Multifunctional Magnetic Nanocolloids for Hybrid Solar-Thermoelectric Energy Harvesting.

Present environmental issues force the research to explore radically new concepts in sustainable and renewable energy production. In the present work, a functional fluid consisting of a stable colloidal suspension of maghemite magnetic nanoparticles in water was characterized from the points of view of thermoelectrical and optical properties, to evaluate its potential for direct electricity generation from thermoelectric effect enabled by the absorption of sunlight. These nanoparticles were found to be an excellent solar radiation absorber and simultaneously a thermoelectric power-output enhancer with only a very small volume fraction when the fluid was heated from the top. These findings demonstrate the investigated nanofluid's high promise as a heat transfer fluid for co-generating heat and power in brand new hybrid flat-plate solar thermal collectors where top-heating geometry is imposed.

Colloidal Stability of Imogolite Nanotube Dispersions: A Phase Diagram Study.

In this article, we revisit the colloidal stability of clay imogolite nanotubes by studying the effect of electrostatic interactions on geo-inspired synthetic nanotubes in aqueous dispersions. The nanotubes in question are double-walled aluminogermanate imogolite nanotubes (Ge-DWINTs) with a well-defined diameter (4.3 nm) and with an aspect ratio around 4. Surface charge properties are assessed by electrophoretic measurements, revealing that the outer surfaces of Ge-DWINT are positively charged up to high pH values. A series of Ge-DWINT dispersions have been prepared by osmotic stress to control both the ionic strength of the dispersion and the volume fraction in nanotubes. Optical observations coupled to small and wide-angle X-ray scattering (SAXS/WAXS) experiments allow us to unravel different nanotube organizations. At low ionic strength (IS < 10-2 mol L-1), Ge-DWINTs are fully dispersed in water while they form an arrested gel phase above a given concentration threshold, which shifts toward higher volume fraction with increasing ionic strength. The swelling law, derived from the evolution of the mean intertube distance as a function of the nanotube concentration, evidences a transition from isotropic swelling at low volume fractions to one-dimensional swelling at higher volume fractions. These results show that the colloidal stability of Ge-DWINT is driven by repulsive interactions for ionic strengths lower than 10-2 mol L-1. By contrast, higher salt concentrations lead to attractive interactions that destabilize the colloid suspension, inducing nanotube coagulation into larger structures that settle over time or form opaque gels. Detailed simulations of the WAXS diagram reveal that aggregates are mainly formed by an isotropic distribution of small bundles (less than four nanotubes) in which the nanotubes organized themselves in parallel orientation. Altogether, these measurements allow us to give the first overview of the phase diagram of colloidal dispersions based on geo-inspired imogolite-like nanotubes.

Dispersion mechanism of polyacrylic acid-coated nanoparticle in protic ionic liquid, N,N-diethylethanolammonium trifluoromethanesulfonate.

HYPOTHESIS: Ionic liquids (ILs) are extremely concentrated electrolyte solutions. The ubiquitous presence of ions induces specific behaviors for chemical reactions compared to reactions in water solutions. This is also the case for the stability of colloidal dispersions, for which the DLVO model cannot be applied as the ionic strength is out of the model range. In a previous work, in the protic IL ethylammonium nitrate (doi: https://doi.org//10.1016/j.jcis.2015.04.059), we observed an unexpected influence of the pH on the stability of dispersion of maghemite nanoparticles coated with poly(acrylic acid) (pAA). EXPERIMENTS: To clarify and generalize these observations, we investigated here the pH response of the dispersion in a second protic ionic liquid with a different acid-base nature, diethylethanolammonium trifluoromethanesulfonate. pH titrations of the dispersions were achieved with an IS-FET electrode and the associated thermodynamic constants determined. The colloid structural properties were examined by small angle X-ray scattering. FINDINGS: Under acidic or mildly basic condition, a stable dispersion was obtained, i.e., when the degree of dissociation of pAA, α, was α < 0.1 or α > 0.7. Dispersions form quite dense but reversible aggregates in the intermediate α range. A model for the solvation layer around the particles is proposed and generalizes the former findings.

