Mode of Coordination and Chemical Reactivity of Alpha-Imine Hydrasone Ligands

Interaction of nickel(I1) and copper(I1) complexes of 4,9-dimethy1-5,8-diazadodeca-4,8diene-2,1 ldione, Ni(baen) and 4,6,9-trimethyl-5, 8diazadodeca-4,8-diene-2,ll-dione, Ni(bapn), with arene diazonium chlorides in buffered solutions of methanol yielded metal derivatives of glyoxaliminearylhydrazones. This typical electrophilic addition at the 3-carbon of the complex occurs owing to the pseudo aromatic behaviour of the chelate ring. A mechanism which predicts the attack of the diazonium cation through the coordination shell of the metal is well documented from the available experimental evidences. The chemical reactivity of a few complexes with a single residual non-substituted y-carbon is reasonably manifested by their reaction with phenyl isocyanate.

A new mode of ring cleavage of 2,3-dihydroxybenzoic acid in Tecoma stans (L.). Partial purification and properties of 2,3-dihydroxybenzoate 2,3-oxygenase.

2,3-Dihydroxybenzoic acid has been shown to be oxidized via the 3-oxoadipate pathway in the leaves of Tecoma stans. The formation of 2-carboxy-cis,cis-muconic acid, a muconolactone, 3-oxoadipic acid and carbon dioxide during its metabolism has been demonstrated using an extract of Tecoma leaves. The first reaction of the pathway, viz., the conversion of 2,3-dihydroxybenzoate to 2-carboxy-cis,cis-muconic acid has been shown to be catalysed by an enzyme designated as 2,3-dihydroxybenzoate 2,3-oxygenase. The enzyme has been partially purified and a few of its properties studied. The enzyme is very labile with a half-life of 3--4 h. It is maximally active with 2,3-dihydroxybenzoate as the substrate and does not exhibit any activity with catechol, 4-methyl catechol, 3,4-dihydroxybenzoic acid, etc. However, 2,3-dihydroxy-p-toluate and 2,3-dihydroxy-p-cumate are also oxidized by the enzyme by about 38% and 28% respectively, compared to 2,3-dihydroxybenzoate. Sulfhydryl reagents inhibit the enzyme reaction and the inhibition can be prevented by preincubation of the enzyme with the substrate. Substrate also affords protection to the enzyme against thermal inactivation. Sulfhydryl compounds strongly inhibit the reaction and the inhibition cannot be prevented by preincubation of the enzyme with its substrates. Data on the effect of metal ions as well as metal chelating agents suggest that copper is the metal cofactor of the enzyme. Evidence is presented which suggests that iron may not be participating in the overall catalytic mechanism.

Two forms of Pf1 Inovirus: X-ray diffraction studies on a structural phase transition and a calculated libration normal mode of the asymmetric unit

Inovirus is a helical array of alpha-helical protein asymmetric units surrounding a DNA core. X-ray fibre diffraction studies show that the Pf1 species of Inovirus can undergo a reversible temperature-induced transition between two similar structural forms having slightly different virion helix parameters. Molecular models of the two forms show no evidence for altered interactions between the protein and either the solvent or the viral DNA; but there are significant differences in the shape and orientation of the protein asymmetric unit, related to the changes in the virion parameters. Normal modes involving libration of whole asymmetric units are in a frequency range with appreciable entropy of libration, and the structural transition may be related to changes in libration.

Two forms of PF1 INOVIRUS: X-ray diffraction studies on a structural phase transition and a calculated libration normal mode of the assymetric unit

Inovirus is a helical array of agr-helical protein asymmetric units surrounding a DNA core. X-ray fibre diffraction studies show that the Pf1 species of Inovirus can undergo a reversible temperature-induced transition between two similar structural forms having slightly different virion helix parameters. Molecular models of the two forms show no evidence for altered interactions between the protein and either the solvent or the viral DNA; but there are significant differences in the shape and orientation of the protein asymmetric unit, related to the changes in the virion parameters. Normal modes involving libration of whole asymmetric units are in a frequency range with appreciable entropy of libration, and the structural transition may be related to changes in libration.

