Synergistic Sustained Drug-Release System Based on Immobilized Rhamnus frangula L. Phytoextract into Layered Double Hydroxide Covered by Biocompatible Hydrogel.

This work focuses on the synergetic effect obtained by immobilization of Rhamnus frangula L. (RfL) phytoextract in layered double hydroxides (LDHs) matrixes and their subsequent encapsulation into biocompatible hydrogels (HG). In this respect, the LDHs were used as hosts for the immobilization of the phytoextract by a reconstruction method, after which the LDHsRfL were embedded into biocompatible hydrogel (HG) matrixes, based on polyethylene glycol diacrylate (PEGDA), by a radical polymerization reaction. The resulted biocompatible hydrogel composites were characterized by modern methods, while the swelling and rheology measurements revealed that the HG composites steadily improved as the content of RfL phytoextract immobilized on LDHs (LDHsRfL) increased. The following in vitro sustained release of the RfL phytoextract was highlighted by measurements at pH 6.8, in which case the composite HGs with LDHsRfL presented an improved release behavior over the LDHsRfL, thus, underlining the synergistic effect of PEGDA network and LDH particles on the slow-release behavior. The kinetic models used in the RfL release from composite HGs clearly indicate that the release is diffusion controlled in all the cases. The final composite HGs described here may find applications in the pharmaceutical field as devices for the controlled release of drugs.

Mo-LDH-GO Hybrid Catalysts for Indigo Carmine Advanced Oxidation.

This paper is focused on the utilization of hybrid catalysts obtained from layered double hydroxides containing molybdate as the compensation anion (Mo-LDH) and graphene oxide (GO) in advanced oxidation using environmentally friendly H2O2 as the oxidation agent for the removal of indigo carmine dye (IC) from wastewaters at 25 °C using 1 wt.% catalyst in the reaction mixture. Five samples of Mo-LDH-GO composites containing 5, 10, 15, 20, and 25 wt% GO labeled as HTMo-xGO (where HT is the abbreviation used for Mg/Al in the brucite type layer of the LDH and x stands for the concentration of GO) have been synthesized by coprecipitation at pH 10 and characterized by XRD, SEM, Raman, and ATR-FTIR spectroscopy, determination of the acid and base sites, and textural analysis by nitrogen adsorption/desorption. The XRD analysis confirmed the layered structure of the HTMo-xGO composites and GO incorporation in all samples has been proved by Raman spectroscopy. The most efficient catalyst was found to be the catalyst that contained 20%wt. GO, which allowed the removal of IC to reach 96.6%. The results of the catalytic tests indicated a strong correlation between catalytic activity and textural properties as well as the basicity of the catalysts.

Synthesis and Characterization of Hematite-Based Nanocomposites as Promising Catalysts for Indigo Carmine Oxidation.

The hematite-based nanomaterials are involved in several catalytic organic and inorganic processes, including water decontamination from organic pollutants. In order to develop such species, a series of bimetallic hematite-based nanocomposites were obtained by some goethite composites-controlled calcination. Their composition consists of various phases such as α-FeOOH, α-Fe2O3 or γ-Fe2O3 combined with amorphous (Mn2O3, Co3O4, NiO, ZnO) or crystalline (CuO) oxides of the second transition ion from the structure. The component dimensions, either in the 10-30 or in the 100-200 nm range, together with the quasi-spherical or nanorod-like shapes, were provided by Mössbauer spectroscopy and powder X-ray diffraction as well as transmission electron microscopy data. The textural characterization showed a decrease in the specific area of the hematite-based nanocomposites compared with corresponding goethites, with the pore volume ranging between 0.219 and 0.278 cm3g-1. The best catalytic activity concerning indigo carmine removal from water in hydrogen peroxide presence was exhibited by a copper-containing hematite-based nanocomposite sample that reached a dye removal extent of over 99%, which correlates with both the base/acid site ratio and pore size. Moreover, Cu-hbnc preserves its catalytic activity even after four recyclings, when it still reached a dye removal extent higher than 90%.

Ce-Containing MgAl-Layered Double Hydroxide-Graphene Oxide Hybrid Materials as Multifunctional Catalysts for Organic Transformations.

