Oxidation of steroid α-diketones by thallium (III) acetate : Crystal and molecular structure of a spiro-cyclopentan-a,s-indaceno derivative obtained from 3,4-diketo steroids

Treatment of 2,3-diketo-cholestane (1) with thallium triacetate in acetic acid afforded mainly 3α-carbomethoxy-A-nor-5α-cholestan-2-one (2). Under similar conditions, the 3,4-diketo steroids (3 and 4) underwent extensive rearrangement affording spiro-lactones (9 and 10), in low yields. The structural assignment of the spiro-cholestane derivative was supported by crystallographic X-ray analysis. This product was the result of A and B-ring contractions followed by acid-catalysed cyclization of an unsaturated carboxy intermediate.     

Ultrafast and bias-free all-optical wavelength conversion using III-V-on-silicon technology

Using a 7.5 μm diameter disk fabricated with III-V-on-silicon fabrication technology, we demonstrate bias-free all-optical wavelength conversion for non-return-to-zero on-off keyed pseudorandom bit sequence (PRBS) data at the speed of 10 Gbits/s with an extinction ratio of more than 12 dB. The working principle of such a wavelength converter is based on free-carrier-induced refractive index modulation in a pump-probe configuration. We believe it to be the first bias-free on-chip demonstration of all-optical wavelength conversion using PRBS data. All-optical gating measurements in the pump-probe configuration with the same device have revealed that it is possible to achieve wavelength conversion beyond 20 Gbits/s.     

DNA damage induced by organotins on ­trout‐nucleated erythrocytes

The effect of tributyltin‐chloride (TBTC), dibutyltin‐chloride (DBTC) and monobutyltin‐chloride (MBTC) on rainbow trout (Salmo irideus) nuclear DNA, was investigated by means of single cell gel electrophoresis (‘comet’ assay). Our data show that TBTC presents a marked genotoxic effect, whereas the genotoxic effect is less pronounced for DBTC and it is completely absent for MBTC. These results could be important in evaluating the environmental risks deriving from the use of these molecules as a antifouling agents in marine paints and as agricultural biocides. Copyright © 2001 John Wiley & Sons, Ltd.

Abbreviations:

TBTC,

tributyltin‐chloride;

DBTC,

dibutyltin‐chloride;

MBTC,

monobutyltin‐chloride;

Hb,

hemoglobin.

     

Azido‐Substituted BODIPY Dyes for the Production of Fluorescent Carbon Nanotubes

A series of azido‐dyes were synthesized through Knoevenagel reactions of an azido‐BODIPY with aromatic aldehydes. The nature of the substituents allowed the fine tuning of their spectroscopic properties. The dyes were used to decorate oxidized multiwalled carbon nanotubes (ox‐MWCNTs), bearing terminal triple bond groups, by CuAAC reactions, affording fluorescent materials. This decoration allowed the efficient determination of the internalization of the ox‐MWCNT derivatives by different model cancer cells, such as MCF7.     

On chaotic extensions of dynamical systems

In this paper, inspired by some results in linear dynamics, we will show that every dynamical system (X,f), where f is a continuous self-map on a separable metric space X, can be extended to a chaotic (in the sense of Devaney) dynamical system in an isometric way.     

Real-space observation of spectral degeneracy breaking in a waveguide-coupled disk microresonator

We report on the real-space observation of resonant frequency splitting in a high-Q waveguide-coupled silicon-on-insulator microdisk resonator. Phase sensitive near-field analysis reveals the stationary nature of the two resonant states, and spectral investigations clearly show their orthogonality. These measurements emphasize the role of the coupling waveguide in this splitting phenomenon. The symmetry of the two stationary whispering gallery modes is clearly observed and is found to follow the axial symmetry of the waveguide-coupled microdisk as it has been reported by earlier theoretical predictions.     

Highly shifted LIPOCEST agents based on the encapsulation of neutral polynuclear paramagnetic shift reagents

Improved LIPOCEST MRI contrast agents with highly shifted intraliposomal water protons were prepared by entrapping neutral polynuclear Tm(III)-based paramagnetic shift reagents in phospholipidic vesicles.     

Synthesis and characterization of a Gd(III) based contrast agent responsive to thiol containing compounds

A novel Gd(III) complex with a modified DO3A-like chelating cage has been synthesized and characterized as a candidate contrast agent responsive to the concentration of free thiols in tissues (essentially represented by reduced glutathione, GSH). The novel compound (called Gd-DO3AS-Act) bears a flexible linker ending with a 2-pyridyl-dithio group, that can promptly react with free thiols (XSH) to form mixed disulfides of the form Gd-DO3AS-SX. Compound Gd-DO3AS-Act is characterized by a millimolar relaxivity as high as 8.1 mM(-1) s(-1) (at 20 MHz, 25 degrees C and pH 7.4). Upon reaction with GSH, the Gd-DO3AS-SG covalent adduct is formed and the millimolar relaxivity drops to 4.1 mM(-1) s(-1). Such a decrease in relaxivity is explained on the basis of the formation of an intramolecular coordinative bond between one of the glutathionyl carboxyl groups and the Gd(III) centre, lowering the hydration state of the paramagnetic centre. (1)H-NMR dispersion profiles together with (17)O-NMR transverse relaxation time versus temperature profiles confirm that the hydration of the Gd(III) centre is strongly reduced ongoing from Gd-DO3AS-Act to the Gd-DO3AS-SG adduct. The relaxivity difference brought about by the reaction of Gd-DO3AS-Act with GSH can be enhanced up to 60% in the presence of poly-beta-cyclodextrin.