Preparation of Original and Calcined Layered Double Hydroxide as Low-Cost Adsorbents: The Role of the Trivalent Cation on Methylene Blue Adsorption.

Layered double hydroxides with the hydrotalcite-like structure, containing Mg2+, Al3+, and Fe3+ (with different Al/Fe ratios) in the layers, have been synthesized and fully characterized, as have the mixed oxides formed upon their calcination at 500 °C. Both series of solids (original and calcined ones) have been tested for methylene blue adsorption. In the case of the Fe-containing sample, oxidation of methylene blue takes place simultaneously with adsorption. For the calcined samples, their reconstruction to the hydrotalcite-like structure plays an important role in their adsorption ability.

Photocatalytic Degradation of Paracetamol in Aqueous Medium Using TiO2 Prepared by the Sol-Gel Method.

Two titania photocatalysts have been prepared using the sol-gel method using TiCl4 as a precursor, and two different alcohols, namely, ethanol or propanol (Et or Pr). The main aim of this work was to study the effect of the nature of the alcohol on the chemical, structural and photocatalytic properties for paracetamol photodegradation of the final solids. The TiCl4/alcohol molar ratio to obtain the corresponding alkoxides (TiEt and TiPr) was 1/10. These alkoxides were calcined at 400 °C to prepare the oxide catalysts (named as TiEt400 and TiPr400). Powder X-ray diffraction (PXRD) of the original samples showed the presence of anatase diffraction peaks in sample TiPr, while TiEt is a completely amorphous material. Contrary to commercial TiO2-P25, the PXRD diagrams of the calcined samples showed anatase as the exclusive crystalline phase in both solids. The specific surface area (SBET) of sample TiPr400 was larger than that of sample TiEt400, and both larger than that of TiO2-P25. The three solids have been tested in the photodegradation of paracetamol in aqueous solution. It has been established that the alcohol used influences the properties and catalytic activity of the final oxides. The synthesized solids exhibit a higher activity than commercial TiO2-P25, because of their structural characteristics and larger SBET.

Fast and Clean Synthesis of Nylon-6/Synthetic Saponite Nanocomposites.

Nylon/saponite nanocomposites were synthesized and characterized. The nanocomposites were prepared by means of a fast, efficient, low cost, and environmentally friendly method. All of the tested preparations resulted in the pre-designed nanocomposites. To this end, delaminated saponites were directly synthesized to be used as a filler in a polymer matrix formed by nylon-6 by the in situ intercalation polymerisation of an ε-caprolactam monomer without the use of surfactants or other organic reagents to organophilise the clay, thus avoiding the drawbacks of contamination. The efficiency of the preparation method increased, and significant savings were achieved in terms of both energy reaction time, savings of 60% and 70%, respectively, by using microwave radiation as an energy source during the synthesis of the nanocomposites. In addition, given that the method that was followed avoids the use of contaminating organophilic agents, it is important to highlight the savings in reagents and the fact that there was zero environmental contamination.

Hydrotalcite stability during long-term exposure to natural environmental conditions.

Hydrotalcite-like compounds are a group of layered double hydroxides widely studied as sorbents to remove organic and inorganic contaminants under laboratory conditions. This study is a proof-of-concept of the long-term fate of hydrotalcite compounds under natural environmental conditions, to bridge the gap between laboratory studies and their field application as sorbents. Hydrotalcite (HT) with intercalated carbonate species (HT-CO3) and dodecyl sulphate (HT-DS) were synthesised and placed in two groundwater monitoring wells in Denmark, one contaminated with chlorinated hydrocarbons and another with uncontaminated groundwater. To assess the structural and surface compositional changes of hydrotalcite compounds upon prolonged exposure to groundwater, the material was analysed with powder X-ray diffraction (PXRD), Fourier-transformed infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The results showed that the stability and dissolution behaviour of hydrotalcite compounds under groundwater conditions depended on the intercalated anion (CO32- > DS) and groundwater dynamics (static flow > dynamic flow), while the hydrotalcite aggregate size only had a minor effect. Groundwater geochemistry influenced the precipitation of insoluble species (CaCO3, and adsorbed sulphate) on the hydrotalcite surface. The instability of hydrotalcite compounds, especially in the case of HT-DS, may constitute a significant limiting factor on their future application as sorbents under dynamic flow conditions.

Bioinorganic magnetic core-shell nanocomposites carrying antiarthritic agents: intercalation of ibuprofen and glucuronic acid into Mg-Al-layered double hydroxides supported on magnesium ferrite.

