Microbial transformation of a fungicide-derived amine, dimethyl-p-phenylene diamine by Alcaligenes DM4

Abstract Microbial transformation of N, N-dimethyl-p-phenylene diamine (DMPDA), a microbial product formed from the fungicide fenaminosulf (p-dimethylaminobenzenediazo sodium sulfonate) was studied by enriching microbes in soils treated with the amine. Microorganisms isolated from DMPDA-treated soil belonged to the genera of Micrococcus, Alcaligenes, and Corynebacterium. Of the various isolates, Alcaligenes DM4 showed maximal growth on DMPDA utilizing it as sources of carbon and nitrogen. When grown in mineral salts basal medium containing 0.05% DMPDA to serve as carbon and nitrogen sources, Alcaligenes DM4 grew exponentially up to 18 h. Even though the characterization of the complete pathway of microbial degradation of DMPDA could not be carried out due to the auto-oxidation of the compound, the initial transformation product of DMPDA by Alcaligenes DM4 has been identified as a dimer. The dimer is generated into the culture medium presumably by the extra-cellular oxidase of Alcaligenes DM4. It is suggested that the risk-benefit evaluation on the use of fenaminosulf is to be made taking into consideration the microbial transformations of the fungicide.

Properties of iron related quenched-in levels in p-silicon

The electrical and optical properties of the thermally induced quenched-in levels in p-silicon which have heen attributed to iron are studied. The two levels, HI and H2, are located at Ev + 0.42 eV and Ev + 0.52 eV, respectively, as determined by TSCAP, DLTS, and transient photocapacitance methods. The photoionization cross sections are well described by Lucovsky's model. The hole capture by H1 is temperature dependent; a barrier of 40 meV is measured. However, multiphonon emission mechanism cannot be invoked to explain this temperature dependence due to the inferred zero lattice relaxation. The source of iron contamination is found to be the ambient conditions, in particular the quartz tube. The conflicting reports regarding the stability and the variation in the reported capture cross section values suggests that the observed Ev + 0.4 eV level must be a complex centre. The inferred near zero lattice relaxation during the electron transition implies weak coupling to the host lattice.

The effect of some catalysts on the curing of oxiranes with p-phenylenediamine

The effect of some alcohols, acetylacetonates of transition metals, and manganese stearate and naphthenate on the curing reaction of a diglycidyl ether of ether of bisphenol-A with p-phenylenediamine is studied. Maximum catalytic activity is shown by the manganese compounds and triethanolamine.

Weak rectifying behaviour of p-SnS/n-ITO heterojunctions

This work explores the electrical properties of p-SnS/n-ITO heterojunction at different temperatures. The p-type SnS film was deposited on n-type ITO substrate using the thermal evaporation technique and its junction properties were studied using two probe method. The as-grown p-n junction exhibited weak rectifying behaviour with a low Saturation current of the order of similar to 10(-6) A. While increasing temperature, the saturation current of the junction is increased and however, its series resistance decreased. At all temperatures the junction exhibited three types of transport mechanisms depending on applied bias-voltage. At lower voltages the junction showed nearly ideal diode characteristics. The junction behaviour with respect to bias-voltage and temperature is discussed with the help of existing theories and energy band diagram.

2-(p-Chlorophenyl)-3-nitro-2H-chromene

C15H10C1NO3, Mr=287.70, triclinic, PI, Z= 2, F(000)= 296, a = 5.422 (1), b = 9.624 (1), c= 12.636 (2) A, ~= 76.66 (2), fl= 78.67 (2), ~= 87.97 (2) ° , V=629.03 A 3, Din= 1.507 (3), Ox= 1.519Mgm -3, 2(CuKa)=l.5418A, p=26.25mm -~, T= 413 K, final R = 0.0577 for 1859 observed reflections [I>2.5e(/)]. Bond lengths [1.512(5)A] and angles [109.2 (3) °] at the phenyl substitution site are comparable with those in other molecules. The bond angle at the nitro substitution site C(7)-C(8)-C(9) is 122.9 (3) ° owing to the electron-withdrawing character of the nitro group. The pyran ring adapts a half-chair conformation.

Kinetics Of The Aminolysis Reactions Of Chlorocyclotriphosphazenes-Changeover From A Sn2(P) To A Sn1(P) Mechanism

A change-over from SN2(P) to SN1(P) mechanism is established for the chlorine replacement reactions of halogenocyclophosphazenes; this mechanistic change-over helps in rationalising the diverse findings reported for this class of reactions.

