Synthetic Studies Towards Taxol Analogs: Chemoselective Cleavage of C-5 Cinnamoyl Group in Taxane Group of Diterpenoids with Hydroxylamine

Taxane group of diterpenoids 2 and 3 which possess cinnamoyl moiety at C-5 position underwent selective cleavage to C-5 hydroxy compounds 4 and 5 on treatment with hydroxylamine. The resulting compounds were characterised based on their spectral data.     

Esterification of butyric acid with n-butanol: Kinetic study using experimental data and modeling

Present study involves the investigation of the esterification kinetics between butyric acid and n-butanol. This reaction was conducted in a batch reactor, utilizing homogeneous methanesulfonic acid (MSA) catalyst. Response surface methodology (RSM) was conducted prior to the kinetic study using “Design Expert; version-11.0” for finding the causal factors influencing the conversion of butyric acid. Most important factors identified with their limits against conversions (during optimization of the process using RSM) were taken up to critically analyze the effect of them on butyric acid conversion. Concentration and activity-based model of the process were proposed assuming second order reversible reaction scheme using homogeneous MSA catalyst. During the study of non-ideal behavior of the system, UNIFAC model was adapted for assessing the activity coefficients of species present in equilibrated liquid phase. Experimental data were used to evaluate kinetic and thermodynamic parameters such as rate constants, activation energy, enthalpy, and entropy of the system. The endothermic nature of esterification was confirmed by positive value of enthalpy obtained. The effect of various levels of causal variables like temperature (60–90°C), catalyst concentration (0.5–1.5 wt.%), and molar ratio of n-butanol to butyric acid (1–3) on conversion kinetics of butyric acid was investigated during transient and equilibrium phase of the reaction. It has been observed that molar ratio of butanol to butyric acid has the highest influence on the conversion. The rate equation derived offered a kinetic and thermodynamic framework to the generated data. It also exhibits a notable degree of conformity of predicted data to the experimental ones and effectively characterizes the system across different reaction temperatures, reactant molar ratio, and catalyst concentration.     

An efficient RuCl3·H2O/I2 catalytic system: A facile access to 3-aroylimidazo[1,2-a]pyridines from 2-aminopyridines and chalcones

A simple and efficient protocol has been demonstrated for the preparation of densely functionalized 3-aroylimidazo[1,2-a]pyridines from 2-aminopyridines and chalcones using RuCl₃·H₂O/I₂ catalytic system. The advantages, such as low catalyst loading, broad substrate scope with respect to substitutions on aminopyridines as well as chalcones, stability of heterocycles such as thiophene under the reaction conditions, operationally simple procedure and higher yields makes this approach remarkable for synthetic applications.     

Viscosity of alumina nanoparticles dispersed in car engine coolant

The present paper, describes our experimental results on the viscosity of the nanofluid prepared by dispersing alumina nanoparticles (<50 nm) in commercial car coolant. The nanofluid prepared with calculated amount of oleic acid (surfactant) was tested to be stable for more than 80 days. The viscosity of the nanofluids is measured both as a function of alumina volume fraction and temperature between 10 and 50 °C. While the pure base fluid display Newtonian behavior over the measured temperature, it transforms to a non-Newtonian fluid with addition of a small amount of alumina nanoparticles. Our results show that viscosity of the nanofluid increases with increasing nanoparticle concentration and decreases with increase in temperature. Most of the frequently used classical models severely under predict the measured viscosity. Volume fraction dependence of the nanofluid viscosity, however, is predicted fairly well on the basis of a recently reported theoretical model for nanofluids that takes into account the effect of Brownian motion of nanoparticles in the nanofluid. The temperature dependence of the viscosity of engine coolant based alumina nanofluids obeys the empirical correlation of the type: log (μ_nf) = A exp(BT), proposed earlier by Namburu et al.     

β-Strand mimetics: formation of bend-strands in oligomers of enantiomeric β-amino acids

Oligomers comprising of enantiomeric cis-oxo-β-norbornene amino acid [2R,3S] and [2S,3R] residues at alternate positions were synthesized and characterized by extensive NMR and MD studies, which showed robust bend-strand secondary structures.     