This paper describes the synthesis and characterization of a composite constituted by an antiarthritic agent (AA) intercalated into a layered double hydroxide (LDH) supported on magnesium ferrite. Core-shell nanocomposites were prepared by depositing Mg-Al-NO(3)-LDH on a MgFe(2)O(4) core prepared by calcination of a nonstoichiometric Mg-Fe-CO(3)-LDH. Intercalation of ibuprofen and glucuronate anions was performed by ion-exchange with nitrate ions. The structural characteristics of the obtained products were investigated by powder X-ray diffraction, element chemical analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Morphologies of the nanocomposite particles were examined by scanning electron microscopy and transmission electron microscopy. The products were shown to intercalate substantial amounts of AA with enhanced thermal stabilities. Room-temperature magnetic measurements by vibrating sample magnetometry revealed that the products show soft ferromagnetic properties suitable for potential utilization in magnetic arthritis therapy.

Sorption of chlorinated hydrocarbons from synthetic and natural groundwater by organo-hydrotalcites: Towards their applications as remediation nanoparticles.

Chlorinated hydrocarbons (CHCs) are recalcitrant compounds frequently found as contaminants in groundwater. Hydrotalcites (HT) have emerged as promising sorbents due to their tunable properties and anion exchange capacity. Here, two types of organo-HT were synthesized, via coprecipitation, by intercalation of two different anionic surfactants, sodium dodecyl sulfate and sodium 1-dodecane sulfonate. These compounds were first characterized by a suite of techniques to quantify surfactant intercalation and to evaluate their physico-chemical properties. Next, the sorption affinity of these organo-HT towards a suite of CHCs was tested under various conditions, including interlayer surfactant type, single and multiple CHCs systems, and different water chemistry (pH, ionic composition). Sorption coefficients (Kd) and organic-matter-normalized partition coefficient (Kom) derived from linear sorption isotherms for individual CHC were inversely correlated to their hydrophobicity in the order of: tetrachloroethylene > tetrachloromethane > trichloroethylene> 1,1,2-trichloroethane > trichloromethane. Kom values were further affected by the organo-HT drying process. In contrast, varying water chemistry and pH, and the co-existence of multiple CHCs had little effect on Kom values, indicating that competition between CHCs and ionic strength have a marginal effect on the sorption affinity. The inverse linear relationship between CHC hydrophobicity and Kom is shown to be a suitable tool to predict organo-HT's sorption efficiency in complex CHCs contaminated groundwaters. Overall, organo-HT's might be used as potential sorbents for ex situ treatment of CHCs in groundwater.

White and Red Brazilian São Simão's Kaolinite-TiO2 Nanocomposites as Catalysts for Toluene Photodegradation from Aqueous Solutions.

The presence of volatile organic compounds in groundwater is a major concern when it is used as a drinking water source because many of these compounds can adversely affect human health. This work reports on the preparation and characterization of white and red Brazilian São Simão's kaolinite-TiO2 nanocomposites and their use as catalysts in the photochemical degradation of toluene, a significant volatile organic compound. The nanocomposites were prepared by a sol-gel procedure, using titanium bis(triethanolaminate)diisopropoxide as a precursor. Thermal treatments of the nanocomposites led to different polymorphic titania phases, while the clay changed from kaolinite to metakaolinite. This structural evolution strongly affected the photocatalytic degradation behavior-all the solids efficiently degraded toluene and the solid calcined at 400 °C, formed by kaolinite and anatase, showed the best behavior (90% degradation). On extending the photochemical treatment up to 48 h, high mineralization levels were reached. The advantage of photodegradation using the nanocomposites was confirmed by comparing the results from isolated components (titanium dioxide and kaolinite) to observe that the nanocomposites displayed fundamental importance to the photodegradation pathways of toluene.

Protein adsorption onto organically modified silica glass leads to a different structure than sol-gel encapsulation.

The secondary structures of two proteins were examined by circular dichroism spectroscopy after adsorption onto a series of organically modified silica glasses. The glasses were prepared by the sol-gel technique and were varied in hydrophobicity by incorporation of 5% methyl, propyl, trifluoropropyl, or n-hexyl silane. Both cytochrome c and apomyoglobin were found to lose secondary structure after adsorption onto the modified glasses. In the case of apomyoglobin, the alpha-helical content of the adsorbed protein ranged from 21% to 28%, well below the 62% helix found in solution. In contrast, these same glasses led to a striking increase in apomyoglobin structure when the protein was encapsulated within the pores during sol-gel processing: the helical content of apomyoglobin increased with increasing hydrophobicity from 18% in an unmodified glass to 67% in a 5% hexyl-modified glass. We propose that proteins preferentially adsorb onto unmodified regions of the silica surface, whereas encapsulated proteins are more susceptible to changes in surface hydration due to the proximity of the alkyl chain groups.

Favourable influence of hydrophobic surfaces on protein structure in porous organically-modified silica glasses.

