Do the Hydrolysis Products, Methylamine and N,N'-Dimethylurea, Play any Role in the Methyl Isocyanate-Induced Haematological and Biochemical Changes in Rabbits?

The subcutaneous administration of methyl isocyanate (MIC) to female rabbits, resulted in significant increases in haemoglobin concentration, erythrocyte volume fraction and leucocyte number in blood, as well as plasma total proteins, and urea. The present study was designed to investigate whether the hydrolytic products of MIC, methylamine (MA) and N,N'-dimethylurea (DMU) play any role in eliciting these changes. Both MA and DMU administered subcutaneously in an equimolar dose to that of 1.0 LD50 MIC, 2.2 mmol kg-1, had no influence on these parameters, although there was a marginal increase in the plasma urea level shortly after the administration of DMU. This study establishes that the observed haematological and biochemical changes induced by MIC intoxication in rabbits are mostly due to MIC.

Influence of methylamine and N,N'-dimethylurea, the hydrolysis products of methyl isocyanate, on its systemic toxicity

Subcutaneous administration of the LD50 dose of methyl isocyanate (MIC) to rats induced severe hyperglycaemia, lactic acidosis and uraemia in rats. Neither methylamine (MA) nor N,N′-dimethylurea (DMU), the hydrolysis products of MIC, administered in equimolar doses had any influence on these parameters except for a marginal transient increase in plasma urea by DMU. Methyl isocyanate administration led to haemoconcentration, resulting in an increase in the plasma concentration of total proteins and a decrease in both the plasma concentration of albumin and the plasma cholinesterase activity. The hydrolysis products of MIC had no influence on any of these parameters. Thus, it seems reasonable to suggest that the systemic effects of MIC are caused by MIC per se, in spite of its high hydrolytic instability.

Potassamide induced in situ alkylation of 5,6-dihydroisoquinolines: Structure of products

Potassamide induced in situ alkylation of 1-alkyl- 4-cyano-3-methoxy-5,6-dihydroisoquinolines (2a & 2b) with alkyl iodides (CH3I, CH3CH2I & cyclohexyl iodide) gave the 5-alkyl- and 5,9-dialkyl-5,6-dihydroisoquinolines (4–ad & 3a–e), isoquinoline derivatives, (5a–b) and diastereomeric mixture of 4- alkyl-1,2,3,4-tetrahydroisoquinolin-3(2H)-ones (6a–e & 6′a–e). Structures were assigned on the basis of spectral data [Mass, 1H & 13C NMR, 2D NOESY & HC-COLOC]. Amide induced in situ alkylation of compounds 3a and 4a with CH3I gave in almost quantitative yield the dimethylated compounds 3d and 3a respectively. While KNH2/liq.NH3 methylation of 1,2- dihydroisoquinoline, 1 with CH3I gave the mixture of compounds, 6a & 6′a and the isoquinoline derivative 5a, NaH/benzene reaction of 1 with CH3I gave exclusively 5a. N-methylation of the mixture of compounds 6a & 6′a with NaH/CH3I gave the methylated derivatives, 7 & 8. A suitable mechanism has been proposed for the formation of products.

Reaction of spironaphthalenones with hydroxylamine: Part III. A novel mechanism for the formation of products and trapping of an intermediate.

A mechanism involving the intermediacy of nitrene 5, formed from the oxime of spironaphthalenone 1 by acid catalysed dehydration, has been proposed to explain the formation of pyrrolotropones/pyrrolo esters from spironaphthalenones. The initially formed nitrene rearranges to the isopyrrole 6, which either undergoes sigmatropic migration to the pyrrolotropone 2 or adds alcohol to form the pyrrolo ester depending on substitution at 1′ position. The isopyrrole intermediate 6 has been trapped as a Diels-Alder adduct 8.

Excision of uracil from the ends of double stranded DNA by uracil DNA glycosylase and its use in high efficiency cloning of PCR products

We show that uracil DNA glycosylase from E. coli excises uracil residues from the ends of double stranded oligos. This information has allowed us to develop an efficient method of cloning PCR amplified DNA. In this report, we describe use of this method in cloning of E. coli genes for lysyl- and methionyl-tRNA synthetases. Efficiency of cloning by this method was found to be the same as that of subcloning of DNA restriction fragments from one vector to the other vector. Possibilities of using other DNA glycosylases for such applications are discussed.

Potassamide induced in situ benzylation of 5,6-dihydroisoquinolines: Structure of novel products

Potassamide induced in situ benzylation of 1-alkyl-4-cyano-3-methoxy-5,6-dihydroisoquinolines (1a-b) with benzyl iodide gave the 5-benzyl-, 5,9-dibenzyl- and 4,4-dibenzyl-5,6-dihydroisoquinolines (9a-b, 8a-b and 10a-b), isoquinoline derivatives (4a-b) and diastereomeric mixture of 4-benzyl-1,2,3,4-tetrahydroisoquinolin-3(2H)-ones (11a-b & 11'a-b). Structures were assigned on the basis of spectral data [Mass, H-1 & C-13 NMR, 2D NOESY]. A few reactions carried out to transform the diastereomeric mixture of compounds 11a and 11's to the spirobenzylisoquinoline system 7a isomeric with naturally occurring ochotensane system ga are discussed.

