A comparison of the binding of metal complexes to duplex and quadruplex DNA

Electrospray ionisation mass spectrometry (ESI-MS) and circular dichroism (CD) spectroscopy were used to compare the binding of mononuclear nickel, ruthenium and platinum complexes to double stranded DNA (dsDNA) and quadruplex DNA (qDNA). CD studies provided evidence for the binding of intact complexes of all three metal ions to qDNA. ESI mass spectra of solutions containing platinum or ruthenium complexes and qDNA showed evidence for the formation of non-covalent complexes consisting of intact metal molecules bound to DNA. However, the corresponding spectra of solutions containing nickel complexes principally contained ions consisting of fragments of the initial nickel molecule bound to qDNA. In contrast ESI mass spectra of solutions containing nickel, ruthenium or platinum complexes and dsDNA only showed the presence of ions attributable to intact metal molecules bound to DNA. The fragmentation observed in mass spectral studies of solutions containing nickel complexes and qDNA is attributable to the lower thermodynamic stability of the former metal complexes relative to those containing platinum or ruthenium, as well as the slightly harsher instrumental conditions required to obtain spectra of qDNA. This conclusion is supported by the results of tandem mass spectral studies, which showed that ions consisting of intact nickel complexes bound to qDNA readily undergo fragmentation by loss of one of the ligands initially bound to the metal. The ESI-MS results also demonstrate that the binding affinity of each of the platinum and ruthenium complexes towards qDNA is significantly less than that towards dsDNA.     

First synthesis of selenadiazolo[3,4‐i] Benzazepine derivatives

5‐Methyl‐4‐nitro‐2,1,3‐benzoselenadiazole ( 1 ) was converted into (E)‐5‐(2‐dimethylamino)vinylbenzo‐[c](1,2,5)selenadiazole‐4‐amine ( 4 ) by initial treatment with dimethylformamide dimethyl acetal (DMFDMA) ( 2 ) followed by selective reduction using ammonium bromide in methanol. Compound 4 afforded the selenadiazolo[3,4‐i][1]benzazepine derivatives ( 7, 10, 13, 15 ) upon treatment with malononitrile ( 5 ), ethyl cyanoacetate ( 8 ) and cyanoacetamide ( 11 ) respectively.     

Real-time quantitative imaging of submolecular layers

Using a recent optical contrast method, real-time and quantitative imaging of submolecular layers was performed with the help of a simple optical microscope. The measuring technique is exposed and documented by three examples. In particular, it allowed label-free detection of peptide-antibody binding interactions with 50 pg/mm2 sensitivity while keeping full optical lateral resolution.     

Characterization by optical measurements of the effects of some stages of champagne technology on the adsorption layer formed at the gas/wine interface

This study analyzes the effects of some important factors of champagne technology on the ellipticity and Brewster angle microscopy (BAM) of the air/champagne interface in view of using the optical properties of the adsorption layer of base wine to forecast the stability of the champagne bubble collar. Using standard, ultrafiltered, and ultraconcentrated wines it was observed that champagne can lose amphiphilic macromolecules which adsorb on the inner glass wall of the bottle during storage, particles such as dead yeasts can adhere to the adsorption layer, a weak increase of the ethanol content during bottle fermentation can reduce significantly the ellipticity of the adsorption layer, and CO2 has no significant effect on the properties of that layer. Surprisingly, no visible differences of the adsorption layer were noticed between the experimental champagnes of the 2004 vintage of three vine varieties (Chardonnay, Pinot noir, and Pinot meunier). From analysis of all samples it is proposed that the mean value and standard deviation of the ellipticity measured during 30 min after pouring the wine in a Petri dish are physical quantities which satisfactorily characterize the adsorption layer of champagne. When needed, further characterization of the adsorption layer may be obtained by a detailed analysis of the kinetics of ellipticity during the same period and inspection of the BAM images of the interface.     

Magnons localised on surface steps: a theoretical model

We present the solution of the full magnetic problem arising from the absence of magnetic translation symmetry in two dimensions due to an extended magnetic surface step on the surface boundary of an insulating magnetic substrate. The calculation concerns in particular the spin fluctuation dynamics of a magnetic atomic step in the surface of a ferromagnetic simple cubic lattice, the spin order being in the direction normal to surface boundary. Only exchange interactions are considered between the spins in the model. The theoretical approach determines the evanescent spin fluctuation field in the two dimensional plane normal to the direction of the step edge. This field arises owing to the absence of magnetic translation symmetry in this plane, and is completely independent of the form of the surface defect, underlying the general character of the calculation. We show the existence of optical localised magnon modes propagating along the step, their fields being evanescent in the plane normal to the step direction. Received 17 February 1999     

Colliding Solitons for the Nonlinear Schrödinger Equation

We study the collision of two fast solitons for the nonlinear Schrödinger equation in the presence of a slowly varying external potential. For a high initial relative speed ||v|| of the solitons, we show that, up to times of order ||v|| after the collision, the solitons preserve their shape (in L ²-norm), and the dynamics of the centers of mass of the solitons is approximately determined by the external potential, plus error terms due to radiation damping and the extended nature of the solitons. We remark on how to obtain longer time scales under stronger assumptions on the initial condition and the external potential.     

Effect of the acyl group and the dodecylsulfonate chain on the inclusion of pyrene inside the cavity of β-cyclodextrin

The solubilization of pyrene in aqueous solution of β-cyclodextrin (β-CD) or its derivatives such as β-CD-hexanoyl, β-CD-benzoyl and β-CD-dodecylsulfonate was investigated by spectrophotometry. Linear and non-linear regression methods were used to estimate the association constants (K₁). A 1:1 stoichiometric ratio and different effects of the hexanoyl, benzoyl and dodecylsulfonate groups on the association constant were observed for the binary inclusion complex between pyrene and β-CD. The formation constant was shown to decrease when β-CD was modified by a dodecylsulfonate chain. The value of K₁ was 190 ± 10 L mol⁻¹ for the [pyrene/β-CD] complex and 145 L mol⁻¹ for the [pyrene/β-CD-dodecylsulfonate] complex. Partitioning of the pyrene molecules between the dodecylsulfonate chains and cyclodextrin cavities can explain the decrease in the association constant value. In the cases of β-CD-hexanoyl and β-CD-benzoyl derivatives, no association constants were detected. Results suggest that the high hydrophobicity of the hexanoyl and benzoyl groups prevents the inclusion of pyrene molecules inside the cyclodextrin cavity.