Transient analysis of mammalian cell growth in hollow fibre bioreactor

A mathematical model describing the dynamics of mammalian cell growth in hollow fibre bioreactor operated in closed shell mode is developed. Mammalian cells are assumed to grow as an expanding biofilm in the extra-capillary space surrounding the fibre. Diffusion is assumed to be the dominant process in the radial direction while axial convection dominates in the lumen of the bioreactor. The transient simulation results show that steep gradients in the cell number are possible under the condition of substrate limitation. The precise conditions which result in nonuniform growth of cells along the length of the bioreactor are delineated. The effect of various operating conditions, such as substrate feed rate, length of the bioreactor and diffusivity of substrate in different regions of the bioreactor, on the bioreactor performance are evaluated in terms of time required to attain the steady-state. The rime of growth is introduced as a measure of effectiveness factor for the bioreactor and is found to be dependent on two parameters, a modified Peclet number and a Thiele modulus. Diffusion, reaction and/or convection control regimes are identified based on these two parameters. The model is further extended to include dual substrate growth limitations, and the relative growth limiting characteristics of two substrates are evaluated. (C) 1997 Elsevier Science Ltd.

Layer-dependent resonant Raman scattering of a few layer MoS2

We report resonant Raman scattering of MoS2 layers comprising of single, bi, four and seven layers, showing a strong dependence on the layer thickness. Indirect band gap MoS2 in bulk becomes a direct band gap semiconductor in the monolayer form. New Raman modes are seen in the spectra of single- and few-layer MoS2 samples which are absent in the bulk. The Raman mode at similar to 230 cm(-1) appears for two, four and seven layers. This mode has been attributed to the longitudinal acoustic phonon branch at the M point (LA(M)) of the Brillouin zone. The mode at similar to 179 cm(-1) shows asymmetric character for a few-layer sample. The asymmetry is explained by the dispersion of the LA(M) branch along the G-M direction. The most intense spectral region near 455 cm(-1) shows a layer-dependent variation of peak positions and relative intensities. The high energy region between 510 and 645 cm(-1) is marked by the appearance of prominent new Raman bands, varying in intensity with layer numbers. Resonant Raman spectroscopy thus serves as a promising non invasive technique to accurately estimate the thickness of MoS2 layers down to a few atoms thick. Copyright (C) 2012 John Wiley & Sons, Ltd.

A general methodology for calculating mixed mode stress intensity factors and fracture toughness of solder joints with interfacial cracks

Solder joints in electronic packages undergo thermo-mechanical cycling, resulting in nucleation of micro-cracks, especially at the solder/bond-pad interface, which may lead to fracture of the joints. The fracture toughness of a solder joint depends on material properties, process conditions and service history, as well as strain rate and mode-mixity. This paper reports on a methodology for determining the mixed-mode fracture toughness of solder joints with an interfacial starter-crack, using a modified compact mixed mode (CMM) specimen containing an adhesive joint. Expressions for stress intensity factor (K) and strain energy release rate (G) are developed, using a combination of experiments and finite element (FE) analysis. In this methodology, crack length dependent geometry factors to convert for the modified CMM sample are first obtained via the crack-tip opening displacement (CTOD)-based linear extrapolation method to calculate the under far-field mode I and II conditions (f(1a) and f(2a)), (ii) generation of a master-plot to determine a(c), and (iii) computation of K and G to analyze the fracture behavior of joints. The developed methodology was verified using J-integral calculations, and was also used to calculate experimental fracture toughness values of a few lead-free solder-Cu joints. (C) 2014 Elsevier Ltd. All rights reserved.

Nonlinear mode coupling and internal resonances in MoS2 nanoelectromechanical system

Atomically thin two dimensional (2D) layered materials have emerged as a new class of material for nanoelectromechanical systems (NEMS) due to their extraordinary mechanical properties and ultralow mass density. Among them, graphene has been the material of choice for nanomechanical resonator. However, recent interest in 2D chalcogenide compounds has also spurred research in using materials such as MoS2 for the NEMS applications. As the dimensions of devices fabricated using these materials shrink down to atomically thin membrane, strain and nonlinear effects have become important. A clear understanding of the nonlinear effects and the ability to manipulate them is essential for next generation sensors. Here, we report on all electrical actuation and detection of few-layer MoS2 resonator. The ability to electrically detect multiple modes and actuate the modes deep into the nonlinear regime enables us to probe the nonlinear coupling between various vibrational modes. The modal coupling in our device is strong enough to detect three distinct internal resonances. (C) 2015 AIP Publishing LLC.

