Here, we present new antimicrobial nanoparticles based on silica nanoparticles (SNPs) coated with a quaternary ammonium cationic surfactant, didodecyldimethylammonium bromide (DDAB). Depending on the initial concentration of DDAB, SNPs immobilize between 45 and 275 μg of DDAB per milligram of nanoparticle. For high concentrations of DDAB adsorbed to SNP, a bilayer is formed as confirmed by zeta potential measurements, thermogravimetry, and diffuse reflectance infrared Fourier transform (DRIFT) analyses. Interestingly, these nanoparticles have lower minimal inhibitory concentrations (MIC) against bacteria and fungi than soluble surfactant. The electrostatic interaction of the DDAB with the SNP is strong, since no measurable loss of antimicrobial activity was observed after suspension in aqueous solution for 60 days. We further show that the antimicrobial activity of the nanoparticle does not require the leaching of the surfactant from the surface of the NPs. The SNPs may be immobilized onto surfaces with different chemistry while maintaining their antimicrobial activity, in this case extended to a virucidal activity. The versatility, relative facility in preparation, low cost, and large antimicrobial activity of our platform makes it attractive as a coating for large surfaces.

The maximum glacial extent in the Central Pyrenees during the Last Glaciation is known to have occurred before the global Last Glacial Maximum, but the succession of cold events afterwards and their impact on the landscape are still relatively unknown. This study focuses on the environmental evolution in the upper valley of the Garonne River since the Last Glaciation. Geomorphological mapping allows analysis of the spatial distribution of inherited and current processes and landforms in the study area. The distribution of glacial records (moraines, till, erratic boulders, glacial thresholds) suggests the existence of four glacial stages, from the maximum expansion to the end of the glaciation. GIS modeling allows quantification of the Equilibrium Line Altitude, extent, thickness and volume of ice in each glacial stage. During the first stage, the Garonne glacier reached 460m in the Loures-Barousse-Barbazan basin, where it formed a piedmont glacier 88km from the head and extended over 960km. At a second stage of glacier stabilization during the deglaciation process, the valley glaciers were 12-23km from the head until elevations of 1000-1850m, covering an area of 157km. Glaciers during stage three remained isolated in the upper parts of the valley, at heights of 2050-2200m and 2.6-4.5km from the head, with a glacial surface of 16km. In stage four, cirque glaciers were formed between 2260m and 2590m, with a length of 0.4-2km and a glacial area of 5.7km. Also, the wide range of periglacial, slope, nival and alluvial landforms existing in the formerly glaciated environments allows reconstruction of the post-glacial environmental dynamics in the upper Garonne basin. Today, the highest lands are organized following three elevation belts: subnival (1500-1900m), nival (1900-2300m) and periglacial/cryonival (2300-2800m).

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Ordered copper integrated mesoporous silicate catalysts (CuMSC) have been synthesized by the utilization of the amphiphilic tri-block copolymer pluronic F127 as a structure directing agent (SDA) under acidic aqueous conditions. The mesophase of the materials was investigated using small-angle powder X-ray diffraction and transmission electron microscopic (TEM) image analysis. N2 adsorption-desorption studies show that the BET surface area of CuMSC (214-407 m(2) g(-1)) is lower than that of pure silica (611 m(2) g(-1)) and has smaller average pore dimensions (4.0-5.0 nm), both prepared following the same synthetic route. The reduction of pore size and surface area points to incorporation of copper within the silicate network. FEG-SEM results suggest that the materials have a plate-like morphology and are composed of very tiny nanoparticles. EDS surface chemical analysis was utilized for the detection of the distribution of Si, O and Cu in the matrix. The FT IR spectral study suggests the complete removal of the surfactants from the calcined materials and the presence of Si-O-Cu bonds for high nominal contents. X-ray photoelectron spectroscopy (XPS) and UV-vis reflectance spectra show the oxidation state of copper and coordination mode, respectively. These mesoporous materials display a good catalytic activity in the oxidation of cyclohexane to cyclohexanone and cyclohexanol in the presence of the green oxidant hydrogen peroxide. The maximum yield (cyclohexanone and cyclohexanol) was ca. 29% and the TON (turnover number) was 276 under optimal reaction conditions. The good catalytic activity could be attributed to the large surface area and the presence of a high number of active sites located at the surface of the material, as well as to its stability. The catalysts showed negligible loss of activity after five cycles.

The interactions between DNA purines (guanine and adenine) and the ruthenium complex Ru(NO)(NO(3))(3) were studied within nanostructured silica matrices prepared by a two-step sol-gel process. By infrared analysis in diffuse reflectance mode, it was proved that encapsulation induces a profound modification on the complex, whereas guanine and adenine preserve their structural integrity. The complex undergoes nitrate ligand exchange and co-condenses with the silica oligomers, but the nitrosyl groups remain stable, which is an unusual behavior in Ru nitrosyl complexes. In turn, the doping molecules affect the sol-gel reactions and eventually the silica structure as it forms: the complex yields a microporous structure, and the purine bases are responsible for the creation of macropores due to hydrogen bonding with the silanol groups of the matrix. In a confined environment, the interactions are much stronger for the coencapsulated pair guanine complex. While adenine only establishes hydrogen bonds or van der Waals interactions with the complex, guanine bonds covalently to Ru by one N atom of the imidazole ring, which becomes strongly perturbed, resulting in a deformation of the complex geometry.