Sustainable Route for Synthesizing Aluminosilicate EU-1 Zeolite.

Developing sustainable routes for the synthesis of zeolites is still a vital and challenging task in zeolite scientific community. One of the typical examples is sustainable synthesis of aluminosilicate EU-1 zeolite, which is not very efficient and environmental-unfriendly under hydrothermal condition due to the use of a large amount of water as solvent. Herein, we report a sustainable synthesis route for aluminosilicate EU-1 zeolite without the use of solvent for the first time. The physicochemical properties of the obtained EU-1 zeolite are characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry-differential thermal analysis (TG-DTA), N2 sorption, inductively coupled plasma (ICP) analysis, and solid nuclear magnetic resonance (NMR), which show the product has high crystallinity, uniform morphology, large BET surface area, and four-coordinated aluminum species. Moreover, the impact of synthesis conditions is investigated in detail. The sustainable synthesis of aluminosilicate EU-1 zeolite under solvent-free.

Design and synthesis of organic rectorite-based composite nanofiber membrane with enhanced adsorption performance for bisphenol A.

Nowadays, most of mineral-based adsorbents are powder form, which makes them inconvenient to collect and always easy to cause secondary pollution. In this work, an organic rectorite composite nanofiber membrane (SRt-PAN) was designed and prepared by electrospinning technique. The as-received composite nanofiber membranes were characterized by XRD and SEM analysis, proving the homodisperse and existence of SRt in PAN nanofiber membrane. A series of batch experiments for BPA adsorption were carried out to investigate the effect of different adsorption parameters, including initial concentration, pH, and temperature of pollutant solution. The influences of modifier dosage and adsorbent dosage on the adsorption performance were investigated as well. On the basis of the experiment results, the adsorption process could be well described by the pseudo-second-order model and the Langmuir isotherm. In addition, the thermodynamic parameters indicate that this adsorption process is exothermic and spontaneous. Moreover, compared with pure nanofiber membranes and organic rectorite powders, the resultant SRt-PAN adsorbents exhibited higher adsorption capacity, superior reusability, and adsorption stability. It is indicated that the hydrophobicity surface of organic rectorite should be the key factor to not only the intimate interfacial combination between the mineral and PAN, but also the enhancement of BPA adsorption capacity.

Facile synthesis and rheological characterization of nanocomposite hyaluronan-organoclay hydrogels.

We report a facile methodology for the synthesis of inorganic-organic hydrogels based on integrative assembly of aminopropyl magnesium phyllosilicate (aminoclay) and sodium salt of hyaluronic acid. The viscoelastic materials produced by electrostatic interactions and crosslinking of hyaluronan in the presence of exfoliated synthetic organoclay results in the formation of gel-like behavior retaining a high amount of water. This was confirmed by a rheological study revealing significant dominance of the elastic response over the entire deformation frequency range used. The mechanical strength of the aminoclay-hyaluronan hydrogels was found to be higher than that for related materials based on poly(vinylpyrrolidone)-aminoclay hydrogels.

Grafting of poly[(methyl methacrylate)-block-styrene] onto cellulose via nitroxide-mediated polymerization, and its polymer/clay nanocomposite.

For the first time, nitroxide-mediated polymerization (NMP) was used for synthesis of graft and block copolymers using cellulose (Cell) as a backbone, and polystyrene (PSt) and poly(methyl metacrylate) (PMMA) as the branches. For this purpose, Cell was acetylated by 2-bromoisobutyryl bromide (BrBiB), and then the bromine group was converted to 4-oxy-2,2,6,6-tetramethylpiperidin-1-oxyl group by a substitution nucleophilic reaction to afford a macroinitiator (Cell-TEMPOL). The macroinitiator obtained was subsequently used in controlled graft and block copolymerizations of St and MMA monomers to yield Cell-g-PSt and Cell-g-(PMMA-b-PSt). The chemical structures of all samples as representatives were characterized by FTIR and (1)H NMR spectroscopies. In addition, Cell-g-(PMMA-b-PSt)/organophilic montmorillonite nanocomposite was prepared through a solution intercalation method. TEM was used to evaluate the morphological behavior of the polymer-clay system. It was demonstrated that the addition of small percent of organophilic montmorillonite (O-MMT; 3wt.%) was enough to improve the thermal stability of the nanocomposite.

Doxycycline-encapsulated nanotube-modified dentin adhesives.