Concentrated assemblies of magnetic nanoparticles in ionic liquids.

Maghemite (γ-Fe2O3) nanoparticles (NPs) can be successfully dispersed in a protic ionic liquid, ethylammonium nitrate (EAN), by transfer from aqueous dispersions into EAN. As the aqueous systems are well controlled, several parameters can be tuned. Their crucial role towards the interparticle potential and the structure of the dispersions is evidenced: (i) the size of the NPs tunes the interparticle attraction monitoring dispersions to be either monophasic or gas-liquid-like phase separated; (ii) the nature of the initial counterion in water (here sodium, lithium or ethylammonium) and the amount of added water (<20 vol%) modulate the interparticle repulsion. Very concentrated dispersions with a volume fraction of around 25% are obtained thanks to the gas-liquid-like phase separations. Such conclusions are derived from a fine structural and dynamical study of the dispersions on a large range of spatial scales by coupling several techniques: chemical analyses, optical microscopy, dynamic light scattering, magneto-optic birefringence and small angle scattering.

Controlling nanoparticles dispersion in ionic liquids by tuning the pH.

HYPOTHESIS: Getting colloidally stable dispersions of nanoparticles in ionic liquids is a challenging task. Indeed, long-range electrostatic repulsions often involved in molecular solvents are screened in ionic liquids and cannot counterbalance the interparticle attractions. Using a polyelectrolyte coating should provide a good stabilisation of the nanoparticles. Investigating the role of the polyelectrolyte charge on the dispersion state should yield to a better comprehension of the stabilisation mechanisms. EXPERIMENTS: Polyacrylate coated maghemite nanoparticles were transferred from water to ethylammonium nitrate, a protic ionic liquid, for various polymer chain length and nanoparticles size. Titrations of coated nanoparticles and of free polymer chains were performed in water and in ethylammonium nitrate. The dispersion state of the nanoparticles was monitored at different pH by small-angle X-ray scattering. FINDINGS: Polyacrylate coating stabilised the nanoparticles in ethylammonium nitrate. However, reversible aggregation with the pH was observed. Surprisingly, this control was not directly related to the surface charge like in water but to the solvent quality for the polyelectrolyte. This study is the first report on the use of the pH to tune the dispersion state of nanoparticles in an ionic liquid. It provides a better understanding of the mechanisms responsible for colloidal stability in ionic liquids.

Micellization of dodecyltrimethylammonium bromide in water-dimethylsulfoxide mixtures: a multi-length scale approach in a model system.

The micellization in mixed solvent was studied using conductimetry, density measurements (molar volumes), and small angle neutron scattering (SANS) to explore dodecyltrimethylammonium bromide (DTABr) micelle formation throughout the entire composition range of water-dimethylsulfoxide (DMSO) mixtures. As the concentration of DMSO was increased in the mixture, the critical micelle concentration (CMC) increased, the aggregation number decreased and the ionization degree increased, until no aggregates could be detected any more for DMSO molar fraction higher than 0.51. The results were consistent with the presence of globular micelles interacting via a coulombic potential. The experimental CMC values and aggregation numbers were successfully reconciled with a molecular thermodynamic model describing the micellization process in solvent mixtures (R. Nagarajan and C.-C. Wang, Langmuir 16 (2000) 5242). The structural and thermodynamic characterization of the micelles agreed with the prediction of a dissymmetric solvation of the surfactant entity: the hydrocarbon chain was surrounded only by DMSO while the polar head was surrounded only by water. The decrease in the ionization degree was due to the condensation of the counterions and was definitely linked to the geometrical characteristics of the aggregates and by no means to the CMC or salinity. This multi-technique study provides new insight into the role of solvation in micellization and the reason for the decrease in ionization degree, emphasizing the dissymmetric solvation of the chain by DMSO and the head by water. This is the first time that, for a given surfactant in solvent mixtures, micellization is described using combined analysis from molecular to macroscopic scale.

Mixtures of hydrogenated and fluorinated lactobionamide surfactants with cationic surfactants: study of hydrogenated and fluorinated chains miscibility through potentiometric techniques.

