Construction of energy-level diagram of oriented benzene using connectivity information obtained by modified z-cosy experiment

Experiments involving selective perturbation of a transition yield information about the directly connected transitions, which in turn yield information for deriving the parameters of the spin Hamiltonian of oriented molecules. Problems involved with selective perturbation are removed by the use of a two-dimensional experiment, namely, the modified Z-COSY-experiment, The use of this experiment is demonstrated for obtaining the connectivity information and for determining the parameters of the spin Hamiltonian of oriented benzene, a strongly coupled six-spin system

Modified Crack Closure Integral (MCCI) For 3-D Problems Using 20-Noded Brick Elements

The Modified Crack Closure Integral (MCCI) technique based on Irwin's crack closure integral concept is very effective for estimation of strain energy release rates G in individual as well as mixed-mode configurations in linear elastic fracture mechanics problems. In a finite element approach, MCCI can be evaluated in the post-processing stage in terms of nodal forces and displacements near the crack tip. The MCCI expressions are however, element dependent and require a systematic derivation using stress and displacement distributions in the crack tip elements. Earlier a general procedure was proposed by the present authors for the derivation of MCCI expressions for 3-dimensional (3-d) crack problems modelled with 8-noded brick elements. A concept of sub-area integration was proposed to estimate strain energy release rates at a large number of points along the crack front. In the present paper a similar procedure is adopted for the derivation of MCCI expressions for 3-d cracks modelled with 20-noded brick elements. Numerical results are presented for centre crack tension and edge crack shear specimens in thick slabs, showing a comparison between present results and those available in the literature.

Texture Evolution in Boron Modified Ti-6Al-4V Alloy

Owing to their high strength-to-weight ratio, excellent mechanical properties and corrosion resistance, titanium (Ti) and its alloys, especially (alpha+beta) alloys like Ti-6Al-4V is the backbone materials for aerospace, energy, and chemical industries. Trace boron addition (similar to 0.1 wt. %) to the alloy Ti-6Al-4V produces a reduction in as-cast grain size by roughly an order of magnitude resulting in enhanced ductility, higher stiffness, strength and good fracture resistance. Boron addition could also affect the evolution of texture and microstructure in the material. The solidification microstructures of Boron free as well as Boron containing Ti-6Al-4V are found to be almost homogeneous from periphery towards the center of as-cast ingot in terms of both alpha-colony size and distribution. Boron addition substantially reduces alpha-colony size (similar to 50-80 mu m). A gradual change in alpha texture from periphery towards the center has been observed with orientations close to specific texture components suggesting the formation of texture zones. The mechanism of texture evolution can be visualized as a result of variant selection during solidification through (alpha+beta) phase field.

Modified crack closure integral (MCCI) for 3-d problems using 20 noded brick elememnts

The Modified Crack Closure Integral (MCCI) technique based on Irwin's crack closure integral concept is very effective for estimation of strain energy release rates G in individual as well as mixed-mode configurations in linear elastic fracture mechanics problems. In a finite element approach, MCCI can be evaluated in the post-processing stage in terms of nodal forces and displacements near the crack tip. The MCCI expressions are however, element dependent and require a systematic derivation using stress and displacement distributions in the crack tip elements. Earlier a general procedure was proposed by the present authors for the derivation of MCCI expressions for 3-dimensional (3-d) crack problems modelled with 8-noded brick elements. A concept of sub-area integration was proposed to estimate strain energy release rates at a large number of points along the crack front. In the present paper a similar procedure is adopted for the derivation of MCCI expressions for 3-d cracks modelled with 20-noded brick elements. Numerical results are presented for centre crack tension and edge crack shear specimens in thick slabs, showing a comparison between present results and those available in the literature.