This article presents details of fabrication, biological activity (i.e., anti-matrix metalloproteinase [anti-MMP] inhibition), cytocompatibility, and bonding characteristics to dentin of a unique doxycycline (DOX)-encapsulated halloysite nanotube (HNT)-modified adhesive. We tested the hypothesis that the release of DOX from the DOX-encapsulated nanotube-modified adhesive can effectively inhibit MMP activity. We incorporated nanotubes, encapsulated or not with DOX, into the adhesive resin of a commercially available bonding system (Scotchbond Multi-Purpose [SBMP]). The following groups were tested: unmodified SBMP (control), SBMP with nanotubes (HNT), and DOX-encapsulated nanotube-modified adhesive (HNT+DOX). Changes in degree of conversion (DC) and microtensile bond strength were evaluated. Cytotoxicity was examined on human dental pulp stem cells (hDPSCs). To prove the successful encapsulation of DOX within the adhesives-but, more important, to support the hypothesis that the HNT+DOX adhesive would release DOX at subantimicrobial levels-we tested the antimicrobial activity of synthesized adhesives and the DOX-containing eluates against Streptococcus mutans through agar diffusion assays. Anti-MMP properties were assessed via ß-casein cleavage assays. Increasing curing times (10, 20, 40 sec) led to increased DC values. There were no statistically significant differences (p > .05) in DC within each increasing curing time between the modified adhesives compared to SBMP. No statistically significant differences in microtensile bond strength were noted. None of the adhesives eluates were cytotoxic to the human dental pulp stem cells. A significant growth inhibition of S. mutans by direct contact illustrates successful encapsulation of DOX into the experimental adhesive. More important, DOX-containing eluates promoted inhibition of MMP-1 activity when compared to the control. Collectively, our findings provide a solid background for further testing of encapsulated MMP inhibitors into the synthesis of therapeutic adhesives that may enhance the longevity of hybrid layers and the overall clinical performance of adhesively bonded resin composite restorations.

Preparation and characteristics of sodium alginate/Na(+)rectorite-g-itaconic acid/acrylamide hydrogel films.

Sodium alginate/Na(+)rectorite-graft-itaconic acid/acrylamide (SA/Na(+)REC-g-IA/AM) hydrogel film was prepared via solution polymerization. The effect of Na(+)REC, KPS, and NMBA content and the ratio of IA to AM on graft ratio, graft efficiency and absorption of liquids were investigated. The structure and morphology were analyzed by FTIR, XRD, TEM and SEM. Results revealed that the optimal Na(+)REC, KPS, and NMBA content and the ratio of IA to AM were 2wt%, 0.8wt%, 0.38wt% and 4, respectively. The hydrogel film was found to exhibit an intercalative structure and coarse surface. The mechanism of graft copolymerization was discussed. A slower and more continuous release of salicylic acid for SA/Na(+)REC-g-IA/AM composite hydrogel film was shown in vitro drug-controlled release studies, in comparison with SA film. The salicylic acid release mechanism of SA/Na(+)REC-g-IA/AM hydrogel film followed Fickian diffusion.

Preparation and characterization of bionanocomposite films based on potato starch/halloysite nanoclay.

In this research casting method was used to prepare potato starch based bio-nanocomposite films with halloysite nanoclay as the reinforcing materials. The composition included potato starch with 40% (w/w) of a mixture of sorbitol/glycerol (weight ratio of 3 to 1as plasticizer) with nanoclay (0-5% w/w). The films were dried under controlled conditions. Physicochemical properties such as solubility in water, water absorption capacity (WAC), water vapour permeability (WVP), oxygen permeability, and mechanical properties of the films were measured. Results showed that by increasing the concentration of nanoclay, mechanical properties of films were improved. Tensile strength was increased from 7.33 to 9.82MPa, and elongation at break decreased from 68.0 to 44.0%. Solubility in water decreased from 35 to 23%, and heat seal strength increased from 375 to 580N/m. Also incorporation of clay nanoparticles in the structure of biopolymer decreased permeability of the gaseous molecules. In summary, addition of halloysite nanoclay, improve the barrier and mechanical properties of potato starch films and this bionanocomposites have high potential to be used for food packaging purposes.

Effect of surfactant types and their concentration on the structural characteristics of nanoclay.

