Phase field simulations of ferroelectrics domain structures in PbZrxTi1−xO3 bilayers

Domain stability and structures in Pb(Zr_0.3Ti_0.7)O₃/Pb(Zr_0.7Ti_0.3)O₃ bilayer films under different substrate strains are studied using the phase field method. It is demonstrated that the domain structure of the bilayer film is very different from those of the corresponding single layer films grown on the same silicon substrate with an incoherent interface. Moreover, the predicted rhombohedral domains in the Pb(Zr_0.7Ti_0.3)O₃ layer of the bilayer film have smaller sizes than those in the single layer case. These results are compared with experimental observations and previous thermodynamic analyses. The polarization distributions of the ferroelectric–paraelectric bilayer are analyzed as a function of the thickness of the bilayer film, where there is a “ferroelectric proximity effect” due to dipole–dipole interactions. The phase diagrams for both the bilayer and single layer films as a function of temperature and effective in-plane substrate strain are constructed.     

Effects of outliers on the identification and estimation of GARCH models

Abstract. This paper analyses how outliers affect the identification of conditional heteroscedasticity and the estimation of generalized autoregressive conditionally heteroscedastic (GARCH) models. First, we derive the asymptotic biases of the sample autocorrelations of squared observations generated by stationary processes and show that the properties of some conditional homoscedasticity tests can be distorted. Second, we obtain the asymptotic and finite sample biases of the ordinary least squares (OLS) estimator of ARCH(p) models. The finite sample results are extended to generalized least squares (GLS), maximum likelihood (ML) and quasi‐maximum likelihood (QML) estimators of ARCH(p) and GARCH(1,1) models. Finally, we show that the estimated asymptotic standard deviations are biased estimates of the sample standard deviations.     

Tracking the Interplay between Bound Peptide and the Lid Domain of DnaK,Using Molecular Dynamics

Hsp70 chaperones consist of two functional domains: the 44 kDa Nucleotide Binding Domain (NBD), that binds and hydrolyses ATP, and the 26 kDa Substrate Binding Domain (SBD), which binds unfolded proteins and reactivates them, utilizing energy obtained from nucleotide hydrolysis. The structure of the SBD of the bacterial Hsp70, DnaK, consists of two sub-domains: A β-sandwich part containing the hydrophobic cavity to which the hepta-peptide NRLLLTG (NR) is bound, and a segment made of 5 α-helices, called the “lid” that caps the top of the β-sandwich domain. In the present study we used the Escherichia coli Hsp70, DnaK, as a model for Hsp70 proteins, focusing on its SBD domain, examining the changes in the lid conformation. We deliberately decoupled the NBD from the SBD, limiting the study to the structure of the SBD section, with an emphasis on the interaction between the charges of the peptide with the residues located in the lid. Molecular dynamics simulations of the complex revealed significant mobility within the lid structure; as the structure was released from the forces operating during the crystallization process, the two terminal helices established a contact with the positive charge at the tip of the peptide. This contact is manifested only in the presence of electrostatic attraction. The observed internal motions within the lid provide a molecular role for the function of this sub-domain during the reaction cycle of Hsp 70 chaperones.     

Ru-Containing Polymeric Catalysts for Cellulose Conversion to Polyols

In this paper Ru-containing catalysts based on hypercrosslinked polystyrene (MN-270) and its functional analogues (MN-100 and MN-500) were studied for the first time in cellulose hydrolytic hydrogenation. The catalysts were characterized using transmission electron microscopy (TEM), high resolution TEM, and porosity measurements. Catalytic studies demonstrated that the catalyst containing 1.0 % Ru and based on MN-270 is the most active. The total yield of sorbitol and mannitol was 50 % on the average at 85 % cellulose conversion.     

