Conformations of three heterocyclic perhydropyrrolobenzofurans and polymeric assembly via co-operative inter-molecular C-H center dot center dot center dot O hydrogen bonds

In 1-cyclo-hexyl-6,6,8a-trimethyl-3a,6,7,8a-tetra-hydro-1H-1-benzofuro2, 3-b]pyrrole-2,4(3H,5H)-dione, C19H27NO3, (I), and the isomorphous compounds 6,6,8a-trimethyl-1-phenyl-3a,6,7,8a-tetra-hydro-1H-1-benzofuro2,3-b]p yrrole-2,4(3H,5H)-dione, C19H21NO3, (II), and 6,6,8a-trimethyl-1-(3-pyridyl)-3a,6,7,8a-tetra-hydro-1H-1-benzofuro2, 3-b]pyrrole-2,4(3H,5H)-dione, C18H20N2O3, (III), the tetra-hydro-benzo-dihydro-furo-pyrrolidine ring systems are folded at the cis junction of the five-membered rings, giving rise to a non-planar shape of the tricyclic cores. The dihydro-furan and pyrrolidine rings in (I) are puckered and adopt an envelope conformation. The cyclo-hexene rings adopt a half-chair conformation in all the mol-ecules, while the substituent N-cyclo-hexyl ring in (I) assumes a chair form. Short intra-molecular C-HcO contacts form S(5) and S(6) motifs. The isomorphous compounds (II) and (III) are effectively isostructural, and aggregate into chains via inter-molecular C-HcO hydrogen bonds.

Probing the inter-tube transport in aligned and random multiwall carbon nanotubes

The temperature and magnetic field dependence of conductivity has been used to probe the inter-tube transport in multiwall carbon nanotubes (MWNTs). The scanning electron microscopy images show highly aligned and random distribution of MWNTs. The conductivity in aligned carbon nanotube (ACNT) and random carbon nanotube (RCNT) samples at low temperature follows T-1/2 (at T < 8 K) and T-3/4 (at T > 8 K) dependence in accordance with the weak localization and electron-electron (e-e) interaction model. The values of diffusion coefficient in ACNT and RCNT are 0.25 x 10(-2) and 0.71 x 10(-2) cm(2) s(-1), respectively, indicating that larger number of inter-tube junctions in later enhances the bulk transport. The positive magnetoconductance (MC) data in both samples show that the weak localization contribution is dominant. However, the saturation of MC at higher fields and lower temperatures indicate that e-e interaction is quite significant in RCNT. The T-3/4 and T-1/2 dependence of inelastic scattering length (l(in)) in ACNT and RCNT samples show that the inelastic e-e scattering is more important in aligned tubes. (C) 2011 American Institute of Physics. doi:10.1063/1.3552911]

Inter And Intramolecular Interactions Of Porphyrins With 5,5′-Dithiobis(2-Nitrobenzoic Acid)

meso-Tetraphenylporphyrin and its metal [zinc(II) and copper(II)] derivatives form both inter and intramolecular complexes with 5,5′-dithiobis(2-nitrobenzoic acid) (DTNB). The nature of interaction is predominantly charge transfer (CT) in origin, with the porphyrin functioning as a II-donor and DTNB as an acceptor. Among the covalently linked intramolecular systems, the magnitude of CT interaction varies with the position (of one of the aryl groups of the porphyrin) to which DTNB is attached as ortho meta > para. Steady-state and time-resolved fluorescence studies revealed electron transfer to be the dominant pathway for the fluorescence quenching in these systems. Steady-state photolysis experiments probed using EPR and optical absorption studies have shown that electron transfer (from the excited singlet state of the porphyrin) to DTNB results in the formation of thiyl radical and production of free thiolate anion. It is found that the products of electrochemical reduction of covalently linked porphyrin-DTNB systems are different from those observed for the photochemical studies.

