Switchable pH-Responsive Morphologies of Coassembled Nucleobase Copolymers.

This work presents supramolecular coassembled nucleobase copolymers with transitional morphologies upon pH changes (from 7.4 to 10). Uracil- and adenine-containing copolymers were prepared by RAFT, which allowed us to finely tailor the polymerization degree and the composition.

Second harmonic scattering reveals different orientational orders inside the hydrophobic cavity of hybrid nanotubes.

Second Harmonic Scattering (SHS) is a suitable technique to investigate the orientational correlations between molecules. This article explores the organization of different dye molecules adsorbed within the hydrophobic porosity of a hybrid organic-inorganic nanotube. Experimental polarization resolved SHS measurements highlight different orientational orders ranking from highly ordered and rigid organizations to disordered assemblies.

Dried hybrid imogolite nanotubes as solids with a changeable surface area: an insight into textural properties based on the correlation between nitrogen gas adsorption, immersion calorimetry into water, and small angle X-ray scattering.

Powdered samples of three imogolite materials with an inner surface covered with Si-CH groups (hybrid IMO-CH) were prepared by ambient drying at 323 K, freeze drying, and spray drying. Reliable estimates of the intra-tube (), inter-tube (), and inter-bundle () specific surface areas of these samples were inferred from a model-guided correlation between the results of measurements by small angle X-ray scattering (SAXS), nitrogen gas adsorption, and immersion calorimetry into water. Since the SAXS studies indicated no significant deformations of IMO-CH nanotubes upon drying, further studies by gaseous N adsorption at 77 K indicated the intra-tube and inter-bundle specific surface areas as being only accessible to this adsorbate.

Competitive adsorption mechanisms of Cd(II), Cu(II) and Pb(II) on bioinspired mesoporous silica revealed by complementary adsorption/isothermal titration calorimetry studies.

This study presents the adsorption properties of a bioinspired grafted mesoporous silica material and the competitive effects between Cd(II) or Cu(II) and Pb(II) during the adsorption process. Glutathione, a natural antioxidant known for its metal binding properties, has been successfully grafted to SBA-15 mesoporous silica and the optimum adsorption parameters were determined. This original and multidisciplinary approach combines classical adsorption studies with thermodynamic investigations to understand the adsorption behavior of Cd(II), Cu(II) and Pb(II) on this material.

α-Aminobisphosphonate Copolymers Based on Poly(ε-caprolactone)s and Poly(ethylene glycol): A New Opportunity for Actinide Complexation.

Original α-aminobisphosphonate-based copolymers were synthesized and successfully used for actinide complexation. For this purpose, poly(α-chloro-ε-caprolactone--ε-caprolactone)--poly(ethylene glycol)--poly(α-chloro-ε-caprolactone--ε-caprolactone) copolymers were first prepared by ring-opening copolymerization of ε-caprolactone (εCL) and α-chloro-ε-caprolactone using poly(ethylene glycol) (PEG) as a macro-initiator and tin(II) octanoate as a catalyst. The chloride functions were then converted to azide moieties by chemical modification, and finally α-aminobisphosphonate alkyne ligand (TzBP) was grafted using click chemistry, to afford well-defined poly(αTzBPεCL--εCL)--PEG--poly(αTzBPεCL--εCL) copolymers.

Hydrophobic dye solubilization hybrid imogolite nanotubes probed using second harmonic scattering.

This article explores the organization and interactions of Disperse Orange 3 (DO3) hydrophobic dye molecules within hybrid organic-inorganic imogolite nanotubes. In pure water, the DO3 dye molecules self assemble into large insoluble 2D nanosheets whose structure is also explored by molecular dynamics simulations. The dye molecules are however efficiently solubilized in the presence of hybrid imogolite nanotubes.

Size and Strain of Zinc Sulfide Nanoparticles Altered by Interaction with Organic Molecules.

Nanosized zinc sulfides (nano-ZnS) have size-dependent and tunable physical and chemical properties that make them useful for a variety of technological applications. For example, structural changes, especially caused by strain, are pronounced in nano-ZnS < 5 nm in size, the size range typical of incidental nano-ZnS that form in the environment. Previous research has shown how natural organic matter impacts the physical properties of nano-ZnS but was mostly focused on their aggregation state.

Driving Forces of Cationic Dye Adsorption, Confinement, and Long-Range Correlation in Zeolitic Materials.

