Pyrazolate-bridged binuclear zinc complexes Zn<Subscript>2</Subscript>(μ-dmpz)<Subscript>2</Subscript>(Hdmpz)<Subscript>2</Subscript>(OOCR)<Subscript>2</Subscript> (R = Me,Ph; Hdmpz = 3,5-dimethylpyrazole)

Triethylamine reacts with aqueous zinc acetate and the product of its thermolysis in the presence of benzoic acid to yield the complexes [Zn₇(μ₄-O)(μ-OOCMe)₁₀][η-OC(Me)OHNEt₃]₂ (1) and [Zn₂(μOOCPh)₄][η-OC(Me)OHNEt₃]₂ (2), respectively. The reactions of 1 and 2 with 3,5-dimethylpyrazole at room temperature in benzene yield pyrazolate-bridged binuclear complexes Zn₂(μdmpz)₂(Hdmpz)₂(OOCR)₂ (R = Me (3), Ph (4)). The structures of complexes 1–4 have been determined by X-ray crystallography.     

Effect of solvent and electrospray mass spectrometer parameters on the charge state distribution of peptides--a case study using liquid chromatography/mass spectrometry method development for beta-endorphin assay

Beta-endorphin was used as a model peptide to study the effect of solvent and electrospray mass spectrometer parameters in the optimisation of an assay method for multiply charged compounds using liquid chromatography/mass spectrometry (LC/MS). Unlike with singly charged compounds, the charge state distribution has a significant impact in the method development of multiply charged compounds such as peptides. Using a 50% acetonitrile/water solvent mixture, we found that the ion spray voltage had no influence on the charge state distribution. However, increasing declustering potential led to deprotonation of the higher charge states of the peptide thus causing a shift to lower charge states. The mechanism leading to the deprotonation was examined. It was concluded that the deprotonation is due to endoergic proton transfer from the peptide to solvent molecules clustered to the peptide that occurs in the declustering region. The extent of deprotonation increases with increasing proton affinity of the molecules of the non-aqueous solvent component used. Thus, if desired, deprotonation can be avoided by selecting a low proton affinity solvent such as methanol. The focusing potential was also found to have a great influence on the charge state distribution observed. The results of this study enabled us to select the optimum ion to be used in single ion/reaction monitoring mode. They also provided the most favourable parameter values to be used in the method to obtain the best sensitivity for the ion of choice. The results demonstrate the importance of considering the charge state distribution in the optimisation of electrospray LC/MS methods for multiply charged compounds.     

The sound generated by a square cylinder with a splitter plate at low Reynolds number

The generation of aerodynamic sound by the interaction of flow at a Reynolds number of 150 and a Mach number of 0.2 with a rigid square cylinder attached to a rigid thin flat plate is numerically investigated. When the length of the plate is varied from L=0.5D to 6D, where D is the side length of the square cylinder, the results can be grouped into three distinct regimes. For the first regime (L?D), the sound levels decrease with increasing plate length. A 3 dB sound reduction is obtained when the length of the plate is D. For the second regime (1.25D?L?4.75D), the sound levels increase with increasing plate length. For the third regime (5D?L?6D), the sound levels decrease as the length of the plate increases but the levels are higher than for the other regimes. Results also show that the lift fluctuation is the dominant sound source. These acoustic results can be explained in terms of the fluid mechanics occurring in the near wake of the cylinder.     

Hardy's paradox and violation of a state-independent Bell inequality in time

Tests such as Bell's inequality and Hardy's paradox show that joint probabilities and correlations between distant particles in quantum mechanics are inconsistent with local realistic theories. Here we experimentally demonstrate these concepts in the time domain, using a photonic entangling gate to perform nondestructive measurements on a single photon at different times. We show that Hardy's paradox is much stronger in time and demonstrate the violation of a temporal Bell inequality independent of the quantum state, including for fully mixed states.     

