The synthesis, structure and photochromism of mercury(II)-iodide complexes of 1-CnH2n+1-2-(arylazo)imidazoles (n = 4, 6, 8)

The reaction of HgI₂ with 1-C_nH_2n+1-2-(arylazo)imidazole (Raai-C_nH_2n+1 where n = 4, 6, 8) has isolated iodide bridging dimeric complexes, [Hg(RaaiC_nH_2n+1)(μ-I)(I)]₂. The structures of the ligand and the complexes have been established by spectral (UV-Vis, IR, ¹H NMR) data. One of these complexes [Hg(1-hexyl-2-(p-tolylazo)imidazole)(μ-I)(I)]₂ has been structurally confirmed by single crystal X-ray diffraction study. The ligand, Raai-C_nH_2n+1 exists at ambient condition in trans geometry about azo (-NN-) group; the UV light irradiation in MeOH solution shows E-to-Z isomerisation. The reverse transformation, Z-to-E, is very slow with visible light irradiation while isomerises rapidly on heating. The coordinated ligand, Raai-C_nH_2n+1 in the complexes exhibit similar behaviour in DMF solution. Quantum yields (?_E→Z) of E-to-Z isomerisation are higher for free ligands than that of their metal complexes. The Z-to-E isomerisation is a thermally induced process. The activation energy (E_a) is calculated by controlled temperature experiment.     

A random maintenance scheduling model to reduce fault diagnosis time

We present a random model for a situation in which some tests of fault detection are to be scheduled to diagnose what type of fault, out of some possible types of faults, has occurred. There are two variants of the model. In the first, the objective is average total diagnosis time. In the second, the objective is a linear combination of average and standard deviation of the diagnosis time, where standard deviation is multiplied with a positive weight. We give an exact solution method for the first case and a heuristic method for the second. A numerical experiment with randomly generated instances is done for the heuristic method. The methods appear to be suitable for practical applications.     

Profiling the binding motif between Be and Mg in the ground state via a single-reference coupled cluster method

We present a study on the performance of our iterative triples correction for the coupled cluster singles and doubles excitations (CCSDT-1a+d) method for computation of potential energy surface (PES), spectroscopic constants, and vibrational spectrum for the ground state (X¹Σ⁺) BeMg, where the ostensible inadequacy of the CCSD and CCSD(T) methods is quite expected. We compare our results with those obtained using state-of-the-art multireference configuration interaction (MRCI) investigations reported earlier by Kerkines and Nicolaides. Our estimated dissociation energy (417.37 cm^?1), equilibrium distance (3.285 Å), and vibrational frequency (82.32 cm^?1) are in good agreement with recent results of advanced MRCI calculations for X¹Σ⁺ BeMg PES, which exhibits a shallow well of 469.4 cm^?1 with a minimum at 3.241 Å and a harmonic vibrational frequency of 85.7 cm^?1. Very weakly bound nature of X¹Σ⁺ BeMg is clearly reflected from these values. In accord with MRCI studies, a comparison of BeMg with iso-valence weakly bound ground-state species, Be₂ and Mg₂, suggests that its characteristics do not exhibit any resemblance to Be₂ rather, it shows a close kinship to Mg₂. The agreement of our derived vibrational levels with those obtained via the high-level MRCI calculations is very encouraging reflecting the potential of the suitably modified single-reference coupled cluster (SRCC) method, CCSDT-1a+d as a tool for the study of multireference van der Waals systems.     

Wear debris generation mechanism for polymers studied by nanoscratching

This paper investigates the debris generation mechanism for polymers due to the actions of the micro-asperities of a hard counterface. Nanoscratching tests were conducted on the surface of five commercially available polymers using a diamond conical tip indenter with three different scratching sequences namely unidirectional multipass, orthogonal multipass and orthogonal omnipass. The scratch damage surface was analysed using an atomic force microscope and a scanning electron microscope to investigate the material removal phenomenon for the selected polymers. The results show that debris generation in polymers is largely a phenomenon of low-cycle fatigue when asperities contribute to the localized plastic deformation of the surface. Hence the rate of material removal is reduced for a polymer which has higher toughness and a higher percentage of elongation before failure. The hardness of the polymer has a counter effect on wear as higher hardness tends to reduce the toughness property in polymers which leads to microcracking and further wear debris generation.     

