Armel Guillermo

NMR investigations into heterogeneous structures of thermosensitive microgel particles

The internal properties of submicron poly(N-isopropylmethacrylamide) latex particles were investigated as a function of the methylene bisacrylamide (MBA) concentration used as a crosslinker. Two experimental approaches were performed. First, quasi-electric light scattering measurements provided the size variation of the particles as a function of temperature, from which the swelling capacity of the particles as a function of MBA were estimated. In addition, the broadening and lowering effects of the volume phase transition temperature were detected from the turbidity of the solutions versus the MBA concentration. Second, observations of the transverse relaxation of protons gave evidence for heterogeneous structures inside the particles; several structural parts were discriminated from one another from different proton mobilities detected through magnetic relaxation rates. Corresponding to the concentration gradients of the crosslinker, the internal particle structures were looser and looser from the core to the shell. The state of the gelation of the polymer particles was governed by the initial amount of the crosslinker introduced into the latex recipe.

NMR and pulsed field gradient NMR approach of water sorption properties in Nafion at low temperature.

The water uptake and the water self-diffusion coefficient were measured in Nafion membranes at subzero temperatures. NMR spectroscopy was used to precisely quantify the actual concentration of water in membranes as a function of the temperature and their hydration rates at room temperature. We find that below 273 K the water concentration decreases with temperature to reach, at around 220 K, a limit value independent of the initial concentration. This regime is observed if the concentration at room temperature is higher than 10%. Below this concentration no membrane deswelling was observed. The water self-diffusion coefficient, measured by pulsed field gradient NMR in function of the temperature, is determined by the actual concentration C(T) whatever the concentration at room temperature. The concentration variation is attributed to a decrease in the relative humidity RH(T) of the water vapor surrounding the membrane induced by the simultaneous presence of supercooled water inside the membrane and ice outside the membrane.

A gadolinium complex confined in silica nanoparticles as a highly efficient T1/T2 MRI contrast agent.

Gd in silica: Noncovalent confinement of a monoaqua Gd chelate into biocompatible silica nanoparticles (NPs; see figure) by a sol-gel method affords a new example of nanosized contrast agents with very high per-Gd relaxivities. Such NPs provide a route to highly efficient multimodal contrast agents. Copyright

Microphase Structure of Poly(N-isopropylacrylamide) Hydrogels As Seen by Small- and Wide-Angle X-ray Scattering and Pulsed Field Gradient NMR

Above the lower critical solution temperature T(c) (ca. 34 degrees C), poly(N-isopropylacrylamide) hydrogels become weakly hydrophobic and undergo microphase separation. Macroscopic deswelling, however, is extraordinarily slow, the out-of equilibrium state of the gel being conserved for many days. In this article the structure of the microphase-separated state above T(c) is probed by small-angle X-ray scattering and by pulsed field gradient NMR of the protons of water, both in the water phase and in the polymer-rich phase. Above T(c) the gel comprises two microphases, separated by smooth interfaces. The cavities occupied by the water phase form a connected network. The diffusion rate of the water molecules in this phase varies from one cavity to another and can be described by a Gaussian distribution. Water molecules belonging to the polymer-rich phase are also mobile, but their self-diffusion coefficient D is greatly diminished. Absence of compartmentalization of the water phase implies that the slow deswelling rate of the gel is not due to trapping of the water phase.

Fast Water Diffusion and Long-Term Polymer Reorganization during Nafion Membrane Hydration Evidenced by Time-Resolved Small-Angle Neutron Scattering

We report a small-angle neutron scattering study of liquid water sorption in Nafion membranes. The swelling of hydrophilic domains was measured on the nanoscale by combining in situ time-resolved and long-term static experiments, yielding kinetic curves recorded over an unprecedented time scale, from hundreds of milliseconds to several years. At low water content, typically below 5 water molecules per ionic group, a limited subdiffusive regime was observed and ascribed to nanoconfinement and local interactions between charged species and water molecules. Further ultrafast and thermally activated swelling due to massive liquid water sorption was observed and analyzed by using Ficks equation. The extracted mutual water diffusion coefficients are in good agreement with pulsed field gradient NMR self-diffusion coefficient values, evidencing a water diffusion-driven process due to concentration gradients within the Nafion membrane. Finally, after completion of the ultrafast regime, the kinetic swelling curves exhibit a remarkable long-term behavior scaling as the logarithm of time, showing that the polymer membrane can continuously accommodate additional water molecules upon hydration stress. The present nanoscale kinetics results provide insights into the vapor-versus-liquid sorption mechanisms, the nanostructure of Nafion, and the role of polymer reorganization modes, highlighting that the membrane can never reach a steady state.

Almost ideal 1D water diffusion in imogolite nanotubes evidenced by NMR relaxometry.