Structure-Activity Relationship of Photocytotoxic Iron(III) Complexes of Modified Dipyridophenazine Ligands

Iron(III) complexes FeL(B)] (1-5) of a tetradentate trianionic phenolate-based ligand (L) and modified dipyridophenazine bases (B), namely, 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) and benzoi]dipyridro3,2-a:2',3'-c]phenazine (dppn in 5), have been synthesized, and their photocytotoxic properties studied along with their dipyridophenazine analogue (6). The complexes have a five. electron paramagnetic iron(III) center, and the Fe(III)/Fe(II) redox couple appears at about 0.69 V versus SCE in DMF-0.1 M TBAP. The physicochemical data also suggest that the complexes possess similar structural features as that of its parent complex FeL(dppz)] with FeO3N3 coordination in a distorted octahedral geometry. The DNA-complex and protein-complex interaction studies have revealed that the complexes interact favorably with the biomolecules, the degree of which depends on the nature of the substituents present on the dipyridophenazine ring. Photocleavage Of pUC19 DNA by the complexes has been studied using visible light of 476, 530, and 647 nm wavelengths. Mechanistic investigations with inhibitors show formation of HO center dot radicals via a photoredox pathway. Photocytotoxicity study of the complexes in HeLa cells has shown that the dppn complex (5) is highly active in causing cell death in visible light with sub micromolar IC50 value. The effect of substitutions and the planarity of the phenazine moiety on the cellular uptake are quantified by determining the total Cellular iron content using the inductively coupled plasma-optical emission spectrometry (ICP-OES) technique. The cellular uptake increases marginally with an increase in the hydrophobicity of the dipyridophenazine ligands whereas complex 3 with dppzs shows very high uptake. Insights into the cell death mechanism by the dppn complex 5, obtained through DAFT nuclear staining in HeLa cells, reveal a rapid programmed cell death mechanism following photoactivation of complex 5 with visible light. The effect of substituent on the DNA photocleavage activity of the complexes has been rationalized from the theoretical studies.

Low cycle fatigue behaviour of a nitrogen modified 316L stainless steel at 823 K

Strain controlled low cycle fatigue tests on solution annealed nitrogen modified 316L stainless steel have been conducted in air at 823 K to ascertain the influence of strain rate and strain amplitude. Effect of strain rate was examined from 3x10(-5) s(-1) to 3 x 10(-2) at a fixed strain amplitude of +/- 0.6%. The influence of strain amplitude was evaluated between +/- 0.25 % and +/- 1.0% at a constant strain rate of 3x10(-3) s(-1). The cyclic stress response at all testing conditions is characterized by an initial hardening followed by saturation. Serrated flow, a characteristic feature of dynamic strain ageing (DSA) was seen at strain rates lower than 3x10(-3) s(-1). Fatigue life was found to decrease with decrease in strain rate. The reduction in fatigue resistance is attributed mainly to the detrimental effects associated with DSA.

On the dual head-discharge characteristics of a modified chimney weir

This paper is concerned with the dual head-discharge characteristics of a modified chimney weir. It is shown by an optimization procedure that the modified chimney weir having an inward trapezoidal weir over an inverted V-notch can produce discharges proportional to both the logarithm of the head as well as the linear power of the head reckoned independently over two different reference planes, within a prefixed maximum allowable percentage error from the theoretical discharge. A new technique is adopted to optimize the weir parameters, in order to obtain the maximum ranges of measurement under logarithmic, linear as well as combined characteristics. In the case of linear weir it is shown that it is possible to enhance the linearity range of the chimney weir by more than 540% and for a weir with constant indication accuracy by more than 350%. In addition, about 86% of the overall depth of the designed linear weir and over 90% of the logarithmic weir is converted as the corresponding measurable ranges. Experiments with four typical weirs give consistent constant average coefficient of discharge for each weir confirming the theory. The practical application of the weir in minor irrigation, hydraulic and other engineering fields is highlighted.