The work reported herein deals with the aqueous behavior of hydrocarbon and/or fluorocarbon ionic and nonionic surfactants mixtures. These mixtures were studied using potentiometric techniques in NaBr (0.1 mol L-1) aqueous solution as well as in pure water. Mixed micelles were formed from a cationic surfactant (dodecyl or tetradecyltrimethylammonium bromide respectively called DTABr or TTABr) and neutral lactobionamide surfactants bearing a hydrogenated dodecyl chain (H12Lac) or a fluorinated chain (CF3-(CF2)5-(CH2)2- or CF3-(CF2)7-(CH2)2-). We showed that concentrations of ionic and nonionic surfactants in the monomeric form as well as the composition of the mixed micelles can be specified thanks to a potentiometric technique. The complete characterization does not request any model of micellization a priori. The activities of the micellar phase constituents, as well as the free enthalpies of mixing, were calculated. The subsequent interpretation only relies on the experimental characterization. Comparison of the behaviors of the various systems with a model derived from the regular solution theory reveals the predominant part of electrostatic interactions in the micellization phenomenon. It also appears that the energy of interaction between hydrogenated and fluorinated chains is unfavorable to mixing and is of much lower magnitude than the electric charges interactions.

Study of beta-cyclodextrin/fluorinated trimethyl ammonium bromide surfactant inclusion complex by fluorinated surfactant ion selective electrode.

The construction and performance of a liquid membrane electrode responsive to N-(1,1,2,2-tetrahydroperfluorooctyl)-N,N,N-trimethylammonium bromide (FTABr) and its use for the study of beta-cyclodextrin/fluorinated surfactant inclusion complex is described. The electrode is based on the use of tetrahydroperfluorooctyltrimethylammonium-tetraphenylborate ion pair as electro active material in polyvinyl chloride (PVC) matrix plasticized using 2-Nitrophenyl octyl ether (NPOE). The electrode exhibits a fast, stable, reproducible and "Nernstian" response (59+/-2 mV) for FTABr over the concentration range of 10(-5) to 2 x 10(-3) mol L(-1) at 298 K. The lowest detection limit is 2 x 10(-6) mol L(-1) and the response time is around 20-30s. The validity of the electrode, for detection of fluorinated surfactant ions and hence to carry out electrochemical measurements to study micellization of fluorinated surfactant, is verified by comparing the critical micelle concentration (cmc) value of FTABr obtained by using the electrode, with that obtained by surface tension measurements. Association constant K for beta-cyclodextrin/FTABr complex is evaluated from the potentiometric measurements carried out using this electrode and is observed to be approximately 1.26 x 10(5). The results suggest that beta-cyclodextrin forms an equimolar association complex with the FTA+ surfactant ion.

Characterization of functional oligosaccharide mimics of the Shigella flexneri serotype 2a O-antigen: implications for the development of a chemically defined glycoconjugate vaccine.

Protection against reinfection with noncapsulated Gram-negative bacteria, such as Shigella, an enteroinvasive bacterium responsible for bacillary dysentery, is mainly achieved by Abs specific for the O-Ag, the polysaccharide part of the LPS, the major bacterial surface Ag. The use of chemically defined glycoconjugates encompassing oligosaccharides mimicking the protective determinants carried by the O-Ag, thus expected to induce an efficient anti-LPS Ab response, has been considered an alternative to detoxified LPS-protein conjugate vaccines. The aim of this study was to identify such functional oligosaccharide mimics of the S. flexneri serotype 2a O-Ag. Using protective murine mAbs specific for S. flexneri serotype 2a and synthetic oligosaccharides designed to analyze the contribution of each sugar residue of the branched pentasaccharide repeating unit of the O-Ag, we demonstrated that the O-Ag exhibited an immunodominant serotype-specific determinant. We also showed that elongating the oligosaccharide sequence improved Ab recognition. From these antigenicity data, selected synthetic oligosaccharides were assessed for their potential to mimic the O-Ag by analyzing their immunogenicity in mice when coupled to tetanus toxoid via single point attachment. Our results demonstrated that induction of an efficient serotype 2a-specific anti-O-Ag Ab response was dependent on the length of the oligosaccharide sequence. A pentadecasaccharide representing three biological repeating units was identified as a potential candidate for further development of a chemically defined glycoconjugate vaccine against S. flexneri 2a infection.

