Determination of selenium and tellurium in silver chloride and uranium oxide

Methods are described for the determination of selenium and tellurium in crude silver chloride produced as a by-product of the refining of gold, and in high-purity uranium oxide. Selenium and tellurium are separated from one another as well as from the numerous other substances in the sample before they are extracted into organic solvents and determined spectrophotometrically. For the determination of selenium 3,3'-diaminobenzidine is used and for tellurium, sym-diphenylthiourea. A minimum of 2 ppm of each element may be determined in silver chloride and 0.3 ppm in uranium oxide. Statistical data are given to show the precision and accuracy of the methods.     

2,6-Mes(2)C(6)H(3)](2)Ga(+)Li[Al(OCH(CF(3))(2))(4)](2)(-) (Mes = 2,4,6-Me(3)C(6)H(2)): A compound containing a linear unsolvated two-coordinate gallium cation

The title compound [2,6-Mes(2)C(2)H(3)](2)Ga(+)Li[Al(OCH(CF(3))(2))(4)](2)(-), 1, containing a linear two-coordinate gallium cation, has been obtained by metathesis reaction of [2,6-Mes(2)C(2)H(3)](2)GaCl with 2 equiv of Li[Al(OCH(CF(3))(2))(4)] in C(6)H(5)Cl solution at room temperature. Compound 1 has been characterized by (1)H, (13)C((1)H), (19)F, and (27)Al NMR spectroscopy and X-ray crystallography. Compound 1 consists of isolated [2,6-Mes(2)C(6)H(3)](2)Ga(+) cations and Li[Al(OCH(CF(3))(2))(4)](2)(-) anions. The C-Ga-C angle is 175.69(7) degrees, and the Ga-C distances are 1.9130(14) and 1.9145(16) A. The title compound is remarkably stable, is only a weak Lewis acid, and polymerizes cyclohexene oxide.     

A palladium complex with a new hemilabile amino- and sulfur-containing phosphinite ligand as an efficient catalyst for the Heck reaction of aryl bromides with styrene. The effect of the amino group

A palladium complex with a new hemilabile amino- and sulfur-containing phosphinite ligand has been synthesised and its crystal structure determined. This system efficiently catalyses the Heck reaction of aryl bromides with styrene at 130°C after 24 h, with turnover numbers of up to 100000 and with a selectivity towards trans-stilbenes ranging from 91.5 to 96.3%. The analogous sulfur-containing phosphinite without the amino group has also been synthesised and subjected to the Heck reaction. The constructive role of the amino group on the formation of the P,S-chelate palladium complex as well as in the Heck reaction is discussed.     

Photochemistry of dianthrylsilanes: a study of sigma,pi-interaction

In this article, we demonstrated by the application of time-resolved spectroscopy, X-ray structural analysis and other spectroscopic techniques that 9-Anthrylsilanes exhibits sigma,pi-interaction between 9-anthryl group and the Si-Si linkage in anthryl-disilanes, ASi(2), ASi(2)A, and ASi(3)A which does not occur in the analogous alkyl derivatives as well as the pyrenylsilane derivatives, in spite of the fact that the 0,0-band of PSi(2) is about 12.8 KJ more energetic than that of ASi(2) (Figure 1). More interestingly, the X-ray structural studies reveal that ASi(3)A exists in a butterfly-like structure in agreement with other spectroscopic analyses that the two anthryl groups do not interact in their excited states, while those in ASi(2)A do. This is in contrast to the analogous pyrenylsilanes; the trisilanes exhibits a stronger excimer interaction than that of disilane.(10b) Our results show that the sigma,pi-interactions in ASi(3)A has imparted rigidity to the tri-silyl linkage. Potential applications of anthrylsilanes in material sciences will be explored.(5) This work provides evidence that sigma,pi-interaction between the 9-anthryl group and disilyl linkage does play an important role in the properties of disilanes. We attribute this enhanced sigma,pi-interaction to the nature of the lowest excited state (S(1) state) of anthracenes, the L(a) transition, which has a much higher oscillator strength than the S(1)L(b)-transition of pyrenes (Figure 1). We define the interaction in anthracene as a sigma,pi(S(1,)L(a)) interaction. This interaction lends a substantial barrier to the Si-Si bond with the excited anthryl nucleus in anthrylsilanes. The scope and potential applications of this phenomenon are discussed.     

Comparison of WKB calculations and experimental results for three-dimensional cochlear models.