Copper(I) complexes of modified nucleobases and vitamin B3 as potential chemotherapeutic agents: In vitro and in vivo studies

Three new complexes of Cu(I) have been synthesized using ancillary ligands like thiopyrimidine (tp) a modified nucleobase, and nicotinamide (nie) or vitamin B3, and characterized by spectroscopy and X-ray crystallography. In vitro cytotoxicity studies of the complexes on various human cancer cell lines such as Colo295, H226, HOP62, K562, MCF7 and T24 show that Cu(PPh3)(2)(tp)Cl] and Cu(PPh3)(2)(tp)ClO4 (2) have in vitro cytotoxicity comparable to cisplatin. Complex Cu(nic)(3)PPh3]ClO4 (3) is non-toxic and increases the life span by about 55 % in spontaneous breast tumor model. DNA binding and cleavage studies show that complex (3) binds to calf thymus DNA with an apparent binding constant of 5.9 x 10(5)M and completely cleaves super-coiled DNA at a concentration of 400 mu M, whereas complexes (1) and (2) do not bind DNA and do not show any cleavage even at 1200 mu M. Thus, complex (3) may exhibit cytotoxicity Via DNA cleavage whereas the mechanism of cytotoxicity of (1) and (2) probably involves a different pathway.

Electrochemical Determination of L-Dopa in Mucuna pruriens Seeds, Leaves and Commercial Siddha Product Using Gold Modified Pencil Graphite Electrode

In the present work a gold modified pencil graphite electrode (GPGE) was used for the determination of L-dopa present in the aqueous extracts of Mucuna pruriens seeds (MPS), Mucuna pruriens leaves (MPL) and Commercial Siddha Product (CSP). The GPGE shows excellent electrocatalytic activity towards the oxidation of both L-dopa and ascorbic acid (AA), with the separation of peak potential of 98 mV. The differential pulse voltammetric (DPV) results indicated that the detection limit for L-dopa was 1.54 mu M (S/N=3). This method can be successfully applied for the determination of L-dopa in real samples.

Variations in the Levels of Aminoacylation and Modified Nucleotide Content Between Total Transfer-RNAS From Chloroplasts and Etioplasts in Cucumber Cotyledons

Total tRNAs isolated from chloroplasts and etioplasts of cucumber cotyledons were compared with respect to amino acid acceptance, isoacceptor distribution and extent of modification. Aminoacylation of the tRNAs with nine different amino acids studied indicated that the relative acceptor activities of chloroplast total tRNAs for four amino acids are significantly higher than etioplast total tRNAs. Two dimensional polyacrylamide gel electrophoresis (2D-PAGE) of chloroplast total tRNAs separated at least 32 spots, while approximately 41 spots were resolved from etioplast total tRNAs. Comparison of the reversed-phase chromatography (RPC-5) profiles of chloroplast and etioplast leucyl-, lysyl-, phenylalanyl-, and valyl-tRNA species showed no qualitative differences in the elution profiles. However, leucyl-, lysyl- and valyl-tRNA species showed quantitative differences in the relative amounts of the isoaccepting species present in chloroplasts and etioplasts. The analysis of modified nucleotides of total tRNAs from the two plastid types indicated that total tRNA from etioplasts was undermodified with respect to ribothymidine, isopentenyladenosine/hydroxy-isopentenyladenosine, 1-methylguanosine and 2-o-methylguanosine. This indicates that illumination may cause de novo synthesis of chloroplast tRNA-modifying enzymes encoded for by nuclear genes leading to the formation of highly modified tRNAs in chloroplasts. Based on these results, we speculate that the observed decrease in levels of aminoacylation, variations in the relative amounts of certain isoacceptors, and differences in the electrophoretic mobilities of some extra tRNA spots in the etioplast total tRNAs as compared to chloroplast total tRNAs could be due to some partially undermodified etioplast tRNAs. Taken together, the data suggested that the light-induced transformation of etioplasts into chloroplasts is accompanied by increases in the relative levels of some functional chloroplast tRNAs by post transcriptional nucleotide modifications.

