Vapor Phase Beckmann Rearrangement of Cyclohexanone Oxime over Different Ferrierite Zeolite Catalysts

Ferrierite zeolite catalysts prepared using different procedures have been tested for their activity for vapor phase Beckmann rearrangement of cyclohexanone oxime to -caprolactam. We report here the results of a study seeking the influence of temperature, nitrogen feed rate, oxime concentration and solvents on the catalyst performance. At low concentration of oxime (2.5 wt%), using acetonitrile as solvent the maximum in the conversion of oxime and selectivity to -caprolactam has been obtained. The presence of weak, medium and strong acid sites as indicated by temperature-programmed desorption of NH₃ corroborates well with the catalytic activities of various ferrierites shown here. Solvent polarity is found to significantly affect the conversion of cyclohexanone oxime.     

Effect of Nanoclay/Nanosilica on the Mechanical Properties,Abrasion and Swelling Resistance of EPDM/SBR Composites

Silicon - In this research work, ethylene-propylene-diene monomer (EPDM)/styrene butadiene rubber (SBR) hybrid composites reinforced with nanoclay (NC) and nanosilica (NS) were prepared and...     

Studies on the copolymerization of methyl methacrylate with N‐(o/m/p‐chlorophenyl) itaconimides

The article describes the synthesis and characterization of N‐aryl itaconimide monomers such as: N‐(p‐chlorophenyl) itaconimide (PI)/N‐(m‐chlorophenyl) itaconimide (MI)/N‐(o‐chlorophenyl) itaconimide (OI) and its copolymerization behavior with MMA. The homopolymers and copolymers of N‐aryl itaconimides and methyl methacrylate (MMA, M₂) were synthesized by varying the mol fraction of N‐aryl itaconimides in the initial feed from 0.1 to 0.5 using azobisisobutyronitrile (AIBN) as an initiator and tetrahydrofuran (THF) as the solvent. Copolymer composition was determined using ¹H‐NMR spectroscopy [by taking the ratio of intensities of signals due to ? OCH₃ of MMA (δ = 3.59 ppm) and the aromatic proton (δ = 7.2–7.5 ppm) of N‐aryl itaconimides] and percent nitrogen content. The reactivity ratios were found to be r₁ = 1.33 and r₂ = 0.36 (PI‐MMA) r₁ = 1.15 and r₂ = 0.32 (MI‐MMA) and r₁ = 0.81 and r₂ = 0.35 (OI‐MMA). Molecular weight as determined using high‐performance liquid chromatography decreased with increasing mol fraction of itaconimides in copolymers. All the polymers had a polydisperstivity index in the range of 1.5–2.6.Thermal characterization was done using differential scanning calorimetry and dynamic thermogravimetry in nitrogen atmosphere. Incorporation of these N‐aryl itaconimides in PMMA backbone resulted in an improvement in glass transition temperature (T_g) and thermal stability. Percent char increased with the increase of PI/MI/OI content in the copolymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2078–2086, 2001     

Citrulline malate supplementation does not improve German Volume Training performance or reduce muscle soreness in moderately trained males and females

Background

Use of supplements to aid performance is common practice amongst recreationally active individuals, including those without a sufficient evidence base. This investigation sought to assess whether acute supplementation with 8 g of citrulline malate (CM) (1.11: 1 ratio) would improve anaerobic performance.

Methods

A randomised double blind placebo control trial was employed, using a counterbalanced design. We recruited recreationally active men and women to take part in an isokinetic chair protocol, based on German Volume Training (GVT) whereby participants attempted to perform 10 sets of 10 repetitions against a force representing 70% of their peak concentric force.

Results

The number of repetitions achieved over the course of the GVT was 94.0?±?7.9 and 90.9?±?13.9 for placebo and CM respectively. There was no significant difference between the placebo and CM treatment for number of repetitions (P?=?0.33), isometric (P?=?0.60), concentric (P?=?0.38), or eccentric (P?=?0.65) peak force following the GVT. Total muscle soreness was significantly higher in the CM compared to the placebo treatment following the GVT protocol over 72 h (P?=?0.01); although this was not accompanied by a greater workload/number of repetitions in the CM group.