Bootstrap prediction intervals in state–space models

Abstract.  Prediction intervals in state–space models can be obtained by assuming Gaussian innovations and using the prediction equations of the Kalman filter, with the true parameters substituted by consistent estimates. This approach has two limitations. First, it does not incorporate the uncertainty caused by parameter estimation. Second, the Gaussianity of future innovations assumption may be inaccurate. To overcome these drawbacks, Wall and Stoffer [ Journal of Time Series Analysis (2002) Vol. 23, pp. 733–751] propose a bootstrap procedure for evaluating conditional forecast errors that requires the backward representation of the model. Obtaining this representation increases the complexity of the procedure and limits its implementation to models for which it exists. In this article, we propose a bootstrap procedure for constructing prediction intervals directly for the observations, which does not need the backward representation of the model. Consequently, its application is much simpler, without losing the good behaviour of bootstrap prediction intervals. We study its finite-sample properties and compare them with those of the standard and the Wall and Stoffer procedures for the local level model. Finally, we illustrate the results by implementing the new procedure to obtain prediction intervals for future values of a real time series.     

Direct <Emphasis Type="SmallCaps">d</Emphasis>-Glucose Oxidation over Noble Metal Nanoparticles Introduced on Polymer and Inorganic Supports

In the present work, nanocatalysts prepared on inorganic supports (zeolites) were investigated in d-glucose oxidation and compared to systems supported on polymer (hypercrosslinked polystyrene (HPS)) previously described. Catalytic activities and selectivities were measured under various reaction conditions. The selectivity of d-glucose oxidation and activity of both Pd-containing zeolites and HPS-Ru were similar (99.7% and TOF 0.013–0.014 mol/(mol Me s)). Physicochemical analysis X-ray photoelectron spectroscopy, liquid nitrogen physisorption, diffuse reflectance infrared Fourier transform spectroscopy of adsorbed CO for metal sites evaluation, CD₃CN for acid sites evaluation showed that Pd species were in oxidic form, while Ru species were in oxidic and reduced form. The catalytic activity decreased when acidic sites were present in Pd-containing zeolites.     

“Arbequina” Olive Oil Composition Is Affected by the Application of Regulated Deficit Irrigation during Pit Hardening Stage

Three new regulated deficit irrigation (RDI) treatments were applied to “Arbequina” olive orchards during pit hardening. Oil quality was determined by measuring analytical parameters for olive oil grading, antioxidant activity, total phenol content, fatty acid profile, volatile compounds profile, and sensory analysis. Oils from RDI were classified as “extra virgin olive oil” and their quality was improved due to their higher antioxidant potential (ABTS⁺ [increased ~75%] and DPPH^˙ [increased ~25%] assays) and phenols (increased ~53%) than control. Concentration of total volatile compounds decreased (~27%) but RDI olive oils showed a more balanced profile (alcohols, aldehydes, and esters). Monounsaturated fatty acid content increased (~5%) and atherogenic and thrombogenic indexes decreased (~8.5%) in RDI olive oil. Regarding sensory analysis, RDI provided more balanced oils with higher fruit aroma than control. Other benefits of RDI olive oil, when compared with oil from full irrigated orchards are reduced use of water and improved functional and sensory quality.     

Synthesis and Biological Evaluation of Papain‐Family Cathepsin L‐Like Cysteine Protease Inhibitors Containing a 1,4‐Benzodiazepine Scaffold as Antiprotozoal Agents

Novel papain‐family cathepsin L‐like cysteine protease inhibitors endowed with antitrypanosomal and antimalarial activity were developed, through an optimization study of previously developed inhibitors. In the present work, we studied the structure–activity relationships of these derivatives, with the aim to develop new analogues with a simplified and more synthetically accessible structure and with improved antiparasitic activity. The structure of the model compounds was significantly simplified by modifying or even eliminating the side chain appended at the C3 atom of the benzodiazepine scaffold. In addition, a simple methylene spacer of appropriate length was inserted between the benzodiazepine ring and the 3‐bromoisoxazoline moiety. Several rhodesain and falcipain‐2 inhibitors displaying single‐digit micromolar or sub‐micromolar antiparasitic activity against one or both parasites were identified, with activities that were one order of magnitude more potent than the model compounds.