A series of organo-modified nanoclays was synthesized using three different surfactants having different alkyl chain lengths and concentrations [0.5-5.0 cation exchange capacity (CEC)]. These surfactants were Ethanolamine (EA), Cetyltrimethylammoniumbromide (CTAB) and Tetraoctadecylammoniumbromide (TO). The obtained modified nanoclays were characterized by X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM) and compared with unmodified nanoclay. The results of XRD analysis indicated that the basal d-spacing has increased with increasing alkyl chain length and surfactant concentration. From the obtained microstructures of these organo-modified nanoclays, the mechanism of surfactant adsorption was proposed. At relatively low loading of surfactant, most of surfactant entered the spacing by an ion-exchange mechanism and is adsorbed onto the interlayer cation sites. When the concentration of the surfactant exceeds the CEC of clay, the surfactant molecules then adhere to the surface adsorbed surfactant. Some surfactants entered the interlayers, whereas the others were attached to the clay surface. When the concentration of surfactant increased further beyond 2.0 CEC, the surfactants might occupy the inter-particle space within the house-of-cards aggregate structure.

HTCC-modified nanoclay for tissue engineering applications: a synergistic cell growth and antibacterial efficiency.

This paper deals with the synthesis of a biocompatible chitosan ammonium salt N-(2-hydroxy) propyl-3-trimethylammonium chitosan chloride (HTCC) and using it in montmorillonite ion-exchange process. HTCC-modified montmorillonite (Mt) with different chemical ratios was successfully synthesized, and their characteristics have been verified by XRD and FTIR analyses. Produced samples have been evaluated in terms of antibacterial efficiency and biocompatibility (cell culture test). Antibacterial efficiency of synthesized HTCC/Mt samples has been confirmed against both gram negative bacteria (Escherichia coli) and gram positive bacteria (Staphylococcus aureus). The results disclosed that the antibacterial efficiency of HTCC-modified montmorillonite was unexpectedly even more than HTCC. This excellent synergistic effect has been referred to entrapping bacteria between the intercalated structures of HTCC-modified montmorillonite. Then HTCC on clay layers can seriously attack and damage the entrapped bacteria. An extraordinary biocompatibility, cell attachment, and cell growth even more than tissue culture polystyrene (TCPS) have been recorded in the case of this novel kind of modified clay. Due to existing concerns about serious and chronic infections after implant placement, this natural-based bioactive and antibacterial modified clay can be used in electrospun nanofibers and other polymeric implants with promising mechanical properties for tissue engineering applications.

Clay: new opportunities for tissue regeneration and biomaterial design.

Seminal recent studies that have shed new light on the remarkable properties of clay interactions suggest unexplored opportunities for biomaterial design and regenerative medicine. Here, recent conceptual and technological developments in the science of clay interactions with biomolecules, polymers, and cells are examined, focusing on the implications for tissue engineering and regenerative strategies. Pioneering studies demonstrating the utility of clay for drug-delivery and scaffold design are reviewed and areas for future research and development highlighted.

Nano-composite of poly(L-lactide) and halloysite nanotubes surface-grafted with L-lactide oligomer under microwave irradiation.

In order to improve the bonding between halloysite nanotubes (HNTs) and poly(L-lactide) (PLLA), and hence to increase the mechanical properties of HNTs/PLLA nano-composite, HNTs were surface-grafted with PLLA under microwave irradiation and then blended with PLLA matrix. The optimal conditions for grafting polymerization are: irradiation time of 30 min, microwave power of 30 W and reaction temperature of 130 degrees C. The structure and properties of the surface-grafted HNTs (g-HNTs) were characterized by Fourier transformation infrared (FTIR), thermal gravimetric analysis (TGA), X-ray diffraction (XRD) and dynamic light scattering (DLS). Nano-composites of g-HNTs/PLLA and non-grafted HNTs/PLLA were subsequently evaluated in terms of crystallinity, dispersion, interfacial interaction, mechanical performance and cytocompatibility by polarized optical microscopy (POM), field scanning electron microscope (FESM), tensile testing and cell culture experiment. Results show that the grafted PLLA chains on the surfaces of HNTs, as inter-tying molecules, played an important role in improving the adhesive strength between the nanotubes and the polymer matrix. The enhanced interaction among g-HNTs and PLLA matrix resulted in a better tensile strength and modulus compared to the pristine PLLA and HNTs/PLLA. Cell culture results indicated that g-HNTs promoted both adhesion and proliferation of M3T3 fibroblasts on the g-HNTs/PLLA composite film.

Preparation, characterization and application of N-2-Pyridylsuccinamic acid-functionalized halloysite nanotubes for solid-phase extraction of Pb(II).

