Phthalocyanine- and Calixarene-Templating Effect on the Catalytic Performance of Solid Supported Vanadates

Abstract  

Catalytic performance of solid supported monovanadate catalysts toward oxidation of propane is significantly affected by the templating effect of: (1) pretreatment of the solid support with calixarene derivatives before deposition of ammonium vanadate, (2) direct deposition of vanadyl phthalocyanine as the vanadate precursor. This effect is believed to be linked to the accessibility of the active sites, and was studied in comparison with a reference mesoporous support.     

Influences of Mesoporosity Generation in ZSM-5 and Zeolite Beta on Catalytic Performance During <Emphasis Type=Italic>n</Emphasis>-Hexane Isomerization

Abstract  

Catalytic performance of Pt impregnated parent and desilicated nano-crystalline zeolites, ZSM-5 and Beta for n-hexane isomerization was studied. Difference in channel systems of the zeolites and absence/presence of mesopores therein were found to be reflected in product distributions. ZSM-5 was desilicated by NaOH and zeolite Beta with tetramethylammonium hydroxide (TMAOH.) Desilication was found to afford comparable catalytic performance to that of the parent counterpart at reaction temperature lower by 25 °C. Observed product distributions could be substantiated with characterizations such as ammonia TPD, surface area determination and SEM. Desilicated zeolite Beta was seen to be less prone to coking as deduced from the TGA study. Location of Pt with reference to proton sites within the channels and that inside the pores viz a viz external surface also have been discussed briefly.     

Characterization of biogenic hydroxyapatite derived from animal bones for biomedical applications

In this work, the viability of producing biogenic hydroxyapatite from bio-waste animal bones, namely bovine (cow), caprine (goat) and galline (chicken), through a heat treatment process has been investigated. The animal bones were locally sourced, cleaned to remove collagen and subsequently heat treated in air atmosphere at different temperatures ranging from 600?°C to 1000?°C. From the range of sintering temperatures investigated, it was found that hydroxyapatite derived from bovine bone showed good thermal stability while those produced from caprine and galline bones exhibited phase instability with traces of tri-calcium phosphate (TCP) being detected after heat treatment beyond 700?°C. The porous nature of the bone samples can be observed from the microstructures obtained and supported by low relative density. Heating the bovine and caprine bones at selected temperatures yielded porous HA body, having hardness values that are comparable with human cortical bone. However, the sintered galline bone sample showed higher porosity levels and low hardness when compared to the other two bone types.     

Annealing effects on the optical and morphological properties of ZnO nanorods on AZO substrate by using aqueous solution method at low temperature

Vertically aligned ZnO nanorods (NRs) on aluminum-doped zinc oxide (AZO) substrates were fabricated by a single-step aqueous solution method at low temperature. In order to optimize optical quality, the effects of annealing on optical and structural properties were investigated by scanning electron microscopy, X-ray diffraction, photoluminescence (PL), and Raman spectroscopy. We found that the annealing temperature strongly affects both the near-band-edge (NBE) and visible (defect-related) emissions. The best characteristics have been obtained by employing annealing at 400°C in air for 2 h, bringing about a sharp and intense NBE emission. The defect-related recombinations were also suppressed effectively. However, the enhancement decreases with higher annealing temperature and prolonged annealing. PL study indicates that the NBE emission is dominated by radiative recombination associated with hydrogen donors. Thus, the enhancement of NBE is due to the activation of radiative recombinations associated with hydrogen donors. On the other hand, the reduction of visible emission is mainly attributed to the annihilation of OH groups. Our results provide insight to comprehend annealing effects and an effective way to improve optical properties of low-temperature-grown ZnO NRs for future facile device applications.     

Regression analysis of surface roughness and micro-structural study in rotary ultrasonic drilling of BK7

Ceramic materials have tremendous demand in manufacturing sectors. However, poor machinability impedes their widespread applications on an industrial scale. BK-7 falls in the same category and is normally processed by ultrasonic machining. But nowadays rotary ultrasonic machining is overtaking the ultrasonic machining for processing difficult to cut materials because of its superlative material removal mechanism. Current study aims to improve the surface quality of BK7 by studying the effect of input factors on surface roughness during rotary ultrasonic machining. Response surface methodology has been used to observe the effect of input variables ― spindle speed, feed rate and ultrasonic power ― on surface roughness (SR). Thereafter, central composite design was employed to estimate the regression coefficients of quadratic model for surface roughness. Fitness of developed quadratic model was checked by ANOVA test, which also revealed that all the model terms of input factors were significant except feed and speed interaction. Feed has the maximum impact over surface roughness descended by moderate impact of power and spindle speed. The study was further reinforced on observing the surface integrity of processed surfaces using scanning electron microscopic images. Mixed flow of material was observed to occur at lower feed rate and higher levels of rpm and ultrasonic power.     

