A New Pathway for the Degradation of a Sesquiterpene Alcohol, Nerolidol by Alcaligenes eutrophus

An oxidative pathway hitherto unknown for tile degradation of a sesquiterpene alcohol, nerolidol (I) by Alcaligenes eutrophus is presented. Fermentation of nerolidol (I) by this organism in a mineral salts medium resulted in the formation of geranylacetone (II) and an optically active alcohol (S)-(+)-geranylacetol (III), as major metabolites. Nerolidol (I) induced cells readily transformed 1,2-epoxynerolidol (IV) and 1,2-dihydroxynerolidol (V) into geranylacetone (II). These cells also exhibited their ability to carry out stereospecific reduction of II into (S)-(+)-geranylacetol (III). Oxygen uptake studies clearly indicated that nerolidol induced cells oxidized compounds II, III, IV, V and ethyleneglycol. Based on these observations a new oxidative pathway for the degradation of I is suggested which envisages the epoxidation of the terminal double bond, opening of the epoxide and cleavage between C-2 and C-3 in a manner similar to the periodate oxidation of diol.

Characteristics of Dynamic Recrystalization Domain in the Processing Map for Hot-Working of OFHC Coper

The constitutive flow behaviour of OFHC copper under working conditions is studied using hot compression in the temperature range 650 to 900-degrees-C and strain rate range 0.001 to 100 s-1. The variation of the efficiency of power dissipation given by [2m/(m + 1)] (where m is the strain rate sensitivity) with temperature and strain rate is represented in the form of a power dissipation map and interpreted on the basis of the Dynamic Materials Model. The map prominently exhibited a domain centered at 850-degrees-C and 100 s-1 with a peak efficiency of 35 %. On the basis of the correlation of variations of grain size, efficiency of power dissipation and hot workability with temperature, the domain is identified to represent dynamic recrystallization (DRX).

Effect of Zirconium on the Processing MAPS For Hot-Working of Alpha-Beta Brass

The effect of zirconium on the hot working characteristics of alpha and alpha-beta brass was studied in the temperature range of 500 to 850-degrees-C and the strain rate range of 0.001 to 100 s-1. On the basis of the flow stress data, processing maps showing the variation of the efficiency of power dissipation (given by [2m/(m+1)] where m is the strain rate sensitivity) with temperature and strain rate were obtained. The addition of zirconium to alpha brass decreased the maximum efficiency of power dissipation from 53 to 39%, increased the strain rate for dynamic recrystallization (DRX) from 0.001 to 0.1 s-1 and improved the hot workability. Alpha-beta brasses with and without zirconium exhibit a domain in the temperature range from 550 to 750-degrees-C and at strain rates lower than 1 s-1 with a maximum efficiency of power dissipation of nearly 50 % occurring in the temperature range of 700 to 750-degrees-C and a strain rate of 0.001 s-1. In the domain, the alpha phase undergoes DRX and controls the hot deformation of the alloy whereas the beta phase deforms superplastically. The addition of zirconium to alpha-beta brass has not affected the processing maps as it gets partitioned to the beta phase and does not alter the constitutive behavior of the alpha phase

Nonlinear finite element analysis of reinforced concrete corbel

Reinforced concrete corbels have been analysed using the nonlinear finite element method. An elasto-plastic-cracking constitutive formulation using Huber-Hencky-Mises yield surface augmented with a tension cut-off is employed. Smeared-fixed cracking with mesh-dependent strain softening is employed to obtain objective results. Multiple non-orthogonal cracking and opening and closing of cracks are permitted. The model and the formulation are verified with respect to available numerical solution for an RC corbel. Results of analyses of nine reinforced concrete corbels are presented and compared with experimental results. Nonlinear finite element analysis of reinforced concrete structures is shown to be a complement and also a feasible alternative to laboratory testing.