Engineered dimer interface mutants of triosephosphate isomerase: the role of inter-subunit interactions in enzyme function and stability

The role of inter-subunit interactions in maintaining optimal catalytic activity in triosephosphate isomerase (TIM) has been probed, using the Plasmodium falciparum enzyme as a model. Examination of subunit interface contacts in the crystal structures suggests that residue 75 (Thr, conserved) and residue 13 (Cys, variable) make the largest number of inter-subunit contacts. The mutants Cys13Asp (C13D) and Cys13Glu (C13E) have been constructed and display significant reduction in catalytic activity when compared with wild-type (WT) enzyme (similar to 7.4-fold decrease in k(cat) for the C13D and similar to 3.3-fold for the C13E mutants). Analytical gel filtration demonstrates that the C13D mutant dissociates at concentrations < 1.25 mu M, whereas the WT and the C13E enzymes retain the dimeric structure. The order of stability of the mutants in the presence of chemical denaturants, like urea and guanidium chloride, is WT > Cys13Glu > Cys13Asp. Irreversible thermal precipitation temperatures follow the same order as well. Modeling studies establish that the Cys13Asp mutation is likely to cause a significantly greater structural perturbation than Cys13Glu. Analysis of sequence and structural data for TIMs from diverse sources suggests that residues 13 and 82 form a pair of proximal sites, in which a limited number of residue pairs may be accommodated.

Inter and intra crystalline ion exchange equilibria in the system Fe Cr Al O

The tie lines delineating ion-exchange equilibria between FeCr2O4FeAl2O4 spinel solid solution and Cr2O3Al2O3 solid solution with corundum structure have been determined at 1373 K by electron microprobe and EDAX point count analysis of oxide phases equilibrated with metallic iron. Activities in the spinel solid solution are derived from the tie lines and the thermodynamic data on Cr2O3Al2O3 solid solution available in the literature. The oxygen potentials corresponding to the tie-line composition of oxide phases in equilibrium with metallic iron were measured using solid oxide galvanic cells with CaOZrO2 and Y2O3ThO2 electrolytes. These electrochemical measurements also yield activities in the spinel solid solution, in good agreement with those obtained from tie lines. The activity-composition relationship in the spinel solid solution is analysed in terms of the intra-crystalline ion exchange between the tetrahedral and octahedral sites of the spinel structures. The ion exchange is governed by site-preference energies of the cations and the entropy of cations mixing on each site.

A Review of Photo-Induced Inter-Diffusion in Nano-Layered Chalcogenide Films

Abstract | A growing interest in the research of chalcogenide glasses can be currently witnessed, which to a large extent is caused by newly opened fields of applications for these materials. Applications in the field of micro- and opto-electronics, xerography and lithography, acousto-optic and memory switching devices and detectors for medical imaging seem to be most remarkable. Accordingly, photo induced phenomena in chalcogenide glasses are attracting much interest. These phenomena can be found both in uniform thin films as well as multilayered films. Among amorphous multilayers, chalcogenide multilayers are attractive because of the potential it has for tailoring the optical properties. I will be presenting some basic idea of photoinduced effects followed by the diffusion mechanisms of Se, Sb and Bi in to As2S3 films.

Fuzzy logic based TCSC supplementary controller for damping of inter area oscillations in power system

This paper describes an application of a FACTS supplementary controller for damping of inter area oscillations in power systems. A fuzzy logic controller is designed to regulate a thyristor controlled series capacitor (TCSC) in a multimachine environment to produce additional damping in the system. Simultaneous application of the excitation controller and proposed controller is also investigated. Simulation studies have been done with different types of disturbances and the results are shown to be consistent with the expected performance of the supplementary controller.

Prediction of inter-laminar stresses in composite honeycomb sandwich panels under mechanical loading using Variational Asymptotic Method

This work focuses on the formulation of an asymptotically correct theory for symmetric composite honeycomb sandwich plate structures. In these panels, transverse stresses tremendously influence design. The conventional 2-D finite elements cannot predict the thickness-wise distributions of transverse shear or normal stresses and 3-D displacements. Unfortunately, the use of the more accurate three-dimensional finite elements is computationally prohibitive. The development of the present theory is based on the Variational Asymptotic Method (VAM). Its unique features are the identification and utilization of additional small parameters associated with the anisotropy and non-homogeneity of composite sandwich plate structures. These parameters are ratios of smallness of the thickness of both facial layers to that of the core and smallness of 3-D stiffness coefficients of the core to that of the face sheets. Finally, anisotropy in the core and face sheets is addressed by the small parameters within the 3-D stiffness matrices. Numerical results are illustrated for several sample problems. The 3-D responses recovered using VAM-based model are obtained in a much more computationally efficient manner than, and are in agreement with, those of available 3-D elasticity solutions and 3-D FE solutions of MSC NASTRAN. (c) 2012 Elsevier Ltd. All rights reserved.