The longitudinal proton relaxation rates R(1) of water diffusing inside synthetic aluminium silicate imogolite nanotubes are measured by fast field-cycling NMR for frequencies between 0.02 and 35 MHz at 25, 37 and 50 degrees C. We give analytical expressions of the dominant intermolecular dipolar spin-spin contribution to R(1) and to the transverse relaxation rate R(2). A remarkable variation of R(1) by more than two orders of magnitude is observed and shown to be close to the theoretical law, inversely proportional to the square root of the resonance frequency, which is characteristic of perfect molecular 1D diffusion. The physics of diffusion is discussed.

Pseudosolid nuclear magnetic resonance approach to poly(ethylene-oxide) chain dynamics in the melt

Residual spin–spin interactions of protons attached to highly entangled chains in molten polymers give rise to a time reversal effect detected from solidlike spin–echoes formed from the transverse magnetization. The quantitative analysis of such pseudosolid spin–echoes, observed on molten poly(ethylene-oxide), reveals that the transverse relaxation curve is the product of two contributions: MxR(t), mainly sensitive to the existence of a temporary network and ΦR(t) arising from fast anisotropic segmental motions which give rise to residual spin–spin interactions. It is shown that the analysis provides a suitable method for distinguishing the two components from each other. The molecular weight was varied over the range 12–450 K. The description of MxR(t) is based on the assumption that there exists two stochastically independent effects. In accordance with a previous study [J. P. Cohen Addad and A. Guillermo, J. Chem. Phys. 111, 7131 (1999)], the first process is interpreted in terms of exponential relaxat...

Quantitative nuclear magnetic resonance characterization of long-range chain dynamics: Polybutadiene, polyethylene-oxide solution

We report two sets of independent nuclear magnetic resonance (NMR) measurements of self-diffusion and proton transverse relaxation in molten cis1,4-polybutadiene (PB) performed in order to investigate chain dynamics properties. Self-diffusion coefficients were measured as a function of temperature and of molecular weight (M) over the range 104 to 6.7×104 g/mol. The crossover from the Rouse-type behavior (D≈M−1) to the reptation one was found to occur for MCross≈3×104 g/mol; for M>MCross the data were consistent with the scaling dependence: D≈M−2.4±0.05, in agreement with the data analysis recently reported in the literature. The thorough analysis of the transverse relaxation of protons attached to highly entangled PB chains (6.7×104⩽M⩽43×104 g/mol) gave evidence for the dynamics partition of one chain into two end-submolecules and one inner part clearly discriminated from one another. The number NEnd of monomeric units in one end-submolecule, independent of M, is shown to be closely related to the monomer...

NMR 1D-imaging of water infiltration into mesoporous matrices.

It is shown that coupling nuclear magnetic resonance (NMR) 1D-imaging with the measure of NMR relaxation times and self-diffusion coefficients can be a very powerful approach to investigate fluid infiltration into porous media. Such an experimental design was used to study the very slow seeping of pure water into hydrophobic materials. We consider here three model samples of nuclear waste conditioning matrices which consist in a dispersion of NaNO(3) (highly soluble) and/or BaSO(4) (poorly soluble) salt grains embedded in a bitumen matrix. Beyond studying the moisture progression according to the sample depth, we analyze the water NMR relaxation times and self-diffusion coefficients along its 1D-concentration profile to obtain spatially resolved information on the solution properties and on the porous structure at different scales. It is also shown that, when the relaxation or self-diffusion properties are multimodal, the 1D-profile of each water population is recovered. Three main levels of information were disclosed along the depth-profiles. They concern (i) the water uptake kinetics, (ii) the salinity and the molecular dynamics of the infiltrated solutions and (iii) the microstructure of the water-filled porosities: open networks coexisting with closed pores. All these findings were fully validated and enriched by NMR cryoporometry experiments and by performing environmental scanning electronic microscopy observations. Surprisingly, results clearly show that insoluble salts enhance the water progression and thereby increase the capability of the material to uptake water.

Investigation of γ-Irradiated Vegetable Seeds with High-Resolution Solid-State 13C NMR

Abstract Bardet, M., Maron, S., Foray, M. F., Berger, M. and Guillermo, A. Investigation of γ-Irradiated Vegetable Seeds with High-Resolution Solid-State 13C NMR. Radiat. Res. 161, 458– 463 (2004). 13C solid-state NMR was used to investigate the effects of γ radiation on vegetable seeds, Pisum sativum and Latuca sativa, at absorbed doses that inhibit their germination. By combining single-pulse excitation and cross-polarization experiments under magic angle spinning, both liquid and solid domains of seeds can be characterized. We showed that the liquid domains, mostly made of triacylglycerols (TAG), of vegetable seeds are not sensitive to radiation. The main structural changes have been observed in the embryonic axes of seeds when the seeds are water-imbibed before irradiation. These results rule out a starting hypothesis concerning the potential role of TAG contained in oil bodies as a potential source of aldehydes that could further react with DNA moiety.