Low-temperature phase transformations of PbZr(1-x)Ti(x)O(3) in the morphotropic phase-boundary region

We present anelastic and dielectric spectroscopy measurements of PbZr(1-x)Ti(x)O(3) with 0.455 < or = x < or = 0.53, which provide new information on the low-temperature phase transitions. The tetragonal-to-monoclinic transformation is first order for x < 0.48 and causes a softening of the polycrystal Young's modulus whose amplitude may exceed the one at the cubic-to-tetragonal transformation; this is explainable in terms of linear coupling between shear strain components and tilting angle of polarization in the monoclinic phase. The transition involving rotations of the octahedra below 200 K is visible both in the dielectric and anelastic losses, and it extends within the tetragonal phase, as predicted by recent first-principle calculations.     

Asymptotics for risk capital allocations based on Conditional Tail Expectation

An investigation of the limiting behavior of a risk capital allocation rule based on the Conditional Tail Expectation (CTE) risk measure is carried out. More specifically, with the help of general notions of Extreme Value Theory (EVT), the aforementioned risk capital allocation is shown to be asymptotically proportional to the corresponding Value-at-Risk (VaR) risk measure. The existing methodology acquired for VaR can therefore be applied to a somewhat less well-studied CTE. In the context of interest, the EVT approach is seemingly well-motivated by modern regulations, which openly strive for the excessive prudence in determining risk capitals.     

A new insight into ortho-(dimesitylboryl)diphenylphosphines: applications in Pd-catalyzed Suzuki-Miyaura couplings and evidence for secondary π-interaction

ortho-(Dimesitylboryl)phenylphosphines 1 and 2 were applied in Pd-catalyzed Suzuki-Miyaura C-C couplings. Coordination studies were performed in order to rationalize the relationship between structure and reactivity. Full characterization of a Pd(0) complex derived from 1 has evidenced a new coordination mode for phosphine-arylboranes involving secondary π-interaction between one of the mesityl groups at boron and the metal centre.     

Counting chemical compositions using Ehrhart quasi-polynomials

To count the number of chemical compositions of a particular mass, we consider an alphabet ${\mathop{\bf a}}$ with a mass function which assigns a mass to each letter in ${\mathop{\bf a}}$ . We then compute the mass of a word (an ordered sequence of letters) by adding the masses of the constituent letters. Our main interest is to count the number of words that have a particular mass, where we ignore the order of the letters within the word. We show first that counting the number of words of a given mass has a geometric interpretation, whose solutions are called Ehrhart quasi-polynomials, a class of functions defined on integers. These special functions are “periodic” in the sense that they use the same polynomial every λ steps. In addition to discovering the connection between counting compositions and Ehrhart quasi-polynomials, we also find number theoretic results that greatly reduce the number of candidates for the period, λ. Finally, we illustrate the usefulness of these results and the use of a software library named barvinok (by Verdoolaege et?al.) by applying them to eight different classes of chemical compositions, including organic molecules, peptides, DNA, and RNA.     

Wear resistance of ZrC/TiN and ZrC/ZrN thin multilayers grown by pulsed laser deposition

ZrC/TiN and ZrC/ZrN multilayers thinner than 350 nm were grown on (100) Si substrates at a temperature of 300 °C by the pulsed laser deposition (PLD) technique using a KrF excimer laser (λ=248 nm, pulse duration τ=25 ns, 8.0 J/cm² fluence and 40 Hz repetition rate). Cross-sectional transmission electron microscopy, Auger electron spectroscopy depth profiling and simulations of X-ray reflectivity curves indicated that there was intermixing between the deposited layers at the interfaces as well as between the first layer and the substrate. Nanoindentation investigations found hardness values between 35 and 38 GPa for the deposited multilayers. Linear unidirectional sliding wear tests were conducted using a ball-on-plate tribometer under 1 N normal force. Wear tracks were produced in a Hysitron nanoindenter with 1 μm radius diamond tip under a 500 μN load. High-resolution cross-sectional transmission electron microscopy studies of the wear tracks showed that the multilayers withstood these tests without significant damage. The results could be explained by the use of a high laser fluence during deposition that resulted in very dense and strongly adherent nanocrystalline layers.     

Introducing axial chirality into mesoionic 4,4'-bis(1,2,3-triazole) dicarbenes

Mesoionic 4,4'-bis(1,2,3-triazole-5,5'-diylidene) Rh(I) complexes having a C2 chiral 4,4'-axis were accessed from 3-alkyltriazolium salts in virtually complete de. Their structure and configurational integrity were assessed by NMR spectroscopy, X-ray crystallography, and chiral HPLC. Computational analysis of the MICs involved in the reaction suggested the formation of a highly stable and unprecedented cation-carbene intermediate species, which could be evidenced experimentally by cyclic voltammetry analysis.     

