Ethoxylation of p-chloronitrobenzene using phase-transfer catalysts by ultrasound irradiation: a kinetic study

Ethoxy-4-nitrobenzene was synthesized by the reaction of 4-chloronitrobenzene with potassium ethoxide in a homogeneous system using benzyltriethylammonium chloride (QCl) as a phase-transfer catalyst at 50 degrees C under ultrasound irradiation conditions. The use of phase-transfer catalysts and ultrasound has been compared and demonstrated in this nucleophilic substitution reactions. The kinetics of the reaction depends on the effect of amount of catalyst, quaternary ammonium salts, agitation speed, amount of potassium hydroxide, amount of ethanol, temperature and the frequency of the ultrasound waves on the conversion of the reaction.     

Synthesis,structural, DFT investigations and antibacterial activity assessment of pyrazoline-thiocyanatoethanone derivatives as thymidylate kinase inhibitors

Two novel compounds 1-(5-[4-fluorophenyl]-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)-2-thiocyanatoethanone (FSCN) and 1-(5-[4-chlorophenyl]-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)-2-thiocyanatoethanone (ClSCN) were synthesized and characterized by SC-XRD, 1H NMR, 13C NMR, FTIR, and UV methods. The X-ray diffraction studies were utilized to prove the 3D crystal structures of FSCN and ClSCN. In both the compounds, the packing is mostly driven by C H⋯N, C H⋯O, and C H⋯π (benzene ring as an acceptor) interactions. In ClSCN, additionally, the π⋯π interaction is observed between the pyrazole ring of one molecule and the benzene ring of the other molecule. The experimental values were compared with the results of DFT/B3LYP/6-311G++(d,p) theoretical computations. The pharmacological screening for FSCN and ClSCN was performed using molinspiration and PreADMET web server. To analyze antibacterial inhibition of the synthesized ligands and Ciprofloxacin (control drug) were interacted with antibacterial protein Thymidylate Kinase (TMK) (PDB ID: 4QGG) with the help of AutoDock Vina tool. The ADMET and docking results of FSCN and ClSCN pointed out the better drug likeness nature and good inhibition behavior with TMK protein. The antibacterial in vitro studies suggested that FSCN compound inhibited well with antibacterial strains than that of ClSCN. The current investigation suggests that with further improvements, our compounds could be preferred as substitute medicine for bacterial diseases.     

Elastic anomalies of La0.67Sr0.33−xBaxMnO3 in the vicinity of TC

With a view to understand the elastic behaviour of a material system, La_0.67Sr_0.33−xBa_xMnO₃ (where x=0, 0.1, 0.2, and 0.33) especially in the vicinity of their magnetic transition temperature T_C, a systematic investigation of ultrasonic velocity over a temperature range 300-400 K has been carried out. The materials prepared by citrate gel route, were characterized structurally by XRD and on analyzing the XRD patterns, it has been concluded that all the samples are having rhombohedral structure with space group of R3?c. The magnetic (T_C) transition temperatures determined by AC susceptibility measurements are found to decrease continuously with increasing barium concentration. Finally, the ultrasonic longitudinal velocities of all the samples are found to exhibit considerable softening in the vicinity of their magnetic transition temperatures, T_C and the observed behaviour is explained using mean field theory and Jahn-Teller theorem.     

Modeling of nonlinear boundary value problems in enzyme-catalyzed reaction diffusion processes

A mathematical model of steady state mono-layer potentiometric biosensor is developed. The model is based on non stationary diffusion equations containing a non linear term related to Michaelis-Menten kinetics of the enzymatic reaction. This paper presents a complex numerical method (He’s variational iteration method) to solve the non-linear differential equations that describe the diffusion coupled with a Michaelis-Menten kinetics law. Approximate analytical expressions for substrate concentration and corresponding current response have been derived for all values of saturation parameter α and reaction diffusion parameter K using variational iteration method. These results are compared with available limiting case results and are found to be in good agreement. The obtained results are valid for the whole solution domain.     

Spectrofluorometric studies on the binding interaction of bioactive imidazole with bovine serum albumin: a DFT based ESIPT process

Bioactive imidazole derivatives were synthesized and characterized by NMR spectra, mass and CHN analysis. An excited state intramolecular proton transfer (ESIPT) process in hydroxy imidazole has been studied using emission spectroscopy. In hydrocarbon solvent, the tautomer emission predominates over the normal emission and in alcoholic solvent like ethanol; a dramatic enhancement of normal emission is observed which was due to increased solvation. DFT calculation on energy, charge distribution of the rotamers in the ground and excited states of the imidazole derivative were performed and discussed. PES calculation indicates that the energy barrier for the interconversion of two rotamers is too high in the excited state than in the ground state. The interaction between bioactive imidazole derivative and bovine serum albumin (BSA) was investigated.     

