Design of novel tripyridinophane-based Eu(III) complexes as efficient luminescent labels for bioassay applications.

In this work, the development of highly luminescent europium(III) complexes in water solution is reported, including their syntheses, analyses of their photophysical properties and applications in bioassays. Three Eu(III) complexes are derived from new ligands based on a tripyridinophane platform. There are four distinct sections in the structure of these ligands: an 18-membered polyaminocarboxylic macrocycle to bind efficiently lanthanide ions in aqueous solutions, three chromophoric subunits (4-(phenylethynyl)pyridine moieties) to effectively sensitize the emission of the metal, two peripheral moieties to solubilise the complex in aqueous media (sulfonate, sulfobetaine or glucose groups) and a free NH2 group available for grafting or bioconjugation. In our synthetic procedure, a pivotal macrocyclic platform is obtained with a high yield in the crucial macrocyclization step due to a metal template ion effect (74% yield). In Tris aqueous buffer (pH 7.4), the Eu(III) complexes show a maximum excitation wavelength at 320 nm, a suitable overall quantum yield (14%), a relatively long lifetime (0.80 ms) and a one-photon brightness in the range of 10 000 M-1 cm-1. Importantly, these photophysical properties are retained at dilute concentrations, even in the presence of a very large excess of potentially competing species, such as EDTA or Mg2+ ions. Furthermore, we report the bioconjugation of a Eu(III) complex labelled by an N-hydroxysuccinimide ester reactive group with an antibody (anti-glutathione-S-transferase) and the successful application of the corresponding antibody conjugate in the detection of GST-biotin in a fluoroimmunoassay. These new complexes provide a solution for high sensitivity in Homogeneous Time-Resolved Fluorescence (HTRF®) bioassays.

Drying kinetics driven by the shape of the air/water interface in a capillary channel.

We look at the drying process in a simple glass channel with dominant capillary effects as is the case in microfluidics. We find drying kinetics commonly observed for confined geometry, namely a constant period followed by a falling rate period. From visualization of the air/water interface with high resolution, we observe that the drying rate decreases without a drying front progression although this is the usually accepted mechanism for confined geometries. We show with FEM that in our specific geometry the falling rate period is due to changes in the shape of the air-water interface at the free surface where most evaporation occurs. Our simulations show that the sensitivity of the drying rate to the shape of the first air-water interface from the sample free surface implies that slight changes of the wetting or pinning conditions can significantly modify the drying rate.

Proton NMR relaxation as a probe for setting cement pastes.

We report a 20-MHz proton nuclear magnetic resonance T1 relaxation study of cement paste hydration in the early stages of setting, using different centimeter-sized samples of cements of various origins and different water-to-cement ratios. In every sample, during the first few minutes of hydration, it is found that inverse Laplace processing of inversion-recovery measurements systematically exhibits at least two T1 values: a long one, around 100 ms, whose value correlates well with water content and which may be attributed to bulk water surrounding cement grains; and a short one, around 2 ms, which is quite insensitive to water-to-cement ratio and which may be attributed to water embedded in floculated cement grains before setting occurs. The time evolution of the longest T1 value for several hours is also shown to exhibit a characteristic five-stage behavior that is well correlated with known stages of the hydration process: initial reaction, induction period, acceleration period, deceleration period and slow hydration reaction. These results are compared with calorimetric measurements and electrical conductivity literature.

Combined time-lapse magnetic resonance imaging and modeling to investigate colloid deposition and transport in porous media.

Colloidal particles can act as vectors of adsorbed pollutants in the subsurface, or be themselves pollutants. They can reach the aquifer and impair groundwater quality. The mechanisms of colloid transport and deposition are often studied in columns filled with saturated porous media. Time-lapse profiles of colloid concentration inside the columns have occasionally been derived from magnetic resonance imaging (MRI) data recorded in transport experiments. These profiles are valuable, in addition to particle breakthrough curves (BTCs), for testing and improving colloid transport models. We show that concentrations could not be simply computed from MRI data when both deposited and suspended colloids contributed to the signal. We propose a generic method whereby these data can still be used to quantitatively appraise colloid transport models. It uses the modeled suspended and deposited particle concentrations to compute modeled MRI data that are compared to the experimental data. We tested this method by performing transport experiments with sorbing colloids in sand, and assessed for the first time the capacity of the model calibrated from BTCs to reproduce the MRI data. Interestingly, the dispersion coefficient and deposition rate calibrated from the BTC were respectively overestimated and underestimated compared with those calibrated from the MRI data, suggesting that these quantities, when determined from BTCs, need to be interpreted with care. In a broader perspective, we consider that combining MRI and modeling offers great potential for the quantitative analysis of complex MRI data recorded during transport experiments in complex environmentally relevant porous media, and can help improve our understanding of the fate of colloids and solutes, first in these media, and later in soils.

An MRI-SPI and NMR relaxation study of drying-hydration coupling effect on microstructure of cement-based materials at early age.

Hydration and drying coupling effect monitoring with single point imaging profiles allowed us to evaluate "free" pore and "bounded" chemical water quantity. White cement pastes inverse Laplace analysis of T1 measurements shown original results with two components during setting. After hardening, we found three components. Single point imaging measures were also used to study the evolution of transition zone in repaired concrete. MRI results demonstrated its interest compared with destructive method for longitudinal study and phenomena kinetic monitoring.