Processing map for hot working of as cast magnesium

The constitutive flow behaviour in hot working of as cast magnesium has been studied with the help of a processing map developed in the temperature range 300-550°C and strain rate range 0·001-100 s−1. The map, interpreted using the dynamic materials model, revealed that the material undergoes dynamic recrystallisation at 425°C and 0·3 s−1, which are the optimum parameters for hot working. Ai temperatures higher than 450°C and strain rates lower than about 0·1 s−1, wedge cracking occurs in as cast magnesium. The wedge cracking domain has a high efficiency of power dissipation (60%), whereas the dynamic recrystallisation domain has a value of 34%. At temperatures below 450°C and strain rates above 10 s−1, the material exhibits flow instability in the form of mechanical twinning. At higher temperatures and strain rates, instability is manifested by flow localisation.

Processing maps for hot working of Cu-Ni-Zn alloys. Part I - Alpha-nickel silver

The constitutive behaviour of agr — nickel silver in the temperature range 700–950 °C and strain rate range 0.001–100 s–1 was characterized with the help of a processing map generated on the basis of the principles of the ldquodynamic materials modelrdquo of Prasadet al Using the flow stress data, processing maps showing the variation of the efficiency of power dissipation (given by 2m/(m+1) wherem is the strain-rate sensitivity) with temperature and strain rate were obtained, agr-nickel silver exhibits a single domain at temperatures greater than 750 °C and at strain rates lower than 1s–1, with a maximum efficiency of 38% occurring at about 950 °C and at a strain rate of 0.1 s–1. In the domain the material undergoes dynamic recrystallization (DRX). On the basis of a model, it is shown that the DRX is controlled by the rate of interface formation (nucleation) which depends on the diffusion-controlled process of thermal recovery by climb. At high strain rates (10 and 100s–1) the material undergoes microstructural instabilities, the manifestations of which are in the form of adiabatic shear bands and strain markings.

Processing maps for hot working of Cu-Ni-Zn alloys Part II Alpha-Beta nickel silver

The constitutive behaviour of agr-beta nickel silver in the temperature range 600�850 °C and strainrate range 0.001�100s�1 was characterized with the help of a processing map generated on the principles of the dynamic materials model. On the basis of the flow-stress data, processing maps showing the variation of the efficiency of power dissipation (given by [2m/(m+1)], wherem is the strain-rate sensitivity) with temperature and strain rate were obtained, agr-beta nickel silver exhibits a single domain at temperatures greater than 700 °C and at strain rates lower than 1 s�1 with a maximum efficiency of power dissipation of about 42% occurring at about 850 °C and at 0.1 s�1. In the domain, the agr phase undergoes dynamic recrystallization and controls the deformation of the alloy, while the beta phase deforms superplastically. Optimum conditions for the processing of agr-beta nickel silver are 850 °C and 0.1 s�1. The material undergoes unstable flow at strain rates of 10 and 100 s�1 and in the temperature range 600�750 °C, manifestated in the form of adiabatic shear bands.

Influence of crack tip constraint on void growth in ductile FCC single crystals

Effect of constraint (stress triaxiality) on void growth near a notch tip in a FCC single crystal is investigated. Finite element simulations within the modified boundary layer framework are conducted using crystal plasticity constitutive equations and neglecting elastic anisotropy. Displacement boundary conditions based on model, elastic, two term K-T field are applied on the outer boundary of a large circular domain. A pre-nucleated void is considered ahead of a stationary notch tip. The interaction between the notch tip and the void is studied under different constraints (T-stress levels) and crystal orientations. It is found that negative T-stress retards the mechanisms of ductile fracture. However, the extent of retardation depends on the crystal orientation. Further, it is found that there exists a particular orientation which delays the ductile fracture processes and hence can potentially improve ductility. This optimal orientation depends on the constraint level. (C) 2010 Published by Elsevier B.V.

A numerical investigation of ductile fracture initiation in a high-strength low-alloy steel

In this work, static and drop-weight impact experiments, which have been conducted using three-point bend fracture specimens of a high-strength low-alloy steel, are analysed by performing finite-element simulations. The Gurson constitutive model that accounts for the ductile failure mechanisms of microvoid nucleation, growth and is employed within the framework of a finite deformation plasticity theory. Two populations of second-phase particles are considered, including large inclusions which initiate voids at an early stage and small particles which require large strains to nucleate voids. The most important objective of the work is to assess quantitatively the effects of material inertia, strain rate sensitivity and local adiabatic temperature rise (due to conversion of plastic work into heat) on dynamic ductile crack initiation. This is accomplished by comparing the evolution histories of void volume fraction near the notch tip in the static analysis with the dynamic analyses. The results indicate that increased strain hardening caused by strain rate sensitivity, which becomes important under dynamic loading, plays a benign role in considerably slowing down the void growth rate near the notch tip. This is partially opposed by thermal softening caused by adiabatic heating near the notch tip.