Organically-modified siloxanes were used as host materials to examine the influence of surface chemistry on protein conformation in a crowded environment. The sol-gel materials were prepared from tetramethoxysilane and a series of monosubstituted alkoxysilanes, RSi(OR')(3), featuring alkyl groups of increasing chain length in the R-position. Using circular dichroism spectroscopy in the far-UV region, apomyoglobin was found to transit from an unfolded state to a native-like helical state as the content of the hydrophobic precursor increased from 0 to 15%. At a fixed molar content of 5% RSi(OR')(3), the helical structure of apomyoglobin increased with the chain length of the R-group, i.e. methyl

Hydrotalcite catalysis for the synthesis of new chiral building blocks.

The use of hydrotalcites for the synthesis of two chiral building blocks in a simple way is described as a new and green methodology. The synthesis of these compounds implies a regioselective Baeyer-Villiger reaction in a very selective way with ulterior opening and lactonisation. This methodology should be considered green for the use of hydrogen peroxide as the only oxidant and hydrotalcites as the catalyst, and because no residues are produced apart from water. The procedure is very adequate for using in gram scale, in order to increase the value of the obtained compounds. The conditions are excellent and can be applied for nonstable compounds, as they are very mild. The synthesised compounds are magnific starting materials for the synthesis of biologically active or natural compounds. The use of a cheap, commercial and chiral compound as carvone disposable in both enantiomeric forms adds an extra value to this methodology.

Organically Modified Saponites: SAXS Study of Swelling and Application in Caffeine Removal.

This study aimed to assess the capacity of saponite modified with n-hexadecyltrimethylammonium bromide (CTAB) and/or 3-aminopropyltriethoxysilane (APTS) to adsorb and remove caffeine from aqueous solutions. Powder X-ray diffraction (PXRD) revealed increased basal spacing in the modified saponites. Small-angle X-ray scattering (SAXS) confirmed the PXRD results; it also showed how the different clay layers were stacked and provided information on the swelling of natural saponite and of the saponites functionalized with CTAB and/or APTS. Thermal analyses, infrared spectroscopy, scanning electron microscopy, element chemical analysis, and textural analyses confirmed functionalization of the natural saponite. The maximum adsorption capacity at equilibrium was 80.54 mg/g, indicating that the saponite modified with 3-aminopropyltriethoxysilane constitutes an efficient and suitable caffeine adsorbent.

Layered double hydroxides as drug carriers and for controlled release of non-steroidal antiinflammatory drugs (NSAIDs): a review.

Non-steroidal anti-inflammatory drugs constitute one of the groups most widely currently used, but show several problems for administration due to low solubility and delivery control. For this reason, several matrices have been tested to support them in order to overcome these drawbacks. Among them, layered double hydroxides have been used in recent years. The aim of this review is to update the current knowledge and findings on this hybrid system, namely, layered double hydroxides intercalated with different NSAIDs. The basic nature of the matrix introduces an additional advantage, i.e., to decrease ulceration damages. We have focused our review mostly on the preparation procedures, as these control, define and determine the performance of the systems in vitro and also in living organisms.

New highly luminescent hybrid materials: terbium pyridine-picolinate covalently grafted on kaolinite.

Luminescent hybrid materials derived from kaolinite appear as promising materials for optical applications due to their specific properties. The spectroscopic behavior of terbium picolinate complexes covalently grafted on kaolinite and the influence of the secondary ligand and thermal treatment on luminescence are reported. The resulting materials were characterized by thermal analysis, element analysis, X-ray diffraction, infrared absorption spectroscopy, and photoluminescence. The thermogravimetric curves indicated an enhancement in the thermal stability up to 300 °C for the lanthanide complexes covalently grafted on kaolinite, with respect to the isolated complexes. The increase in the basal spacing observed by X-ray diffraction confirmed the insertion of the organic ligands into the basal space of kaolinite, involving the formation of a bond between Al-OH and the carboxylate groups, as evidenced by infrared spectroscopy. The luminescent hybrid material exhibited a stronger characteristic emission of Tb(3+) compared to the isolated complex. The excitation spectra displayed a broad band at 277 nm, assigned to a ligand-to-metal charge transfer, while the emission spectra presented bands related to the electronic transitions characteristic of the Tb(3+) ion from the excited state (5)D(4) to the states (7)F(J) (J=5, 4, and 3), with the 4→5 transition having high intensity with green emission.

Inclusion and release of fenbufen in mesoporous silica.

This work reports the immobilization of Fenbufen, a nonsteroidal anti-inflammatory drug, into two different hexagonal mesoporous silicas (MCM-41) which exhibit some differences in terms of morphology and pore size, and their behavior as systems for sustained release at pH 7.5. The drug/mesoporous silica systems have been characterized by powder X-ray diffractometry (PXRD), Fourier transform infrared spectroscopy (FT-IR), N(2) adsorption-desorption, and transmission electron microscopy (TEM). The results show that the drug is mainly incorporated inside the pores, and its loading is dependent on both the pore size and the impregnation temperature. The Fenbufen/mesoporous-silica systems give a well-sustained release profile, releasing 100% of the initially loaded drug at the end of the in vitro assays.