Solvatochromic analysis of some N-nitroso oxime derivatives--Taft and Catalan approach

Some novel N-nitroso oxime derivatives were synthesized and characterized by (1)H, (13)C, (1)H-(1)H and (1)H-(13)C COSY NMR spectra. The spectra of all these N-nitroso oximes reveal the presence of two isomers labelled as E (-NOH group is anti to N-N=O moiety) and Z (-NOH group is syn to N-N=O moiety) in solution and the coupling constants ruled out the possibility of normal chair conformation. From the theoretical studies and coupling constant values it was found that both E (major) and Z (minor) isomers of N-nitroso oximes exist as an equilibrium mixture of CA and boat conformation (B(1)) and this was also supported by DFT calculation. The photophysical properties of these oxime derivatives were studied and the observed lower fluorescence quantum yield may be due to an increase in the non-radiative deactivation rate constant. This is attributed due to the presence of non-chair conformation of N-nitroso oxime derivatives.     

A microfluidic platform for high-sensitivity, real-time drug screening on C. elegans and parasitic nematodes

This paper describes a new microfluidic platform for screening drugs and their dose response on the locomotion behavior of free living nematodes and parasitic nematodes. The system offers a higher sensitivity drug screening chip which employs a combination of existing and newly developed methods. Real-time observation of the entire drug application process (i.e. the innate pre-exposure locomotion, the transient response during drug exposure and the time-resolved, post-exposure behavior) at a single worm resolution is made possible. The chip enables the monitoring of four nematode parameters (number of worms responsive, number of worms leaving the drug well, average worm velocity and time until unresponsiveness). Each parameter generates an inherently different dose response; allowing for a higher resolution when screening for resistance. We expect this worm chip could be used as a robust cross species, cross drug platform. Existing nematode motility and migration assays do not offer this level of sophistication. The device comprises two principal components: behavioral microchannels to study nematode motility and a drug well for administering the dose and observing drug effects as a function of exposure time. The drug screening experiment can be described by three main steps: (i) 'pre-exposure study'- worms are inserted into the behavioral channels and their locomotion is characterized, (ii) 'dose exposure'- worms are guided from the behavioral microchannels into the drug well and held for a predefined time, during which time their transient response to the dose is characterized and (iii) 'post-exposure study'- worms are guided back into the behavioral microchannels where their locomotion (i.e. their time-resolved response to the dose) is characterized and compared to pre-exposure motility. The direction of nematodes' movement is reliably controlled by the application of an electric field within a defined range. Control experiments (e.g. in the absence of any drug) confirm that the applied electric fields do not affect the worms' motility or viability. We demonstrate the workability of the microfluidic platform on free living Caenorhabditis elegans (wild-type N2 and levamisole resistant ZZ15 lev-8) and parasitic Oesophagotomum dentatum (levamisole-sensitive, SENS and levamisole-resistant, LEVR) using levamisole (a well-studied anthelmintic) as the test drug. The proposed scheme of drug screening on a microfluidic device is expected to significantly improve the resolution, sensitivity and data throughput of in vivo testing, while offering new details on the transient and time-resolved exposure effects of new and existing anthelmintics.     

High pressure behavior and structural properties of transition metal carbides

A pressure induced structural phase transition from NaCl-type (B₁) to CsCl-type (B₂) structure has been predicted in transition metal carbides, namely TiC, ZrC, NbC, HfC, and TaC by using an interionic potential theory with modified ionic charge (Z_m ), which includes Coulomb screening effect due to d-electron. The phase transition pressure (P_T ) relies on large volume discontinuity in pressure–volume relationship, and identifies the structural phase transition from B₁ phase to B₂ phase. The variation of second-order elastic constants with pressure follows a systematic trend identical to that observed in other compounds of NaCl-type structure. The Born criterion for stability is found to be valid in transition metal carbides.     

Structural,electrical, magnetic,elastic, and internal friction studies of Nd1−xCaxMnO3 (x=0.2, 0.33, 0.4, and 0.5) manganites

A series of Nd_1?xCa_xMnO₃ (x=0.2, 0.33, 0.4, and 0.5) manganites was prepared by sol–gel route by sintering at 1300 °C, mainly to understand the correlation between electron, spin, and phonon couplings. The internal friction and longitudinal modulus along with electrical and magnetic properties have been measured. All the samples are found to exhibit anomalies at T_C, T_N, and T_CO transition temperatures. The anomalies in longitudinal modulus and the internal friction peak at T_CO are attributed to Jahn–Teller effect. A strong correlation between the temperature dependent elastic, anelastic, resistivity, and ac susceptibility properties has been observed and an effort has been made to explain the observed anomalous behavior by a qualitative model.