Structures and energetics of electrosprayed uracil(n)Ca2+ clusters (n = 14-4) in the gas phase

Clusters of uracil (U) about a calcium dication, U(n)Ca(2+) (n = 14-4), have been studied in the gas phase by both experimental and theoretical methods. Temperature dependent blackbody infrared radiative dissociation (BIRD) experiments were performed on U(n)Ca(2+) clusters with n = 14-5 and the observed Arrhenius parameters are reported here. Master equation modeling of the BIRD kinetics data was carried out to determine threshold dissociation energies. Initial geometry calculations were performed using the B3LYP density functional and 3-21G(d) basis set. A sample of ten conformations per cluster was obtained through a simulated annealing study. These structures were optimized using B3LYP/6-31G(d) level of theory. Fragment-based hybrid many body interaction (HMBI) MP2/6-311++G(2df,2p)/Amoeba calculations were performed on representative conformations to determine theoretical binding energies. Results were examined in relation to cluster size (n). A significant increase in the energy required to remove uracil from U(6)Ca(2+) when compared to larger clusters supports previous reports that the calcium ion is coordinated by six uracil molecules in the formation of an inner shell. For clusters larger than n = 6, an odd-even alternation in threshold dissociation energies was observed, suggesting that the outer shell uracil molecules bind as dimers to the inner core. Proposed binding schemes are presented. Multiple structures of U(5)Ca(2+) are suggested as being present in the gas phase where the fifth uracil may be either part of the first or second solvation shell.     

Pushing the limit: synthesis, photophysical and DNA binding studies of a NIR-emitting Ru(II)-polypyridyl probe with 'light switch' behaviour

The new Ru(II) polypyridyl complex 1 was synthesised using microwave irradiation from the new polypyridyl ligand 2'DipyTAP', and its photophysical properties, and DNA binding abilities were investigated using various spectroscopic techniques; and 1 was shown to act as a 'NIR molecular light switch' for DNA with an emission window between 680 and 860 nm.     

Moore-paradoxical Assertion,Fully Conscious Belief and the Transparency of Belief

I offer a novel account of the absurdity of Moore-paradoxical assertion in terms of an interlocutor’s fully conscious beliefs. This account starts with an original argument for the principle that fully conscious belief collects over conjunction. The argument is premised on the synchronic unity of consciousness and the transparency of belief.     

Low-power,phase-preserving 2R amplitude regenerator

We propose a modification of a NALM-based 2R regenerator of phase-encoded signals which operates at considerably lower input powers than was studied earlier. Our modification consists of replacing the core-matched and lossless fiber coupler in the NALM by a coupler with a propagation constant mismatch and loss asymmetrically distributed between the two cores. The performance of the modified regenerator and the one studied earlier is approximately the same.     

Composition of the essential oil of wild growing Artemisia vulgaris from Erie, Pennsylvania

Essential oil from wild growing Artemisia vulgaris L. originating in Erie, Pennsylvania was obtained by hydrodistillation of the aerial parts of the plant. Gas chromatographic-mass spectral analysis was used to identify the major volatiles present. Up to 22 components were detected in the essential oils. Germacrene D (25%), Caryophyllene (20%), alpha-Zingiberene (15%) and Borneol (11%) represent the major components of leaf oil, while the buds were rich in 1,8-Cineole (32%), Camphor (16%), Borneol (9%), and Caryophyllene (5%). trans-2-Hexenal was also detected in the aerial parts of the plant. alpha-Zingiberene and trans-2-Hexenal have not been previously reported for Artemisia vulgaris L. The major analytes are compared to those from Artemisia vulgaris L, originating outside of the United States.     

Palladium-catalysed direct arylation of a tris-cyclometallated Ir(III) complex bearing 2,2'-thienylpyridine ligands: a powerful tool for the tuning of luminescence properties

Palladium-catalysed direct 5-arylation of metallated thiophenes of fac-Ir(N^C(3')-thpy)(3) with aryl bromides via C-H bond functionalisation allows the synthesis of a variety of new Ir complexes in only one step (thpyH = 2,2'-thienylpyridine). The method offers simple modification of the nature of the ligand and hence of the photophysical properties of such complexes.     

Photophysical and biological investigation of novel luminescent Ru(II)-polypyridyl-1,8-naphthalimide Tröger's bases as cellular imaging agents

The synthesis and photophysical properties of 1 and 2, two Ru(II)-polypyridyl based-1,8-naphthalimide Tr?ger's bases, are described; these were found to stabilize double stranded DNA, undergo rapid cellular uptake, displaying good luminescence without affecting cell viability even after 24 hours of incubation.     

Dibenz[a,c]anthracene derivatives exhibiting columnar mesophases over broad temperature ranges

We report the synthesis and characterization of a series of novel hexaalkoxydibenz[a,c]anthracenes. While the parent compound is not mesomorphic, the introduction of substituents in the 10- and 13-positions yields compounds with columnar liquid crystalline phases over very broad temperature ranges.     

Poly[2-(methacryloyloxy)ethylphosphorylcholine]-coated iron oxide nanoparticles: synthesis, colloidal stability and evaluation for stem cell labelling

Poly[2-(methacryloyloxy)ethylphosphorylcholine]-coated SPIONs were prepared through ATRP and amidation coupling reactions. The coated SPIONs exhibited high stability and re-dispersability in phosphate buffered saline and uptake in a stem cell line, with high T(2) relaxivity.     

Discriminant analysis in the presence of interferences: Combined application of target factor analysis and a Bayesian soft-classifier

A method is described for performing discriminant analysis in the presence of interfering background signal. The method is based on performing target factor analysis on a data set comprised of contributions from analyte(s) and interfering components. A library of data from representative analyte classes is tested for possible contributing factors by performing oblique rotations of the principal factors to obtain the best match, in a least-squares sense, between test and predicted vectors. The degree of match between the test and predicted vectors is measured by the Pearson correlation coefficient, r, and the distribution of r for each class is determined. A Bayesian soft classifier is used to calculate the posterior probability based on the distributions of r for each class, which assist the analyst in assessing the presence of one or more analytes. The method is demonstrated by analyses performed on spectra obtained by laser induced breakdown spectroscopy (LIBS). Single and multiple bullet jacketing transfers to steel and porcelain substrates were analyzed to identify the jacketing materials. Additionally, the metal surrounding bullet holes was analyzed to identify the class of bullet jacketing that passed through a stainless steel plate. Of 36 single sample transfers, the copper jacketed (CJ) and non-jacketed (NJ) class on porcelain had an average posterior probability of the metal deposited on the substrate of 1.0. Metal jacketed (MJ) bullet transfers to steel and porcelain were not detected as successfully. Multiple transfers of CJ/NJ and CJ/MJ on the two substrates resulted in posterior probabilities that reflected the presence of both jacketing materials. The MJ/NJ transfers gave posterior probabilities that reflected the presence of the NJ material, but the MJ component was mistaken for CJ on steel, while non-zero probabilities were obtained for both CJ and MJ on porcelain. Jacketing transfer from a bullet to steel as the projectile passed through the steel also proved difficult to analyze. Over 50% of the samples left insufficient transfer to be identified. Transfer from NJ and CJ jacketing was successfully identified by posterior probabilities greater than 0.8.