Low-cost synthesis of titanium dioxide anatase nanoclusters as advanced materials for hydrogen photoproduction

Research on Chemical Intermediates - Sub-nm titanium dioxide (TiO2) clusters are synthesized via the hydrolysis of TiCl4 in order to produce clean and surfactant-free oxide surfaces. By controlling...     

Viscous dissipation of Rankine vortex profile in zero meridional flow

An analytical solution is given for a time-decay Rankine vortex profile due to viscous effects. The vortex filament is assumed to be isolated, strong, concentrated and having zero-meridional flow (i.e. radial and axial velocities are equal to zero). Zero-meridional renders the governing equations for an unsteady, incompressible and axisymmetric vortex in a simple form. Based on the tangential momentum equation, the spatial-temporal distributions of the swirl velocity are given in terms of Fourier-Bessel series by using separation of variables technique. A general formula is derived by total differentiation of the swirl velocity with respect to time, depicting the viscous dissipation for Oseen and Taylor-like vortex profiles. This analysis is validated by comparison with previous experimental data. The English text was polished by Yunming Chen.     

Synthesis,characterization and pharmacological investigations of some novel heterocyclic derivatives incorporating pyrene and sugar moieties

A series of substituted pyrene derivatives 2–15 incorporated heterocyclic and sugar moieties were synthesized and evaluated as antiviral activities using 1-acetylpyrene as a starting material. The structure assignment of the new compounds was based on chemical and spectroscopic evidence. The detailed synthesis, spectroscopic data and pharmacological activities of the synthesized compounds were reported.     

Structural characterization and activation energy of NiTiO3 nanopowders prepared by the co-precipitation and impregnation with calcinations

In this paper, we report on the formation of novel hexagonal NiTiO₃ nanopowders synthesized by the impregnation or co-precipitation methods through the thermal decomposition reaction of the precursors. The decomposition course was followed using differential thermal analysis (DTA) and thermogravimetric analysis (TGA) techniques. The intermediate decomposition products as well as the formed titanate were characterized using X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. XRD patterns of the precursors calcined at 1000 °C showed the formation of the single ilmenite-type rhombohedral structure only with the impregnated precursor, while with the precipitated NiTiO₃ powders one it indicates the presence of some NiO and TiO₂ impurities. Transmission electron microscopy (TEM) exhibited loosely agglomerated hexagonal particles with uniform morphology having a size around 61 nm. The Brunauer-Emmett-Teller (BET) surface area measurements showed a type III isotherm with calculated surface area of 152 m²/g. The plot of ln σ_ac vs. temperature as a function of frequency indicates a semiconducting behavior with ferroelectric phase transition at 605 K. The calculated activation in the ferroelectric region is 0.93 eV suggests the predominance of hopping conduction mechanism. Kinetic analysis of TG data according to different integral methods showed that in the NiC₂O₄·2H₂O–TiO₂ precursor, the water molecules are coordinately bounded and the presence of TiO₂ reduces the activation energy needed to the oxalate decomposition reaction.     

Modeling the evolution of stress due to differential shrinkage in powder-processed functionally graded metal–ceramic composites during pressureless sintering

Pressureless sintering of powder-processed functionally graded materials is being pursued to economically produce metal–ceramic composites for a variety of high-temperature (e.g., thermal protection) and energy-absorbing (e.g., armor) applications. During sintering, differential shrinkage induces stresses that can compromise the integrity of the components. Because the strength evolves as the component is sintered, it is important to model how the evolution of the differential shrinkage governs the stress distribution in the component in order to determine when the strength will be exceeded and cracking initiated. In this investigation, a model is proposed that describes the processing/microstructure/property/performance relationship in pressurelessly sintered functionally graded plates and rods. This model can be used to determine appropriate shrinkage rates and gradient architectures for a given component geometry that will prevent the component from cracking during pressureless sintering by balancing the evolution of strength, which is assumed to be a power law function of the porosity, with the evolution of stress. To develop this model, the powder mixture is considered as a three-phase material consisting of voids, metal particles, and ceramic particles. A micromechanical thermal elastic–viscoplastic constitutive model is then proposed to describe the thermomechanical behavior of the composite microstructure. The subsequent evolution of the thermomechanical properties of the matrix material during sintering is assumed to obey a power law relationship with the level of porosity, which is directly related to the shrinkage strain, and was refined to account for the evolving interparticle cohesion of the matrix phase due to sintering. These thermomechanical properties are incorporated into a 2-D thermomechanical finite element analysis to predict the stress distributions and distortions that arise from the evolution of differential shrinkage during the pressureless sintering process. Differential shrinkage results were verified quantitatively through comparison with the shape profile for a pressurelessly sintered functionally graded nickel–alumina composite plate with a cylindrical geometry, and the stress distribution results verified from qualitative observations of the absence or presence of cracking as well as the location in specimens with different gradient architectures. The cracking was mitigated using a reverse gradient at one end of the specimen, and the resulting distortions associated with the shape profile were determined to be no more than 15% reduced from the predictions. The effects of geometry were also studied out-of-plane by transforming the plate into a rod through an increase in thickness, while in-plane effects were studied by comparing the results from the cylindrical specimen with a specimen that has a square cross-sectional geometry. By transforming from a plate to a rod geometry, the stress no longer exceeds critical levels and cracks do not form. The results from the in-plane geometric study indicated that critical stresses were reached in the square geometry at temperatures 100 °C less than in the cylindrical geometry. Additionally, the location of primary cracking was shifted towards the metal-rich end of the specimen, while the stress distribution associated with this shift and the lower temperature for the critical stress resulted in secondary cracking.     

