Grafting of m-isopropenyl-alpha, alpha-dimethylbenzyl-isocyanate (m-TMI) onto isotactic polypropylene: Synthesis and characterization

A novel vinyl monomer with an isocyanate functional group, m-isopropenyl-alpha,alpha-dimethylbenzyl-isocyanate (m-TMI), was grafted onto isotactic polypropylene (i-PP) using dicumyl peroxide (DCP) as the initiator. This would open up the possibility of using the grafted polymer with the reactive isocyanate group as compatibilizer for blending carbohydrates such as cellulose with. polypropylene. The grafting was carried out in a Brabender Plasticoder at 180degreesC. The effects of monomer and initiator concentrations on the yield of grafting were investigated by performing statistical analysis. While the grafting yield increased with the concentration of DCP at any given concentration of m-TMI, the variation of the grafting yield with m-TMI concentration, for a given concentration of DCP, went through a maximum, the optimum yield of 7.8% (w/w) being obtained at 10 wt.% concentration of both DCP and m-TMI. The grafting reaction is. accompanied by considerable chain scission of I-PP, resulting in a decrease in the molecular weight of the grafted polymer. While the molecular weight drops sharply even at a low concentration of DCP, there occurs no further significant change in the molecular weight even at much higher concentrations of the initiator.

Electric Field Directed Growth of Molecular Wires of Charge Transfer Molecules on Prefabricated Metal Electrodes

Molecular wires of charge transfer molecules were formed by co-evaporating the 7 7 8 8-Tetracyanoquinodimethane [TCNQ] (acceptor) and Tetrathiafulvalene [TTF] (donor) molecules across prefabricated metal electrodes. Molecular wires of TTF TCNQ were also formed by evaporating single complex of TTF:TCNQ across prefabricated metal electrodes The prefabricated metal electrodes were made using electron beam lithography on SiO2 and glass cover slip substrates. Even though TTF: TCNQ wires grown from both co-evaporation and evaporation techniques show semiconductor like behavior in temperature dependence of resistance they show different activation energies due the difference in stoichiometry of TTF and TCNQ.

LTCC ultra wide band filter

This article presents the analysis of ultra wide band (UWB) filler designed using a symmetrical three parallel coupled line resonator in low temperature co-fired ceramic (LTCC) medium: The ground plane with an aperture incorporated in it improves the coupling. Based on circuit models, the designed UWB filter has been analyzed, and the results have been confirmed by experiments. The filter has been realized with Dupont LTCC tape DuPont 951 (that has dielectric constant of 7.8). Maximum insertion loss of the experimental filter is 1.5 dB. The group variation over the pass band of the filter is within 0.2 us. Dimensions of the experimental LTCC filter are 20 x 10 x 0.72 mm. (C) 2011 Wiley Periodicals, Inc. Microwave Opt Technol Lett 53:2580-2583,2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/mop.26311

Filling Characteristics for an Activated Carbon Based Adsorbed Natural Gas Storage System

The storage capacity of an activated carbon bed is studied using a 2D transport model with constant inlet flow conditions. The predicted filling times and variation in bed pressure and temperature are in good agreement with experimental observations obtained using a 1.82 L prototype ANG storage cylinder. Storage efficiencies based on the maximum achievable V/V (volume of gas/volume of container) and filling times are used to quantify the performance of the charging process. For the high permeability beds used in the experiments, storage efficiencies are controlled by the rate of heat removal. Filling times, defined as the time at which the bed pressure reaches 3.5 MPa, range from 120 to 3.4 min for inlet flow rates of 1.0 L min(-1) and 30.0 L min(-1), respectively. The corresponding storage efficiencies, eta(s), vary from 90% to 76%, respectively. Simulations with L/D ratios ranging from 0.35 to 7.8 indicate that the storage efficiencies can be improved with an increase in the LID ratios and/or with water cooled convection. Thus for an inlet flow rate of 30.0 L min(-1), an eta(s) value of 90% can be obtained with water cooling for an L/D ratio of 7.8 and a filling time of a few minutes. In the absence of water cooling the eta(s) value reduces to 83% at the same L/D ratio. Our study suggests that with an appropriate choice of cylinder dimensions, solutions based on convective cooling during adsorptive storage are possible with some compromise in the storage capacity.