The WKB asymptotic method is applied to the calculation of cochlear models with square scala cross section, for which the fluid motion is fully three dimensional. The analysis begins with the exact solution for wave propagation in a duct with constant properties. This solution is somewhat tedious but straightforward, since it requires a Fourier series expansion across the duct. Then with the formulation of Whitham [Linear and Nonlinear Waves (Wiley, New York, 1974)], the approximate solution is readily generated for the duct with properties which vary slowly along the length. Numerical calculations are carried out for the experimental models of Cannel [Ph.D. thesis, Univ. of Warwick (1969)] and Helle [Dr.-Ing. disser., Technische Univ., Müchen (1974)] who furnish quantitative details of both "basilar membrane" response and model parameters. Without any free parameters for adjusting, the present WKB solution shows quite satisfactory agreement with the experimental model results. Computer time is reasonable; the calculation of displacement envelope and phase at a number of stations along the cochlea for a given frequency requires only one second of CPU time. Thus the credibility and practically of the approach is established for the investigation of yet more realistic and more elaborate cochlear models.     

Photo-induced self-cleaning and biocidal behaviour of titania and copper oxide multilayers

This paper describes the deposition of films of titania and copper oxide by atmospheric pressure chemical vapour deposition (CVD). The films were investigated as part of multilayer systems to assess their potential to offer the dual functionality of self-cleaning and biocidal films. The multilayer systems were achieved by deposition of copper oxide with subsequent titanium dioxide deposition and vice versa. Two different CVD approaches were employed in combination, thermal CVD and flame-assisted CVD. It is shown that by careful choice of the experimental growth conditions, multilayers can be formed with both biocidal and ‘self-clean’ functionality under UV photo-induced conditions.     

Parameters contributing to efficient ion generation in aerosol MALDI mass spectrometry

The Bioaerosol Mass Spectrometry (BAMS) system was developed for the real-time detection and identification of biological aerosols using laser desorption ionization. Greater differentiation of particle types is desired; consequently MALDI techniques are being investigated. The small sample size ( approximately 1 microm3), lack of substrate, and ability to simultaneously monitor both positive and negative ions provide a unique opportunity to gain new insight into the MALDI process. Several parameters known to influence MALDI molecular ion yield and formation are investigated here in the single particle phase. A comparative study of five matrices (2,6-dihydroxyacetophenone, 2,5-dihydroxybenzoic acid, alpha-cyano-4-hydroxycinnamic acid, ferulic acid, and sinapinic acid) with a single analyte (angiotensin I) is presented and reveals effects of matrix selection, matrix-to-analyte molar ratio, and aerosol particle diameter. The strongest analyte ion signal is found at a matrix-to-analyte molar ratio of 100:1. At this ratio, the matrices yielding the least and greatest analyte molecular ion formation are ferulic acid and alpha-cyano-4-hydroxycinnamic acid, respectively. Additionally, a significant positive correlation is found between aerodynamic particle diameter and analyte molecular ion yield for all matrices. SEM imaging of select aerosol particle types reveals interesting surface morphology and structure.     

Lower bounds for algebraic decision trees

A topological method is given for obtaining lower bounds for the height of algebraic decision trees. The method is applied to the knapsack problem where an $\text{Ω(n}{}^2\text{)}$ bound is obtained for trees with bounded-degree polynomial tests, thus extending the Dobkin-Lipton result for linear trees. Applications to the convex hull problem and the distinct element problem are also indicated. Some open problems are discussed.     

Below-unitarity-threshold branch cut in the\left\langle {\bar qq} \right\rangle coefficient of the axial-vector two-current correlation function

The dimension-3 quark-condensate component of the flavour-diagonal axial-vector two-current correlation function is evaluated to all orders in the quark massm _qk through use of the quark-condensate component of the nonperturbative fermion propagator. The result obtained is analytic inp ² except for a branch cut for 0<p ²<(2m _qk )², corresponding to a branch cut occurringbelow the \(\bar qq\) kinematic threshold. The deep Euclidean region of the longitudinal component of this correlation function is utilized to obtain leading and subleading contributions to the QCD sum-rule relatingm _qk to \(\left\langle {\bar qq} \right\rangle \) . These same sum-rule results are obtained by means of an alternative derivation involving integration over the discontinuity in the correlation function along the branch cut, demonstrating the consistency of the physical-momentum-region branch cut with results obtained via standard means in the deep Euclidean region.