Intracavity laser absorption spectroscopy of platinum sulfide in the near infrared

A new electronic transition of PtS with a red degraded band head at 12 460 cm⁻¹ was recorded and analyzed. Gas phase PtS was produced in a platinum-lined hollow cathode with a trace of SF₆ gas, and the spectrum was recorded at near Doppler resolution using intracavity laser absorption spectroscopy. Molecular constants for the newly identified excited state are presented.     

Palladium-catalyzed, asymmetric Baeyer-Villiger oxidation of prochiral cyclobutanones with PHOX ligands

Described in this report is a general method for the conversion of prochiral 3-substituted cyclobutanones to enantioenriched γ-lactones through a palladium-catalyzed Baeyer-Villiger oxidation using phosphinooxazoline ligands in up to 99% yield and 81% ee. Lactones of enantiopurity ≥93% could be obtained through a single recrystallization step. Importantly, 3,3-disubtituted cyclobutanones produced enantioenriched lactones containing a β-quaternary center.     

Dielectric friction as a mechanism for selectivity alteration in capillary electrophoresis using acetonitrile-water media

The mobilities of a series of aromatic carboxylates and sulfonates, ranging in charge from -1 to -4, were investigated as a function of acetonitrile concentration in the electrophoretic buffer. Absolute mobilities were determined by extrapolation of the effective mobilities to zero ionic strength according to the Pitts' equation. In general, anions of higher charge were more strongly influenced by ionic strength, with similarly charged anions experiencing ionic strength effects that were not significantly different at the 95% confidence level. Furthermore, the relative magnitudes of the Onsager slopes varied with acetonitrile content according to the z/(etaepsilon(1/2)) dependence in the electrophoretic effect of the Pitt's equation. Addition of acetonitrile to the electrophoretic media resulted in changes in the absolute mobilities of the anions. These acetonitrile-induced selectivity alterations were attributed to dielectric friction. As predicted by the Hubbard-Onsager model of dielectric friction, changes in sulfonate mobility were shown to correlate to changes in solvent viscosity (eta), dielectric constant (epsilon), and relaxation time (tau). The combined effects of ionic strength and dielectric friction caused analytes with higher charge-to-size ratios to be slowed to a greater extent upon addition of acetonitrile compared to those with lower charge-to-size. For example, at 75% acetonitrile and 20 mM ionic strength, a migration order reversal occurred between the triply and singly charged sulfonates.     

Heavy-atom kinetic isotope effects,cocatalysts, and the propagation transition state for polymerization of 1-hexene using the rac-(C(2)H(4)(1-indenyl)(2))ZrMe(2) catalyst precursor

Using 13C NMR techniques, the 12C/13C kinetic isotope effects (KIEs) for the polymerization of 1-hexene catalyzed by rac-(C2H4(1-indenyl)2)ZrMe2 in the presence of four different cocatalysts (tris(pentfluorophenyl)borane, tris(pentafluorophenyl)alane, anilinium tetrakis(pentafluorophenyl)borate, and methylalumoxane) have been determined. All cocatalysts yield similar KIEs within experimental uncertainty, with values of 1.009(1) and 1.017(2) at C1 and C2, respectively. Ab initio DFT computational modeling of the polymerization KIE indicates that alkene binding to the catalyst must be reversible, with the majority of the KIE developing in the subsequent migratory insertion reaction.     

Variational principles for average exit time moments for diffusions in Euclidean space

Let be a smoothly bounded domain in Euclidean space and let be a diffusion in Euclidean space. For a class of diffusions, we develop variational principles which characterize the average of the moments of the exit time from of a particle driven by where the average is taken over all starting points in

     

Development of an anomalous Heck reaction: skeletal rearrangement of divinyl and enyne carbinols

[reaction: see text] A general set of conditions that achieves the union of aryl halides and divinyl or enyne carbinols to afford tri- or tetrasubstituted olefins in good yields (up to 83%) is described. The mechanism by which this proceeds is believed to involve the intermediacy of a cyclopropanol, followed by a novel skeletal reorganization. The ability to suppress beta-hydride elimination of organopalladium intermediates appears to be critical to the success of these processes.     

A Novel Treatment for Hypophonic Voice: Twang Therapy

A hypophonic voice, characterized perceptually as weak and breathy, is associated with voice disorders such as vocal fold atrophy and unilateral vocal fold paralysis. Although voice therapy programs for hypophonia typically address the vocal folds or the sound source, twang voice quality was examined in this study as an alternative technique for increasing vocal power by altering the epilarynx or the sound filter. OBJECTIVE: This study investigated the effect of twang production on physiologic, acoustic, and perceived voice handicap measures in speakers with hypophonia. DESIGN/METHODS: This prospective pilot study compared the vocal outcomes of six participants with hypophonia at pre- and posttreatment time points. Outcome measures included mean airflow rate, intensity in dB sound pressure level (SPL), maximum phonation time, and self-report of voice handicap. RESULTS: All subjects improved in at least three of the four vocal outcome measures. Wilcoxon signed-rank test of paired differences revealed significant differences between pre- and posttherapy group means for airflow rate, SPL, and Voice Handicap Index scores. CONCLUSION: The twang voice quality as a manipulation of the sound filter offers a clinical complement to traditional voice therapies that primarily address the sound source.     

Diverse antidepressants increase CDP-diacylglycerol production and phosphatidylinositide resynthesis in depression-relevant regions of the rat brain

Background  

Major depression is a serious mood disorder affecting millions of adults and children worldwide. While the etiopathology of depression remains obscure, antidepressant medications increase synaptic levels of monoamine neurotransmitters in brain regions associated with the disease. Monoamine transmitters activate multiple signaling cascades some of which have been investigated as potential mediators of depression or antidepressant drug action. However, the diacylglycerol arm of phosphoinositide signaling cascades has not been systematically investigated, even though downstream targets of this cascade have been implicated in depression. With the ultimate goal of uncovering the primary postsynaptic actions that may initiate cellular antidepressive signaling, we have examined the antidepressant-induced production of CDP-diacylglycerol which is both a product of diacylglycerol phosphorylation and a precursor for the synthesis of physiologically critical glycerophospholipids such as the phosphatidylinositides. For this, drug effects on [³H]cytidine-labeled CDP-diacylglycerol and [³H]inositol-labeled phosphatidylinositides were measured in response to the tricyclics desipramine and imipramine, the selective serotonin reuptake inhibitors fluoxetine and paroxetine, the atypical antidepressants maprotiline and nomifensine, and several monoamine oxidase inhibitors.     

A new approach to the busy period of the M/M/1 queue

In this paper, we provide a new approach to the computation of the Laplace transform of the length of the busy period of the M/M/1 queue with constrained workload (finite dam), without the use of complex analysis. This revised version was published online in June 2006 with corrections to the Cover Date.