Natural clay as a sorbent to remove pharmaceutical micropollutants from wastewater.

Worldwide, the aquatic environment is contaminated by micro-pollutants, such as ingredients of personal care products, pesticides and pharmaceuticals. This contamination is one of the major environmental issues of global concern. Adsorption is one of approach, which has been most extensively discussed within recent years for the reduction of the input of micro-pollutants into the environment. In the present study, the natural clay classified as Na-montmorillonite, was characterized and tested for its potential to remove four model compounds representing different polarity and ionizability: i) diatrizoic acid (DAT), ii) iopamidol (IOP), iii) metformin (MTF), and iv) carbamazepine (CBZ). The adsorption efficiency of clay was evaluated by initial compound concentration, effect of pH, contact time and temperature. The results indicated that clay was able to remove the pharmaceuticals from aqueous medium with an efficiency of 70% for CBZ and MTF. In contrast, clay showed a lower removal of 30% for DAT and no removal for IOP. The results indicate that clay could rapidly and efficiently reduce the concentration of CBZ and MTF, which could provide a solution to remove some substances, without undesirable by-product generation. However, this study clearly demonstrated that removal rates strongly depend on the compound. Albeit chemical structure may play a role for the different degree of removal, this study could not completely explain the sorption mechanism between sorbent-sorbate interactions.

Highly hydrophilic surfaces from polyglycidol grafts with dual antifouling and specific protein recognition properties.

Homopolymer grafts from α-tert-butoxy-ω-vinylbenzyl-polyglycidol (PGL) were prepared on gold and stainless steel (SS) substrates modified by 4-benzoyl-phenyl (BP) moieties derived from the electroreduction of the parent salt 4-benzoyl benzene diazonium tetrafluoroborate. The grafted BP aryl groups efficiently served to surface-initiate photopolymerization (SIPP) of PGL. In similar conditions, SIPP of hydroxyethyl methacrylate (HEMA) permitted the production of PHEMA grafts as model surfaces. Water contact angles were found to be 66°, 15°, and 0° for SS-BP, SS-PHEMA, and SS-PPGL, respectively. The spontaneous spreading of water drops on SS-PPGL was invariably observed with 1.5 µL water drops. PPGL thus appears as a superhydrophilic polymer. Resistance to nonspecific adsorption of proteins of PPGL and PHEMA grafts on gold was evaluated by surface plasmon resonance (SPR) using antibovine serum albumin (anti-BSA). The results conclusively show that PPGL-grafts exhibit enhanced resistance to anti-BSA adsorption compared to the well-known hydrophilic PHEMA. PPGL grafts were further modified with BSA through the carbonyldiimidazole activation of the OH groups providing immunosensing surfaces. The so-prepared PPGL-grafted BSA hybrids specifically interacted with anti-BSA in PBS as compared to antimyoglobin. It is clear that the superhydrophilic character of PPGL grafts opens new avenues for biomedical applications where surfaces with dual functionality, namely, specific protein grafting together with resistance to biofouling, are required.

Electrografted aryl diazonium initiators for surface-confined photopolymerization: a new approach to designing functional polymer coatings.

This article reports on the preparation of polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(2-hydroxyethyl methacrylate) (PHEMA) ultrathin grafts on gold substrates modified by 4-benzoylphenyl (BP) moieties derived from the electroreduction of the parent diazonium salt BF(4)(-), (+)N(2)-C(6)H(4)-CO-C(6)H(5) (DS). The grafted organic species -C(6)H(4)-CO-C(6)H(5) was found to be very effective in the surface-initiating photopolymerization (SIPP) of vinylic monomers in the presence of an aromatic tertiary amine co-initiator acting as a hydrogen donor. This novel tandem diazonium salt electroreduction/SIPP was found to be effective in grafting PS, PMMA, and PHEMA from the surface of gold-coated silicon wafers. The polymer films were characterized in terms of chemical structure and wettability by infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy, and contact angle measurements, respectively. The polymer grafts were further evaluated as adsorbents for bovine serum albumin (BSA) used as a model protein. It was found gold/PHEMA resisted BSA adsorption because of its hydrophilic character, whereas PS and PMMA grafts adsorbed BSA via interfacial hydrophobic interaction. The XPS-determined extent of adsorbed BSA was found to increase linearly with the hydrophobic character of the polymer grafts as measured by water contact angles. This work shows that this novel tandem diazonium salt electroreduction/SIPP is a facile, ultrafast, efficient protocol for grafting polymer chains to surfaces. It broadens the enormous possibilities offered by aryl diazonium salts to generate functional organic coatings.