Thermal degradation products of poly(styrenesulfides) investigated by direct pyrolysis�mass spectrometry and flash pyrolysis�gas chromatography/mass spectrometry

The thermal degradation products of two sulfur polymers, poly(styrenedisulfide) (PSD) and poly(styrenetetrasulfide) (PST), were investigated in parallel by direct pyrolysis-mass spectrometry (DPMS) and by flash pyrolysis-GC/MS (Py-GC/MS). The time-scale of the two pyrolysis techniques is quite different, and therefore they were able to detect significantly different products in the pyrolysis of PSD and PST because of the thermal lability of sulfur-containing compounds. However, the results obtained are not contradictory, and satisfactory mechanisms for the thermal degradation of PSD and PST have been derived from the overall evidence available. Pyrolysis compounds containing sulfur, styrene, and a number of cyclic styrene sulfides and diphenyldithianes have been observed by DPMS. However, in flash pyrolysis-GC/MS, styrene, sulfur, only one cyclic styrene sulfide, and two isomers of diphenylthiophene have been detected. These thiophene derivatives were indeed absent among the compounds obtained by DPMS because they were the terminal (most thermally stable) species arising from further decomposition of the cyclic styrene sulfides formed in the primary thermal degradation processes of PSD and PST.

Primary pyrolysis products of thiokol liquid polysulfide

An analysis of the primary degradation products of the widely used commercial polysulfide polymer Thiokol LP-33 by direct pyrolysis-mass spectrometry (DP-MS) is reported. The mechanism of degradation is through a radical process involving the random cleavage of a formal C-O bond followed by backbiting to form the cyclic products.

Towards the total synthesis of tashironin related allo-cedrane natural products: further exploitation of the oxidative dearomatization-IMDA-RCM triad based strategy

Synthetic studies directed towards allo-cedrane based, tashironin sibling natural products, involving some deft functional group manipulations on a preformed tetracyclic scaffold, are delineated. (C) 2011 Elsevier Ltd. All rights reserved.

Plate-shaped transformation products in zirconium-base alloys

Plate-shaped products resulting from martensitic, diffusional, and mixed mode transformations in zirconium-base alloys are compared. in the present study. These alloys are particularly suitable for the comparison in view of the fact that the lattice correspondence between the parent beta (bcc) and the product alpha (hcp) or gamma-hydride (fct) phases are remarkably similar for different types of transformations. Crystallographic features such as orientation relations, habit planes, and interface structures associated with these transformations have been compared:, with a view toward examining whether the transformation mechanisms have characteristic imprints on these experimental observables. Martensites exhibiting dislocated lath, internally twinned plate, and self-accommodating three-plate cluster morphologies have been encountered in Zr-2.5Nb alloy. Habit planes corresponding to all these morphologies have been found to be consistent with the predictions based on the invariant plane strain (IFS) criterion. Different morphologies have been found to reflect the manner in which the neighboring martensite variants are assembled. Lattice-invariant shears (LISs) for all these cases have been identified to be either {10 (1) over bar 1}(alpha) ((1) over bar 123)(alpha) slip or twinning on (10 (1) over bar 1)(alpha) planes. Widmanstatten alpha precipitates, forming in a step-quenching treatment, have been shown to have a lath morphology, the alpha/beta interface being decorated with a periodic array of (c + a) dislocations at a spacing of 8 to 10 nm. The line vectors of these dislocations are nearly parallel to the invariant lines. The alpha precipitates, forming in the retained beta phase on aging, exhibit an internally twinned structure with a zigzag habit plane. Average habit planes for the morphologies have been found to lie near the {103}(beta) - {113}(beta) poles, which are close to the specific variant of the {112}(beta) plane, which transforms into a prismatic plane of the type {1 (1) over bar 00}(alpha). The crystallography of the formation of the gamma-hydride phase (fct) from both the alpha and beta phases is seen to match the IFS predictions. While the beta-gamma transformation can be treated approximately as a simple shear on the basal plane involving a change in the stacking sequence, the alpha-gamma transformation call be conceptually broken into a alpha --> beta transformation following the Burgers correspondence and the simple beta-gamma shear process. The active eutectoid decomposition in the Zr-Cu system, beta --> alpha + beta', has been described in terms of cooperative growth of the alpha phase from the beta phase through the Burgers correspondence and of the partially ordered beta' (structurally similar to the equilibrium Zr2Cu phase) through an ordering process. Similarities and differences in crystallographic features of these transformations have been discussed. and the importance of the invariant line vector in deciding the geometry of the corresponding habit planes has been pointed out.

Synthetic studies towards novel terpenic natural products kelsoene and poduran: Construction of the complete 4-5-5-fused tricarbocyclic core

A common synthetic approach to the recently reported sesquiterpene kelsoene 1 and the tetraterpene poduran 5, bearing a novel tricyclo[6.2.0.0(2,6)]decane framework, from commercially available 1,5-COD and leading to the first construction of the carbocyclic core present in these natural products is delineated.

Synthesis of nanocomposites of Ni-Zn ferrite in aniline formaldehyde copolymer and studies on their pyrolysis products

Synthesis of nanoparticles of Ni-Zn ferrite dispersed in aniline formaldehyde copolymer using a room temperature route and the effect of heat treatment on these samples were studied using XRD, FTIR spectroscopy, Fe-57 Mossbauer spectroscopy and TEM microscopy. The results show the formation of nanosized particles of Ni-Zn ferrite in the polymer matrix at room temperature. On pyrolysis, the Ni-Zn ferrite phase persists up to 500 degreesC. However, heating of composites to 700 degreesC results in the partial reduction of the spinet ferrite leading to the formation of Ni-Fe alloy under ambient conditions and complete reduction of the alloy on heating in inert atmosphere. (C) 2003 Elsevier B.V. All rights reserved.