Dye-Mediated Interactions in Chitosan-Based Polyelectrolyte/Organoclay Hybrids for Enhanced Adsorption of Industrial Dyes.

Noncovalent, dye-mediated interactions between organo-montmorillonites ("organoclays") and a chitosan-based polyelectrolyte are exploited for highly effective and fast removal of different, industrially important anionic dyes (single-azo, double-azo, and anthraquinone) from aqueous solutions. The addition of only 10 wt % of the polyelectrolyte to conventional organoclay results in a 100% increase in absolute dye uptake capacity, an acceleration of dye uptake kinetics by up to 500%, and the flocculation of large, easily separable sorbent aggregates. These substantial improvements in adsorption performance are driven by the mediating effect of the anionic dyes (acting as the electrostatic mediator between the positively charged polyelectrolyte chains and organoclays), enabling the formation of true hybrid sorbent structures without the need for covalent cross-linking chemistry. The dye-mediated sorption and hybrid formation mechanism is further evidenced by structural and chemical characterization of the hybrid sorbents (small-angle X-ray diffraction and IR mapping) as well as by analysis of dye sorption kinetics according to the intraparticle diffusion model. Importantly, the organoclay/polyelectrolyte hybrid system provides a highly interesting adsorbent for the treatment of dye mixtures. Our study shows that structurally different anionic dyes localize at different sites within the hybrid structure (organoclay intergallery spaces vs polyelectrolyte/organoclay interface), enabling the simultaneous adsorption of different dyes with high efficiency. Consequently, the total uptake capacity for dye mixtures was 50% larger than that of individual dyes, demonstrating the enormous potential of the hybrids for industrial wastewater purification, where dye mixtures are ubiquitous.

Fabrication of Hybrid Materials from Titanium Dioxide and Natural Phenols for Efficient Radical Scavenging against Oxidative Stress.

Oxidative stress caused by free radicals is one of the great threats to inflict intracellular damage. Here, we report a convenient approach to the synthesis, characterization, and evaluation of the radical activity of titanium-based composites. We have investigated the potential of natural antioxidants (curcumin, quercetin, catechin, and vitamin E) as radical scavengers and stabilizers. The titanium oxide composites were prepared via three steps including sol-gel synthesis, carboxylation, and esterification. The characterization of the titanium-phenol composites was carried out by FTIR, PXRD, UV-vis and SEM methods. The radical scavenging ability of the novel materials was evaluated using DPPH and an in vitro LPO assay using isolated rat liver mitochondria. The novel materials exhibit both a higher stability and an antioxidant activity in comparison to bare TiO2. It was found that curcumin and quercetin based composites show the highest antioxidant efficiency among the composites under study followed by catechin and vitamin E based materials. The results from an MTT assay carried out on the Caco-2 cell line indicate that the composites do not contribute to the cytotoxicity in vitro. This study demonstrates that a combination of powerful antioxidants with titanium dioxide can change its functional properties and provide a convenient strategy against oxidative stress.

Determining the Mechanism and Efficiency of Industrial Dye Adsorption through Facile Structural Control of Organo-montmorillonite Adsorbents.

The structural evolution of cost-effective organo-clays (montmorillonite modified with different loadings of CTAB (cetyltrimethylammonium bromide)) is investigated and linked to the adsorption uptake and mechanism of an important industrial dye (hydrolyzed Remazol Black B). Key organo-clay characteristics, such as the intergallery spacing and the average number of well-stacked layers per clay stack, are determined by low-angle X-ray diffraction, while differential thermogravimetric analysis is used to differentiate between surface-bound and intercalated CTAB. Insights into the dye adsorption mechanism are gained through the study of the adsorption kinetics and through the characterization of the organo-clay structure and surface charge after dye adsorption. It is shown that efficient adsorption of anionic industrial dyes is driven by three key parameters: (i) sufficiently large intergallery spacing to enable accommodation of the relatively large dye molecules, (ii) crystalline disorder in the stacking direction of the clay platelets to facilitate dye access, (iii) and positive surface charge to promote interaction with the anionic dyes. Specifically, it is shown that, at low modifier loadings (0.5 cation exchange capacity (0.5CEC)), CTAB molecules exclusively intercalate as a monolayer into the clay intergallery spaces, while, with increasing modifier loadings, the CTAB molecules adopt a bilayer arrangement and adsorb onto the exterior clay surface. Bilayer intercalation results in sufficiently large expansion of the intergallery spaces and significant disordering along the (001) stacking direction to enable high and relatively fast dye uptake via intraparticle diffusion. Poor and slow dye uptake is observed for the organo-clays with a monolayer structure, suggesting relatively inefficient dye adsorption at the clay edges. The optimized bilayer organo-clays (montmorillonite modified with 3CEC of CTAB) also show enhanced adsorption efficiencies for other important industrial dyes, highlighting the importance of structural control in organo-clays while also showing the adsorbents' great potential for use in industry where dye mixtures are encountered.

A vegetable oil-based organogel for use in pH-mediated drug delivery.

Organogels prepared with vegetable oils as the liquid organic phase present an excellent platform for the controlled delivery of hydrophobic guest molecules. We disclose a graft copolymer comprised of a poly(L-serine) backbone linked to alkane side-chains by hydrolytically susceptible ester bonds, that is capable of gelating edible safflower oil. The thermoresponsive organogel formed, which is non-cytotoxic, is capable of withholding guest molecules before undergoing targeted disassembly upon incubation in solutions of acidic pH, permitting the directed release of payload molecules. The presented material offers an extremely promising candidate for the controlled delivery of hydrophobic agents within acidic environments, such as cancer tumour sites.

The formation of biodegradable micelles from a therapeutic initiator for enzyme-mediated drug delivery.

The direct grafting of amphiphilic macromolecules by sequential n-carboxyanhydride ring-opening polymerisation (NCA ROP) from a therapeutic initiator enables the formation of monodisperse drug-containing micelles. The subsequent enzyme-mediated hydrolysis of the peptide component permits the programmed release of the encapsulated drug molecules, demonstrating a controlled drug delivery platform that negates any challenging payload loading procedures.