Controlled release of ketorolac through nanocomposite films of hydrogel and LDH nanoparticles

A novel nanocomposite film for sustained release of anionic ophthalmic drugs through a double-control process has been examined in this study. The film, made as a drug-loaded contact lens, consists principally of a polymer hydrogel of 2-hydroxyethyl methacrylate (HEMA), in whose matrix MgAl-layered double hydroxide (MgAl-LDH) nanoparticles intercalated with the anionic drug are well dispersed. Such nanocomposite films (hydrogel-LDH-drug) contained 0.6–0.8 mg of MgAl-LDH and 0.08–0.09 mg of the ophthalmic drug (ketorolac) in 1.0 g of hydrogel. MgAl-drug-LDH nanoparticles were prepared with the hydrodynamic particle size of 40–200 nm. TEM images show that these nanoparticles are evenly dispersed in the hydrogel matrix. In vitro release tests of hydrogel-LDH-drug in pH 7.4 PBS solution at 32 °C indicate a sustained release profile of the loaded drug for 1 week. The drug release undergoes a rapid initial burst and then a monotonically decreasing rate up to 168 h. The initial burst release is determined by the film thickness and the polymerization conditions, but the following release rate is very similar, with the effective diffusion coefficient being nearly constant (3.0 × 10⁻¹² m²/s). The drug release from the films is mechanistically attributed to anionic exchange and the subsequent diffusion in the hydrogel matrix.     

Identifying distress among banks prior to a major crisis using non-oriented super-SBM

We illustrate how data envelopment analysis (DEA) can be used as a forward-looking method to flag bank holding companies (BHCs) likely to become distressed. Various financial performance models are tested in the period leading up to the recent global financial crisis. Results generally support DEA’s discriminatory and predictive power, suggesting that it can identify distressed banks up to 2 years in advance. Robustness tests reveal that DEA has a stable efficient frontier and its discriminatory and predictive powers prevail even after data perturbations. DEA can be used as a preliminary off-site screening tool by regulators, by business managers to ascertain their standing among competitors, and by investors. Attention by regulators can be further directed at potentially distressed banks as some of them would be candidates for closer monitoring. In conclusion, DEA may be useful in making economic decisions because there is an identifiable link between inefficiency and financial distress. To the best of our knowledge, application of DEA to predict financial distress among BHCs prior to a major crisis has not been published.     

Aggregation of Malmquist productivity indexes allowing for reallocation of resources

In this paper we consider aggregate Malmquist productivity index measures which allow inputs to be reallocated within the group (when in output orientation). This merges the single period aggregation results allowing input reallocation of Nesterenko and Zelenyuk (2007) with the aggregate Malmquist productivity index results of Zelenyuk (2006) to determine aggregate Malmquist productivity indexes that are justified by economic theory, consistent with previous aggregation results, and which maintain analogous decompositions to the original measures. Such measures are of direct relevance to firms or countries who have merged (making input reallocation possible), allowing them to measure potential productivity gains and how these have been realised (or not) over time.     

The effect of solute on ultrasonic grain refinement of magnesium alloys

An experimental study has been conducted to assess the structural refinement of magnesium and its alloys by ultrasonic irradiation during solidification. It is shown that (i) ultrasonic irradiation leads to significant refinement only in the presence of adequate solute, which is alloy dependent; (ii) the attendant grain density increases linearly with increase in solute content at a given irradiation level; (iii) increasing the solute content at a low irradiation level above the cavitation threshold is more effective than substantially increasing the irradiation intensity; and (iv) the difference in the grain size between two ultrasonicated magnesium alloys is mainly determined by the solute content rather than the irradiation intensity. In view of these, the effect of ultrasonic irradiation on solute redistribution in a solidifying magnesium alloy seems rather limited even at a substantial intensity level such as 1700 W cm⁻². The implications of these findings are discussed and a mechanism is proposed to account for the experimental observations.     

Nonlinear strain gradient elastic thin shallow shells

The governing equilibrium equations for strain gradient elastic thin shallow shells are derived, considering nonlinear strains and linear constitutive strain gradient elastic relations. Adopting Kirchhoff’s theory of thin shallow structures, the equilibrium equations, along with the boundary conditions, are formulated through a variational procedure. It turns out that new terms are introduced, indicating the importance of the cross-section area in bending of thin plates. Those terms are missing from the existing strain gradient shallow thin shell theories. Those terms highly increase the stiffness of the structures. When the curvature of the shallow shell becomes zero, the governing equilibrium for the plates is derived.