Novelties of liquid–liquid–liquid phase transfer catalysis Alkoxylation of p-chloronitrobenzene

Liquid–liquid–liquid phase transfer catalysis (L–L–L PTC) offers orders of magnitude intensification of rates of reaction and better selectivities than the biphasic PTC. The catalyst-rich middle phase is the main reaction phase. The etherification or alkoxylation of p-chloronitrobenzene (PCNB) was conducted by using alkanol and alkali instead of the metal alkoxide. A kinetic model is presented and validated.     

Selectivity engineering in isopropylation of mesitylene with isopropyl alcohol over cesium substituted heteropolyacid supported on K-10 clay

Alkylation of aromatics catalyzed by solid acids constitutes a class of reactions of both academic and industrial importance. Among alkylation reactions, isopropylation of aromatic compounds has attracted considerable attention. Use of propylene as alkylating agent at very high temperatures leads to coke formation which results in deactivation of the catalyst. The use of isopropanol (IPA) as an alkylating agent is attractive when propylene is not readily available. In situ dehydration of IPA leads to prolonged activity since water of reaction suppresses coke formation. Further, IPA dehydration also generates diisopropyl ether which itself is an excellent alkylating agent. Alkylation of mesitylene with propylene or IPA results in the formation of 2-isopropyl-mesitylene (2-IPMT), which is almost extensively used as a precursor in a number of industrial chemicals. This work covers the evaluation of clay-supported heteropolyacids and sulfated zirconia. A variety of solid acid catalysts such as K-10 clay, sulfated zirconia, Filtrol-24, 20% w/w dodecatungstophosphoric acid (H₃PW₁₂O₄₀, DTP) supported on K-10 montmorillonite clay and 20% w/w cesium substituted dodecatungstophosphoric acid (Cs_2.5H_0.5PW₁₂O₄₀, Cs-DTP) supported on K-10 montmorillonite clay were investigated for the liquid phase isopropylation of mesitylene to 2-IPMT using IPA at much milder conditions vis-à-vis other catalysts reported so far. 20% w/w Cs-DTP/K-10 clay was found to be the best catalyst which gives 98% conversion of limiting component, IPA and 98% selectivity towards the desired product, 2-IPMT after 2 h of total reaction time. This catalyst could be reused without any further chemical treatment, eliminating the effluent disposal problems. The reaction was carried out without using any solvent and the process subscribes to the principles of green chemistry. The catalytic activity is in the following order: 20% w/w Cs-DTP/K-10 clay (most active) > 20% w/w DTP/K-10 clay > Filtrol-24 > Sulfated zirconia > K-10 clay (least active). The effect of various operating parameters and catalyst reusability were also systematically investigated. A mathematical model was proposed to probe into the intricate reaction kinetics and mechanism consistent with the experimental results. The reaction is free from any external mass transfer as well as intraparticle diffusion limitations and is intrinsically kinetically controlled. An overall second order kinetic equation was used to fit the experimental data, under the assumption that all the species are weakly adsorbed on the catalytic sites.     

Effect of Growth Temperature on Bamboo-shaped Carbon–Nitrogen (C–N) Nanotubes Synthesized Using Ferrocene Acetonitrile Precursor

This investigation deals with the effect of growth temperature on the microstructure, nitrogen content, and crystallinity of C–N nanotubes. The X-ray photoelectron spectroscopic (XPS) study reveals that the atomic percentage of nitrogen content in nanotubes decreases with an increase in growth temperature. Transmission electron microscopic investigations indicate that the bamboo compartment distance increases with an increase in growth temperature. The diameter of the nanotubes also increases with increasing growth temperature. Raman modes sharpen while the normalized intensity of the defect mode decreases almost linearly with increasing growth temperature. These changes are attributed to the reduction of defect concentration due to an increase in crystal planar domain sizes in graphite sheets with increasing temperature. Both XPS and Raman spectral observations indicate that the C–N nanotubes grown at lower temperatures possess higher degree of disorder and higher N incorporation.     

Aesthetical design of a car profile: a Kano model-based hybrid approach

An amicable aesthetical design of a product is prudent for its wide acceptability and viability. Selection of shape parameters with customer satisfaction is critical in aesthetical design and a challenging task for designers. In the present work, the authors proposed a sequential approach to design a car profile with aesthetical aspects. The methodology is based on Kano model that provides a framework for incorporation of customer satisfaction with the design requirements. Further, Taguchi's robust design approach has been used to find the optimum level of the parameter to achieve initial design estimates and thereafter, response surface method (RSM) is applied to refine the optimum values, precisely. The methodology has been illustrated with a case study.     

A kinetic model for the enzyme-catalyzed self-epoxidation of oleic acid

This paper reports a kinetic model for the selfepoxidation of oleic acid with toluene as solvent and Novozym 435 (a commercially available preparation of immobilized Candida antarctica lipase) as catalyst at 30°C. The effects of various parameters on the conversion and rates of reaction were studied. Both the initial rate and the progress curve data were used to fit an ordered bi-bi model. At low temperatures, the rate of epoxidation was faster than the rate of deactivation of the enzyme by hydrogen peroxide.     