In-situ measurements of concentration and temperature during transient solidification of aqueous solution of ammonium chloride using laser interferometry

The variation in temperature and concentration plays a crucial role in predicting the final microstructure during solidification of a binary alloy. Most of the experimental techniques used to measure concentration and temperature are intrusive in nature and affect the flow field. In this paper, the main focus is laid on in-situ, non-intrusive, transient measurement of concentration and temperature during the solidification of a binary mixture of aqueous ammonium chloride solution (a metal-analog system) in a top cooled cavity using laser based Mach-Zehnder Interferometric technique. It was found from the interferogram, that the angular deviation of fringe pattern and the total number of fringes exhibit significant sensitivity to refractive index and hence are functions of the local temperature and concentration of the NH4Cl solution inside the cavity. Using the fringe characteristics, calibration curves were established for the range of temperature and concentration levels expected during the solidification process. In the actual solidification experiment, two hypoeutectic solutions (5% and 15% NH4Cl) were chosen. The calibration curves were used to determine the temperature and concentration of the solution inside the cavity during solidification of 5% and 15% NH4Cl solution at different instants of time. The measurement was carried out at a fixed point in the cavity, and the concentration variation with time was recorded as the solid-liquid interface approached the measurement point. The measurement exhibited distinct zones of concentration distribution caused by solute rejection and Rayleigh Benard convection. Further studies involving flow visualization with laser scattering confirmed the Rayleigh Benard convection. Computational modeling was also performed, which corroborated the experimental findings. (C) 2011 Elsevier Ltd. All rights reserved.

Solvatochromic Effect on the Photophysical Properties of Two Coumarins

The absorption and emission spectra of two coumarins namely 7, 8 benzo-4-azidomethyl coumarin (C-1) and 6-methoxy-4-azidomethyl coumarin (C-2) have been recorded at room temperature in solvents of different polarities. The ground state dipole moments (mu(g)) of two coumarins were determined experimentally by Guggenheim method. The exited state (mu(e)) dipole moments were estimated from Lippert's, Bakhshievs and Chamma-Viallet's equations by using the variation of Stoke's shift with the solvent dielectric constant and refractive index. The ground and excited state dipole moments were calculated by means of solvatochromic shift method and also the excited state dipole moments are determined in combination with ground state dipole moments. It was observed that dipole moments of excited state were higher than those of the ground state, indicating a substantial redistribution of the pi-electron densities in a more polar excited state for two coumarins.

Sensitive Liquid Chromatography-Tandem Mass Spectrometry Method for the Determination of Olanzapine in Human Urine

A sensitive and selective liquid chromatographic-tandem mass spectrometric (LC-MS-MS) method was developed to determine olanzapine (OLZ) in human urine. After solid-phase extraction with SPE cartridge, the urine sample was analysed on a C-18 column (Symmetry 3.5 mu m, 50 x 4.6 mm i.d) interfaced with a triple quadrupole tandem mass spectrometer. Positive electrospray ionization was employed as the ionization source. The mobile phase consisted of ammonium acetate (pH 7.8)-acetonitrile (10:90, v/v). The method was linear over a concentration range of 1-100 ngml(-1). The lower limit of quantitation was 1 ngml(-1). The intra-day and inter-day relative standard deviation across three validation runs over the entire concentration range was < 11.5 %. The accuracy determined at three concentrations (8.0, 50.0 and 85.0 ngml(-1) OLZ) was within +/- 1.21 % in terms of relative errors.

Quantum capacitance in bilayer graphene nanoribbon

We address a physically based analytical model of quantum capacitance (C-Q) in a bilayer graphene nanoribbon (BGN) under the application of an external longitudinal static bias. We demonstrate that as the gap (Delta) about the Dirac point increases, a phenomenological population inversion of the carriers in the two sets of subbands occurs. This results in a periodic and composite oscillatory behavior in the C-Q with the channel potential, which also decreases with increase in Delta. We also study the quantum size effects on the C-Q, which signatures heavy spatial oscillations due to the occurrence of van Hove singularities in the total density-of-states function of both the sets of subbands. All the mathematical results as derived in this paper converge to the corresponding well-known solution of graphene under certain limiting conditions and this compatibility is an indirect test of our theoretical formalism. (C) 2012 Elsevier By. All rights reserved.

Comparative Transcriptomics of H. pylori Strains AM5, SS1 and Their hpyAVIBM Deletion Mutants: Possible Roles of Cytosine Methylation

Helicobacter pylori is an important human pathogen and one of the most successful chronic colonizers of the human body. H. pylori uses diverse mechanisms to modulate its interaction with the host in order to promote chronic infection and overcome host immune response. Restriction-modification genes are a major part of strain-specific genes present in H. pylori. The role of N-6 -adenine methylation in bacterial gene regulation and virulence is well established but not much is known about the effect of C-5 -cytosine methylation on gene expression in prokaryotes. In this study, it was observed by microarray analysis and RT-PCR, that deletion of an orphan C-5 -cytosine methyltransferase, hpyAVIBM in H. pylori strains AM5and SS1 has a significant effect on the expression of number of genes belonging to motility, adhesion and virulence. AM Delta DhpyAVIBM mutant strain has a different LPS profile and is able to induce high IL-8 production compared to wild-type. hpyAVIBM from strain 26695 is able to complement mutant SS1 and AM5 strains. This study highlights a possible significance of cytosine methylation in the physiology of H. pylori.