Evidence for the involvement of multiple pathways in the biodegradation of 1- and 2-methylnaphthalene by pseudomonas putida CSV86

Pseudomonas putida CSV86, a soil bacterium, grows on 1- and 2-methylnaphthalene as the sole source of carbon and energy. In order to deduce the pathways for the biodegradation of 1- and 2-methylnaphthalene, metabolites were isolated from the spent medium and purified by thin layer chromatography. Emphasis has been placed on the structural characterisation of isolated intermediates by CC-MS, demonstration of enzyme activities in the cell free extracts and measurement of oxygen uptake by whole cells in the presence of various probable metabolic intermediates. The data obtained from such a study suggest the possibility of occurrence of multiple pathways in the degradation of 1- and 2-methylnaphthalene. We propose that, in one of the pathways, the aromatic ring adjacent to the one bearing the methyl moiety is oxidized leading to the formation of methylsalicylates and methylcatechols. In another pathway the methyl side chain is hydroxylated to -CH2-OH which is further converted to -CHO and -COOH resulting in the formation of naphthoic acid as the end product. In addition to this, 2-hydroxymethylnaphthalene formed by the hydroxylation of the methyl group of 2-methylnaphthalene undergoes aromatic ring hydroxylation. The resultant dihydrodiol is further oxidised by a series of enzyme catalysed reactions to form 4-hydroxymethyl catechol as the end product of the pathway.

Utility of microbes in organic-synthesis - selective transformations of acyclic isoprenoids by aspergillus-niger

Bioconversion of acyclic isoprenoids using a strain of Aspergillus niger results in hydroxylated metabolites with regio- and stereoselectivity. The organism carries out oxidation of the terminal allylic methyl group and the remote double bond in all the compounds tested (I-VII). However, these two activities seem to have preferential structural requirements. When an acyclic isoprenoid with a ketone functionality such as geranylacetone is used as the substrate, the organism also carries out the asymmetric reduction of the keto group. All the metabolites formed have been purified and characterized by conventional spectroscopic methods and quantification has been made by gas chromatographic analyses.

Flow Instabilities and fracture in Ti-6Al-4V deformed in compression at 298 K to 673 K

Uniaxial compression tests were conducted on Ti-6Al-4V specimens in the strain-rate range df 0.001 to 1 s(-1) and temperature range of 298 to 673 K. The stress-strain curves exhibited a peak flow stress followed by flow softening. Up to 523 K, the specimens cracked catastrophically after the flow softening started. Adiabatic shear banding was observed in this regime. The fracture surface exhibited both mode I and II fracture features. The state of stress existing in a compression test specimen when bulging occurs is responsible for this fracture. The instabilities observed in the present tests are classified as ''geometric'' in nature and are state-of-stress dependant, unlike the ''intrinsic'' instabilities, which are dependant on the dynamic constitutive behavior of the material.

Transformation of 16-dehydroprogesterone and 17?-hydroxyprogesterone by Mucor piriformis