The combination of layered double hydroxides (LDH) with graphene oxide (GO) enables the formation of nanohybrids with improved properties. This work focuses on the structural and catalytic properties of Ce-containing MgAl LDH-GO composites bearing different concentrations of GO in the range of 5-25 wt.%. The synthesis of the composites was performed by co-precipitating the LDH phase in the presence of GO, while their characterization was performed using XRF, XRD, DRIFT, Raman, SEM, nitrogen adsorption-desorption, and acidity-basicity measurements. The LDH-GO composites, showing redox, basic, and acid catalytic functions, were tested in two different types of organic transformations: (i) Knoevenagel condensation and (ii) one-pot cascade oxidation-Knoevenagel condensation. (i) The cinnamic acid was synthesized by the Knoevenagel condensation of benzaldehyde with diethylmalonate. The composites showed catalytic performances in strong contrast to neat LDH or GO, suggesting a synergistic interaction between the two components. During Knoevenagel condensation, the catalytic activity increased with the GO content in the hybrids up to 15 wt.% and decreased afterwards. (ii) 2-Benzoyl-3-phenylacrylonitrile was synthesized by the aerobic oxidation of benzyl alcohol followed by the Knoevenagel condensation with benzoyl acetonitrile using three different non-polar solvents, i.e., toluene, benzene, and mesitylene. The conversion of benzyl alcohol was higher for the hybrid materials compared to the individual components but decreased with the increase of the graphene oxide concentration.

The Influence of the Preparation Method on the Physico-Chemical Properties and Catalytic Activities of Ce-Modified LDH Structures Used as Catalysts in Condensation Reactions.

Mechanical activation and mechanochemical reactions are the subjects of mechanochemistry, a special branch of chemistry studied intensively since the 19th century. Herein, we comparably describe two synthesis methods used to obtain the following layered double hydroxide doped with cerium, Mg3Al0.75Ce0.25(OH)8(CO3)0.5·2H2O: the mechanochemical route and the co-precipitation method, respectively. The influence of the preparation method on the physico-chemical properties as determined by multiple techniques such as XRD, SEM, EDS, XPS, DRIFT, RAMAN, DR-UV-VIS, basicity, acidity, real/bulk densities, and BET measurements was also analyzed. The obtained samples, abbreviated HTCe-PP (prepared by co-precipitation) and HTCe-MC (prepared by mechanochemical method), and their corresponding mixed oxides, Ce-PP (resulting from HTCe-PP) and Ce-MC (resulting from HTCe-MC), were used as base catalysts in the self-condensation reaction of cyclohexanone and two Claisen-Schmidt condensations, which involve the reaction between an aromatic aldehyde and a ketone, at different molar ratios to synthesize compounds with significant biologic activity from the flavonoid family, namely chalcone (1,3-diphenyl-2-propen-1-one) and flavone (2-phenyl-4H-1benzoxiran-4-one). The mechanochemical route was shown to have indisputable advantages over the co-precipitation method for both the catalytic activity of the solids and the costs.

Soft synthesis and characterization of goethite-based nanocomposites as promising cyclooctene oxidation catalysts.

Goethite based nanocomposites with a different composition such as 6FeO(OH)·MnO(OH)·0.5H2O (Mn-composite), xFeO(OH)·M(OH)2·yH2O (Co-composite (M: Co, x = 12, y = 3), Ni-composite (M: Ni, x = 7, y = 2)) and xFeO(OH)·MO·yH2O (Cu-composite (M: Cu, x = 5.5, y = 3), Zn-composite (M: Zn, x = 6, y = 1.5)) have been prepared by a soft chemical synthesis consisting in acetate hydrolysis. The data provided by Fourier transform infrared (FTIR), ultraviolet-visible-near infrared (UV-Vis-NIR), electron paramagnetic resonance (EPR) and Mössbauer spectra account for a slight modification of all composites' physicochemical properties compared to the starting material. Powder X-ray diffraction and transmission electron microscopy (TEM) investigations revealed the secondary phase nature and presence along with that of goethite. The TEM data are also consistent with a nano rod-like morphology with a 5-10 nm width and an average length of 40 nm. The catalytic oxidation of cyclooctene with O2 using isobutyraldehyde as reductant and acetonitrile as a solvent was performed in batch conditions for 5 h at room temperature. The selectivity for the epoxide was higher than 99% for all tested solids. The conversion of cyclooctene decreased from 55% to 4% following the same order of variance as the base/acid sites ratio: Mn-composite > Fe-composite > Co-composite > Ni-composite > Zn-composite > Cu-composite. The 6FeO(OH)·MnO(OH)·0.5H2O (Mn-composite) exhibited the most promising catalytic activity in cyclooctene oxidation, which can be correlated with the redox ability of Mn(iii) combined with the increased base character of this solid. The catalytic activity of this sample decreases by 10% after several successive reaction cycles.