Coalescent Method in Conjunction with Niche Modeling Reveals Cryptic Diversity among Centipedes in the Western Ghats of South India

Background: There has been growing interest in integrative taxonomy that uses data from multiple disciplines for species delimitation. Typically, in such studies, monophyly is taken as a proxy for taxonomic distinctiveness and these units are treated as potential species. However, monophyly could arise due to stochastic processes. Thus here, we have employed a recently developed tool based on coalescent approach to ascertain the taxonomic distinctiveness of various monophyletic units. Subsequently, the species status of these taxonomic units was further tested using corroborative evidence from morphology and ecology. This inter-disciplinary approach was implemented on endemic centipedes of the genus Digitipes (Attems 1930) from the Western Ghats (WG) biodiversity hotspot of India. The species of the genus Digitipes are morphologically conserved, despite their ancient late Cretaceous origin. Principal Findings: Our coalescent analysis based on mitochondrial dataset indicated the presence of nine putative species. The integrative approach, which includes nuclear, morphology, and climate datasets supported distinctiveness of eight putative species, of which three represent described species and five were new species. Among the five new species, three were morphologically cryptic species, emphasizing the effectiveness of this approach in discovering cryptic diversity in less explored areas of the tropics like the WG. In addition, species pairs showed variable divergence along the molecular, morphological and climate axes. Conclusions: A multidisciplinary approach illustrated here is successful in discovering cryptic diversity with an indication that the current estimates of invertebrate species richness for the WG might have been underestimated. Additionally, the importance of measuring multiple secondary properties of species while defining species boundaries was highlighted given variable divergence of each species pair across the disciplines.

An Antitubulin Agent BCFMT Inhibits Proliferation of Cancer Cells and Induces Cell Death by Inhibiting Microtubule Dynamics

Using cell based screening assay, we identified a novel anti-tubulin agent (Z)-5-((5-(4-bromo-3-chlorophenyl)furan-2-yl)methylene)-2-thioxothiazoli din-4-one (BCFMT) that inhibited proliferation of human cervical carcinoma (HeLa) (IC50, 7.2 +/- 1.8 mu M), human breast adenocarcinoma (MCF-7) (IC50, 10.0 +/- 0.5 mu M), highly metastatic breast adenocarcinoma (MDA-MB-231) (IC50, 6.0 +/- 1 mu M), cisplatin-resistant human ovarian carcinoma (A2780-cis) (IC50, 5.8 +/- 0.3 mu M) and multi-drug resistant mouse mammary tumor (EMT6/AR1) (IC50, 6.5 +/- 1 mu M) cells. Using several complimentary strategies, BCFMT was found to inhibit cancer cell proliferation at G2/M phase of the cell cycle apparently by targeting microtubules. In addition, BCFMT strongly suppressed the dynamics of individual microtubules in live MCF-7 cells. At its half maximal proliferation inhibitory concentration (10 mu M), BCFMT reduced the rates of growing and shortening phases of microtubules in MCF-7 cells by 37 and 40%, respectively. Further, it increased the time microtubules spent in the pause (neither growing nor shortening detectably) state by 135% and reduced the dynamicity (dimer exchange per unit time) of microtubules by 70%. In vitro, BCFMT bound to tubulin with a dissociation constant of 8.3 +/- 1.8 mu M, inhibited tubulin assembly and suppressed GTPase activity of microtubules. BCFMT competitively inhibited the binding of BODIPY FL-vinblastine to tubulin with an inhibitory concentration (K-i) of 5.2 +/- 1.5 mu M suggesting that it binds to tubulin at the vinblastine site. In cultured cells, BCFMT-treatment depolymerized interphase microtubules, perturbed the spindle organization and accumulated checkpoint proteins (BubR1 and Mad2) at the kinetochores. BCFMT-treated MCF-7 cells showed enhanced nuclear accumulation of p53 and its downstream p21, which consequently activated apoptosis in these cells. The results suggested that BCFMT inhibits proliferation of several types of cancer cells including drug resistance cells by suppressing microtubule dynamics and indicated that the compound may have chemotherapeutic potential.