Electrical transport in layered crystalline semiconductors GeS doped with Ag, P impurities at high pressure

A study of the transport properties of layered crystalline semiconductors GeS (undoped and doped with Ag, P impurity) under quasihydrostatic pressure using Bridgman anvil system is made for the first time. Pressure-induced effects in undoped crystals reveal initial rise in resistivity followed by two broad peaks at higher pressures. Silver doping induces only minor changes in the behaviour except removing the second peak. Phosphorous impurity is found to have drastic effect on the transport properties. Temperature dependence of the resistivity exhibits two activation energies having opposite pressure coefficients. Results are discussed in the light of intrinsic features of the layered semiconductors.

Choice of the End Functional Groups in Tri(p-phenylenevinylene) Derivatives Controls Its Physical Gelation Abilities

New supramolecular organogels based on all-trans-tri(p-phenylenevinylene) (TPV) systems possessing different terminal groups, e.g., oxime, hydrazone, phenylhydrazone, and semicarbazone have been synthesized. The self-assembly properties of the compounds that gelate in specific organic solvents and the aggregation motifs of these molecules in the organogels were investigated using UV−vis, fluorescence, FT-IR, and 1H NMR spectroscopy, electron microscopy, differential scanning calorimetry (DSC), and rheology. The temperature variable UV−vis and fluorescence spectroscopy in different solvents clearly show the aggregation pattern of the self-assemblies promoted by hydrogen bonding, aromatic π-stacking, and van der Waals interactions among the individual TPV units. Gelation could be controlled by variation in the number of hydrogen-bonding donors and acceptors in the terminal functional groups of this class of gelators. Also wherever gelation is observed, the individual fibers in gels change to other types of networks in their aggregates depending on the number of hydrogen-bonding sites in the terminal functions. Comparison of the thermal stability of the gels obtained from DSC data of different gelators demonstrates higher phase transition temperature and enthalpy for the hydrazone-based gelator. Rheological studies indicate that the presence of more hydrogen-bonding donors in the periphery of the gelator molecules makes the gel more viscoelastic solidlike. However, in the presence of more numbers of hydrogen-bonding donor/acceptors at the periphery of TPVs such as with semicarbazone a precipitation as opposed to gelation was observed. Clearly, the choice of the end functional groups and the number of hydrogen-bonding groups in the TPV backbone holds the key and modulates the effective length of the chromophore, resulting in interesting optical properties.

N-[2-naphthyl]-glycine hydrazide, a potent inhibitor of dna-dependent rna-polymerase of mycobacterium-tuberculosis h37rv

N-[2-Naphthyl]-glycine hydrazide has been shown for the first time as a potent inhibitor of the DNA-dependent RNA polymerase (EC 2.7.7.6) of Mycobacterium tuberculosis H37Rv. At a concentration of 10 to the power -9 M, the compound shows maximum inhibition of the enzyme, the inhibition being less at higher concentrations. It is suggested that the novel type of inhibition pattern may be due to hydrophobic interactions occurring between the molecules of the compound at higher concentrations. The finding that there is a shift in the max of the compound could also account for this phenomenon. The effect of this compound was also tested on DNA-dependent RNA polymerases from an eukaryotic fungus, Microsporum canis. At a concentration of 10 to the power-9 M it inhibits RNA polymerase II (32 percent) but not RNA polymerases I and III.

Regulation of cytochrome P-450 gene expression. Studies with a cloned probe

A cDNA clone for cytochrome P-450e, a phenobarbitone-inducible species in rat liver, has been isolated and characterized. With the use of this cloned DNA, an attempt has been initiated to elucidate the factors regulating the cytochrome P-450 gene expression. Inhibitors of heme synthesis such as cobalt chloride and 3-amino-1,2,4-triazole block the induction of cytochrome P-450e by phenobarbitone at the level of transcription. This is evident from the decrease in the rate of synthesis of cytochrome P-450e, a decrease in the levels of specific translatable messenger RNA, a decrease in the specific cytoplasmic and nuclear messenger RNA contents, and nuclear transcription of cytochrome P-450e gene, as revealed by hybridization to the cloned probe, under these conditions. It is proposed that heme is a general regulator of cytochrome P-450 gene expression at the level of transcription, whereas the drug or its metabolite would impart the specificity needed for the induction of a particular species.

Low-Temperature Fluorination Of Sulfur-Compounds With Elemental Fluorine

Low temperature fluorination technique is adopted for fluorination of the following sulphur compounds in freon-11 medium (1) Sulphur dioxide (2) Thionyl chloride (3) Sulphuryl chloride (4) Tetrasulphur tetra nitride and (5) Sulphur bromide. All the compounds undergo oxidative fluorination to give rise to sulphur-fluorine compounds except sulphuryl chloride which resists fluorination. Sulphuryl chloride thus behaves as a good solvent medium for fluorination of other reactive compounds like elemental sulphur. Details of the experimental procedures adopted and the identification of the products will be presented

