Shift to Pseudomonic acid B production in P. fluorescens NCIMB10586 by mutation of mupirocin tailoring genes mupO, mupU, mupV, and macpE

Mupirocin, a polyketide-derived antibiotic from Pseudomonas fluorescens NCIMB10586, is a mixture of pseudomonic acids (PA) that target isoleucyl-tRNA synthase. The mup gene cluster encodes both type I polyketide synthases and monofunctional enzymes that should play a role during the conversion of the product of the polyketide synthase into the active antibiotic (tailoring). By in-frame deletion analysis of selected tailoring open-reading frames we show that mupQ, mupS, mupT, and mupW are essential for mupirocin production, whereas mupO, mupU, mupV, and macpE are essential for production of PA-A but not PA-B. Therefore, PA-B is not simply produced by hydroxylation of PA-A but is either a precursor of PA-A or a shunt product. In the mupW mutant, a new metabolite lacking the tetrahydropyran ring is produced, implicating mupW in oxidation of the 16-methyl group.     

Halogen-substituted thiophenol molecules on Cu(111)

Para-halosubstituted thiophenols (X-TPs, where X is Br, Cl, or F) form ordered islands and monolayers on Cu(111) at temperatures as low as 81 K. At incomplete coverages, all X-TPs adsorb with the dehydrogenated thiol group attached to the substrate and the substituted ring inclined toward the surface, as verified experimentally and theoretically. The structure of ordered islands has a pronounced dependence on the nature of the halogen substituent: while unsubstituted TP and pentafluoro-TP molecules do not self-assemble into extended ordered patterns at 81 K, X-TP molecules form a range of different structures which depend both on the size and electronegativity of the substituent, as well as on the coverage.     

Stabilization of γ-sterilized biomedical polyolefins by synergistic mixtures of oligomeric stabilizers

The stabilization of polyolefins against γ-sterilization has been studied with single or binary additive system. The present attempt is to utilize synergistic mixtures of stabilizers which are approved for food contact applications. Ethylene-propylene (EP) copolymer has been melt-mixed with hindered amine stabilizers (HAS), phenolic antioxidants and organo-phosphites (hydroperoxide decomposer). Samples were sterilized with different doses of γ-radiation. Stabilization was characterized in terms of changes in the functional groups (oxidation products), tensile properties, yellowing and surface morphology by FTIR spectroscopy, Instron, colorimetry (reflectance) and scanning electron microscopy (SEM), respectively. Results were discussed by comparing the stabilizing efficiency of mixtures with and without phenol system. Among phenol containing systems, where we mostly observe discoloration due to the oxidation of hindered phenol and the combination of secondary HAS, tertiary HAS, organo-phosphite and hindered phenol exhibited improved stabilization efficiency than single or binary additive systems. The mixture of secondary HAS and tertiary HAS, has shown antagonistic effect of stabilization whereas their combination with organo-phosphite has exhibited synergistic effect of stabilization even at higher doses of γ-sterilization. The effects have been explained through the interaction between the stabilizers.     

Microwave Assisted Deprotection of N,N-Dimethylhydrazones in Water Using Palladium Chloride–Tin Chloride as Catalyst

Summary.  N,N-Dimethylhydrazones of ketones and aldehydes undergo facile cleavage to the corresponding carbonyl compounds upon exposure to microwaves in water containing a catalytic amount of PdCl₂–SnCl₂ in high yields. Corresponding authors. E-mail: rahman@umz.ac.ir Received December 27, 2001. Accepted (revised) February 6, 2002     

Patterned langmuir-blodgett films of monodisperse nanoparticles of iron oxide using soft lithography

Langmuir-Blodgett (LB) films of monodisperse iron oxide nanoparticles have been successfully deposited onto patterned poly(dimethylsiloxane) surfaces. These patterned LB films of iron oxide nanoparticles were transferred onto solid substrates using micro contact printing.     

Challenges in validating the sterilisation dose for processed human amniotic membranes

Most of the tissue banks in the Asia Pacific region have been using ionising radiation at 25 kGy to sterilise human tissues for save clinical usage. Under tissue banking quality system, any dose employed for sterilisation has to be validated and the validation exercise has to be a part of quality document. Tissue grafts, unlike medical items, are not produced in large number per each processing batch and tissues relatively have a different microbial population. A Code of Practice established by the International Atomic Energy Agency (IAEA) in 2004 offers several validation methods using smaller number of samples compared to ISO 11137 (1995), which is meant for medical products. The methods emphasise on bioburden determination, followed by sterility test on samples after they were exposed to verification dose for attaining of sterility assurance level (SAL) of 10⁻¹. This paper describes our experience in using the IAEA Code of Practice in conducting the validation exercise for substantiating 25 kGy as sterilisation dose for both air-dried amnion and those preserved in 99% glycerol.     