Structural characteristics of a giant tropical liana and its mode of canopy spread in an alien environment

To circumvent the practical difficulties in research on tropical rainforest lianas in their natural habitat due to prevailing weather conditions, dense camouflaging vegetation and problems in transporting equipment for experimental investigations, Entada pursaetha DC (syn. Entada scandens Benth., Leguminosae) was grown inside a research campus in a dry subtropical environment. A solitary genet has attained a gigantic size in 17 years, infesting crowns of semi-evergreen trees growing in an area roughly equivalent to 1.6 ha. It has used aerially formed, cable-like stolons for navigating and spreading its canopy across tree gaps. Some of its parts which had remained unseen in its natural habitat due to dense vegetation are described. The attained size of this liana in a climatically different environment raises the question as to why it is restricted to evergreen rainforests. Some research problems for which this liana will be useful are pointed out.

Nano-indentation studies on polymer matrix composites reinforced by few-layer graphene

The mechanical properties of polyvinyl alcohol (PVA) and poly(methyl methacrylate) (PMMA)-matrix composites reinforced by functionalized few-layer graphene (FG) have been evaluated using the nano-indentation technique. A significant increase in both the elastic modulus and hardness is observed with the addition of 0.6 wt% of graphene. The crystallinity of PVA also increases with the addition of FG. This and the good mechanical interaction between the polymer and the FG, which provides better load transfer between the matrix and the fiber, are suggested to be responsible for the observed improvement in mechanical properties of the polymers.

A do-it-yourself (DIY) switched mode power conversion laboratory

In the education of physical sciences, the role of the laboratory cannot be overemphasised. It is the laboratory exercises which enable the student to assimilate the theoretical basis, verify the same through bench-top experiments, and internalize the subject discipline to acquire mastery of the same. However the resources essential to put together such an environment is substantial. As a result, the students go through a curriculum which is wanting in this respect. This paper presents a low cost alternative to impart such an experience to the student aimed at the subject of switched mode power conversion. The resources are based on an open source circuit simulator (Sequel) developed at IIT Mumbai, and inexpensive construction kits developed at IISc Bangalore. The Sequel programme developed by IIT Mumbai, is a circuit simulation program under linux operating system distributed free of charge. The construction kits developed at IISc Bangalore, is fully documented for anyone to assemble these circuit which minimal equipment such as soldering iron, multimeter, power supply etc. This paper puts together a simple forward dc to dc converter as a vehicle to introduce the programming under sequel to evaluate the transient performance and small signal dynamic model of the same. Bench tests on the assembled construction kit may be done by the student for study of operation, transient performance and closed loop stability margins etc.

Influence of Elastic-Constants on Mode-I Stress-Intensity Factors in 3-Dimensional Crack Problems

Plates with V-through edge notches subjected to pure bending and specimens with rectangular edge-through-notches subjected to combined bending and axial pull were investigated (under live-load and stress-frozen conditions) in a completely nondestructive manner using scattered-light photoelasticity. Stress-intensity factors (SIFs) were evaluated by analysing the singular stress distributions near crack-tips. Improved methods are suggested for the evaluation of SIFs. The thickness-wise variation of SIFs is also obtained in the investigation. The results obtained are compared with the available theoretical solutions.

Fibre diffraction of lithium DNA shows structural variability and deviation from a regular helical structure for the B-form

Recently, reports have appeared which show structural variations in B-DNA and indicate deviations from a uniform helical structure. We report for the first time that these indications are also present in the B-form fibre diffraction patterns for the lithium salt of natural DNA. We have used an improved method of controlling the salt concentration in the fibres. Our results are based on the appearance and disappearance of meridional reflections on different layer lines depending upon the salt.

Photoelastic parametric studies of mode I stress intensity factors

Results of photoelastic investigations on single edge-notch tension specimens of varying notch angle and crack length are reported. The experimental results of Mode I stress intensity factors are compared with analytical results.