Halloysite nanotubes (HNTs) were chemically modified with N-2-Pyridylsuccinamic acid (PSA) to produce a new nano-adsorbent (HNTs-PSA) for selective solid-phase extraction of Pb(II). The new adsorbent was characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscope (TEM), thermogravimetric analysis (TGA), and elemental analysis to evaluate the surface modification. Under the optimized conditions (pH 5, flow rate 1.5 mL min(-1)), Pb(II) was retained on the column packed with HNTs-PSA, and then was quantitatively eluted by 1.5 mL 0.5 mol L(-1) HCl and determined by inductively coupled plasma-optical emission spectrometry. An enrichment factor of 67 was obtained using 30 mg of HNTs-PSA. The maximum adsorption capacity for Pb(II) was found to be 23.58 mg g(-1). The detection limits of this method for Pb(II) was 0.32 µg L(-1). The relative standard deviation under optimum conditions was 3.4% (n = 11). The developed method was validated by analyzing a certified reference material, and then successfully applied to the determination of Pb(II) in actual samples.

Ultralow thermal conductivity in organoclay nanolaminates synthesized via simple self-assembly.

Because interfaces impede phonon transport of thermal energy, nanostructuring can transform fully dense solids into ultralow thermal conductivity materials. Here we report a simple self-assembly approach to synthesizing organoclay nanolaminates with cross-planar thermal conductivities below 0.10 W m(-1) K(-1)-a 5-fold decrease compared to unmodified clay. These organoclays are produced via alkylammonium cation exchange with colloidally dispersed montmorillonite clay sheets followed by solvent casting. Time-domain thermoreflectance (TDTR) is used to evaluate the thermal conductivity of the organoclay nanolaminates. Variations in both organic layer thickness and cation chemistry are investigated. At these interface densities (1.0-1.5 interfaces/nm), we demonstrate that thermal conductivity is relatively independent of nanolaminate spacing. A simple series resistance model describes the behavior and gives an interfacial thermal conductance value of ≈150 MW m(-2) K(-1) for the organic/clay interface, consistent with similar organic-inorganic interfaces. The wide range of compositional substitutions and structural variations possible in these materials, make organoclays a versatile new platform for investigating the underlying physics of nanolaminate structures.

Montmorillonite clay based polyurethane nanocomposite as substrate for retinal pigment epithelial cell growth.

The subretinal transplantation of retinal pigment epithelial cells (RPE cells) grown on polymeric supports may have interest in retinal diseases affecting RPE cells. In this study, montmorillonite based polyurethane nanocomposite (PU-NC) was investigated as substrate for human RPE cell growth (ARPE-19 cells). The ARPE-19 cells were seeded on the PU-NC, and cell viability, proliferation and differentiation were investigated. The results indicated that ARPE-19 cells attached, proliferated onto the PU-NC, and expressed occludin. The in vivo ocular biocompatibility of the PU-NC was assessed by using the HET-CAM; and through its implantation under the retina. The direct application of the nanocomposite onto the CAM did not compromise the vascular tissue in the CAM surface, suggesting no ocular irritancy of the PU-NC film. The nanocomposite did not elicit any inflammatory response when implanted into the eye of rats. The PU-NC may have potential application as a substrate for RPE cell transplantation.

Harvesting of oleaginous Chlorella sp. by organoclays.

In microalgae-based biorefinement, one of the highest practical priorities is to reduce the costs of downstream processes. As one potential solution, microalgae harvesting by organoclays has received particularly keen research interest. In the present study, cationic charged aluminum- and magnesium-backboned organoclays were synthesized and solubilized in aqueous solution due to their high-density of amino sites. Each, within 30 min of its injection into 1.7 g/L-concentration microalgal feedstocks, effected harvesting efficiencies of almost 100% at concentrations above 0.6 g/L while maintaining a neutral pH. Conclusively, organoclays, if recycled efficiently, can be uniquely effective microalgae harvesting agents.

A systematic examination of colour development in synthetic ultramarine according to historical methods.

A number of historical texts are investigated to ascertain the optimum conditions for the preparation of synthetic ultramarine, using preparative methods that would have been available to alchemists and colour chemists of the nineteenth century. The effect of varying the proportion of sulphur in the starting material on the colour of the final product is investigated. The optimum preparation involves heating a homogenised, pelletised mixture of kaolin (100 parts), sodium carbonate (100 parts), bitumen emulsion (or any 'sticky' carbon source) (12 parts) and sulphur (60 parts) at 750°C for ca. 4 hours. At this stage the ingress of air should be limited. The sample is allowed to cool in the furnace to 500°C, the ingress of air is permitted and additional sulphur (30 parts) is introduced before a second calcination step is undertaken at 500°C for two hours. The products obtained from the optimum synthesis have CIE ranges of x  = 0.2945-0.3125, y  = 0.2219-0.2617, Y  = 0.4257-0.4836, L* = 3.8455-4.3682, a*  = 4.2763-7.6943, b* = -7.6772-(-)3.3033, L  = 3.8455-4.3682, C = 5.3964-10.8693, h = 315.0636-322.2562. The values are calculated using UV/visible near infrared spectra using Lazurite [1], under D65 illumination, and the 1931 2° observer.