Slurry sampling techniques for the determination of lead in Bangladeshi fish samples by electrothermal atomic absorption spectrometry with a metal tube atomizer

Ultrasonic slurry sampling electrothermal atomic absorption spectrometry with a metal tube atomizer has been applied to the determination of lead in Bangladeshi fish samples. The slurry sampling conditions, such as slurry stabilizing agent, slurry concentration, pyrolysis temperature for the slurried fish samples, particle size and ultrasonic agitation time, were optimized for electrothermal atomic absorption spectrometry with the Mo tube atomizer. Thiourea was used as the chemical modifier for the interference of matrix elements. The detection limit was 53 fg (3S/N). The determined amount of lead in Bangladeshi fish samples was consistent with those measured in the dissolved acid-digested samples. The advantages of the proposed methods are easy calibration, simplicity, low cost and rapid analysis.     

The first aldehyde-derived crystalline geminal diol lacking internal electronic stabilization

The first stable crystalline geminal diol of an aldehyde lacking electron-withdrawing groups on the-carbon was synthesized fromd-sorbitol and characterized by¹H and¹³C nuclear magnetic resonance (NMR) and single-crystal x-ray studies. Each hydroxyl is a donor for a single, unique intermolecular hydrogen bond. Only one hydroxyl acts as an acceptor. No intramolecular hydrogen bonding is observed in the crystal.     

A simple convenient synthesis of trans-1,2,3,4,4a,5,6,10b-octahydrophenanthridines

trans-1,2,3,4,4a,5,6,10b-Octahydrophenanthridine, the 9-methoxy analog, and 5-methyl derivatives ( 6a,6b ) of each have been synthesized from trans-phenylcyclohexylamines ( 2a,2b ) and ethyl chloroformate followed by cyclization and reduction or by cyclization, N-methylation and reduction. The oximes ( la,1b ) of 2-phenylcyclohexanone and the m-methoxy relative, a mixture of the syn and anti isomers, were reduced to 2a and 2b with sodium and ethanol. Hydrogenation (platinum oxide-acetic acid) of 1a gave in addition to 2a , a small yield of 2-cyclohexylcyclohexyl-amine. Similar hydrogenation of 1b gave only this fully reduced compound.     

Preparation,and infrared and thermal properties of six adducts of tetrakis-(8-hydroxyquinolinato)thorium(IV)

Six adducts of the tctrakis(8-hydroxyquinolinato) complex of thorium(IV) with 8-hydroxyquinoline, pyridine, urea, dimethylsulphoxide, dimethylformamide and 1,10-phenanthroline were prepared and characterized, the infrared bands for the room-temperature forms are given and their particular thermal properties are reported. The thermal analyses were performed mostly in the presence of air, but in some cases an argon atmosphere was used for comparison. The adducts were lost from the principal complex at temperatures varying between 110 and 290°. Intermediate oxygenated complexes were formed in each case at about 400°. The thermal data suggest the standardization of a procedure for the formation of Th(C₉H₆NO)₄.

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Zusammenfassung Sechs Addukte des Tetrakis(8-hydroxyquinolinato)-Komplexes von Thorium(IV) mit 8-Hydroxyquinolin, Pyridin, Harnstoff, Dimethylsulphoxid, Dimethylformamid und 1,10-Phenanthrolin wurden dargestellt und charakterisiert. Infrarotbanden und spezielle thermische Eigenschaften der Raumtemperatur-Formen sind angegeben. Die thermischen Analysen wurden meist in Luft ausgeführt, in einigen Fällen zu Vergleichszwecken aber auch in Argonatmosphäre. Die Addukte wurden vom Komplex bei Temperaturen zwischen 110 und 290 °C abgegeben. Intermediäre oxydierte Komplexe wurden in jedem Fall bei etwa 400 °C gebildet. Die thermischen Daten ermöglichen die Standardisierung eines Verfahrens zur Darstellung von Th(C₉H₆NO)₄.

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-(8- ) (IV) 8- , , , - , 1,10-. - , . , , . 110–290°. 400° . Th(C₉H₆NO)₄.

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We are grateful to the Bangladesh University Grants Commission for a Fellowship Grant to AR.