Vertices of degree k in random unlabeled trees

Let ??_n be the class of unlabeled trees with n vertices, and denote by H _n a tree that is drawn uniformly at random from this set. The asymptotic behavior of the random variable deg_k(H _n) that counts vertices of degree k in H _n was studied, among others, by Drmota and Gittenberger in [J Graph Theory 31(3) (1999), 227–253], who showed that this quantity satisfies a central limit theorem. This result provides a very precise characterization of the “central region” of the distribution, but does not give any non‐trivial information about its tails. In this work, we study further the number of vertices of degree k in H _n. In particular, for k = ??((logn/(loglogn))^1/2) we show exponential‐type bounds for the probability that deg_k(H _n) deviates from its expectation. On the technical side, our proofs are based on the analysis of a randomized algorithm that generates unlabeled trees in the so‐called Boltzmann model. The analysis of such algorithms is quite well‐understood for classes of labeled graphs, see e.g. the work [Bernasconi et al., SODA '08: Proceedings of the 19th Annual ACM‐SIAM Symposium on Discrete Algorithms, Society for Industrial and Applied Mathematics, Philadelphia, PA, 2008, pp. 132–141; Bernasconi et al., Proceedings of the 11th International Workshop, APPROX 2008, and 12th International Workshop, RANDOM 2008 on Approximation, Randomization and Combinatorial Optimization, Springer, Berlin, 2008, pp. 303–316] by Bernasconi, the first author, and Steger. Comparable algorithms for unlabeled classes are unfortunately much more complex. We demonstrate in this work that they can be analyzed very precisely for classes of unlabeled graphs as well. © 2011 Wiley Periodicals, Inc. J Graph Theory. 69:114‐130, 2012     

Creating a collimated ultrasound beam in highly attenuating fluids

We have devised a method, based on a parametric array concept, to create a low-frequency (300-500 kHz) collimated ultrasound beam in fluids highly attenuating to sound. This collimated beam serves as the basis for designing an ultrasound visualization system that can be used in the oil exploration industry for down-hole imaging in drilling fluids. We present the results of two different approaches to generating a collimated beam in three types of highly attenuating drilling mud. In the first approach, the drilling mud itself was used as a nonlinear mixing medium to create a parametric array. However, the short absorption length in mud limits the mixing length and, consequently, the resulting beam is weak and broad. In the second improved approach, the beam generation process was confined to a separate “frequency mixing tube” that contained an acoustically non-linear, low attenuation medium (e.g., water) that allowed establishing a usable parametric array in the mixing tube. A low-frequency collimated beam was thus created prior to its propagation into the drilling fluid. Using the latter technique, the penetration depth of the low frequency ultrasound beam in the drilling fluid was significantly extended. We also present measurements of acoustic nonlinearity in various types of drilling mud.     

Three-dimensional simulation of triode-type MIG for 1 MW, 120 GHz gyrotron for ECRH applications

In this paper, the three-dimensional simulation of triode-type magnetron injection gun (MIG) for 120 GHz, 1 MW gyrotron is presented. The operating voltages of the modulating anode and the accelerating anode are 57 kV and 80 kV respectively. The high order TE_22,6 mode is selected as the operating mode and the electron beam is launched at the first radial maxima for the fundamental beam-mode operation. The initial design is obtained by using the in-house developed code MIGSYN. The numerical simulation is performed by using the commercially available code CST-Particle Studio (PS). The simulated results of MIG obtained by using CST-PS are validated with other simulation codes EGUN and TRAK, respectively. The results on the design output parameters obtained by using these three codes are found to be in close agreement.     

The Balance between Hydrogen Bonds,Halogen Bonds,and Chalcogen Bonds in the Crystal Structures of a Series of 1,3,4-Chalcogenadiazoles

In order to explore how specific atom-to-atom replacements change the electrostatic potentials on 1,3,4-chalcogenadiazole derivatives, and to deliberately alter the balance between intermolecular interactions, four target molecules were synthesized and characterized. DFT calculations indicated that the atom-to-atom substitution of Br with I, and S with Se enhanced the σ-hole potentials, thus increasing the structure directing ability of halogen bonds and chalcogen bonds as compared to intermolecular hydrogen bonding. The delicate balance between these intermolecular forces was further underlined by the formation of two polymorphs of 5-(4-iodophenyl)-1,3,4-thiadiazol-2-amine; Form I displayed all three interactions while Form II only showed hydrogen and chalcogen bonding. The results emphasize that the deliberate alterations of the electrostatic potential on polarizable atoms can cause specific and deliberate changes to the main synthons and subsequent assemblies in the structures of this family of compounds.     

Phytosynthesis of Silver Nanoparticles Using Andrographis paniculata Leaf Extract and Evaluation of Their Antibacterial Activities

Use of nanotechnology in biological systems by the synthesis of metallic nanoparticles is a burning area of research in recent times. In the present investigation, aqueous extract of Andrographis paniculata was used to produce silver nanoparticles by reduction of silver nitrate. It was noted that the synthesizing process was quite rapid and silver nanoparticles form within minutes of silver ions coming in contact with plant extract. UV-Vis spectrum of the aqueous medium containing silver ions indicated a peak at 432 nm corresponding to the plasmon absorbance of the silver nanoparticles. Fourier transform infrared spectroscopic analysis of the silver nanoparticles showed the presence of proteins that might be acting as capping agents around the nanoparticles. From scanning electron microscopy analysis, the size of the silver nanoparticles was measured and it was found that the average size was between 40 and 60 nm. Furthermore, the antibacterial activity of synthesized silver nanoparticles exhibited effective inhibition zones against seven bacterial strains tested. Among the bacteria tested Pseudomonas aeruginosa was found to be most susceptible to the silver nanoparticles. Phytochemical screening of the plant extract indicated the presence of alkaloids, flavonoids, amino acids, saponins, tannins, and terpenoids.