The valence state of M-ions in the chemically stabilized YSr2Cu3-xMxO7+δ (M=Mo, W and Re) superconductors

 Single phase Ba-free Sr-based YSr₂Cu _3-x M _x O_7+δ (M=Mo, W and Re) compounds have been stabilized by chemical doping. Superconductivity is observed for these phases in the range 30–45 K. X-ray diffraction studies suggest a relatively small orthorhombicity compared to Ba-analogue. X-ray photoelectron spectroscopic investigations reveal that the stabilizing cations are in the hexavalent state. The observation of the higher oxidation state of M-ions accounts for the excess oxygen content in these phases which is in accordence with the diffraction results. Received: 10 June 1996 / Accepted: 20 September 1996     

Viscoelastic characterization of selected foods over an extended frequency range

Three disparate food systems (gummy candy, Mozzarella cheese, and cooked ham) were characterized for their viscoelastic behavior under isothermal conditions over an extended frequency range of 10⁻³ to 10⁴ Hz using broadband viscoelastic spectroscopy (BVS). The materials were tested for any stress-induced fluid flow. However, no evidence of fluid flow was found under the tested frequency range. Validity of time–temperature superposition for the selected materials was also tested and compared with data from BVS.     

Biased Online Parameter Inference for State-Space Models

We consider Bayesian online static parameter estimation for state-space models. This is a very important problem, but is very computationally challenging as the state-of-the art methods that are exact, often have a computational cost that grows with the time parameter; perhaps the most successful algorithm is that of SM C² (Chopin et al., J R Stat Soc B 75: 397–426 2013). We present a version of the SM C² algorithm which has computational cost that does not grow with the time parameter. In addition, under assumptions, the algorithm is shown to provide consistent estimates of expectations w.r.t. the posterior. However, the cost to achieve this consistency can be exponential in the dimension of the parameter space; if this exponential cost is avoided, typically the algorithm is biased. The bias is investigated from a theoretical perspective and, under assumptions, we find that the bias does not accumulate as the time parameter grows. The algorithm is implemented on several Bayesian statistical models.     

Traction data analysis in reference to a unique zero condition

The lack of a unique definition for the zero condition leads to innumerable zero conditions resulting in different amounts of net traction at the same value of slip. In this paper, an attempt has been made to discuss various aspects of different zero conditions and finally result in a unique definition of the zero condition. Based on this definition, a traction prediction model using mobility number approach has been developed to evaluate the performance of tractor tyres in sandy clay loam soils.     

Direct numerical simulations of two-layer viscosity-stratified flow

Two-dimensional simulations of flow instability at the interface of a two-layer, density-matched, viscosity-stratified Poiseuille flow are performed using a front-tracking/finite difference method. We present results for the small-amplitude (linear) growth rate of the instability at small to medium Reynolds number for varying thickness ratio n, viscosity ratio m, and wavenumber. We also present results for large-amplitude non-linear evolution of the interface for varying viscosity ratio and interfacial tension. For the linear case, the interfacial mode is neutrally stable for as predicted by analysis. The growth rate is proportional to Reynolds number for small Re, and increases with viscosity ratio. The growth rate also increases when the thickness of the more viscous layer is reduced. Strong non-linear behavior is observed for relatively large initial perturbation amplitude. The higher viscosity fluid is drawn out as a finger that penetrates into the lower viscosity layer. The simulated interface shape compares well with previously reported experiments. Increasing interfacial tension retards the growth rate of the interface as expected, whereas increasing the viscosity ratio enhances it. Drop formation at the small Reynolds number considered in this study is precluded by the two-dimensional nature of the calculations.     

Detection and identification of alkylphosphonic acids by positive electrospray ionization tandem mass spectrometry using a tricationic reagent

