Birefringence dispersion of N-(4-methoxybenzylidene)-4-butylaniline (MBBA) determined from channeled spectra

The birefringence of MBBA, determined from the channeled spectra, decreases when the wavelength increases, showing a normal dispersion. The changes induced by an external electrostatic field acting perpendicular on the nematic director in the birefringence values were evidenced. The birefringence increases with the electrostatic field intensity which enhances the preferential alignment by the big values of the electric dipole moments induced parallel to the long MBBA molecule. The main refractive indices were interferometrically measured for three visible monochromatic radiations and the birefringence values were concordant with those estimated from the channeled spectra. The main molecular polarizabilities were estimated.     

Bis(alpha-diimine)nickel complexes: molecular and electronic structure of three members of the electron-transfer series [Ni(L)(2)](z)() (z = 0, 1+, 2+) (L = 2-Phenyl-1,4-bis(isopropyl)-1,4-diazabutadiene). A combined experimental and theoretical study

From the reaction of Ni(COD)(2) (COD = cyclooctadiene) in dry diethylether with 2 equiv of 2-phenyl-1,4-bis(isopropyl)-1,4-diazabutadiene (L(Ox))(0) under an Ar atmosphere, dark red, diamagnetic microcrystals of [Ni(II)(L*)(2)] (1) were obtained where (L*)(1-) represents the pi radical anion of neutral (L(Ox))(0) and (L(Red))(2-) is the closed shell, doubly reduced form of (L(Ox))(0). Oxidation of 1 with 1 equiv of ferrocenium hexafluorophosphate in CH(2)Cl(2) yields a paramagnetic (S = 1/2), dark violet precipitate of [Ni(I)(L(Ox))(2)](PF(6)) (2) which represents an oxidatively induced reduction of the central nickel ion. From the same reaction but with 2 equiv of [Fc](PF(6)) in CH(2)Cl(2), light green crystals of [Ni(II)(L(Ox))(2)(FPF(5))](PF(6)) (3) (S = 1) were obtained. If the same reaction was carried out in tetrahydrofuran, crystals of [Ni(II)(L(Ox))(2)(THF)(FPF(5))](PF(6)) x THF (4) (S = 1) were obtained. Compounds 1, 2, 3, and 4 were structurally characterized by X-ray crystallography: 1 and 2 contain a tetrahedral neutral complex and a tetrahedral monocation, respectively, whereas 3 contains the five-coordinate cation [Ni(II)(L(Ox))(2)(FPF(5))](+) with a weakly coordinated PF(6)(-) anion and in 4 the six-coordinate monocation [Ni(II)(L(Ox))(2)(THF)(FPF(5))](+) is present. The electro- and magnetochemistry of 1-4 has been investigated by cyclic voltammetry and SQUID measurements. UV-vis and EPR spectroscopic data for all compounds are reported. The experimental results have been confirmed by broken symmetry DFT calculations of [Ni(II)(L*)(2)](0), [Ni(I)(L(Ox))(2)](+), and [Ni(II)(L(Ox))(2)](2+) in comparison with calculations of the corresponding Zn complexes: [Zn(II)((t)L(Ox))(2)](2+), [Zn(II)((t)L(Ox))((t)L*)](+), [Zn(II)((t)L*)(2)](0), and [Zn(II)((t)L*)((t)L(Red))](-) where ((t)L(Ox))(0) represents the neutral ligand 1,4-di-tert-butyl-1,4-diaza-1,3-butadiene and ((t)L*)(1-) and ((t)L(Red))(2-) are the corresponding one- and two-electron reduced forms. It is clearly established that the electronic structures of both paramagnetic monocations [Ni(I)(L(Ox))(2)](+) (S = 1/2) and [Zn(II)((t)L(Ox))((t)(L*)](+) (S = 1/2) are different.     