Rhodium-catalyzed Reformatsky-type reaction for asymmetric synthesis of difluoro-β-lactams using menthyl group as a chiral auxiliary

We developed a new methodology for the asymmetric Reformatsky-type reaction of (−)-menthyl bromodifluoroacetate (2) with imine in the presence of RhCl(PPh₃)₃. Ester 2 with the cost-effective chiral auxiliary gave (S)-difluoro-β-lactams in moderate to good yields and high diastereoselectivities through spontaneous removal of the auxiliary.     

A comparative study of first-derivative spectrophotometry and column high-performance liquid chromatography applied to the determination of repaglinide in tablets and for dissolution testing

A fast and reliable method for the determination of repaglinide is highly desirable to support formulation screening and quality control. A first-derivative UV spectroscopic method was developed for the determination of repaglinide in tablet dosage form and for dissolution testing. First-derivative UV absorbance was measured at 253 nm. The developed method was validated for linearity, accuracy, precision, limit of detection (LOD), and limit of quantitation (LOQ) in comparison to the U.S. Pharmacopeia (USP) column high-performance liquid chromatographic (HPLC) method. The first-derivative UV spectrophotometric method showed excellent linearity [correlation coefficient (r) = 0.9999] in the concentration range of 1-35 microg/mL and precision (relative standard deviation < 1.5%). The LOD and LOQ were 0.23 and 0.72 microg/mL, respectively, and good recoveries were achieved (98-101.8%). Statistical comparison of results of the first-derivative UV spectrophotometric and the USP HPLC methods using the t-test showed that there was no significant difference between the 2 methods. Additionally, the method was successfully used for the dissolution test of repaglinide and was found to be reliable, simple, fast, and inexpensive.     

Gel electrophoresis/electroelution sorting fractionator combined with filter-aided sample preparation for deep proteomic analysis

Sample preparation and protein fractionation are important issues for proteomic studies. Protein extraction procedures strongly affect the performance of fractionation methods by provoking protein dispersion in several fractions. The most notable exception is the gel-based electrophoretic protein fractionation due to its resolution and effectiveness of sodium dodecyl sulfate as a solubilizing agent, while its main limitation lies in the poor recovery of the gel-trapped proteins. We created a fractionator device to separate complex mixture of proteins and peptides that is based on the continuous gel electrophoresis/electroelution sorting of these molecules. In an unsupervised process, complex mixtures of proteins or peptides are fractionated into the gel while separated fractions are simultaneously and sequentially electroeluted to the solution containing wells. The performance of the device was studied for protein fractionation in terms of reproducibility, protein recovery, and loading capacity. In a setup free of sodium dodecyl sulfate, complex peptide mixtures can also be fractionated. More than 11,700 proteins were identified in the whole-cell lysate of the CaSki cell line by using the fractionator combined with the filter-aided sample preparation method and mass spectrometry analysis. Fractionator-based proteome characterization increased 1.7-fold the number of identified proteins compared to the unfractionated sample analysis.     

Stability criteria of an immersed annulus swirling jet in a zero gravity environment

The present work deals with the stability properties of an immersed annulus swirling jet in a zero gravity environment. The considered system is composed of two streaming coaxial fluid cylinders, embedded in a third streaming fluid, where the intermediate one (annulus) has a uniform swirl speed. The fluids are immiscible, inviscid, and incompressible. The linear stability criteria of the model are discussed analytically and stability diagrams are obtained. We conclude that the radii ratio, the Weber number and the swirl number play a significant role in determining the dynamics of the developing interfacial patterns.