single water molecule. A conformational relaxation mechanism is suggested also for the 2-PE x H2O complex.     

Ozonolysis of oleic acid adsorbed to polar and nonpolar aerosol particles

Single-particle kinetic studies of the reaction between oleic acid and O 3 have been conducted on two different types of core particles: polystyrene latex (PSL) and silica. Oleic acid was found to adsorb to both particle types in multilayer islands that resulted in an adsorbed layer of a total volume estimated to be less than one monolayer. The rate of the surface reaction between surface-adsorbed oleic acid and O 3 has been shown for the first time to be influenced by the composition of the aerosol substrate in a mixed organic/inorganic particle. A Langmuir-Hinshelwood mechanism was applied to the observed dependence of the pseudo-first-order rate constant with [O 3], and the resulting fit parameters for the ozone partition coefficient ( K O 3 ) and maximum first order rate constant ( k 1,max ) suggest that the reaction proceeded faster on the less polar PSL core at lower [O 3] due to the increased residence time of O 3 on the PSL surface, but the reaction was ultimately more efficient on the silica surface at high [O 3]. Values for the uptake coefficient, gamma oleic , for reaction of oleic acid on PSL spheres decrease from 2.5 x 10 (-5) to 1 x 10 (-5) with increasing [O 3] from 4 to 25 ppm and overlap at high [O 3] with the estimated values for gamma oleic on silica, which decrease from 1.6 x 10 (-5) to 1.3 x 10 (-5). The relationship between gamma oleic and the more common expression for gamma O 3 is discussed.     

Entropic order quantity (EnOQ) model for deteriorating items

Jaber et al. [M.Y. Jaber, R.Y. Nuwayhid, M.A. Rosen, Price-driven economic order systems from a thermodynamic point of view, Int. J. Prod. Res. 42 (24) (2004) 5167–5184] suggested that it might be possible to improve production systems performance by applying the first and second laws of thermodynamics to reduce system entropy (or disorder). They then used these laws to modify the economic order quantity (EOQ) model to derive an equivalent entropic order quantity (EnOQ). The results suggested that larger quantities should be ordered than is suggested by the classical EOQ model.     

Mach stem hysteresis: Experiments addressing a novel explanation of clumpy astrophysical jet emission

Recent time-series observations of shock waves in stellar jets taken with the Hubble Space Telescope reveal localized bright knots that persist over nearly 15 years. While some of these features represent shock fronts caused by variable velocities in the flow, others appear at the intersection points between distinct bow shocks. Theoretically, when the angle between two intersecting shocks exceeds a certain critical value, a third shock (Mach stem) should form. Because Mach stems form perpendicular to the direction of flow, incoming particles encounter a normal shock instead of an oblique one, which results in brighter emission at this location. To study this phenomenon in a controlled laboratory setting, we have carried out experiments on the Omega laser aimed at understanding the formation, growth, and destruction of Mach stems in the warm dense plasma regime. Our experimental results indicate how the growth rate depends upon included angle, and numerical simulations indicate that it may be possible to stabilize an already-formed Mach stem below the critical angle when certain conditions are satisfied.     

Validity and Reliability of the Reflux Symptom Index (RSI)

Laryngopharyngeal reflux (LPR) is present in up to 50% of patients with voice disorders. Currently, there is no validated instrument that documents symptom severity in LPR. We developed the reflux symptom index (RSI), a self-administered nine-item outcomes instrument for LPR. The purpose of this investigation was to evaluate the psychometric properties of the RSI. For validity assessment, 25 patients with LPR were evaluated prospectively before and six months after b.i.d. treatment with proton pump inhibitors (PPI). Each patient completed the RSI as well as the 30-item voice handicap index (VHI). For reliability assessment, the study patients were given the RSI on two separate occasions before the initiation of treatment. Normative RSI data were derived from 25 age-matched and gender-matched controls taken from an existing database of asymptomatic individuals without any evidence of LPR. The mean RSI (+/- standard deviation) of patients with LPR improved from 21.2 (+/- 10.7) to 12.8 (+/- 10.0), and the mean VHI improved from 52.2 (+/- 24.7) to 41.5 (+/- 25.0) after 6 months of therapy (p = 0.001 and 0.065, respectively). Of the three VHI subscales (emotional, physical, functional), only the functional subscale improved significantly (p = 0.037). Patients who experienced a five point or better improvement in RSI were 11 times more likely to experience a five-point improvement in VHI (95% confidence interval = 1.7, 76.8). For reliability assessment, the first and second pretreatment RSIs were 19.9 (+/- 11.1) and 20.9 (+/- 9.6), respectively (correlation coefficient = 0.81, p < 0.001). The single-item correlation coefficients ranged from 0.41 to 0.91 (p < 0.05 for all items). The mean pretreatment RSI in patients with LPR was significantly higher than controls (21.2 versus 11.6; p < 0.001). The mean RSI of patients with LPR after 6 months of PPI therapy approached that of asymptomatic controls (p > 0.05). The RSI is easily administered, highly reproducible, and exhibits excellent construct and criterion-based validity.     

Fibronectin: An Interesting Vocal Fold Protein

A great deal of information is accruing regarding the function of the extracellular matrix. Once thought to be simply a structural entity to surround cells, it is now known to do much more. Fibronectin in particular has received specific attention. Fibronectin is a ubiquitous glycoprotein found most abundantly in the extracellular matrix of regenerating, healing, and embryonic tissue. Vast evidence supports the fact that fibronectin participates in many diverse functions throughout the body that are relevant to vocal fold biology. This article introduces the structure of fibronectin and its isoforms and provides an introduction to some of the many functions it plays. It also reviews the evidence about fibronectin's place in vocal folds and vocal fold pathology. It discusses fibronectin's presence in vocal nodules, vocal polyps, vocal scarring, and Reinke's edema, and reviews the data on its role in mucosal wave impairment. Lastly, it discusses preliminary microarray data that show gene expression for fibronectin to be upregulated in true vocal folds when compared to false vocal folds.