Mucor piriformis was used to study the mode of transformation of 16-dehydroprogesterone (I, pregna-4, 16-diene-3, 20-dione) and 17 alpha-hydroxyprogesterone (II, 17 alpha-hydroxypregn-4-ene-3, 20-dione). Biotransformation products formed from I were 14 alpha-hydroxypregna-4, 16-diene-3, 20-dione (Ia), 7 alpha, 14 alpha-dihydroxypregna-4 16-diene-3, 20-dione (Ib), 3 beta, 7 alpha, 14 alpha-trihydroxy-5 alpha-pregn-16-en-20-one (Ic), and 3 alpha, 7 alpha, 14 alpha-trihydroxy-5 alpha-pregn-16-en-20-one (Id). Metabolites Ic and Id appear to be hitherto unknown. Timecourse studies suggested that the transformation is initiated by hydroxylation at the 14 alpha-position (Ia) followed by hydroxylation at the 7 alpha-position (Ib). Microsomes (105,000 g sediment) prepared from 16-dehydroprogesterone-induced cells hydroxylate I to its 14 alpha-hydroxy derivative (Ia) in the presence of NADPH. Incubation of Ia with the organism resulted in the formation of Ib, Ic and Id. Biotransformation products formed from compound II were 17 alpha, 20 alpha-dihydroxypregn-4-en-3-one (IIa), 7 alpha, 17 alpha-dihydroxypregn-4-ene-3, 20-dione (IIb), 6 beta, 17 alpha, 20 alpha-trihydroxypregn-4-en-3-one (IIc) and 11 alpha, 17 alpha, 20 alpha-trihydroxypregn-4-en-3-one (IId). Time-course studies indicated that IIa is the initial product formed, which is further hydroxylated either at the 6 beta or 11 alpha position. Incubation of IIa with the organism resulted in the formation of IIc and IId. Reduction of the 4-en-3-one system and 20-keto group has not been observed before in organisms of the order Mucorales. In addition, M. piriformis has been shown to carry out hydroxylation at the C-6, C-7, C-11 and C-14 positions in the steroid molecules tested.

A pathway for biodegradation of 1-naphthoic acid by Pseudomonas maltophilia CSV89

Pseudomonas maltophilia CSV89, a bacterium isolated from soil in our laboratory, grows on 1-naphthoic acid as the sole source of carbon and energy. To elucidate the pathway for degradation of 1-naphthoic acid, the metabolites were isolated from spent medium, purified by TLC, and characterized by gas chromatography-mass spectrometry. The involvement of various metabolites as intermediates in the pathway was established by demonstrating relevant enzyme activities in cell-free extracts, oxygen uptake and transformation of metabolites by the whole cells. The results obtained from such studies suggest that the degradation of 1-naphthoic acid is initiated by double hydroxylation of the aromatic ring adjacent to the one bearing the carboxyl group, resulting in the formation of 1,2-dihydroxy-8-carboxynaphthalene. The resultant diol was oxidized via 3-formyl salicylate, 2-hydroxyisophthalate, salicylate and catechol to TCA cycle intermediates.

Mechanism of growth inhibition of intraerythrocytic stages of Plasmodium falciparum by 5-aminoimidazole-4-carboxamide ribonucleoside (AICAR)

Purine nucleotide synthesis in Plasmodium falciparum takes place solely by the purine salvage pathway in which preformed purine base(s) are salvaged from the host and acted upon by a battery of enzymes to generate AMP and GMP. Inhibitors of this pathway have a potent effect on the in vitro growth of P. falciparum and are hence, implicated as promising leads for the development of new generation anti-malarials. Here, we describe the mechanism of inhibition of the intraerythrocytic growth of P. falciparum by the purine nucleoside precursor, 5-aminoimidazole-4-carboxamide ribonucleoside (AICAR). Our results show that AICAR toxicity is mediated through the erythrocyte in which AICAR is phosphorylated to its nucleotide, ZMP. Further, purine metabolite labeling of the parasitized erythrocytes by H-3]-hypoxanthine, in the presence of AICAR, showed a significant decrease in radioactive counts in adenylate fractions but not in guanylate fractions. The most dramatic effect on parasite growth was observed when erythrocytes pretreated with AICAR were used in culture. Pretreatment of erythrocytes with AICAR led to significant intracellular accumulation of ZMP and these erythrocytes were incapable of supporting parasite growth. These results implicate that in addition to the purine salvage pathway in P. falciparum, AICAR alters the metabolic status of the erythrocytes, which inhibits parasite growth. As AICAR and ZMP are metabolites in the human serum and erythrocytes, our studies reported here throw light on their possible role in disease susceptibility, and also suggests the possibility of AICAR being a potential prophylactic or chemotherapeutic anti-malarial compound. (C) 2011 Elsevier B.V. All rights reserved.