Catalyst-free one-pot synthesis of 2,4,5-tri- and 1,2,4,5-tetrasubstituted imidazoles

The present work emphasizes catalyst-free 2,4,5-tri- and 1,2,4,5-tetra substituted imidazole synthesis using diversified aldehydes with benzil, ammonium acetate, or amines. Ammonium acetate plays a vital role as a reactant catalyst by dissociating into acetic acid to afford imine and diamine formation to ascertain the 2,4,5-tri- and 1,2,4,5-tetra substituted imidazoles. The key advantages of the current approach are efficient, greener, eco-friendly, and facile, with moderate to excellent yield in shorter reaction time at the temperature of 80°C. Ethanol:water as a solvent makes the reaction process eco-friendly. Overall, the described approach offers a promising route for the efficient and sustainable synthesis of substituted imidazoles, which have a wide range of applications in various fields, including pharmaceuticals, agrochemicals, and materials science.     

Investigation on mechanical properties of some thiourea complex crystals: Important nonlinear optical materials

In this work the authors have grown good quality single crystals of zinc thiourea sulphate, bis thiourea cadmium acetate, bis zinc thiourea acetate and bis thiourea zinc chloride were grown from slow evaporation solution growth method at ambient temperature and studied their mechanical properties. The crystal system and lattice parameters were confirmed by powder X-ray diffraction analysis. Vickers microhardness of the grown crystals was investigated by using Leitz-Wetzlar (Miniload 2) hardness tester up to an applied load of 120 g. It was observed that, upto 40 g applied load the hardness of the grown crystals increases with increasing the load and thereafter it is practically independent of the indentation load. Meyer's law and Hays–Kendall's law fail to explain the observed load variations. But the variation could be satisfactorily explained by PSR model proposed by Li and Bradt. Classification of cracks and their transition from Palmqvist to median types is explained. The average value of fracture toughness, brittleness index, Young's modulus and yield strength were calculated using expressions for Palmqvist and median types of cracks. Anisotropic nature of the grown crystals was studied using Knoop indentation technique.     

Studies of a molecular hourglass: synthesis and magnetic characterisation of a cyclic dodecanuclear {Cr10Cu2} complex

The synthesis, structure, EPR, and magnetic studies of two dodecanuclear heterometallic cyclic clusters are reported. The compounds have the general formula [R(2)NH(2)](2)[Cr(10)Cu(2)F(14)(O(2)CCMe(3))(22)] (R=Me, 1 or iPr, 2). Both structures contain an array of metal centers which describe an approximate "hourglass", with an ammonium cation in the center of each half of the figure. The chromium sites are all six-coordinate, with the two copper sites five-coordinate. The majority of metal-metal edges are bridged by a single fluoride and two pivalate ligands, while two Cr--Cu edges are bridged by a single fluoride and a single pivalate. Magnetic studies show that 1 and 2 exhibit similar (but not identical) behavior, which can be attributed to ten antiferromagnetic and two ferromagnetic exchange interactions around the ring which gives an S=0 ground state. Quantum Monte Carlo calculations have been used to quantify the exchange interactions by successfully simulating the susceptibility for the full temperature range and thus clarifying the distinction between 1 and 2. EPR spectroscopy shows signals due to excited states, and a variable-temperature study has provided an estimate of the energy gap between the first excited state (S=1) and second excited state (S=2) for 1 that is consistent with the value obtained using the QMC method.     

Generation of hydrophilic, bamboo-shaped multiwalled carbon nanotubes by solid-state pyrolysis and its electrochemical studies

A simple, efficient, and novel method was developed for the direct preparation of hydrophilic, bamboo-shaped carbon nanotubes by the pyrolysis of ruthenium(III) acetylacetonate in a Swagelock cell is reported. The obtained product exhibits mostly bamboo-shaped, straight, periodic twisted, multiwalled carbon nanotubes possessing diameters of 50-80 nm and lengths of around 10 microm. The pyrolyzed product was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), micro-Raman, and cyclic voltammetric techniques. HRTEM studies showed that the walls of bamboo-shaped carbon nanotubes consisted of oblique grapheme planes with respect to the tube axis. The interlayer spacing between two graphitic layers was found to be 0.342 nm. XPS measurements have suggested that as-prepared carbon nanotubes consist the surface functional groups on the surface of carbon nanotubes. The electrochemical properties of synthesized carbon nanotubes have been evaluated. Thermogravimetric analysis (TGA), IR, and cyclic voltammetric studies showed the presence of oxygen functionalities. Raman studies revealed the presence of disorder in the graphitic carbon and the presence of exposed edge plane defects in the generated carbon nanotubes for influencing the surface behavior and electrochemical properties. The electrochemical behavior of electrodes made of bamboo-shaped carbon nanotubes served for an oxygen reduction reaction.     