Cellular uptake and remarkable photocytotoxicity of pyrenylter pyridine oxovanadium(IV) complexes of dipyridophenazine bases

Pyrenylterpyridine (pytpy) oxovanadium(IV) complexes VO(pytpy)(L)]Cl-2 (1-6) of the dipyridophenazine bases (L), viz., dipyrido-6,7,8,9-tetrahydrophenazine (dpqC in 1), dipyrido3,2-a:2',3'-c]phenazine-2-carboxylic acid (dppzc in 2), dipyrido3,2-a:2',3'-c]phenazine-11-sulfonic acid (dppzs in 3), 7-aminodipyrido3,2-a:2',3'-c]phenazine (dppza in 4), benzo-i]dipyrido3,2-a:2',3'-c]phenazine (dppn in 5) and dipyrido3,2-a:2',3'-c]phenazine (dppz in 6) were prepared, characterized and their DNA binding, photocleavage activity and photocytotoxicity studied. The complexes which showed a d-d band near 750 nm in DMF are efficient binders to calf thymus DNA (K-b: 3.2 x 10(5)-2.9 x 10(6) M-1). The complexes showed significant pUC19 DNA cleavage in near-IR light of 785 nm forming center dot OH radicals and photocytotoxicity in HeLa cells in visible light with the benzo-i] dipyrido3,2-a:2',3'-c]phenazine complex 5 showing a remarkably low IC50 value of 0.036 mu M. Flow-cytometric analysis shows a high sub-G1 phase cell cycle arrest in HeLa cells by the complexes on photo-irradiation. The photocytotoxicity correlates well with the hydrophobicity, photosensitizing ability and DNA binding propensity of the complexes. (C) 2012 Elsevier B.V. All rights reserved.

Enhancing the photocytotoxic potential of curcumin on terpyridyl lanthanide(III) complex formation

Lanthanide(III) complexes Ln(R-tpy)(cur)(NO3)(2)] (Ln = La(III) in 1, 2; Gd(III) in 5, 6) and Ln(R-tpy)(scur)(NO3)(2)] (Ln = La(III) in 3, 4; Gd(III) in 7, 8), where R-tpy is 4'-phenyl-2,2':6',2 `'-terpyridine (ph-tpy in 1, 3, 5, 7), 4'-(1-pyrenyl)-2,2':6',2 `'-terpyridine (py-tpy in 2, 4, 6, 8), Hcur is curcumin (in 1, 2, 5, 6) and Hscur is diglucosylcurcumin (in 3, 4, 7, 8), were prepared and their DNA photocleavage activity and photocytotoxicity studied. Complexes La(ph-tpy)(cur)(NO3)(2)] (1) and Gd(ph-tpy)(cur)(NO3)(2)] (5) were structurally characterized. The complexes in aqueous-DMF showed an absorption band near 430 nm and an emission band near 515 nm when excited at 420 nm. The complexes are moderate binders to calf-thymus DNA. They cleave plasmid supercoiled DNA to its nicked circular form in UV-A (365 nm) and visible light (454 nm) via O-1(2) and (OH)-O-center dot pathways. The complexes are remarkably photocytotoxic in HeLa cells in visible light (lambda = 400-700 nm) and are non-toxic in the dark. FACScan analysis of the HeLa cells treated with 2 and 4 showed cell death via an apoptotic pathway. Nuclear localization of 1-4 is evidenced from confocal imaging on HeLa cells. The hydrolytic instability of curcumin gets significantly reduced upon binding to the lanthanide ions while retaining its photocytotoxic potential.

Ballistic Studies on TiB2-Ti Functionally Graded Armor Ceramics

The objective of this paper is to discuss the results of the ballistic testing of spark plasma sintered TiB2-Ti based functionally graded materials (FGMs) with an aim to assess their performance in defeating small-calibre armor piercing projectiles. We studied the efficacy of FGM design and compared its ballistic properties with those of TiB2-based composites as well as other competing ceramic armors. The ballistic properties are critically analyzed in terms of depth of penetration, ballistic efficiency, fractographs of fractured surfaces as well as quantification of the shattered ceramic fragments. It was found that all the investigated ceramic compositions exhibit ballistic efficiency (eta) of 5.1 -5.9. We also found that by increasing the thickness of FGM from 5 mm to 7.8 mm, the ballistic property of the composite degraded. Also, the strength of the ceramic compositions studied is sufficient to completely fracture the nose of the pointed projectile used. Analysis of the ceramic fragments (2 mu m-10 mm) showed that harder the ceramic, coarser were the fragments formed. On comparing the results with available armor systems, it has been concluded that TiB2 based composites can show better ballistic properties, except B4C. SEM analysis of the fragments obtained after testing with FGM showed formation of cleavage steps as well as presence of intergranular cracks, indicating that the FGM fractured by mixed mode of failure. It can be concluded that the FGM developed has lower ballistic properties compared to its monolith TiB2-20 wt.% Ti.