Reaction of Hexachlorocyclotriphosphazene with Sodium p-Cresoxide

The reaction of hexachlorocyclotriphosphazene (N3P3Cl6) with sodium p-cresoxide proceeds by a predominantly nongeminal pathway. The presence of geminal isomers at the bis- and tris-stages of substitution in tiny quantities (< 5%) has also been observed. All the chloro(p-cresoxy)cyclotriphosphazenes and their dimethylamino derivatives have been characterized by 1H-, 13C{1H}-, and 31P{1H}-NMR spectroscopy. The reaction of N3P3Cl6 with sodium phenoxide has been reinvestigated. The relative yields of the products at various stages of substitution and their isomeric compositions are almost the same for both phenoxy and p-cresoxy systems. Possible mechanisms to explain the observed isomeric compositions are discussed. A through-space interaction involving oxygen-2p and phosphorus-3d orbitals is invoked to explain the greater yield of the cis isomer of N3P3Cl4(OAr)2 than that of its trans isomer.

3-Amino-1,2,4-triazole is an inhibitor of protein synthesis on mitoribosomes in Neurospora crassa

The effects of the herbicide, 3-amino-1,2,4-triazole, an inhibitor of heme synthesis in rat liver, have been examined in the mold Neurospora crassa. The drug is a potent inhibitor of the growth of the mold and produces biochemical changes identical to those produced by chloramphenicol. 3-Amino-1,2,4-triazole, like chloramphenicol, is a direct and specific inhibitor of protein synthesis on mitoribosomes. A decrease in the levels of mitochondrial proteins which are completely or partly made on mitoribosomes and an accumulation in the levels of mitochondrial proteins of cytosolic origin have been observed. Both drugs depress porphyrin and heme levels, but there is actually an elevation in the levels of δ-aminolevulinate dehydratase, the rate-limiting enzyme of the heme-biosynthetic pathway in Neurospora crassa. In liver the enzyme is present in non-limiting amounts and the levels are depressed under conditions of 3-amino-1,2,4-triazole treatment. In Neurospora crassa the ‘derepression’ of δ-aminolevulinate dehydratase under conditions of 3-amino-1,2,4-triazole or chloramphenicol treatment is only partial because the drugs inhibit protein synthesis on mitoribosomes. It is concluded that an optimal rate of protein synthesis on mitoribosomes is necessary to maintain an adequate rate of heme synthesis.

A comparative study of tbe regulation of cytochrome P-450 and glutathione transferase gene expression in rat liver

A cDNA clone for the Ya subunit of glutathione transferase from rat liver was constructed in E.coli. The clone hybridized to Ya and Yc subunit messenger RNAs. On the basis of experiments involving cell-free translation and hybridization to the cloned probe, it was shown that prototype inducers of cytochrome P-450 such as phenobarbitone and 3-methylcholanthrene as well as inhibitors such as CoCl2 and 3-amino-l,2,4-triazole enhanced the glutathione transferase (Ya+Yc) messenger RNA contents in rat liver. A comparative study with the induction of cytochrome P-450 (b+e) by phenobarbitone revealed that the drug manifested a striking increase in the nuclear pre-messenger RNAs for the cytochrome at 12 hr, but did not significantly affect the same in the case of glutathione transferase (Ya+Yc). 3-Amino-l, 2,4-tnazole and CoCl- blocked the phenobarbitone mediated increase in cytochrome P-450 (b+e) nuclear pre-messenger RNAs. These compounds did not significantly affect the glutathione transferase (Ya+Yc) nuclear pre-messenger RNA levels. The polysomal, poly (A)- containing messenger RNAs for cytochrome P-450 (b+e) increased by 12–15 fold after phenobarbitone administration, reached a maximum around 16hr and then decreased sharply. In comparison, the increase in the case of glutathione transferase (Ya+Yc) mesenger RNAs was sluggish and steady and a value of 3–4 fold was reached around 24 hr. Run-off transcription rates for cytochrome P-450 (b+e) increased by nearly 15 fold in 4 hr after phenobarbitone administration, whereas the increase for glutathione transferase (Ya+Yc) was only 2.0 fold. At 12 hr after the drug administration, the glutathione transferase (Ya+Yc) transcription rates were near normal. Administration of 3-amino-l,2,4-triazole and CoCl2 blocked the phenobarbitone-mediated increase in the transcription of cytochrome P-450 (b+e) messenger RNAs. These compounds at best had only marginal effects on the transcription of glutathione transferase (Ya+Yc) messenger RNAs. The half-life of cytochrome P-450 (b+e) messenger RNA was estimated to be 3–4 hr, whereas that for glutathione transferase (Ya+Yc) was found to be 8-9 hr. Administration of phenobarbitone enhanced the half-life of glutathione transferase (Ya+Yc) messenger RNA by nearly two fold. It is suggested that while transcription activation may play a primary role in the induction of cytochrome P-450 (b+e), the induction of glutathione transferase (Ya+Yc) may essentially involve stabilization of the messenger RNAs.