Influence of Undercooling and Nd4Ba2Cu2O10 Content on the Growth Rate of Large-Grain Bulk Nd-Ba-Cu-O Superconductor

The dependence of growth rate on isothermal undercooling and composition has been investigated for Nd-Ba-Cu-O single grains containing various amounts of nonsuperconducting Nd₄Ba₂Cu₂O₁₀ (Nd-422) phase inclusions and fabricated under a 1% O₂ in N₂ atmosphere using a top seeded melt growth technique. The growth rate along the crystallographic c -direction is observed to exceed that along the a / b direction at all undercooling temperatures and exhibits a maximum for a Nd-422 content of ∼10 mol%. The samples have been examined by optical microscopy and the results interpreted within an established planar solidification model.     

Rapid screening of doping agents in human urine by vacuum MALDI-linear ion trap mass spectrometry

Detection of doping agents in urine frequently requires extensive separation prior to chemical analyses. Gas or liquid chromatography coupled to mass spectrometry has produced accurate and sensitive assays, but chromatographic separations require time and, sometimes, chemical derivatization. To avoid such tedious and lengthy procedures, vacuum matrix-assisted laser desorption ionization (vMALDI) coupled with the linear ion trap mass spectrometry (LIT/MS) technique is tested for its applicability as a rapid screening technique. Commonly used doping agents like nandrolone, boldenone, trenbolone, testosterone, and betamethasone were chosen as study compounds. Different MALDI matrixes like alpha-cyano-4-hydroxycinnamic acid (CHCA), dihyroxy benzoic acid (DHB) with and without cetyl trimethyl ammonium bromide (CTAB), a surfactant, and meso-tetrakis(pentafluorophenyl) porphyrin (F20TPP) were tested. Among them, F20TPP (MW 974.57 Da) was selected as the preferred matrix owing to the lack of interfering matrix peaks at the lower mass range (m/z 100-700). Urine samples spiked with study compounds were processed by solid-phase extraction (SPE) and consistently detected through a linear range of 0.1-100 ng/mL. The limit of detection and lower limit of quantification for all five analytes have been determined to be 0.03 and 0.1 ng/mL, respectively, in urine samples. Testosterone-d3 was used as an internal standard, and the quantitative measurements were achieved by the selective reaction monitoring (SRM) mode. The method was validated and showed consistency in the results. Hence, vMALDI-LIT/MS can be used as a rapid screening method to complement the traditional GC/MS and LC/MS techniques for simultaneous identification, confirmation, and quantification of doping agents in urine.     

Photoluminescence properties and energy transfer in γ-irradiated Dy3+, Eu3+-codoped fluoroaluminoborate glasses

The photoluminescence (PL) properties of singly doped (Dy³⁺) and codoped (Dy³⁺, Eu³⁺) fluoroaluminoborate glasses, with an emphasis on the white light generation, are studied. The γ-irradiation led to the formation of defects in Dy³⁺-doped glasses and photoreduction of Eu³⁺ to Eu²⁺ in codoped (Dy³⁺, Eu³⁺) glasses. The electron paramagnetic resonance spectra confirm the presence of divalent europium ions and defects in Dy³⁺, Dy³⁺–Eu³⁺-doped glasses. The FTIR spectra mainly establish the compaction of glass network due to γ-irradiation. From the PL spectra, the intensity ratio of Dy³⁺ emission bands yellow to blue (⁴F_9/2–⁶H_13/2/⁴F_9/2–⁶H_15/2) defines the site symmetry, covalency, and feasibility of extracting white light. The existence of an energy transfer (ET) from Dy³⁺ to Eu³⁺ ions are established due to the decrease in intensity of Dy³⁺ peaks with an increase of Eu₂O₃ content. Moreover, the non-exponential nature of decay curves was well fitted with the generalization of Yokota–Tanimoto model for electric dipole-quadrupole (S = 8) interaction that is responsible for ET process from sensitizer (Dy³⁺) to activator (Eu³⁺).     

Cobalt catalyzed hydroformylation of higher olefins in the presence of chemically modified cyclodextrins

The cobalt catalyzed hydroformylation of higher olefins in the presence of chemically modified cyclodextrins was investigated in an aqueous biphasic system. The effect of various parameters, such as the nature of the cyclodextrin and olefin, the temperature, the CO/H₂ pressure, the concentration of the cyclodextrin and TPPTS was studied. The results demonstrate that the partially methylated β-cyclodextrin gives good conversion (>92%) and selectivity (>92%) for the hydroformylation of higher olefins without impeding the recovery of the catalytic system.     

Crystallization, microstructure development and dielectric behaviour of glass ceramics in the system [SrO · TiO2]-[2SiO2 · B2O3]-La2O3

Various glasses in the system (65 – x)[SrO · TiO₂]-(35)[2SiO₂ · B₂2O₃]-(x)La₂O₃, where x = 1,5,10 (wt%) were prepared by melting in alumina crucible (1375–1575 K). Heat treatment schedules were selected from DTA plots of respective glasses. X-ray diffraction studies of glass ceramic samples containing different concentrations of La₂O₃ revealed the formation of Sr₂B₂O₅, Sr₃Ti₂O₇ and TiO₂ (rutile) phases. The addition of La₂O₃ results in the development of well formed, elongated crystallites of different phases. Results of the dielectric behaviour demonstrate higher values of dielectric constant for some of the glass ceramic samples. This can be ascribed to the relaxation polarization at the crystal-glass interface due to conductivity differences between crystalline and glassy phases.