Solution Structure and Constrained Molecular Dynamics Study of Vitamin B12 Conjugates of the Anorectic Peptide PYY(3–36)

Vitamin B₁₂–peptide conjugates have considerable therapeutic potential through improved pharmacokinetic and/or pharmacodynamic properties imparted on the peptide upon covalent attachment to vitamin B₁₂ (B₁₂). There remains a lack of structural studies investigating the effects of B₁₂ conjugation on peptide secondary structure. Determining the solution structure of a B₁₂–peptide conjugate or conjugates and measuring functions of the conjugate(s) at the target peptide receptor may offer considerable insight concerning the future design of fully optimized conjugates. This methodology is especially useful in tandem with constrained molecular dynamics (MD) studies, such that predictions may be made about conjugates not yet synthesized. Focusing on two B₁₂ conjugates of the anorectic peptide PYY(3–36), one of which was previously demonstrated to have improved food intake reduction compared with PYY(3–36), we performed NMR structural analyses and used the information to conduct MD simulations. The study provides rare structural insight into vitamin B₁₂ conjugates and validates the fact that B₁₂ can be conjugated to a peptide without markedly affecting peptide secondary structure.     

Scaling Effects in Perovskite Ferroelectrics: Fundamental Limits and Process‐Structure‐Property Relations

Ferroelectric materials are well‐suited for a variety of applications because they can offer a combination of high performance and scaled integration. Examples of note include piezoelectrics to transform between electrical and mechanical energies, capacitors used to store charge, electro‐optic devices, and nonvolatile memory storage. Accordingly, they are widely used as sensors, actuators, energy storage, and memory components, ultrasonic devices, and in consumer electronics products. Because these functional properties arise from a noncentrosymmetric crystal structure with spontaneous strain and a permanent electric dipole, the properties depend upon physical and electrical boundary conditions, and consequently, physical dimension. The change in properties with decreasing physical dimension is commonly referred to as a size effect. In thin films, size effects are widely observed, whereas in bulk ceramics, changes in properties from the values of large‐grained specimens is most notable in samples with grain sizes below several micrometers. It is important to note that ferroelectricity typically persists to length scales of about 10 nm, but below this point is often absent. Despite the stability of ferroelectricity for dimensions greater than ~10 nm, the dielectric and piezoelectric coefficients of scaled ferroelectrics are suppressed relative to their bulk counterparts, in some cases by changes up to 80%. The loss of extrinsic contributions (domain and phase boundary motion) to the electromechanical response accounts for much of this suppression. In this article, the current understanding of the underlying mechanisms for this behavior in perovskite ferroelectrics is reviewed. We focus on the intrinsic limits of ferroelectric response, the roles of electrical and mechanical boundary conditions, grain size and thickness effects, and extraneous effects related to processing. In many cases, multiple mechanisms combine to produce the observed scaling effects.     

Thermal stability of HfO2-on-GaAs nanopatterns

We have evaluated the effect of thermal annealing on the morphology, crystalline phase and elemental composition of high-k dielectric HfO(2)-on-GaAs nanopatterns at 500-620 °C by using atomic force microscopy (AFM), high-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (EDS). While the HfO(2)-GaAs interface continues to be atomically abrupt at 620 °C, we have found a gradual shrinkage in the pattern linewidth and period with increasing temperature. Facet formation triggered by a nanoscale-modulated sequence of tensile and compressive stresses on the GaAs substrate, observed at 620 °C, has been attributed to a volumetric expansion of the HfO(2) nanostructures, caused by the tetragonal/cubic to monoclinic HfO(2) phase transformation and, to a lesser extent, by solid-state diffusion of As into HfO(2).     

The speed of sound and isentropic bulk modulus of biodiesel at 21°C from atmospheric pressure to 35 MPa

Biodiesel, an alternative diesel fuel consisting of the alkyl monoesters of fatty acids from vegetable oils and animal fats, can be used in existing diesel engines without modification. However, property changes associated with the differences in chemical structure between biodiesel and petroleumbased diesel fuel may change the engine's injection timing. These injection timing changes can change the exhaust emissions and performance from the optimized settings chosen by the engine manufacturer. This study presents the results of measurements of the speed of sound and the isentropic bulk modulus for methyl and ethyl esters of fatty acids from soybean oil and compares them with No. 1 and No. 2 diesel fuel. Data are presented at 21±1°C and for pressures from atmospheric to 34.74 MPa. The results indicate that the speed of sound and bulk modulus of the monoesters of soybean oil are higher than those for diesel fuel and these can cause changes in the fuel injection timing of diesel engines. Linear equations were used to fit the data as a function of pressure, and the correlation constants are given.     

