Adsorption of nickel ions by oleate-modified magnetic iron oxide nanoparticles.

In this work, magnetic nanoparticles of iron oxide (MNPs) were synthesized, and then the surface was recovered with an oleate double layer in order to investigate the ability of this material to adsorb nickel ions. First, the solution chemistry of oleate ions was investigated in order to determine the critical micellar concentration (CMC) value and the arrangements of ions above the CMC. Then, the synthesized oleate-modified MNP was characterized (TEM, DLS, XRD, FTIR, zeta potential, magnetometry). Finally, adsorption experiments were carried out as a function of pH and as a function of nickel concentration in 0.1 g L-1 suspensions of oleate-modified MNP. The results show that CMC of oleate ranges from 1 to 2.5∙10-3 mol L-1. Above CMC, arrangement of oleate ions as droplets, vesicles, or micelles depends on pH and influences the average size and solution absorbance. Potentiometric titrations allowed determining a pKa value of 7.8 for sodium oleate. The high stability in aqueous suspensions and characterization of oleate-modified MNP confirm that oleate ions are arranged as a bilayer coating at the surface of MNP. Retention of nickel was found to be highly dependent on pH, with a maximum adsorption (90%) beginning from pH = 7.5. The sorption isotherms were well fitted with the Langmuir model and the maximum nickel adsorption capacities were found to be 44 and 80 mg g-1 for pH = 6.8 and 7.2, respectively. The efficient removal of nickel combined with the magnetic properties of the NMP make the oleate-modified MNP an interesting water purification tool.

Insertion of indigo molecules in the sepiolite structure as evidenced by 1H-29Si heteronuclear correlation spectroscopy.

Despite the numerous studies of the famous indigo-based pigment Maya Blue, there are still many questions regarding the elucidation of its structure. Here, two-dimensional (2D) (1)H-(29)Si heteronuclear correlation (HETCOR) spectroscopy with frequency-switched Lee-Goldburg (FSLG) homonuclear decoupling is applied to sepiolite and sepiolite-indigo complexes. Owing to the high resolution in the (1)H dimension of the 2D (1)H-(29)Si HETCOR spectrum obtained by FSLG homonuclear decoupling, the assignment of the (29)Si cross-polarization magic-angle spinning (CPMAS) spectrum of sepiolite is clearly confirmed. Moreover, 2D (1)H-(29)Si FSLG-HETCOR spectroscopy gives the first direct evidence that some indigo molecules are inserted in the sepiolite structure whereas no interaction between indigo and the external side surface (silanol groups) is observed in the (29)Si CPMAS spectra. These results are consistent with the fact that indigo molecules interact with water coordinated to magnesium and suggest that Maya Blue made from sepiolite is not a surface complex.

The incorporation of indigo molecules in sepiolite tunnels.

Evidence for access of molecules the size of acetone or pyridine to the intracrystalline tunnels of nanofibre clay (sepiolite) has indicated formation of a new type of organic-inorganic nanocomposites. However, the introduction of larger molecules has been a recurring problem. It is now agreed that for indigo, the molecules are located on the external surface and at the ends of the fibres, thus blocking access to internal tunnels. We claim, however, that it is possible for indigo molecules to access the internal channels of sepiolite. FTIR and XRD analyses have provided evidence for folding of the sepiolite structure preheated at high temperature (above 350 degrees C). By comparison, we have shown that for indigo/sepiolite mixtures treated in the same conditions, no change in the crystalline structure of the sepiolite is observed, and that blue samples, related to Maya blue, with indigo molecules incorporated deeply enough into sepiolite to prevent folding of the tunnels, can be obtained. NMR, FTIR and thermal analysis confirm the interaction of indigo with the water coordinated to magnesium(II) and located inside the internal and external channels of sepiolite. Two other hypotheses are excluded; we show both that zeolitic water is not blocked in the tunnels by indigo, and that if thermal decomposition products of indigo can be formed, they are in a minority.

Tubular microstructures made from nonchiral single-chain fluorinated amphiphiles: impact of the structure of the hydrophobic chain on the rolling-up of bilayer membrane.

The nonchiral, single-chain fluorinated amphiphiles derived from dimorpholinophosphate, C(n)F(2n+1)(CH(2))(m)OP(O)[N(CH(2)CH(2))(2)O](2) (FnCmDMPs), form hollow tubular bilayer-based self-assemblies when dispersed in water, ethanol/water mixtures, and dimethylformamide. The fluorinated tubules are highly stable and sturdy. Upon heating, they transform reversibly into giant multilamellar vesicles. Uncommon U-shaped and V-shaped coiled membranes were obtained from mixtures of FnCmDMPs. Depending on conditions, fluorinated tubules can evolve with time into collapsed flattened crystallized needles. The successive steps involved in the formation and evolution of these tubules were identified, and the specific features of fluorinated chains that are relevant to membrane coiling and tubule formation are discussed.