One pot synthesis of side chain fluorinated heterocyclic compounds by microwave irradiation

2- Or 4-Difluoronitromethyl and 2- or 4-fluoronitrobenzyl substituted pyridines, quinolines, phenantheridine, benzothiazol and benzoxazol were synthesized by reaction of the corresponding nitro compounds in the presence of 1-chloromethyl-4-fluoro-1,4-diazoiabicyclo[2,2,2]octane bis(tetrafluoroborate) (Select-Fluor) and ammonium acetate as a base under microwave irradiation. This method is very efficient and the yields were significantly improved in comparison to the previous reports.     

Engineering artificial redox chains by molecular 'Lego'

This work reports on a novel approach for building artificial redox chains: the molecular 'Lego' approach. This exploits the scaffold of natural redox proteins by fusing together functional protein modules with the desired properties. The molecular 'Lego' mimics the natural molecular evolution that proceeded by modular assembly of genes/DNA segments. Non-physiological electron transfer partners, flavodoxin (fld) and cytochrome c553 (c553) from Desulfovibrio vulgaris and the haem domain of P450 BM3 (BMP) from Bacillus megaterium have been used as building blocks in different combinations to build artificial redox chains. The kinetic characterization of the electron transfer (ET) between the separate building blocks has been carried out. Under pseudo-first order conditions, a limiting ET rate, klim, of 0.48 +/- 0.05 s-1 and 43.77 +/- 2.18 s-1 and an apparent binding constant, Kapp, of 21 +/- 6 microM and 1.23 +/- 0.32 microM have been found for the fld/c553 and fld/BMP redox pairs, respectively. These results show that fld can be used as a module for transferring electrons to c553 and BMP. A 3D model of the fld/c553 and fld/BMP complexes was used to guide the construction of covalently linked assemblies via engineered disulfide bridges or by fusion of the relevant genes via an engineered loop. The first approach led to the construction, expression and characterization of the S35C and S64C mutants of fld and M23C and G51C mutants of c553. Although the redox potentials of the separate mutants were found to be the same as those of recombinant wild type proteins (-408 mV for the semiquinone/hydroquinone couple of fld and +32 mV for the c553), the c553 homo-dimers M23C-M23C and G51C-G51C were found to have redox potentials of +88 and +105 mV, respectively. These differences have been analysed in terms of exposure of the haem cofactors to the solvent, and these lead to some interesting questions on the redox potentials of the transient redox complexes in physiological systems. The fld-c553 S64C-M23C and S35C-M23C chimeras were constructed, expressed and purified but the FMN was found to be destabilised resulting in the apo-form of these proteins. The gene fusion strategy was used to produce covalently linked assemblies of both fld-c553 and fld-BMP. The former was expressed using a seven amino acid (GPGPGPG) loop linking the C-terminus of fld to the N-terminus of c553. The fld-BMP fusion protein was successfully expressed by using the naturally occurring loop of the P450 BM3 (residues 471-479) to link the BMP domain at the N-terminus with fld domain at the C-terminus. This fusion was found to be correctly folded and functional. Efficient ET from the FMN to the haem domain (370 s-1) was also found to be in the same region of the physiological redox partners (250 s-1). This work demonstrates the feasibility of the molecular 'Lego' approach in generating functional multi-domain proteins with designed properties, beyond the restrictions imposed by the naturally occurring protein domains.     

Sonochemical fluorination of heterocyclic nitro compounds with Selectfluor

Methine and methylene groups attached to a nitro function and heterocycle (and Ph for CH) were rapidly mono- or di-fluorinated by reaction with 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis-tetrafluoroborate (Selectfluor) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), preferably with ultrasonic irradiation.     

An improved procedure for the synthesis ofp-(dichlorosulfamoyl)benzoic acid (Halazone)

Oxidation of Dichloramine-T with KMnO₄ in mild alkaline medium affords N,N-dichlorosulfamoylbenzoic acid (Halazone) in high yield with 18–20% chlorine content.

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Eine verbesserte Vorschrift für die Synthese vonp-(Dichlorsulfamoyl)benzoesäure (Halazon) (Kurze Mitteilung)

Zusammenfassung Die Oxidation von Dichloramin-T mit KMnO₄ ergab unter mild alkalischen Bedingungen N,N-Dichlorsulfamoylbenzoesäure (Halazon) in hohen Ausbeuten mit einem Chlorgehalt von 18–20%.