Inter-domain interactions influence the stability and catalytic activity of the bi-domain protein tyrosine phosphatase PTP99A

The two protein tyrosine phosphatase (PTP) domains in bi-domain PTPs share high sequence and structural similarity. However, only one of the two PIP domains is catalytically active. Here we describe biochemical studies on the two tandem PTP domains of the bi-domain PTP, PTP99A. Phosphatase activity, monitored using small molecule as well as peptide substrates, revealed that the inactive (D2) domain activates the catalytic (D1) domain. Thermodynamic measurements suggest that the inactive D2 domain stabilizes the bi-domain (D1-D2) protein. The mechanism by which the D2 domain activates and stabilizes the bi-domain protein is governed by few interactions at the inter-domain interface. In particular, mutating Lys990 at the interface attenuates inter-domain communication. This residue is located at a structurally equivalent location to the so-called allosteric site of the canonical single domain PIP, PTP1B. These observations suggest functional optimization in bi-domain PTPs whereby the inactive PTP domain modulates the catalytic activity of the bi-domain enzyme. (C) 2012 Elsevier B.V. All rights reserved.

Dung as a potential medium for inter-sexual chemical signaling in Asian elephants (Elephas maximus)

Chemical signaling is a prominent mode of male-female communication among elephants, especially during their sexually active periods. Studies on the Asian elephant in zoos have shown the significance of a urinary pheromone (Z7-12:Ac) in conveying the reproductive status of a female toward the opposite sex. We investigated the additional possibility of an inter-sexual chemical signal being conveyed through dung. Sixteen semi-captive adult male elephants were presented with dung samples of three female elephants in different reproductive phases. Each male was tested in 3 separate trials, within an interval of 1-3 days. The trials followed a double-blind pattern as the male and female elephants used in the trials were strangers, and the observer was not aware of the reproductive status of females during the period of bioassays. Males responded preferentially (P < 0.005), in terms of higher frequency of sniff, check and place behavior toward the dung of females close to pre-ovulatory period (follicular-phase) as compared to those in post-ovulatory period (luteal-phase). The response toward the follicular phase samples declined over repeated trials though was still significantly higher than the corresponding response toward the non-ovulatory phase in each of the trials performed. This is the first study to show that male Asian elephants were able to distinguish the reproductive phase of the female by possibly detecting a pre-ovulatory pheromone released in dung. (C) 2012 Elsevier B.V. All rights reserved.

Determination of favorable inter-particle interactions for formation of substitutionally ordered solid phases from a binary mixture of oppositely charged colloidal suspensions

The solid phase formed by a binary mixture of oppositely charged colloidal particles can be either substitutionally ordered or substitutionally disordered depending on the nature and strength of interactions among the particles. In this work, we use Monte Carlo molecular simulations along with the Gibbs-Duhem integration technique to map out the favorable inter-particle interactions for the formation of substitutionally ordered crystalline phases from a fluid phase. The inter-particle interactions are modeled using the hard core Yukawa potential but the method can be easily extended to other systems of interest. The study obtains a map of interactions depicting regions indicating the type of the crystalline aggregate that forms upon phase transition.

Ultrasonic guided wave sensing properties of PVDF thin film with inter digital electrodes

Ultrasonic strain sensing performance of the large area PVDF with Inter Digital Electrodes (IDE) is studied in this work. Procedure to obtain IDE on a beta-phase PVDF is explained. PVDF film with IDE is bonded on a plate structure and is characterized for its directional sensitivity at different frequencies. Guided waves are induced on the IDE-PVDF sensor from different directions by placing a piezoelectric wafer actuator at different angles. Strain induced on the IDE-PVDF sensor by the guided waves in estimated by using a Laser Doppler Vibrometer (LDV) and a wave propagation model. Using measured voltage response from IDE-PVDF sensor and the strain measurements from LDV the piezoelectric coefficient is estimated in various directions. The variation of 11 e at different angles shows directional sensitivity of the IDE-PVDF sensor to the incident guided waves. The present study provides an effective technique to characterize thin film piezoelectric sensors for ultrasonic strain sensing at very high frequencies of 200 kHz. Often frequency of the guided wave is changed to alter the wavelength to interrogate damages of different sizes in Structural Health Monitoring (SHM) applications. The unique property of directional sensitivity combined with frequency tunability makes the IDE-PVDF sensor most suitable for SHM of structures.