Electronic structures of tris(dioxolene)chromium and tris(dithiolene)chromium complexes of the electron-transfer series [Cr(dioxolene)(3)](z) and [Cr(dithiolene)(3)](z) (z = 0, 1-, 2-, 3-). A combined experimental and density functional theoretical study

From the reaction mixture of 3,6-di-tert-butylcatechol, H2[3,6L(cat)], [CrCl3(thf)3], and NEt3 in CH3CN in the presence of air, the neutral complex [CrIII(3,6L*(sq))3] (S = 0) (1) was isolated. Reduction of 1 with [Co(Cp)2] in CH2Cl2 yielded microcrystals of [Co(Cp)2][CrIII(3,6L*(sq))2(3,6L(cat))] (S = 1/2) (2) where (3,6L*(sq)(1-) is the pi-radical monoanionic o-semiquinonate of the catecholate dianion (3,6Lcat)(2-). Electrochemistry demonstrated that both species are members of the electron-transfer series [Cr(3,6LO,O)]z (z = 0, 1-, 2-, 3-). The corresponding tris(benzo-1,2-dithiolato)chromium complex [N(n-Bu)4][CrIII(3,5L*S,S)2(3,5LS,S)] (S = 1/2) (3) has also been isolated; (3,5LS,S)(2-) represents the closed-shell dianion 3,5-di-tert-butylbenzene-1,2-dithiolate(2-), and (3,5L*S,S)(1-) is its monoanionic pi radical. Complex 3 is a member of the electron-transfer series [Cr(3,5L(S,S))3]z (z = 0, 1-, 2-, 3-). It is shown by Cr K-edge and S K-edge X-ray absorption, UV-vis, and EPR spectroscopies, as well as X-ray crystallography, of 1 and 3 that the oxidation state of the central Cr ion in each member of both electron-transfer series remains the same (+III) and that all redox processes are ligand-based. These experimental results have been corroborated by broken symmetry density functional theoretical calculations by using the B3LYP functional.     

Characterization of self-assembled monolayers (SAMs) on silicon substrate comparative with polymer substrate for Escherichia coli O157:H7 detection

This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti-Escherichia coli O157:H7 polyclonal purified antibody.A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti-E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab′)₂ fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results.These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7.     

Monitoring the synthesis of new polymer nanocomposites based on different polyhedral oligomeric silsesquioxanes using Raman spectroscopy

The kinetic behavior of the urethane dimethacrylate (UDMA) copolymerized and reinforced by different concentrations of polyhedral oligomeric silsesquioxane (POSS) with methacrylic groups was studied through Raman spectroscopy. UDMA‐POSS networks have been synthesized with three different types of POSS, two monofunctional POSS (1‐propylmethacrylate)‐heptaisobutyl substituted (HISO‐POSS) and heptacyclopentyl‐octasiloxan‐1‐yloxy) dimethylsilyl] propyl methacrylate (CPENTYL‐POSS) and one octafunctional POSS‐methacryl substituted (MA‐POSS). In order to show the influence of POSS on the final conversion, the hybrid systems were cured using three types of initiators which decompose at different temperatures: azobisisobutyronitrile (AIBN) (65 °C), benzoyl peroxide (BP) (80 °C) and di‐tert‐butyl peroxide (DTBP) (120 °C). The structure of the hybrid's surface was investigated by X‐ray photoelectron spectroscopy (XPS) and the T_g values were calculated from dynamic mechanical analysis (DMA) tests. Copyright © 2009 John Wiley & Sons, Ltd.     

Metallophthalocyanine Based Carbon Paste Electrodes for the Determination of 2′,3′‐Dideoxyinosine

Novel electrochemical sensors based on carbon paste impregnated with metallopthalocyanine (MPc, M=Co, Fe) complexes, have been constructed for the assay of anti‐HIV drug 2′,3′‐dideoxyinosine (didanosine, DDI). Both modified electrodes showed electrocatalytic activity towards the oxidation of dideoxyinosine in phosphate buffer pH 7.4 with a working concentration range of 10^?6–10^?4 mol/L and a detection limit of 10^?7 mol/L magnitude order. The sensor proved to be highly reliable for the assay of the purity of DDI ‐ raw material as well as for the uniformity content test of Videx tablets.     

Edge quantisation of elliptic operators

The ellipticity of operators on a manifold with edge is defined as the bijectivity of the components of a principal symbolic hierarchy , where the second component takes values in operators on the infinite model cone of the local wedges. In the general understanding of edge problems there are two basic aspects: Quantisation of edge-degenerate operators in weighted Sobolev spaces, and verifying the ellipticity of the principal edge symbol which includes the (in general not explicitly known) number of additional conditions of trace and potential type on the edge. We focus here on these questions and give explicit answers for a wide class of elliptic operators that are connected with the ellipticity of edge boundary value problems and reductions to the boundary. In particular, we study the edge quantisation and ellipticity for Dirichlet–Neumann operators with respect to interfaces of some codimension on a boundary. We show analogues of the Agranovich–Dynin formula for edge boundary value problems. Nicoleta Dines and Bert-Wolfgang Schulze were supported by Chinese-German Cooperation Program “Partial Differential Equations”, NNSF of China and DFG of Germany. Xiaochun Liu was supported by NNSF of China through Grant No. 10501034, and Chinese-German Cooperation Program “Partial Differential Equations”, NNSF of China and DFG of Germany.     

