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Phthalocyanines, naphthalocyanins, and their derivatives are frequently used as light modulating materials. These compounds, with their stable planar square structure and highly delocalized -electron system, are being used in numerous technological applications, such as pigments in chemical sensors, and more recently as photosensitizers for photodynamic therapy. The nonlinear optical properties (NLO) of these compounds are of particular importance. Using density functional method (DFT), we calculated the optical properties of phthalocyanine and naphthalocyanine complexes with Si as a central atom. We examined the effect of hydrophilic axial substituents and the size of polycyclic aromatic hydrocarbons surrounding the porphyrazine-Si kernel on the optical properties of title molecules. Both UV−vis and RSA spectra are calculated and are compared with available experimental results. The time-dependent DFT (TDDFT) with the B3LYP functional predicts that the characteristic UV−vis absorption maxima are blue-shifted; however, the relative error is almost constant for phthalocyanine and naphthalocyanine compounds. The TDDFT triplet−triplet absorption spectra of Si-phthalocyanine and Si-naphthalocyanine complexes reproduce experimental data well.

The accurate mass and time tag mass spectrometry method and clustering analysis were used to compare the abundance change of 992 Yersinia pestis proteins under four contrasting growth conditions (26 and 37 °C, with or without Ca2) that mimicked growth states in either a flea vector or mammalian host. Eighty-nine proteins were observed to have similar abundance change profiles to 29 known virulence associated proteins, providing identification of additional biomarker candidates. Eighty-seven hypothetical proteins, which clustered into 5 distinct clusters of like-protein abundance change, were identified as unique biomarkers related specifically to growth condition.

The sensitivity of proteomics measurements using liquid chromatography (LC) separations interfaced with electrospray ionization-mass spectrometry (ESI-MS) improves approximately inversely with liquid flow rate (for the columns having the same separation efficiency, linear velocity, and porosity), making attractive the use of smaller inner diameter LC columns. We report the development and initial application of 10 m i.d. silica-based monolithic LC columns providing more sensitive proteomics measurements. A 50-m-i.d. micro solid-phase extraction precolumn was used for ease of sample injection and cleanup prior to the reversed-phase LC separation, enabling the sample volume loading speed to be increased by ∼50-fold. Greater than 10-fold improvement in sensitivity was obtained compared to analyses using more conventional capillary LC, enabling e.g. the identification of >5000 different peptides by MS/MS from 100-ng of aShewanella oneidensistryptic digest using an ion trap MS. The low nL/min LC flow rates provide more uniform responses for different peptides, and provided improved quantitative measurements compared to conventional separation systems without the use of internal standards or isotopic labeling. The improved sensitivity allowed LC-MS measurements of immunopurified protein phosphatase 5 that were in good agreement with quantitative Western blot analyses.

The synthesis of a series of phenethanolamine aniline agonists that contain an aniline ring on the right-hand side of the molecule substituted at the meta position with a benzoic acid or a pyridyl carboxylate is described. Several of the analogues (e.g., 34, 36−38, 40, and 44) have high β3 adrenergic receptor (AR) potency and selectivity against β1 and β2 ARs in Chinese hamster ovary (CHO) cells expressing β ARs. The dog pharmacokinetic profile of some of these analogues showed >25% oral bioavailability and po half-lives of at least 1.5 h. Among the compounds described herein, the 3,3‘-biarylaniline carboxylate derivatives 36, 38 and the phenylpyridyl derivative 44 demonstrated outstanding in vitro properties and reasonable dog pharmacokinetic profiles. These three analogues also showed dose dependent β3 AR mediated responses in mice. The ease of synthesis and superior dog pharmacokinetics of compound 38 relative to that of 44 in combination with its in vitro profile led us to choose this compound as a development candidate for the treatment of type 2 diabetes.

Abstract:Knowledge of how deaf children use speech outside the classroom or therapy room may enhance our ability to improve their speech in a variety of situations and with a variety of communication partners. Past research has shown that deaf children's interactions in informal settings with their mothers and hearing peers create situations that can foster improved linguistic skills. In the current study, the amount and intelligibility of spoken language output in 15 deaf children ages 4-5 to 9-8 years during 15 minutes of free play with their mothers was compared with output and intelligibility during a similar session with a self-selected hearing peer. The results, which indicated that significantly more speech was produced during the children's interaction with their mothers, are discussed in terms of future research.

The X-ray crystal structure of 3-ethynylcyclopropene shows that the carbon–carbon double bond of the molecule is unusually short [1.255(2) Å], whereas theoretical calculations suggest a relative insensitivity of the bond length to adjacent orbital interactions.