Linear SPDEs Driven by Stationary Random Distributions

Using tools from the theory of stationary random distributions developed in It? (Mem. Coll. Sci., Univ. Kyoto, Ser. A: Math., 28:209?C223,?1954) and Yaglom (Theory Probab. Appl., 2:273?C320,?1957), we introduce a new class of processes which can be used as a model for the noise perturbing an SPDE. This type of noise is not necessarily Gaussian, but it includes the spatially homogeneous Gaussian noise introduced in Dalang (Electron. J. Probab. 4(6)?1999), and the fractional noise considered in Balan and Tudor (Stoch. Process. Appl., 120:2468?C2494,?2010). We derive some general conditions for the existence of a random field solution of a linear SPDE with this type of noise, under some mild conditions imposed on the Green function of the differential operator which appears in this equation. This methodology is applied to the study of the heat and wave equations (possibly replacing the Laplacian by one of its fractional powers), extending in this manner the results of Balan and Tudor (Stoch. Process. Appl., 120:2468?C2494,?2010) to the case H<1/2.     

Zero cancellation for general rational matrix functions

The problem of cancelling a specified part of the zeros of a completely general rational matrix function by multiplication with an appropriate invertible rational matrix function is investigated from different standpoints. Firstly, the class of all factors that dislocate the zeros and feature minimal McMillan degree are derived. Further, necessary and sufficient existence conditions together with the construction of solutions are given when the factor fulfills additional assumptions like being J-unitary, or J-inner, either with respect to the imaginary axis or to the unit circle. The main technical tool are centered realizations that deliver a sufficiently general conceptual support to cope with rational matrix functions which may be polynomial, proper or improper, rank deficient, with arbitrary poles and zeros including at infinity. A particular attention is paid to the numerically-sound construction of solutions by employing at each stage unitary transformations, reliable numerical algorithms for eigenvalue assignment and efficient Lyapunov equation solvers.     

Study of microstructural evolutions in phosphorus-doped ZnO films grown by pulsed laser deposition

The microstructure of P-doped ZnO films grown on the c-plane sapphire substrate by pulsed laser deposition (PLD) was investigated. ZnO films were highly textured along c-axis with two different in-plane orientations. The textured domain was surrounded by the threading dislocations, resulting in the formation of low-angle grain boundary. It was found that the degree of texture and crystalline quality of P-doped ZnO films decreased with increasing the phosphorus atomic percent. For the microstrain study, X-ray diffraction line profile analysis (LPA) was performed. The 0.5 at% P-doped ZnO film showed much higher microstrain than the 1.0 at% P-doped ZnO film as well as as-grown film, which indicated that the phosphorus in former film was effectively incorporated into ZnO film. X-ray photoelectron spectroscopy (XPS) results showed that the phosphorus in 1.0 at% P-doped ZnO film tended towards segregation, which was well consistent with XRD results.     

High-Resolution Tandem Mass Spectrometry Identifies a Particular Ganglioside Pattern in Early Diabetic Kidney Disease of Type 2 Diabetes Mellitus Patients

Considering the valuable information provided by glycosphingolipids as molecular markers and the limited data available for their detection and characterization in patients suffering from Type 2 diabetic kidney disease (DKD), we developed and implemented a superior method based on high-resolution (HR) mass spectrometry (MS) and tandem MS (MS/MS) for the determination of gangliosides in the urine of DKD patients. This study was focused on: (i) testing of the HR MS and MS/MS feasibility and performances in mapping and sequencing of renal gangliosides in Type 2 DM patients; (ii) determination of the changes in the urine gangliosidome of DKD patients in different stages of the disease—normo-, micro-, and macroalbuminuria—in a comparative assay with healthy controls. Due to the high resolution and mass accuracy, the comparative MS screening revealed that the sialylation status of the ganglioside components; their modification by O-acetyl, CH₃COO⁻, O-fucosyl, and O-GalNAc; as well as the composition of the ceramide represent possible markers for early DKD detection, the assessment of disease progression, and follow-up treatment. Moreover, structural investigation by MS/MS demonstrated that GQ1d(d18:1/18:0), GT1α(d18:1/18:0) and GT1b(d18:1/18:0) isomers are associated with macroalbuminuria, meriting further investigation in relation to their role in DKD.