Covalent Grafting of Polydimethylsiloxane over Surface-Modified Alumina Nanoparticles

The synthesis of ``smart structured'' conducting polymers and the fabrication of devices using them are important areas of research. However, conducting polymeric materials that are used in devices are susceptible to degradation due to oxygen and moisture. Thus, protection of such devices to ensure long-term stability is always desirable. Polymer nanocomposites are promising materials for the encapsulation of such devices. Therefore, it is important to develop suitable polymer nanocomposites as encapsulation materials to protect such devices. This work presents a technique based on grafting between surface-decorated gamma-alumina nanoparticles and polymer to make nanocomposites that can be used for the encapsulation of devices. Alumina was functionalized with allyltrimethoxysilane and used to conjugate polymer molecules (hydride-terminated polydimethylsiloxane) through a platinum-catalyzed hydrosilylation reaction. Fourier transform infrared spectroscopy, X-ray-photoelectron spectroscopy, and Raman spectroscopy were used to characterize the surface chemistry of the nanoparticles after surface modification. The grafting density of alkene groups on the surface of the modified nanoparticles was calculated using CHN and thermogravimetric analyses. The thermal stability of the composites was also evaluated using thermogravimetric analysis. The nanoindentation technique was used to analyze the mechanical characteristics of the composites. The densities of the composites were evaluated using a density gradient column, and the morphology of the composites was evaluated by scanning electron microscopy. All of our studies reveal that the composites have good thermal stability and mechanical flexibility and, thus, can potentially be used for the encapsulation of organic photovoltaic devices.

Modified Kirchhoffs theory of plates including transverse shear deformations

A primary flexure problem defined by Kirchhoff theory of plates in bending is considered. Significance of auxiliary function introduced earlier in the in-plane displacements in resolving Poisson-Kirchhoffs boundary conditions paradox is reexamined with reference to reported sixth order shear deformation theories, in particular, Reissner's theory and Hencky's theory. Sixth order modified Kirchhoff's theory is extended here to include shear deformations in the analysis. (C) 2011 Elsevier Ltd. All rights reserved.

Growth inhibitory, apoptotic and anti-inflammatory activities displayed by a novel modified triterpenoid, cyano enone of methyl boswellates

Triterpenoids are pentacyclic secondary metabolites present in many terrestrial plants. Natural triterpenoids have been reported to exhibit anti-inflammatory and anti-carcinogenic activities. Here, we show that modifications of ring A of boswellic acid (2 cyano, 3 enone) resulted in a highly active growth inhibitory, anti-inflammatory, pro-differentiative and anti-tumour triterpenoid compound called cyano enone of methyl boswellates (CEMB). This compound showed cytotoxic activity on a number of cancer cell lines with IC50 ranging from 0.2 to 0.6 mu M. CEMB inhibits DNA synthesis and induces apoptosis in A549 cell line at 0.25 mu M and 1 mu M concentrations, respectively. CEMB induces adipogenic differentiation in 3T3-L1 cells at a concentration of 0.1 mu M. Finally, administration of CEMB intra-tumourally significantly inhibited the growth of C6 glioma tumour xenograft in immuno-compromised mice. Collectively, these results suggest that CEMB is a very potent anti-tumour compound.

Performance analysis of a modified spatial smoothing technique for direction estimation

The statistical performance analysis of ESPRIT, root-MUSIC, minimum-norm methods for direction estimation, due to finite data perturbations, using the modified spatially smoothed covariance matrix, is developed. Expressions for the mean-squared error in the direction estimates are derived based on a common framework. Based on the analysis, the use of the modified smoothed covariance matrix improves the performance of the methods when the sources are fully correlated. Also, the performance is better even when the number of subarrays is large unlike in the case of the conventionally smoothed covariance matrix. However, the performance for uncorrelated sources deteriorates due to an artificial correlation introduced by the modified smoothing. The theoretical expressions are validated using extensive simulations. (C) 1999 Elsevier Science B.V. All rights reserved.