Mercury detection in a microfluidic device by using a molecular sensor soluble in organoaqueous solvent.

A series of fluorescent sensor molecules based on a phosphane sulfide derivative that is soluble in an organoaqueous solvent were designed and synthesized. The structure of the fluorophore has been optimized in order to have the best compromise in terms of solubility and photophysical properties. The obtained properties are in full agreement with quantum chemical calculations. A fluorescent molecular sensor containing one polyoxoethylene group has been synthesized and an efficient quenching upon mercury complexation has been observed. Finally, this sensing molecule has been introduced in a microfluidic chip in which fluorescence detection has been integrated. An efficient fluorescence response was observed upon mercury addition.

A novel ruthenium(II) complex for two-photon absorption-based optical power limiting in the near-IR range.

In this article, the synthesis of a novel high-conjugated ligand and its corresponding Ru(II) complex PTFTF:Ru is reported, along with the linear and nonlinear optical characterizations. Two-photon absorption based optical power limiting properties (OPL), especially in the near infrared, are described and compared to those of the analogous complexes previously published. Combined with a preliminary theoretical approach, this allows us to highlight several key parameters for OPL optimization in such molecular systems and more particularly the spectral overlap between TPA and excited-state absorption.

Pi-stacking functionalization of carbon nanotubes through micelle swelling.

We report on a new, original and efficient method for pi-stacking functionalization of single-wall carbon nanotubes. This method is applied to the synthesis of a high-yield light-harvesting system combining single-wall carbon nanotubes and porphyrin molecules. We developed a micelle-swelling technique that leads to controlled and stable complexes presenting an efficient energy transfer. We demonstrate the key role of the organic solvent in the functionalization mechanism. By swelling the micelles, the solvent helps the non-water-soluble porphyrins to reach the micelle core and allows a strong enhancement of the interaction between porphyrins and nanotubes. This technique opens new avenues for the functionalization of carbon nanostructures.

Fluorimetric lead detection in a microfluidic device.

A microfabricated device has been developed for the selective detection of lead in water. It is based on the use of a selective and sensitive fluorescent molecular sensor for lead (Calix-DANS4) which contains a calix[4]arene bearing four dansyl groups. The microchip-based lead sensor contains a Y-shape microchannel equipped with a passive mixer and moulded on a glass substrate. An optimization of the microcircuit length has been performed in order to have a full complexation of the Calix-DANS4. The detection is performed by using a configuration in which the sensing molecules are excited by two optical fibres, each one connected to a 365 nm UV LED, and the light collection is made by another optical fibre with a photomultiplier. By using this configuration we have shown the possibility to detect lead with a detection limit of 5 ppb. The effect of interfering cations such as calcium has been evaluated. The obtained measurements have been validated by an alternative method (ASV).

Carbon nanotube-acridine nanohybrids: spectroscopic characterization of photoinduced electron transfer.

Single-walled carbon nanotubes (NT) were covalently functionalized with either 9-phenyl acridine (PhA) or 10-methyl-9-phenyl acridinium (PhMeA(+)). Absorption and fluorescence properties of acridine derivatives tethered to the nanotubes were studied in homogeneous dispersions. Exciplex emission was observed for NT functionalized with 9-phenylacridine. This phenomenon was attributed to an "intramolecular" interaction between excited phenyl acridine and carbon nanotubes. Interestingly, reverse photoinduced electron transfer from the nanotube to 10-methyl-9-phenylacridinium was detected for the NT-PhMeA(+) nanohybrid. This electron transfer led to a strong quenching of the acridinium fluorescence and to the formation of a metastable acridine radical. Evidence for the formation of this radical was obtained by ESR studies.

Versatile synthesis of small NLO-active molecules forming amorphous materials with spontaneous second-order NLO response.

A novel synthetic approach to a series of bulky triarylamines substituted by various electron-withdrawing groups and forming amorphous materials is presented. Under vacuum evaporation, thin films with high optical quality are obtained and exhibit spontaneous second-order nonlinear optical activity. This unprecedented result is likely due to subtle balance between strong dipole-dipole interactions and steric crowding causing self-assembly and noncentrosymmetric local ordering, stable up to one year.

Photochromic compounds as optical limiters in the nanosecond time range: the example of mercury dithizonate complex.

Although being an efficient photochromic compound which absorbs in the blue in its stable form and in the orange in its photoactivated form, the mercury dithizonate complex is shown to be a poor optical limiter for nanosecond laser pulses at the wavelengths where both isomers absorb. Optical limiting effect, which is a consequence of reverse saturable absorption due to the photoactivated form, is demonstrated to be weak because of the back photobleaching of this form, which is important all the more as the laser intensity is high. Numerical integration of the spatiotemporal evolution of the laser beam intensity across the solution helps the understanding of the respective roles of the laser fluence and pulse duration. Finally, we draw the conclusion that photochromic compounds can only be used as optical limiters if the time constant for the back photochemical reaction is slow compared to the pulse duration.