The retrospective detection and identification of degradation products of chemical warfare agents are of immense importance in order to prove their spillage and use. A highly sensitive liquid chromatography/electrospray ionization tandem mass spectrometric (LC/ESI-MS/MS) method--using an imidazolium-based tricationic reagent--was developed for the detection and identification of the anionic degradation products of nerve agents. A commercially available solution of 1,3-imidazolium-bis-(1-hexylbenzylimidazolium) trifluoride (IBHBI) formed adducts with alkylphosphonic acids (APAs), allowing detection of the APAs by positive mode ESI-MS. Tandem mass spectrometry was used for the unambiguous identification of the APAs. Parameters influencing the formation and stability of these adduct during mass spectrometric analysis, such as solvent composition, concentration of IBHBI, effect of pH and interferences by salts, were optimized. The absolute limits of detection (0.1 ng) for achieved for the APAs were better than those previously reported, and linear dynamic ranges of 10-2000 ng mL(-1) were achieved. The method was repeatable with a relative standard deviation ≤7.3%. APAs present in aqueous samples provided by the Organization for the Prohibition of Chemical Weapons during the 22(nd) and 24(th) Official Proficiency tests were detected and identified as IBHBI adducts. The added advantage of this method is that low-mass analytes are detected at higher mass, thus obviating the problem with background noise at low mass.     

A synthetic route to highly substituted 1,2,3,4-tetrahydroisoquinolines via Yb(OTf)3 -catalyzed diastereoselective ring opening of bridged oxazolidines: asymmetric synthesis of 2-azapodophyllotoxin

We herein report a robust and efficient synthetic route to highly functionalized enantiopure 1,2,3,4-tetrahydroisoquinolines (THIQs) from Garner aldehyde. We utilized the inherent chirality of Garner aldehyde through 1,2- and 1,3-/1,4-asymmetric inductions iteratively to obtain 1,2,3,4-tetrasubstitued THIQs using rigid and isolable bridged oxazolidines without any external chiral sources. All possible stereoisomers of bridged oxazoliodines were efficiently synthesized from L- and D-Garner aldehydes and transformed into fully functionalized THIQs via diastereoselective ring opening with various nucleophiles in the presence of Yb(OTf)(3). This methodology furnished four out of eight possible diastereomers of 1,2,3,4-tetrasubstituted THIQs despite the electronic nature of substituents on the aryl rings. Finally, the enantioselective synthesis of 2-azapodophyllotoxin was achieved with an overall yield of 35.4% (eight steps) from D-Garner aldehyde using this synthetic route.     

Secretory protein profiling reveals TNF-α inactivation by selective and promiscuous Sec61 modulators

Cotransins are cyclic heptadepsipeptides that bind the Sec61 translocon to inhibit cotranslational translocation of a subset of secreted and type I transmembrane proteins. The few known cotransin-sensitive substrates are all targeted to the translocon by?a cleavable signal sequence, previously shown to be a critical determinant of cotransin sensitivity. By profiling two cotransin variants against a panel of secreted and transmembrane proteins, we demonstrate that cotransin side-chain differences profoundly affect substrate selectivity. Among the most sensitive substrates we identified is the proinflammatory cytokine tumor necrosis factor alpha (TNF-α). Like all type II transmembrane proteins, TNF-α is targeted to the translocon by its membrane-spanning domain, indicating that a cleavable signal sequence is not strictly required for cotransin sensitivity. Our results thus reveal an unanticipated breadth of translocon substrates whose expression is inhibited by Sec61 modulators.     

Essential norm of products of multiplication composition and differentiation operators on weighted Bergman spaces

Let ψ be a holomorphic function on the open unit disk D and φ a holomorphic self-map of D. Let C_φ,M_ψ and D denote the composition, multiplication and differentiation operator, respectively. We find an asymptotic expression for the essential norm of products of these operators on weighted Bergman spaces on the unit disk. This paper is a continuation of our recent paper concerning the boundedness of these operators on weighted Bergman spaces.     

Spectroscopic characterization of aminoacetonitrile,its ions and protonated aminoacetonitrile using quantum chemical methods

We present theoretical vibrational and absorption spectra of aminoacetonitrile, its cation, anion, cyanoprotonated, and aminoprotonated aminoacetonitrile. We used second‐order Moller–Plesset perturbation method (MP2) with TZVP basis set to obtain ground state geometries and vibrational spectra. Time dependent density functional theory method was used to obtain absorption spectra. Shifts in vibrational modes for aminoacetonitrile upon ionization and protonation are determined. The C≡N stretching mode which is the most important mode in detection of nitriles in space is more intense in aminoacetonitrile ions and its two protonated form and is less IR active for neutral aminoacetonitrile. The nature of electronic transition for these molecules is identified. All the electronic transitions for neutral aminoacetonitrile and its cation are the σ → σ* electronic transitions, whereas its anion and protonated aminoacetonitrile display the σ → σ* as well as π → π* transitions. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011