Ultrasonic treatment and synthesis of sugar alcohol modified Na+-montmorillonite clay.

Na(+)-montmorillonite clay (generally referred to as MMT) is very useful for reinforcing polymeric matrix at very low concentrations (typically, 2-5% wt). These clay particles are typically exfoliated before they can demonstrate the significant gains in heat deflection temperature, modulus, and elongation properties. In the case of hydrophilic biopolymer based matrices, such as carbohydrates and chitosan, exfoliating these nanoclay particles needs greater attention because the exfoliation is typically carried out using hydrophobic oligomers through ion-exchange. This study reports a new method of synthesizing completely hydrophilic MMT-assemblages using hydrophilic plasticizers for biopolymers. We used sugar alcohols (glycerol, xylitol with 3 and 5 hydroxyl groups) and polysaccharide maltodextrin to exfoliate the MMT. Sonication was conducted for MMT nanoclay and plasticizers at different weight ratios. It was confirmed that all plasticizer/modifier led to expansion of MMT gallery spacing (d-spacing) and the change in d-spacing could be related to the molecular structure of the plasticizer. Meanwhile, the extent of exfoliation was maximum with maltodextrin (fully exfoliation with 1:10 and 1:20 ratio of MMT:plasticizer) across all test samples and interestingly, glycerol and xylitol samples quickly established within the MMT galleries and exhibited minimal influence with further increase in relative concentrations.

Toughening of CAD/CAM all-ceramic crowns by staining slurry.

The ability of staining slurries containing silver and/or potassium compounds to enhance the mechanical properties of a leucite-reinforced glass ceramic (IPS Empress CAD) was investigated by measuring the Vickers hardness, median crack length, toughness, and compressive residual stress of specimens. A staining slurry containing potassium ions was found to increase the toughness of IPS specimens more than a staining slurry containing only silver ions when applied prior to sintering. None of the staining slurries produced any color changes. Thus, the results obtained in this study demonstrate that staining slurries increase the Vickers hardness and the fracture toughness of the surface and subsurface regions of all-ceramic IPS blocks fabricated by a CAD/CAM system without sacrificing their aesthetics.

In situ synthesis, characterization, and catalytic performance of tungstophosphoric acid encapsulated into the framework of mesoporous silica pillared clay.

Mesoporous silica pillared clay (SPC) incorporated with tungstophosphoric acid (HPW) has been synthesized via in situ introducing P and W source in the acidic suspension of the clay interlayer template during the formation of the silica pillared clay. The samples were characterized by XRD, XRF, FT-IR, TG-DTA, N(2) adsorption-desorption, and SEM techniques. The results showed that the HPW formed by in situ method has been effectively introduced into the framework of mesoporous silica pillared clay and its Keggin structure remained perfectly after formation of the materials. In addition, samples with similar HPW loadings were also prepared by impregnation method using SPC as the support. HPW in the incorporated samples was better dispersed into the silica pillared clay than in the impregnated samples. The results of catalytic tests indicated that the encapsulated materials demonstrated better catalytic performance than the impregnated samples in oxidative desulfurization (ODS) of dibenzothiophene (DBT).

Mesoporous aluminosilica monoliths for the adsorptive removal of small organic pollutants.

Water treatment for the removal of organic or inorganic pollutants has become a serious global issue because of the increasing demand for public health awareness and environmental quality. The current paper, reports the applicability of mesoporous aluminosilica monoliths with three-dimensional structures and aluminum contents with 19≤Si/Al≥1 as effective adsorbents of organic molecules from an aqueous solution. Mesocage cubic Pm3n aluminosilica monoliths were successfully fabricated using a simple, reproducible, and direct synthesis. The acidity of the monoliths significantly increased with increasing amounts of aluminum species in the silica pore framework walls. The batch adsorption of the organic pollutants onto (10 g/L) aluminosilica monoliths was performed in an aqueous solution at various temperatures. These adsorbents exhibit efficient removal of organic pollutants (e.g., aniline, p-chloroaniline, o-aminophenol, and p-nitroaniline) of up to 90% within a short period (in the order of minutes). In terms of proximity adsorption, the functional acid sites and the condensed and rigid monoliths with tunable periodic scaffolds of the cubic mesocages are useful in providing easy-to-use removal assays for organic compounds and reusable adsorbents without any mesostructural damage, even under chemical treatment for a number of repeated cycles.