Identification of a Unique Cationic Impurity in Preladenant™ Using Accurate MS and NMR

High resolution MS, 1D, and 2D NMR were used to determine the structure of a unique cationic impurity generated during the synthesis of Preladenant? H/D exchange experiments were performed by both MS and NMR to confirm the acidic nature of the cationic dihydroimidazole proton. The presence of three exchangeable protons was established by MS experiments and the disappearance of the C11 proton in ¹H‐NMR spectrum on equilibration with D₂O confirmed the acidic nature of the cationic dihydroimidazole proton. A piperazine ring contraction mechanism is proposed for the formation of the cationic dihydroimidazole.     

Silicon migration during MBE growth of doped (A1, Ga)As films

Silicon migration during MBE growth of (Al, Ga)As and (Al, Ga)As/GaAs or AlAs/GaAs superlattices has been studied by electrochemical C-V and secondary ion mass spectrometry (SIMS) concentration-depth profiling. It is found to be concentration dependent, with no preferential migration towards or away from the growth front. At high concentrations, superlattice disordering during growth is observed using photovoltage and transmission electron microscopy (TEM) techniques. On the basis of C-V, SIMS and TEM data we propose that silicon migration occurs as the result of a concentration-dependent diffusion process. This is substantiated by measurements of the two-dimensional electron-gas mobility in selectively doped heterojunctions as a function of growth temperature and silicon concentration.     

Symmetric latin square and complete graph analogues of the evans conjecture

With the proof of the Evans conjecture, it was established that any partial latin square of side n with a most n ? 1 nonempty cells can be completed to a latin square of side n. In this article we prove an analogous result for symmetric latin squares: a partial symmetric latin square of side n with an admissible diagonal and at most n ? 1 nonempty cells can be completed to a symmetric latin square of side n. We also characterize those partial symmetric latin squares of side n with exactly n or n + 1 nonempty cells which cannot be completed. From these results we deduce theorems about completing edge-colorings of complete graphs K_2m and K_{2m ? 1} with 2m ? 1 colors, with m + 1 or fewer edges getting prescribed colors. © 1994 John Wiley & Sons, Inc.     

Binding energies of π- and “lone-pair”-levels in mono- and diaza-phenanthrenes and anthracenes: An He(I) photoelectron spectroscopic study

The He(I) photoelectron spectra of a number of monoaza and diaza derivatives of anthracene and phenanthrene, and also of the parent hydrocarbons, have     

Application of unsymmetrical indirect covariance NMR methods to the computation of the (13)C <--> (15)N HSQC-IMPEACH and (13)C <--> (15)N HMBC-IMPEACH correlation spectra

Utilization of long-range (1)H--(15)N heteronuclear chemical shift correlation has continually grown in importance since the first applications were reported in 1995. More recently, indirect covariance NMR methods have been introduced followed by the development of unsymmetrical indirect covariance processing methods. The latter technique has been shown to allow the calculation of hyphenated 2D NMR data matrices from more readily acquired nonhyphenated 2D NMR spectra. We recently reported the use of unsymmetrical indirect covariance processing to combine (1)H--(13)C GHSQC and (1)H--(15)N GHMBC long-range spectra to yield a (13)C--(15)N HSQC-HMBC chemical shift correlation spectrum that could not be acquired in a reasonable period of time without resorting to (15)N-labeled molecules. We now report the unsymmetrical indirect covariance processing of (1)H--(13)C GHMBC and (1)H--(15)N IMPEACH spectra to afford a (13)C--(15)N HMBC-IMPEACH spectrum that has the potential to span as many as six to eight bonds. Correlations for carbon resonances long-range coupled to a protonated carbon in the (1)H--(13)C HMBC spectrum are transferred via the long-range (1)H--(15)N coupling pathway in the (1)H--(15)N IMPEACH spectrum to afford a much broader range of correlation possibilities in the (13)C--(15)N HMBC-IMPEACH correlation spectrum. The indole alkaloid vincamine is used as a model compound to illustrate the application of the method.     

Behavior of the Cricopharyngeal Segment During Esophageal Phonation in Laryngectomized Patients

BACKGROUND: After total laryngectomy, the interruption of the upper digestive tube and the section of the cricopharyngeal segment alter the high-pressure zone of the pharyngoesophageal transition, which will not only start to have a digestive function, but also be stimulated to take on the production of voice and speech. The pressure observed in the cricopharyngeal segment seems to act as a critical factor for the development of esophageal sound production, and manometry is the procedure capable of quantifying the pressure observed in this region. OBJECTIVE: The objective of the current study was to assess the upper esophageal sphincter pressure in laryngectomized patients who are either successful or unsuccessful esophageal speakers, both at rest and during esophageal phonation, using manometry. METHODS: Twenty laryngectomized persons aged 32 to 83 years (mean, 44.2 years) were submitted to evaluation by a speech pathologist and divided into two groups, ie, successful esophageal speakers (N=12) and unsuccessful esophageal speakers (N=8), according to a scale validated by Wepman et al (1953). The upper esophageal sphincter (UES) pressure was assessed by manometry both at rest and during the following voice emissions in Portuguese: the vowel "a," the monosyllable "pa," and the sentence "papai papou pipoca." The amplitude, the duration of the pressure wave, and the area under the curve were measured. RESULTS: At rest, the mean UES pressure was 11.83 mm Hg for successful esophageal speakers and 9.92 mm Hg for unsuccessful esophageal speakers, with no significant difference between groups; the mean for the two groups as a whole was 11.06 mm Hg. During the voice and speech sequence tests, no significant difference was observed when the emissions in Portuguese of "a," "pa," and the sentence were analyzed separately. CONCLUSION: As the pressure observed at rest did not differ between the successful esophageal speakers and the unsuccessful esophageal speakers, and the amplitude, the duration of the pressure wave, and the area under the amplitude x duration curve were also equal for both groups, we conclude that the cricopharyngeal segment pressure is not a preponderant factor for the acquisition of esophageal voice and speech.     

Enhanced photosusceptibility near Tc for the light-induced insulator-to-metal phase transition in vanadium dioxide

We use optical-pump terahertz-probe spectroscopy to investigate the near-threshold behavior of the photoinduced insulator-to-metal (IM) transition in vanadium dioxide thin films. Upon approaching Tc a reduction in the fluence required to drive the IM transition is observed, consistent with a softening of the insulating state due to an increasing metallic volume fraction (below the percolation limit). This phase coexistence facilitates the growth of a homogeneous metallic conducting phase following superheating via photoexcitation. A simple dynamic model using Bruggeman effective medium theory describes the observed initial condition sensitivity.