Conclusions

We conclude that an acute dose of CM does not significantly affect anaerobic performance using an isokinetic chair in recreational active participants. Practical implications include precaution in recommending CM supplementation. Coaches and athletes should be aware of the disparity between the chemical analyses of the products reviewed in the present investigation versus the manufacturers’ claims.

     

Isolation of High Oleate Recombinants in Peanut by Near Infra‐Red Spectroscopy and Confirmation With Allele Specific Polymerase Chain Reaction Marker

Near infrared (NIR) spectrophotometer offers rapid, noninvasive, nondestructive, and high‐throughput phenotyping of seed samples for use in agriculture and industry. In this study, a reflectance‐based NIR spectrophotometer was calibrated and used for the isolation of desirable higher‐oleic‐acid peanut recombinants from single‐seed‐derived segregating populations at F₇ and F₈ generations. A calibration model was developed through partial least‐square regression using wet chemistry data from 158 peanut genotypes. Desirable prediction for oil, palmitic acid, oleic acid, and linoleic acid in intact seed was obtained based on this calibration. It detected significant high correlations (r) and coefficient of determination (R²) between the actual gas chromatography values and NIR predicted values of fatty acid profile in another 123 peanut genotypes that were generated from crosses involving a high‐oleate mutant and Spanish bunch varieties with early maturity. From this recombinant single‐seed‐derived progenies, 15 higher‐oleate recombinants were isolated and later genotyped through an in‐house developed polymerase chain reaction‐based allele specific marker. The present study has generated high‐oleate peanut recombinants with early maturity in Spanish bunch background. The breeding materials generated here will be evaluated for yield attributing traits at different locations in future.     

Structural,magnetic, and textural properties of iron oxide-reduced graphene oxide hybrids and their use for the electrochemical detection of chromium

Superparamagnetic Fe₃O₄ nanoparticles were anchored on reduced graphene oxide (RGO) nanosheets by co-precipitation of iron salts in the presence of different amounts of graphene oxide (GO). A pH dependent zeta potential and good aqueous dispersions were observed for the three hybrids of Fe₃O₄ and RGO. The structure, morphology and microstructure of the hybrids were examined by X-ray diffraction, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, Raman and X-ray photoelectron spectroscopy. TEM images reveal lattice fringes (d₃₁₁ = 0.26 nm) of Fe₃O₄ nanoparticles with clear stacked layers of RGO nanosheets. The textural properties including the pore size distribution and loading of Fe₃O₄ nanoparticles to form Fe₃O₄–RGO hybrids have been controlled by changing the concentration of GO. An observed maximum (～10 nm) in pore size distribution for the sample with 0.25 mg ml^?1 of GO is different from that prepared using 1.0 mg ml^?1 GO. The superparamagnetic behavior is also lost in the latter and it exhibits a ferrimagnetic nature. The electrochemical behavior of the hybrids towards chromium ion was assessed and a novel electrode system using cyclic voltammetry for the preparation of an electrochemical sensor platform is proposed. The textural properties seem to influence the electrochemical and magnetic behavior of the hybrids.     

Transport phenomena in the electrodeionization of cesium from AMP-PAN

Electrodeionization (EDI) of cesium from cesium-sorbed ammonium molybdophosphate-polyacrylonitrile (AMP-PAN) was investigated by passing eluant through the packed bed of ion-exchange resin in an electrodialysis cell. The deionized cesium from the packed bed was recovered in catholyte by migration and in the eluant by convection. Recovery percentage of Cs by migration increased while the recovery by convection decreased with increase in current density from 20 to 40 mA/cm². Increased eluant concentration resulted in low migration percentage of cesium. Increased catholyte concentration had a negligible effect on total recovery. Apparent diffusion coefficients evaluated using the Nernst–Plank relation increased with increase in current density and catholyte concentration while a decreasing trend was observed with increase in eluant concentration.     