     

A novel Mn PVC membrane electrode based on a recently synthesized Schiff base

A new PVC membrane electrode for manganese(II) ion based on a recently synthesized Schiff base of 5-[(4-nitrophenylazo)-N-hexylamine]salicylaldimine is reported. The electrode exhibits a Nernstian response for Mn²⁺ ions over a wide concentration range (4.0 × 10⁻⁷ to 1.8 × 10⁻² mol L⁻¹) with a slope of 30.1 (±1.0). The limit of detection is 1.0 × 10⁻⁷ mol L⁻¹. The electrode has a fast response time (∼10 s), a satisfactory reproducibility and relatively long life time. The proposed sensor revealed good selectivities over a wide variety of other cations include hard and soft metals. This electrode could be used in a pH range of 4.5-7.5. It was used as an indicator electrode in potentiometric titration of manganese(II) ions with EDTA solution.     

Effect of nanoplatelet dispersion on mechanical behavior of polymer nanocomposites

By manipulating processing conditions, three levels of exfoliation of synthetic α-zirconium phosphate (α-ZrP) nanoplatelets in epoxy matrices have been achieved. Transmission electron microscopy and wide angle X-ray diffraction were utilized to confirm the three different levels of exfoliation of nanoplatelets in epoxy/α-ZrP nanocomposites. As expected, it was found that modulus and strength of the nanocomposite are affected by how well the nanoplatelets disperse. It was also found that the operative fracture mechanisms depend strongly on the state of the nanoplatelets dispersion. The crack deflection mechanism, which leads to a tortuous path crack growth, was only observed for poorly dispersed nanocomposites. Delamination of intercalated nanoplatelets and crack deflection were observed in a moderately dispersed system. In the case of fully exfoliated system, the crack only propagated in a straight fashion, which indicates that the fully exfoliated individual nanoplatelet can not affect the propagation of crack at all. The implication of the present findings for structural applications of polymer nanocomposites is discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1459–1469, 2007     

Effect of PVDF characteristics on extruded film morphology and porous membranes feasibility by stretching

Three different polyvinylidene fluoride (PVDF) resins were selected to develop porous membranes through melt extrusion and stretching. The effect of the polymer rheology on chain elongation in the melt state was studied. The possibility of generating a row‐nucleated lamellar crystallization for precursor films was investigated. The arrangement and orientation of the crystalline phase were examined by wide angle X‐ray diffraction (WAXD) and Fourier Transform Infrared Spectroscopy (FTIR). The extrusion conditions and the blend compositions were adjusted to obtain uniform precursor films with appropriate morphology. Annealing, cold and hot stretching were consequently employed to generate and enlarge the pores. It was found that a proper crystalline structure of the precursor films was strongly dependent on molecular weight of PVDF and process conditions. Blending of two PVDF resins having low and high molecular weights improved the water vapor permeability of the obtained membranes. The tensile response was monitored during the stretching process for membrane development and the results revealed a distinct behavior for the membranes having low or high permeability. The membranes with low permeability did not show any significant strain hardening during stretching whereas for highly permeable membranes, a noticeable strain hardening behavior was observed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1219–1229, 2009     

One-pot synthesis of functionalized hydantoin derivatives via a four-component reaction between an amine, an arylsulfonyl isocyanate and an alkyl propiolate or dialkyl acetylenedicarboxylate in the presence of triphenylphosphine

An effective route to functionalized hydantoin derivatives is described, involving the reaction of a urea derivative resulting from the addition of a primary amine to an arylsulfonyl isocyanate, and an alkyl propiolate or dialkyl acetylenedicarboxylate in the presence of triphenylphosphine. The reactive 1:1 intermediate obtained from the addition of triphenylphosphine to the alkyl propiolate or dialkyl acetylenedicarboxylate was trapped by NH-acids such as the urea derivative to produce functionalized hydantoin derivatives.     

Bidirectional Teleportation of a Two-Qubit State by Using Eight-Qubit Entangled State as a Quantum Channel

In this paper, a new scheme of bidirectional quantum teleportation (BQT) making use of an eight-qubit entangled state as the quantum channel is presented. This scheme is the first protocol without controller by which the users can teleport an arbitrary two-qubit state to each other simultaneously. This protocol is based on the ControlledNOT operation, appropriate single-qubit unitary operations and single-qubit measurement in the Z-basis and X-basis.     

Silicon carbide nanotubes (SiCNTs) serving for catalytic decomposition of toxic diazomethane (DAZM) gas: a DFT study

In the present study, the adsorption and decomposition of diazomethane (DAZM) on the surface of (6,0) zigzag silicon carbide nanotube (SiCNT) are investigated using density functional theory calculations. The geometry structures of the three stable configurations, adsorption energies and electronic properties of DAZM adsorption on the surface of SiCNT are investigated. It was found that the DAZM molecule is decomposed over the surface of (6,0) SiCNT with activation energy (E_act) of 0.523 eV. The curvature effect on the adsorption energies of the DAZM molecule is also considered by studying (5,0) and (7,0) SiCNTs. The results display that DAZM adsorption over smaller diameter of SiCNT is thermodynamically more favourable than larger one.