International audience | In order to better understand the fate of the toxic element Ag(I), sorption of Ag(I) was studied from batch experiments, at different pHs (2–8) and at 298K. A pure quartz sand (99.999% SiO2) and “natural” quartz sand (99% SiO2, and traces of Fe, Al, Mn (hydr)oxides, of clays and of pyrite) were used as sorbents. The Ag(I) sorption behavior depends strongly on pH with isotherm shapes characteristic of Langmuir-type relationship for initial Ag concentration [Ag(I)], range between 5.0×10−7 and 1.0×10−3M. Even if the Ag (I) sorption capacity on pure quartz sand is very low compared to the natural quartz sands, its affinity is rather high. From speciation calculations, several sites were proposed: at pHi 4, 6 and 8, the first surface site is assumed to be due to iron (hydr)oxides while the second surface site is attributed to silanols. At pHi 2, sorption of Ag(I) was assumed to be on two surface sites of iron (hydr)oxides and a third surface site on silanol groups. Even if the sand is mainly composed of silica, the trace minerals play an important role in sorption capacity compared to silica. The conditional surface complexation constants of Ag(I) depend on pH. On the other hand, it is shown that the Ag speciation depends strongly on the history of “natural” quartz sand due to initial applied treatment, little rinsing or longer washing. In the presence of low amount of pyrite, strong complexes between Ag(I) and sulfur compounds such as thiosulfates due to oxidative dissolution of pyrite are formed what decreases Ag sorption capability. SEM–EDS analyses highlighted the surface complexation–precipitation of Ag2S and Ag(0) colloids which confirmed the important role of pyrite on Ag(I) speciation.

A series of transition metal acetylacetonates and acetates were used as precursors to generate high loadings of metal sites finely dispersed on SBA-15 silica. To achieve this, grafting of chelated transition metal precursors was performed directly to the surface of the as-synthesized SBA-15/P123 composite material. The thus-obtained metal/SBA-15 materials were studied by a variety of methods, e.g., elemental analysis, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance UV–visible spectroscopy (DR-UV–vis), X-ray photoelectron spectroscopy (XPS) and N2 physisorption measurements at −196°C. From the results, the proposed functionalization method was found to be a highly tunable and reproducible strategy to disperse transition metal oxides in mesoporous silica materials. The results from elemental analysis of the modified materials confirmed that the amount of grafted species is a function of the initial concentration of precursor in the solution used for grafting. The chelated complexes were found to strongly interact with the silanol groups of the silica material, resulting in a ligand-exchange process, as corroborated by FTIR. However, different metal precursors showed distinct reactivity towards the surface of mesoporous silica, owing to differences in the stability of the complexes under the conditions used for grafting. DR-UV–vis and XPS analyses suggest that when the stability of a given precursor decreases, the grafting procedure can lead to the formation of small clusters of the metal oxide on the silica surface. XRD and SEM also show that grafting of lower stability complexes, such as Mn(acac)3, Cu(acetate)2 and VO(acac)2, on the silica surface can result in the formation of large crystals on the external surface of the SBA-15 particles. Nevertheless, it was established by XPS analysis that only a small percentage of the grafted species leads to the formation of bulk crystals while the remaining species are substituted into the silica framework. Obviously, a well-controlled and increased dispersion of the metal cations/oxides on the surface of highly porous silica materials is of great interest since these MxOy–SiO2 mixed oxides could demonstrate high catalytic activity in a large variety of reactions.

The availability of sensitive, reproducible and stable substrate is critically important for surface enhanced Raman scattering (SERS)-based application, but it still remains a challenge up to now. In this work, urchin-like LaVO4 microspheres prepared by a hydrothermal method were used as a template to fabricate SERS substrate by deposition of Au nanoparticle onto the surfaces of LaVO4 microspheres. The coverage of Au nanoparticles on the surfaces of LaVO4 microspheres can be easily controlled by varying the amount of Au precursor. SERS measurement showed that the coverage of Au nanoparticles on the surfaces of LaVO4 microspheres had a great effect on SERS activity. The SERS signals collected from 80 microspheres indicated that as-prepared SERS substrate exhibited a good reproducibility. Detection of melamine molecules with a low concentration (1.0×10⁻⁹M) was used as an example to show the possible application of such substrate. In addition, the effect of iron ion (Fe³⁺) on detection melamine from the mixture of melamine and benzoic acid was also investigated. It was found that the interference of benzoic acid in detecting melamine from the mixture can be removed by adding Fe³⁺.