Expanding the conformational pool of cis-beta-sugar amino acid: accommodation of beta-hGly motif in robust 14-helix

Tendencies of forming stable helices of heterooligomers composed of alternating rigid cis-beta-sugar amino acid and flexible beta-hGly motifs have been investigated, using a combination of molecular mechanics, CD, FT-IR, and NMR techniques. The results show that the solution structures of these oligomers exist as robust right-handed 14-helices. Here, we examine the role of conformationally rigid cis-beta-sugar amino acid in preorganizing the conformation of beta-hGly to form the 14-helix. Our findings also show that a right-handed 14-helix can be formed with as few as four properly sequenced heterogeneous residues. These results represent the expansion of the conformational pool of sugar amino acid in the design of well-folded 14-helices, which can be used to develop beta-peptides endowed with biological activity.     

Oligomers of cis-beta-norbornene amino acid: formation of beta-strand mimetics

The oligomers of constrained cis-exo-beta-norbornene amino acid were synthesised and characterised by extensive NMR, CD, IR and MD studies. The results showed the formation of both right and left handed consecutive 6-membered hydrogen-bonded strands for [2S,3R] and [2R,3S] enantiomers, respectively.     

The e‐tongue‐based classification and authentication of mineral water samples using cross‐correlation‐based PCA and Sammon's nonlinear mapping

The present paper elaborates on the design of classifiers based on cross‐correlation‐based principal component analysis (PCA) and Sammon's nonlinear mapping (NLM) using current signals obtained from electronic tongue (e‐tongue) with commercial mineral water samples available in the Indian market. The pulse‐voltammetric method is used to capture the electroanalytical/electrochemical characteristics of the sampled mineral waters by considering a real model for the liquid–electrode interface in a given e‐tongue apparatus. Then the cross‐correlation coefficients between the output and input signals are determined. Both PCA and Sammon's NLM create a subspace from high‐dimensional mineral water data by considering the principal eigenvectors and minimising the stress function, respectively. The proposed cross‐correlation‐based PCA and Sammon's classifiers establish the highest separation distance among the investigated water brands and carries out the authentication of more than one unknown sample of the same brand with a certain degree of variability with respect to their sources. Copyright © 2013 John Wiley & Sons, Ltd.     

Enantioselective synthesis of (S)-3,7-dimethyl-2-oxo-6-octene-1,3-diol: a Colorado potato beetle pheromone

The recent identification of a male-produced aggregation pheromone [(S)-3,7-dimethyl-2-oxo-6-octene-1,3-diol, (S)-CPB] offers a new tool for Colorado potato beetle (CPB) management. We developed a novel synthetic approach to produce CPB pheromone in seven steps and 46.54% overall yield. Grignard reaction, oxidation, and stereoselective methylation using organometallic reagent are the key steps in the commercially viable total synthesis, generating CPB pheromone in 98.6% enantiomeric purity and gram quantity.     

Role of interfacial layer and clustering on the effective thermal conductivity of CuO-gear oil nanofluids

Copper oxide nanoparticles (∼40 nm) are dispersed in gear oil (IBP Haulic-68) at different volume fractions (0.005-0.025) with oleic acid added as a surfactant to stabilize the system. Prepared nanofluids are characterized by Fourier Transform Infrared spectroscopy (FTIR) and Dynamic light scattering (DLS) measurements. DLS data confirmed the presence of agglomerated nanoparticles in the prepared nanofluids. Thermal conductivity measurements are performed both as a function of CuO volume fraction and temperature between 5 and 80 °C. An enhancement in thermal conductivity at 30 °C of 10.4% with 0.025 volume fraction of CuO nanoparticle loading is observed. Measured volume fraction dependence of the thermal conductivity enhancement at room temperature is predicted fairly well considering contributions from both nanolayer at the solid-liquid interface and particle agglomeration in the suspension, as visualized by Feng et al.