Attenuation of ultrasonic waves in V, Nb and Ta at low temperatures

Variation of ultrasonic attenuation and velocities with temperature have been evaluated in the temperature range 5-50 K due to electron-phonon interaction mechanism in transition metals vanadium, niobium and tantalum for longitudinal and shear waves. For this evaluation, we have also computed the second order elastic constants using Morse potential. Behaviour of acoustical phonons in these bcc metals is different from other normal metals, intermetallics, semimetallics and alloys. Some characteristic features of these materials connected to ultrasonic parameters are discussed.     

Amperometric determination of tyramine in sauce and beer by epoxy resin biocomposite membrane bound tyramine oxidase

A method is described for construction of an amperometric biosensor for specific determination of tyramine, using black gram tyramine oxidase immobilized covalently on an epoxy resin membrane. The biosensor had optimum response within 10 s at pH 8.5 and 35 °C. A linear relationship was observed between tyramine concentrations and current (mA) in the range of 0.24 to 3.47 mg/dL. The biosensor was employed for determination of tyramine in beer and sauce. The detection limit of sensor was 0.24 mg/dL. The mean analytical recovery of added tyramine (0.5 and 1.0 mg/dL) was 97.3 ± 2.3 and 95.9 ± 3.4%. Within and between batch coefficient of variation were 5.1 and 5.34%, respectively. Enzyme electrode showed 35% loss in its initial activity after its regular use over a period of 2 months. The biosensor has the advantage that it does not suffer from leaching of enzyme and measures tyramine specifically.     

Isatin compounds as corrosion inhibitors for N80 steel in 15% HCl

The inhibition effect of two synthesized isatin compounds namely 1-morpholinomethyl-3-(1-N-dithiooxamide)iminoisatin [MMTOI] and 1-diphenylaminomethyl-3-(1-N-dithiooxamide)iminoisatin [PAMTOI] on the corrosion inhibition of N80 steel in 15% HCl solution was studied by polarization, EIS and weight loss measurements. It was found that both the inhibitors were effective and their inhibition efficiency was significantly increased with increasing concentration. Polarization curves revealed that the used inhibitors represent mixed-type inhibitors. Adsorption of these inhibitors led to a reduction in the double layer capacitance and an increase in the charge transfer resistance, and was found also to obey Langmuir isotherm.     

Enhanced antibacterial activity of tetramethylguanidinium-conjugated linear polyethylenimine polymers

In the present study, varying amounts of tetramethylguanidinium moiety have been conjugated to linear polyethylenimine to obtain linear polyethylenimine-tmg (LPTG) polymers. Incorporation of hydrophobic and highly basic moiety in the polymeric backbone resulted in the significant improvement in the antibacterial activity which was confirmed by zone of inhibition and MIC assays. Further, the results of transmission electron microscopy and confocal studies revealed that the projected LPTG polymers possessed higher antibacterial activity than the native polymer. In addition, these modified polyethylenimine (PEI) polymers were capable of reducing auric chloride into stable gold nanoparticles. These polyamine-stabilized gold nanoparticles can be used in various biomedical applications.     

Study of crystal structure,dielectric, magnetic and magnetoelecrtic properties of xCoFe2O4-(1-x)Na0.5Bi0.5TiO3 composites

Multiferroic composites of spinel ferrite and ferroelectric xCoFe₂O₄ – (1-x)Na_0.5Bi_0.5TiO₃ (with x = 0.10,0.30,0.50) were efficiently prepared by standard solid state reaction mechanism. X-ray diffractometer was used to analyze crystal structure of the prepared composites. The observed XRD patterns of the composites comprise peaks of both the phases i.e. ferrite and ferroelectric, with no sign of secondary peaks. Rietveld refinement of XRD data further confirms the coexistence of these two phases with cubic (Fd3m) and rhombohedral (R3c) symmetry corresponding to ferrite and ferroelectric phase respectively. The 3-dimensional overview of crystal structure of pure CoFe₂O₄ and Na_0.5Bi_0.5TiO₃ and of composite 0.50CoFe₂O₄?0.50Na_0.5Bi_0.5TiO₃ is generated by using refined parameters. The dielectric constant (ε´) and dielectric loss (tanδ) values were recorded as a function of frequency ranging from 100?Hz to 7?MHz and at different temperatures. Both ε´ and tanδ follow dispersion pattern at lower frequencies while show frequency independent behavior at higher frequencies. The magnetic evaluation carried by analyzing M-H hysteresis loop reveals the ferrimagnetic characteristics of these composites. The highest value of magnetic moment is 1.12μ_B observed for composite 0.50CoFe₂O₄ – 0.50Na_0.5Bi_0.5TiO_3. Magnetoelectric (ME) voltage coefficient (α) was also demonstrated to observe the interaction between ferrite and ferroelectric phases. The highest value of α (72.72μV/Oe cm) is obtained for low ferrite composition 0.10CoFe₂O₄ – 0.90Na_0.5Bi_0.5TiO₃, which suggests the dependence of magnetoelectric response on the resistivity of the composites.