Toward a better understanding of the basis of the molecular mimicry of polysaccharide antigens by peptides: the example of Shigella flexneri 5a.

Protein conjugates of oligosaccharides or peptides that mimic complex bacterial polysaccharide antigens represent alternatives to the classical polysaccharide-based conjugate vaccines developed so far. Hence, a better understanding of the molecular basis ensuring appropriate mimicry is required in order to design efficient carbohydrate mimic-based vaccines. This study focuses on the following two unrelated sets of mimics of the Shigella flexneri 5a O-specific polysaccharide (O-SP): (i) a synthetic branched pentasaccharide known to mimic the average solution conformation of S. flexneri 5a O-SP, and (ii) three nonapeptides selected upon screening of phage-displayed peptide libraries with two protective murine monoclonal antibodies (mAbs) of the A isotype specific for S. flexneri 5a O-SP. By inducing anti-O-SP antibodies upon immunization in mice when appropriately presented to the immune system, the pentasaccharide and peptides p100c and p115, but not peptide p22, were qualified as mimotopes of the native antigen. NMR studies based on transferred NOE (trNOE) experiments revealed that both kinds of mimotopes had an average conformation when bound to the mAbs that was close to that of their free form. Most interestingly, saturation transfer difference (STD) experiments showed that the characteristic turn conformations adopted by the major conformers of p100c and p115, as well as of p22, are clearly involved in mAb binding. These latter experiments also showed that the branched glucose residue of the pentasaccharide was a key part of the determinant recognized by the protective mAbs. Finally, by using NMR-derived pentasaccharide and peptide conformations coupled to STD information, models of antigen-antibody interaction were obtained. Most interestingly, only one model was found compatible with experimental data when large O-SP fragments were docked into one of the mIgA-binding sites. This newly made available system provides a new contribution to the understanding of the molecular mimicry of complex polysaccharides by peptides and short oligosaccharides.

Detergent binding as a sensor of hydrophobicity and polar interactions in the binding cavities of proteins.

To evaluate the role of hydrophobic and electrostatic or other polar interactions for protein-ligand binding, we studied the interaction of human serum albumin (HSA) and beta-lactoglobulin with various aliphatic (C10-C14) cationic and zwitterionic detergents. We find that cationic detergents, at levels that do not cause unfolding, interact with a single site on beta-lactoglobulin and with two primary and five to six secondary sites on HSA with an affinity that is approximately the same as that with which zwitterionic (dimethylamineoxide) detergents interact, suggesting the absence of significant electrostatic interactions in the high-affinity binding of these compounds. The binding affinity for all of the groups of compounds was dependent upon hydrocarbon chain length, suggesting the predominant role of hydrophobic forces, supported by polar interactions at the protein surface. A distinct correlation between the binding energy and the propensity for micelle formation within the group of cationic or noncharged (nonionic and zwitterionic) detergents indicated that the critical micellar concentration (CMC) for each of these detergent groups, rather than the absolute length of the hydrocarbon chain, can be used to compare their hydrophobicities during their interaction with protein. Intrinsic fluorescence data suggest that the two primary binding sites on serum albumin for the zwitterionic and cationic compounds are located in the C-terminal part of the albumin molecule, possibly in the Sudlow II binding region. Comparisons with previous binding data on anionic amphiphiles emphasize the important contribution of ion bond formation and other polar interactions in the binding of fatty acids and dodecyl sulfate (SDS) by HSA but not by beta-lactoglobulin. Electrostatic interactions by cationic detergents played a significant role in destabilizing the protein structure at high binding levels, with beta-lactoglobulin being more susceptible to unfolding than HSA. Zwitterionic detergents, in contrast to the cationic detergents, had no tendency to unfold the proteins at high concentrations.