Zeolitic materials are commonly used to capture emergent contaminants in water or complex aqueous effluents. The efficiency of this adsorption depends strongly on the guest-host interactions and on the surrounding environment with possible coadsorption of the solvent. Only a few experimental techniques are available to probe in situ the sequestration processes at the solid/liquid interface.

MUSIC Speciation of γ-AlO at the Solid Liquid Interface: How DFT Calculations Can Help with Amorphous and Poorly Crystalline Materials.

Transition aluminum oxides, such as γ-AlO or alumina, are widely used in many different technical applications that rely on the surface reactivity of this material at the solid liquid interface. The speciation of surface sites of this material confronts several obstacles. On the one hand, alumina is a poorly crystalline oxide, thus allowing for a limited amount of empirical structural information for an important number of surface sites with different trends in reactivity and, on the other hand, it is a metastable material.

Microwave-assisted hydrothermal synthesis of manganate nanoflowers for selective retention of strontium.

An alternative microwave-assisted hydrothermal route for the preparation of manganate nanoflowers under basic conditions has been proposed in view of potential uses in selective retention of strontium from multicomponent aqueous streams. Based on the combination of such characterization techniques as Scanning and Transmission Electronic Microscopy, X-ray photoelectron spectroscopy, and X-ray Diffraction, as well as taking advantage of the computer-aided structure simulation, homogeneous nanoflower morphology possessing a layered structure and K compensating cations was evidenced as corresponding to the KMnO chemical formula. The nanoflower sample was subsequently tested for the selective adsorption of strontium and cesium by measuring the individual adsorption isotherms from single-solute and multicomponent aqueous solutions.

The effect of chelating anions on the retention of Co(II) by γ-alumina from aqueous solutions under the unadjusted pH condition of supported catalyst preparation.

This study analyzes the effect of the addition of acetate, citrate, and nitrilotriacetate anions on the retention of Co(II) cations by the γ-alumina surface in view of the preparation of alumina supported cobalt catalysts. The emphasis was placed on the way the Co(II) species attach to the solid surface when adsorbed from aqueous solutions under the unadjusted pH condition. The individual adsorption isotherms onto γ-AlO support for cobalt and a given ligand were determined by following the solution depletion method in single-solute and bi-solute systems.

Second-Harmonic Scattering in Layered Double Hydroxide Colloids: A Microscopic View of Adsorption and Intercalation.

The interaction of methyl orange dye with a layered double hydroxide colloidal material is investigated using real-time polarization-resolved second-harmonic scattering (SHS). Interlayer charge compensating anion exchange is studied from initial carbonate or nitrate anions to methyl orange negatively charged dye. A theoretical model, taking into account the field retardation effect, is presented to simulate the polarization-resolved SHS experiments.

Recent developments in nanostructured inorganic materials for sorption of cesium and strontium: Synthesis and shaping, sorption capacity, mechanisms, and selectivity-A review.

Liquid wastes containing non-ferrous heavy metal ions and some radionuclides, Cs and Sr in particular, represent one of the most dangerous sources of environmental contamination. The remediation of wastewater containing such pollutants continue to be among the biggest challenges of Sustainable Development and Environmental Safety. Sorption-based technologies have proven their efficiency also in reducing the radionuclide content in aqueous streams to low-level residual activity, with the concomitant decrease in the amount of ultimate solid waste generated.

Capture of actinides (Th, [UO]) and surrogating lanthanide (Nd) in porous metal-organic framework MIL-100(Al) from water: selectivity and imaging of embedded nanoparticles.

Aluminium-based metal-organic framework MIL-100 was utilized for the capture of actinide ([UO], Th) and lanthanide (Nd) cations. The results indicate a very quick sorption process, leading to very high cation uptakes together with selectivity for Th.

Interactions between Oppositely Charged Polyelectrolytes by Isothermal Titration Calorimetry: Effect of Ionic Strength and Charge Density.

In this study, binding of linear poly(l-lysine) to a series of acrylamide and 2-acrylamido-2-methyl-1-propanesulfonate copolymers was examined by isothermal titration calorimetry (ITC). Binding constant and stoichiometry were systematically determined at different ionic strengths and for different polyanion charge densities varying between 15% and 100%. The range of investigated ionic strengths was carefully adjusted according to the polyanion charge densities to get measurable binding constants (i.