Bioencapsulation of apomyoglobin in nanoporous organosilica sol-gel glasses: influence of the siloxane network on the conformation and stability of a model protein.

Nanoporous sol-gel glasses were used as host materials for the encapsulation of apomyoglobin, a model protein employed to probe in a rational manner the important factors that influence the protein conformation and stability in silica-based materials. The transparent glasses were prepared from tetramethoxysilane (TMOS) and modified with a series of mono-, di- and tri-substituted alkoxysilanes, R(n)Si(OCH(3))(4-n) (R = methyl-, n = 1; 2; 3) of different molar content (5, 10, 15%) to obtain the decrease of the siloxane linkage (-Si-O-Si-). The conformation and thermal stability of apomyoglobin characterized by circular dichroism spectroscopy (CD) was related to the structure of the silica host matrix characterized by (29)Si MAS NMR and N(2) adsorption. We observed that the protein transits from an unfolded state in unmodified glass (TMOS) to a native-like helical state in the organically modified glasses, but also that the secondary structure of the protein was enhanced by the decrease of the siloxane network with the methyl modification (n = 0 < n = 1 < n = 2 < n = 3; 0 < 5 < 10 < 15 mol %). In 15% trimethyl-modified glass, the protein even reached a maximum molar helicity (-24,000 deg. cm(2) mol(-1)) comparable to the stable folded heme-bound holoprotein in solution. The protein conformation and stability induced by the change of its microlocal environment (surface hydration, crowding effects, microstructure of the host matrix) were discussed owing to this trend dependency. These results can have an important impact for the design of new efficient biomaterials (sensors or implanted devices) in which properly folded protein is necessary.

Rotational fluctuations of water confined to layered oxide materials: nonmonotonous temperature dependence of relaxation times.

The rotational molecular dynamics of water confined to layered oxide materials with brucite structure was studied by dielectric spectroscopy in the frequency range from 10(-2) to 10(7) Hz and in a broad temperature interval. The layered double hydroxide samples show one relaxation process, which was assigned to fluctuations of water molecules forming a layer, strongly adsorbed to the oxide surface. The temperature dependence of the relaxation rates has an unusual saddlelike shape characterized by a maximum. The model of Ryabov et al. (J. Phys. Chem. B 2001, 105, 1845) recently applied to describe the dynamics of water molecules in porous glasses is employed also for the layered materials. This model assumes two competing effects: rotational fluctuations of water molecules that take place simultaneously with defect formation, allowing the creation of free volume necessary for reorientation. The activation energy of rotational fluctuations, the energy of defect formation, a pre-exponential factor, and the defect concentration are obtained as main parameters from a fit of this model to the data. The values of these parameters were compared with those found for water confined to nanoporous molecular sieves, porous glasses, or bulk ice. Several correlations were discussed in detail, such as the lower the value of the energy of defect formation, the higher the number of defects. The pre-exponential factor increases with increasing activation energy, as an expression of the compensation law, and indicates the cooperative nature of the motional process. The involvement of the surface OH groups and of the oxygen atoms of the interlayer anions in the formation of hydrogen bonds was further discussed. For the birnessite sample, the relaxation processes are probably overlaid by a dominating conductivity contribution, which is analyzed in its frequency and temperature dependence. It is found that the conductivity of birnessite obeys the characteristics of semiconducting disordered materials. Especially the Barton/Nakajima/Namikawa relationship is fulfilled. Analyzing the temperature dependence of the direct current (dc) conductivity sigma0 in detail gives some hint that sigma0(T) has also an unusual saddlelike form.

Flash vacuum pyrolysis over solid catalysts. 2. pyrazoles over hydrotalcites.

Flash vacuum pyrolysis (fvp) reactions of NH-pyrazole (1) and 3,5-diphenylpyrazole (2) were investigated in the presence of anionic clays having hydrotalcite structure (HT). Solid catalysts with Mg:Al ratio equal to 2:1 containing carbonate (HT-1), nitrate (HT-2), and silicate (HT-3) as interlayer anions were employed. Between 400 and 600 degrees C, compound 1 remained almost unchanged and only unidentified volatile products were detected in small amounts. In contrast, 2 afforded benzonitrile (3) and phenylacetonitrile (4) by a ring fragmentation reaction at 450 degrees C. At a higher temperature (660 degrees C), the same products obtained in homogeneous fvp reactions, i.e., 2-phenylindene (5) and 3-phenylindene (6), were obtained showing no catalysis by HT under these conditions. Results showed that the yield is strongly dependent on the nature of the interlayer anion in the hydrotalcite structure. In comparison with reactions of 2 over zeolites, HTs exhibit selectivity for ring fragmentation reaction.