Pulsed sonoelectrochemical synthesis of size-controlled copper nanoparticles stabilized by poly(N-vinylpyrrolidone)

A novel sonoelectrochemical method for the size-controlled synthesis of spherical copper nanoparticles in an aqueous phase was developed. In this study, poly(N-vinylpyrrolidone) (PVP) was used as the stabilizer for the copper clusters. The copper nanoparticles were characterized by XRD, UV-vis, IR, DLS, TEM, and HRTEM. The PVP was found to greatly promote the formation rate of copper particles and to significantly reduce the copper deposition rate, thereby making monodispersed copper nanoparticles. We could control the particle size by adjusting various parameters such as current density, deposition, temperature, and sonic power, and improve the homogeneity of the copper particles. The results also showed that the transfer rate of PVP-stabilized copper clusters from the cathodic vicinity to the bulk solution played an important role in the preparation of the monodispersed nanoparticles.     

Self-assembled monolayers (SAMs) of alkoxycyanobiphenyl thiols on gold--a study of electron transfer reaction using cyclic voltammetry and electrochemical impedance spectroscopy

Self-assembled monolayers (SAMs) of liquid crystalline thiol-terminated alkoxycyanobiphenyl molecules with different alkyl chain lengths on Au surface have been studied for the first time using electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The barrier property of the SAM-modified surfaces was evaluated using two different redox probes, namely potassium ferro/ferri cyanide and hexaammineruthenium(III) chloride. It was found that for short-length alkyl chain thiol (C5) the electron transfer reaction of hexaammineruthenium(III) chloride takes place through tunneling mechanism. In contrast, redox reaction of potassium ferro/ferri cyanide is almost completely blocked by the SAM-modified Au surface. From the impedance data, a surface coverage value of >99.9% was calculated for all the thiol molecules.     

Cyclohexanyl peptide nucleic acids (chPNAs) for preferential RNA binding: effective tuning of dihedral angle beta in PNAs for DNA/RNA discrimination

[structures: see text] A serious drawback of peptide nucleic acids (PNAs) from an application perspective that has not been adequately dealt with is nondiscrimination of identical DNA and RNA sequences. An analysis of the available X-ray and NMR solution structures of PNA complexes with DNA and RNA suggested that it might be possible to rationally impart DNA/RNA duplex binding selectivity by tuning the dihedral angle beta of the flexible ethylenediamine part of the PNA backbone (II) via suitable chemical modifications. Cyclohexanyl PNAs (chPNAs) with beta approximately = 65 degrees were designed on the basis of this rationale. The chPNAs introduced remarkable differences in duplex stabilities among their DNA and RNA complexes, with melting temperatures (deltaTm(RNA-DNA) = +16-50 degrees C) depending on the number of modifications and the stereochemistry. This is a highly significant, exceptional binding selectivity of a mix sequence of PNA to RNA over the same DNA sequence as that seen to date. In contrast, cyclopentanyl PNAs (cpPNAs) with beta approximately = 25 degrees hybridize to DNA/RNA strongly without discrimination because of the ring puckering of the cyclopentane ring. The high affinity of chPNAs to bind to RNA without losing base specificity will have immediate implications in designing improved PNAs for therapeutic and diagnostic applications.     

A Petrov‐Galerkin method with quadrature for semi‐linear second‐order hyperbolic problems

We propose and analyze a Crank–Nicolson quadrature Petrov–Galerkin (CNQPG) ‐spline method for solving semi‐linear second‐order hyperbolic initial‐boundary value problems. We prove second‐order convergence in time and optimal order H² norm convergence in space for the CNQPG scheme that requires only linear algebraic solvers. We demonstrate numerically optimal order H^k, k = 0,1,2, norm convergence of the scheme for some test problems with smooth and nonsmooth nonlinearities. © 2006 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2006     

Silane decorated metallic nanorods for hydrophobic applications

A novel technique to modify a metallic surface for anti-icing applications is presented. An oblique angle deposition (OAD) technique has been used to fabricate metallic nanorods of Aluminum and Tungsten on a glass substrate. A conformal coating of a silane has been applied using a molecular vapor deposition technique. The resulting surface has shown a static contact angle of 134° with the water droplet. SEM, AFM and XPS have been used to study the surface modification. This is a highly promising approach for anti-icing applications due to its scalability at a very low cost.     

Synthesis, gene silencing, and molecular modeling studies of 4'-C-aminomethyl-2'-O-methyl modified small interfering RNAs

The linear syntheses of 4'-C-aminomethyl-2'-O-methyl uridine and cytidine nucleoside phosphoramidites were achieved using glucose as the starting material. The modified RNA building blocks were incorporated into small interfering RNAs (siRNAs) by employing solid phase RNA synthesis. Thermal melting studies showed that the modified siRNA duplexes exhibited slightly lower T(m) (～1 °C/modification) compared to the unmodified duplex. Molecular dynamics simulations revealed that the 4'-C-aminomethyl-2'-O-methyl modified nucleotides adopt South-type conformation in a siRNA duplex, thereby altering the stacking and hydrogen-bonding interactions. These modified siRNAs were also evaluated for their gene silencing efficiency in HeLa cells using a luciferase-based reporter assay. The results indicate that the modifications are well tolerated in various positions of the passenger strand and at the 3' end of the guide strand but are less tolerated in the seed region of the guide strand. The modified siRNAs exhibited prolonged stability in human serum compared to unmodified siRNA. This work has implications for the use of 4'-C-aminomethyl-2'-O-methyl modified nucleotides to overcome some of the challenges associated with the therapeutic utilities of siRNAs.