The fundamental mechanisms governing reduction and growth of palladium on the genetically engineered Tobacco mosaic virus in the absence of an external reducer have been elucidated via in situ X-ray absorption spectroscopy. In recent years, many virus-inorganic materials have been synthesized as a means to produce high quality nanomaterials. However, the underlying mechanisms involved in virus coating have not been sufficiently studied to allow for directed synthesis. We combined XAS, via XANES and EXAFS analysis, with TEM to confirm an autocatalytic reduction mechanism mediated by the TMV1Cys surface. This reduction interestingly proceeds via two first order regimes which result in two linear growth regimes as spherical palladium nanoparticles are formed. By combining this result with particle growth data, it was discovered that the first regime describes growth of palladium nanoparticles on the virion while the second regime describes a second layer of larger particles which grew sporadically on the first palladium nanoparticle layer. Subsequent aggregation of free solution based spherical particles and metallized nanorods characterize a third and final regime. At the end of the second reduction regime, the average particle diameter of particles tethered to the TMV1Cys surface are approximately 4.5nm. The use of XAS to simultaneously monitor the kinetics of biotemplated reactions along with growth of metal nanoparticles will provide insight into the pertinent reduction and growth mechanisms so that nanorod properties can be controlled through their populating nanoparticles.

Structural forces play an important role in the rheology, processing and stability of colloidal systems and complex fluids, with polyelectrolytes representing a key class of structuring colloids. Here, we explore the interactions between soft colloids, in the form of air bubbles, in solutions of monodisperse sodium poly(styrene sulfonate) as a model polyelectrolyte. It is found that by self-consistently modelling the force oscillations due to structuring of the polymer chains along with deformation of the bubbles, it is possible to precisely predict the interaction potential between approaching bubbles. In line with polyelectrolyte scaling theory, two distinct regimes of behaviour are seen, corresponding to dilute and semi-dilute polymer solutions. It is also seen that by blending monodisperse systems to give a bidisperse sample, the interaction forces between soft colloids can be controlled with a high degree of precision. At increasing bubble collision velocity, it is revealed that hydrodynamic flow overwhelms oscillatory structural interactions, showing the important disparity between equilibrium behaviour and dynamic interactions.

Zinc chloride was utilized as the multi-functional modifier with dicyandiamide to synthesize porous g-C3N4, it not only played the role of pore-former in the resulting composite, but also acted as the assistant in succeeding adsorption of methyl orange (MO). Adjusting the quantity of ZnCl2 additive combined with the concentration of acidic washing liquid could control the amount and distribution of residual zinc species in the g-C3N4, in order to enhance the activity of the photocatalyst. The resulting composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–vis diffuse reflection spectroscopy (UV–vis) and X-ray photoelectron spectroscopy (XPS) as well as photoluminescence (PL) to assess the influence of residual zinc species on the physical and optical property of the composite. And they were evaluated in the photocatalytic degradation of MO in the visible light region, exhibiting an activity 240% higher than that of g-C3N4.

Enzymatic supramolecular hydrogelation is a simple, controllable, and novel strategy for preparation of soft colloidal materials, which allows the integration of self-assembly with enzyme associated biological processes. The development of more enzymes involve in hydrogelation is a subject of developing useful soft colloids. In this work, an ectoenzyme, CD73, was found to trigger the formation of nanofibers as matrices of hydrogels. CD73 is an important cell surface enzyme which converts extracellular adenosine monophosphate (AMP) to adenosine. It is broadly expressed in many cancer cells and participates in tumor growth. The successful application of CD73 in self-assembly and hydrogelation may provide new strategies for CD73-guided materials and therapies.

In this study, novel zwitterionic glycosyl modified polyethersulfone (PES) ultrafiltration membranes were prepared via in-situ cross-linking polymerization coupled with phase inversion technique, and the following reactions. The membranes were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), ¹HNMR spectrum, and static water contact angles (WCAs) measurements. The modified membranes showed excellent anti-fouling property, and the flux recovery ratio could reach almost 100%. Meanwhile, the blood compatibility of the membranes was measured by protein adsorption, platelet adhesion, activated partial thromboplastin time (APTT), and thrombin time (TT). The results implied that the zwitterionic glycosyl modified PES membranes had good anti-fouling property and blood compatibility.

Surfactants that can provide a more natural substitute for lipid bilayers are important in the purification and in vitro study of membrane proteins. Here we investigate the structural response of a model membrane protein, bacteriorhodopsin (BR), to phosphocholine biosurfactants. Phosphocholine biosurfactants are a type of biomimetic amphiphile that are similar to phospholipids, in which membrane proteins are commonly embedded. Multiple spectroscopic and zeta potential measurements are employed to characterize the conformational change, secondary and tertiary structure, oligomeric status, surface charge distribution and the structural stability of BR solubilized with phosphocholine biosurfactants of varying tail length. The process of phosphocholine micelle formation is found to facilitate the solubilization of BR, and for long-chain phosphocholines, concentrations much higher than their critical micelle concentrations achieve good solubilization. Phosphocholine biosurfactants are shown to be mild compared with the ionic surfactant SDS or CTAB, and tend to preserve membrane protein structure during solubilization, especially at low micelle concentrations, by virtue of their phospholipid-like zwitterionic head groups. The increase of alkyl chain length is shown to obviously enhance the capability of phosphocholine biosurfactants to stabilize BR. The underlying mechanism for the favorable actions of phosphocholine biosurfactant is also discussed.