Modeling Critical Air Exchange Rates (CAERs) for aerosol number concentrations from nano-particle sources using an “effective coagulation coefficient” approach

An important issue in the context of air pollution by indoor combustion sources pertains to the joint effect of source strength, coagulation, and ventilation rate on the ultrafine particle exposure metrics. It was recently predicted by detailed numerical analysis of the Smoluchowski coagulation equation with continuous source and sink terms that the ultrafine particle number, mass, and surface area concentrations do not monotonically decrease with increasing air exchange rate, but display peak concentrations at certain Critical Air Exchange Rates (CAERs). As these results are of considerable significance for exposure assessment as well as for implementing particle control technologies, it is necessary to assess the CAER for different aerosol characteristics. Given the fact that the numerical method of solving coagulation equation with realistic Fuchs kernel is computationally intensive, simpler semi-analytical approaches are desired for providing reasonable estimates of CAER and clearer insight into the counter-intuitive, peaking behavior. In this article, we present such an approach by replacing the Fuchs kernel by a spectrum-averaged effective coagulation coefficient, within the framework of the steady-state model. The effective coagulation coefficient is size independent but depends implicitly on the aerosol concentration thus capturing the combined effect of coagulation and removal processes. The number concentrations obtained from this method have been compared and validated against the numerical solutions. The model predicts more pronounced effects on the peaking behavior as well as larger CAER values for fractal particles as compared to compact particles. The results are further discussed.

Copyright © 2017 American Association for Aerosol Research     

Durable adhesives based on electrospun poly(vinylidene fluoride) fibers

Herein, the fabrication of poly(vinylidene fluoride) (PVDF) fibrous membrane using electrospinning is reported and its use for dry‐adhesive applications is demonstrated. The shear and normal adhesion performance of the samples was investigated using an Instron tensile tester and an atomic force microscope (AFM) respectively. For shear adhesion measurements, the electrospun membrane was finger pressed on to a glass slide and pulled in shear mode using a tensile tester. The thickness of the electrospun membrane was varied and the effect of thickness on shear adhesion was investigated. The shear adhesion strength increased when the thickness of the samples was reduced. Shear adhesion strength of a 200 µm thick sample was determined to be approximately 0.165 N/cm. For normal adhesion measurements, a flat tipless cantilever was used to indent the sample and then retract back to measure the pull‐off force. High shear adhesion strength and normal pull‐off force recorded are attributed to the fine size of the fibers that conform to the asperities present on the surfaces of the glass slide and the AFM cantilever. The durability of the adhesive was also verified by repeating the AFM adhesion measurements over 1000 consecutive attachment–detachment cycles. The pull‐off force was seen to be constant over 1000 attachment–detachment cycles. Our results indicate that these electrospun fibrous membranes can potentially be used as reusable dry‐adhesives. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44393.     

Fabrication and morphological control of three-dimensional cage type mesoporous titanosilicate with extremely high Ti content

TiSBA-1 materials with extremely high Ti content, up to silicon to titanium ratio (n_Si/n_Ti) of 2.4, have been successfully prepared through direct synthesis method by controlling the molar ratio of hydrochloric acid to silicon (n_HCl/n_Si). It has been found that the amount of Ti content and the structure of the TiSBA-1 can easily be controlled by the simple adjustment of n_HCl/n_Si ratio. X-ray diffraction pattern (XRD) of the obtained materials revealed that the materials are highly ordered and possess cubic three-dimensional cage type structure with open windows. N₂ adsorption–desorption measurement confirmed the narrow pore size distribution, high specific surface area (1317–1491 m² g⁻¹), and large specific pore volume (0.68–0.75 cm³ g⁻¹) for all the samples. UV–vis DR spectra of the prepared materials confirmed that Ti atoms are exclusively incorporated within silica framework and occupy the tetrahedral position while the presence of isolated bulk titania could be negligible. Morphologies of the TiSBA-1 materials have been also controlled by simply adjusting the n_Si/n_Ti ratio. With the appropriate Ti content, TiSBA-1 materials can be obtained as regular fine spheres. Moreover, the detailed mechanism on the morphological and phase transition control, and the incorporation of high amount of Ti in the framework of TiSBA-1 materials has been also discussed in detail.