Self-organization of polybases neutralized with mesogenic wedge-shaped sulfonic acid molecules: an approach toward supramolecular cylinders

Complexes consisting of poly(4-vinylpyridine) and mesogenic wedge-shaped ligands 4'-[3",4",5"-tris(dodecyloxy)benzoyloxy]azobenzene-4-sulfonic acid and 4'-[3",4",5"-tris(octyloxy)benzoyloxy]azobenzene-4-sulfonic acid have been prepared with different monomer/ligand ratios. Upon protonation of the poly(4-vinylpyridine) chains by the wedge-shaped sulfonic acid molecules a hypsochromic and hyperchromic effect was observed with the pi-pi* transition of the azo-chromophor, allowing us to monitor the neutralization process by means of UV-vis spectroscopy in solution. The changes of the absorption characteristics implied a conformational change of the polymer backbone. In the bulk the interaction between pyridine and sulfonic acid moieties was proved by FT-IR spectroscopy. Polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction measurements were used to study the bulk structure of the complexes. The complexes formed a liquid crystalline lamellar phase at low degrees of substitution, while a hexagonal columnar mesophase was observed at degrees of neutralization of 80% and higher.     

Vanadium bromoperoxidase-coupled fluorescent assay for flow cytometry sorting of glucose oxidase gene libraries in double emulsions

A Vanadium bromoPeroxidase-coupled fluorescent assay (ViPer) for ultrahigh-throughput screening of glucose oxidase (GOx) gene libraries employing double emulsions and flow cytometry was developed. The assay is based on detection of the product of a GOx reaction, hydrogen peroxide, that is first converted to a hypobromide by vanadium bromoperoxidase in the presence of sodium bromide. The hypobromide is afterwards detected in a reaction with a fluorogenic probe, 3-carboxy-7-(4'-aminophenoxy)-coumarine, where fluorescent 3-carboxy-coumarine is released. The ViPer screening system is three times more sensitive than a horseradish peroxidase coupled detection system and more resistant to bleaching of fluorescence in excess of peroxide. Using the ViPer screening system a high epPCR gene library containing 100,000 different GOx variants was screened for active clones in less than 1 h by flow cytometry. A library containing 0.15% of yeast cells expressing active enzyme variants and with an average GOx activity in the liquid culture of 0.47 U/mL, after one round of sorting, had 28.12% of the yeast cells expressing the active GOx (an enrichment factor of 200) and 26.8 U/mL of the GOx activity in the liquid culture (an enrichment factor of 57). The developed screening system could be adapted and used in a directed evolution of GOx and other hydrogen peroxide-producing enzymes (oxidases) and glycosidases if coupled with a carbohydrate oxidase.     

Heterogeneous reactivity of chlorine atoms with ammonium sulfate and ammonium nitrate particles

In this laboratory study, model particles of ammonium sulfate (AS) and ammonium nitrate (AN) were exposed to chlorine atoms and uptake experiments were performed in a coated wall flow tube reactor coupled to a molecular beam mass spectrometer. The reactive surfaces were prepared by coating the inner surface of the reactor using two different methods: either by depositing size-selected particles on the halocarbon wax or by spray depositing thin films using a constant output atomizer. The observed uptake coefficients vary for (NH(4))(2)SO(4), ranging from γ(Cl)(AS)≈ 1 × 10(-3) for size-selected particles to γ(Cl)(AS)≈ 6 × 10(-2) for thin films prepared by spray. An uptake coefficient of γ(Cl)(AN)≈ 2.5 × 10(-3) of Cl˙ on size-selected NH(4)NO(3) particles was measured. A heterogeneous recombination of Cl atoms to from Cl(2) molecules was observed for the two surfaces. Furthermore, an ageing process was observed for AS particles, this phenomenon leading to the formation of new chlorine species on the solid substrate.