Hydrothermal conversion of FAU zeolite into aluminous MTN zeolite

The hydrothermal conversion of FAU zeolite into aluminous MTN zeolite is described here. In the presence of both benzyltrimethylammonium hydroxide (BTMAOH) and sodium chloride (NaCl) the highly crystalline and pure MTN zeolites with Si/Al ratios of 21-23 could be obtained from the hydrothermal conversion of FAU zeolite. Based on powder XRD refinement and ¹³C CP/MAS NMR spectra, BTMA⁺ ions were not present in cages of the obtained zeolites, but TMA⁺ ions existed instead. It means that BTMAOH underwent degradation during the conversion. Moreover, the effects of Si/Al ratio of starting FAU zeolite, synthesis parameters (BTMAOH/SiO₂ and H₂O/SiO₂ ratios) and the addition of alkali metal chlorides on the hydrothermal conversion of FAU zeolite into MTN zeolite are discussed. As compared to amorphous SiO₂/γ-Al₂O₃, which produced impurity, the hydrothermal conversion of FAU zeolite showed a fast crystallization rate and a high selectivity to MTN zeolite formation. These phenomena indicate that the assembly of locally ordered aluminosilicate species coming from the decomposition or dissolution of FAU zeolite should be taking part in the conversion process.     

Analytical Method for Forming Limit Diagram Prediction with Application to a Magnesium ZEK100-O Alloy

A significant barrier to broader implementation of magnesium alloys is their poor room temperature formability, a consequence of the anisotropic response of the Mg hexagonal closed-packed (hcp) crystal structure. Additions of rare earth (RE) elements, such as in the ZEK100 alloys, weaken the texture and improve formability. Room temperature forming limit analyses of RE-containing Mg alloys, particularly Mg ZEK100, have not been explored to any significant extent in the literature. In this paper, strain-based forming limit diagrams (FLDs) are derived for an Mg ZEK100-O alloy (Zn1.34Zr0.23Nd0.182, wt.%) using an analytical method that combines the vertex theory of Storen and Rice (J Mech Phys Solids, 23:421-441, 1979), the anisotropic yield criterion of Barlat and Lian (Int J Plast, 5:51-66, 1989), and a hardening law. The method does not rely on assumptions about pre-existing defects, is broadly applicable to sheet alloys exhibiting in-plane anisotropy requiring a higher-order yield criterion, and requires only minimal experimental inputs. Results from the analytical method are compared with experimentally derived FLDs based upon the well-known Nakajima test and tensile deformation, and with predictions from an existing analytical method for FLDs. Close agreement between the experimentally derived FLDs and the present theoretical method was obtained. Sheet materials where the theoretical method does not apply are also discussed.     

Rheological Characterization and Coagulation Casting of Al2O3–Nano Zirconia Suspensions

The rheological behavior of electrosterically dispersed aqueous suspensions composed of submicrometer alumina and nano zirconia particles in different ratios and solids contents (from 34 to 40 vol%) has been studied during in situ coagulation casting. Glucono-δ-lactone was used as the coagulant to achieve destabilization of the ceramic suspensions by acidifying the suspension so that the pH became close to the isoelectric point for both powders. The effects of the lactone content (from 0.5 to 6.7 wt%) and the solids loading on the rheological parameters (dynamic and static measurements) during the coagulation process were studied. Dynamic measurements showed an increasing elastic modulus, G', with time and lactone content (viz. 180 and 340 kPa for 6.7 wt% lactone addition after 40 and 60 min, respectively, and 57.3 kPa for 0.5 wt% lactone after 60 min), suggesting the formation of stronger green bodies at higher additions and longer times. The conditions were optimized to yield homogeneous green samples with a uniform nanozirconia distribution and densities between 58% and 60% of the theoretical. These were subsequently sintered to yield composites with a final density up to 97%.     

Steam reforming of liquid hydrocarbon fuels for micro-fuel cells. Pre-reforming of model jet fuels over supported metal catalysts

The present work deals with pre-reforming of logistic hydrocarbon fuel (jet fuel) as a part of an integrated approach to developing an on-board fuel reformer for use in a micro-solid-oxide fuel cell system. The purpose of doing pre-reforming is to ensure carbon-free reformulation of JP-8 jet fuel into hydrogen and carbon monoxide for use in a micro-solid-oxide fuel cell. Several model jet fuels have been tested for the pre-reforming at low temperature (450–550 °C) in a lab-scale reforming reactor. Proper temperature control and pre-mixing of feed fuels and steam have been found to be important for the prevention of coke formation prior to pre-reforming. Both noble metal and base-metal catalysts have been prepared and tested. As compared with an Al₂O₃-supported Ni catalyst, supported Rh catalysts show not only high activity but also high resistance to deactivation due to carbon formation. Removal of residual Cl⁻ from Rh/CeO₂–Al₂O₃ improves the metal dispersion and the pre-reforming activity. The reformates from the current pre-reformer contain mainly CH₄, CO, H₂, in which CH₄ can be further converted to H₂ and CO by subsequent main-reforming.