Ionosilicas as efficient sorbents for anionic contaminants: Radiolytic stability and ion capacity.

Ammonium based hybrid ionosilicas were prepared from tetrasilylated ammonium precursors. The formed material exhibited high specific surface area together with mesoporosity. Our results indicate that ionosilicas display high exchange capacity for iodide.

On the real performance of cation exchange resins in wastewater treatment under conditions of cation competition: the case of heavy metal pollution.

Sorption performance of cation-exchange resins Amberlite® IRN77 and Amberlite™ IRN9652 toward Cs(I) and Sr(II) has been tested in single-component aqueous solutions and simulated waste effluents containing other monovalent (Effluent 1) or divalent (Effluent 2) metal cations, as well as nitrate, borate, or carbonate anions. The individual sorption isotherms of each main component were measured by the solution depletion method. The differential molar enthalpy changes accompanying the ion-exchange between Cs+ or Sr2+ ions and protons at the resin surface from single-component nitrate solutions were measured by isothermal titration calorimetry and they showed a higher specificity of the two resins toward cesium.

Demonstrating the benefits and pitfalls of various acidity characterization techniques by a case study on bimodal aluminosilicates.

A new combination of a volumetric with a dynamic method to investigate the acidity properties of aluminosilicates is introduced. In the first step, the total acidity is determined volumetrically by the measurement of two-cycle adsorption (TCA) isotherms with ammonia as a probe, directly followed by a dynamic temperature-programmed desorption (TPD) experiment to define the acid strength distribution. Furthermore, the results obtained by the new direct combination of TCA and TPD are validated by comparison with an in-situ FTIR (Fourier transform infrared) study with the same probe molecule on the same materials.

What are the main contributions to the total enthalpy of displacement accompanying the adsorption of some multivalent metals at the silica-electrolyte interface?

The integral molar enthalpies of displacement, Δdplh, accompanying adsorption of Mg(II), Ca(II), Sr(II), Ba(II), Cd(II), Co(II), Zn(II), and Eu(III) cations from aqueous solutions of metal nitrate onto Spherosil XO75LS at 298K were determined based on the combination of liquid flow calorimetry and classical adsorption for two degrees of surface coverage: 0.035μmolm(-2) and 0.08μmolm(-2), in the presence of 0.

Driving force for the hydration of the swelling clays: case of montmorillonites saturated with alkaline-earth cations.

Important structural modifications occur in swelling clays upon water adsorption. The multi-scale evolution of the swelling clay structure is usually evidenced by various experimental techniques. However, the driving force behind such phenomena is still not thoroughly understood.

Bulk hydrolysis and solid-liquid sorption of heavy metals in multi-component aqueous suspensions containing porous inorganic solids: are these mechanisms competitive or cooperative?

Fundamental aspects of the removal of heavy metals from aqueous streams under conditions of competition among the various species have been studied between pH 3 and 9 on Spherosil XO75LS, ordered mesoporous MCM-41 and MCF silicas, as well as a MCF sample grafted with (3-aminopropyl)methoxydimethylsilane (AMPS-MCF). Cd(II), Co(II), Pb(II), or Sr(II) nitrate solutions were used to determine the percentage of metal uptake by each solid at 298 K as a function of the pH of the equilibrium solution, at an initial metal concentration of 0.0001 mol L(-1) and the ionic strength being fixed with 0.

Structural-chemical disorder of manganese dioxides II. Influence on textural properties.

Relationships between structural parameters of MnO2 and their surface properties at the solid-gas interface were investigated. The studied series ranged from ramsdellite to pyrolusite and encompassed disordered gamma-MnO2 samples. The structural model used takes into account structural defects: Pr (rate of pyrolusite intergrowth in the ramsdellite network) and Tw (rate of microtwinning).

Morphology and surface heterogeneities in synthetic goethites.

In the framework on a study of the acido-basic and sorption properties of iron oxides, a thorough characterization of two types of goethite powders was performed in several laboratories joined in a common project. Chemical analysis by ICPAES; high-resolution SEM, TEM, and AFM observations; XRD with line width analysis; and argon and nitrogen sorption isotherms were used for that purpose. The main crystallographic faces of goethite particles could be identified as {001}, {101}, and {121}, and their abundance correlated with the distribution of low-pressure argon adsorption local isotherms.