Pablo R. Bonelli

Development and characterization of activated hydrochars from orange peels as potential adsorbents for emerging organic contaminants

Activated hydrochars obtained from the hydrothermal carbonization of orange peels (Citrus sinensis) followed by various thermochemical processing were assessed as adsorbents for emerging contaminants in water. Thermal activation under flows of CO2 or air as well as chemical activation with phosphoric acid were applied to the hydrochars. Their characteristics were analyzed and related to their ability to uptake three pharmaceuticals (diclofenac sodium, salicylic acid and flurbiprofen) considered as emerging contaminants. The hydrothermal carbonization and subsequent activations promoted substantial chemical transformations which affected the surface properties of the activated hydrochars; they exhibited specific surface areas ranging from 300 to ∼620 m(2)/g. Morphological characterization showed the development of coral-like microspheres dominating the surface of most hydrochars. Their ability to adsorb the three pharmaceuticals selected was found largely dependent on whether the molecules were ionized or in their neutral form and on the porosity developed by the new adsorbents.

Batch and dynamic biosorption of basic dyes from binary solutions by alkaline-treated cypress cone chips.

A simple alkaline pre-treatment of Cupressus sempervirens cone chips was performed to improve their biosorption capacity towards methylene blue and rhodamine B from aqueous solutions, in batch and continuous modes. Biosorption kinetics were determined from single and binary dyes solutions, and properly described by the pseudo-second-order rate model. Experimental single-dye equilibrium isotherms fitted the Langmuir-Freundlich model, with maximum biosorption capacities of 0.68mmol/g for methylene blue and 0.50mmol/g for rhodamine B. Single-dye dynamic biosorption showed that breakthrough time for methylene blue biosorption was almost four times longer than for rhodamine B and that the alkaline modification of the chips greatly improved the biosorption performance. Competitive dynamic biosorption demonstrated the preference of the modified cone chips for biosorbing methylene blue, confirmed by the exit concentration overshoots obtained in the breakthrough curves of rhodamine B.

Effect of alignment on adsorption characteristics of self-oriented multi-walled carbon nanotube arrays

The adsorption characteristics of self-oriented multi-walled carbon nanotube (MWCNT) arrays are examined from N2 (−196u2009°C) adsorption measurements. The arrays were synthesized in a laboratory by in situ chemical vapour deposition of iron or cobalt phthalocyanines at 880 and 950u2009°C, under otherwise constant conditions, in an attempt to obtain different morphological structures. For both precursors, increasing the temperature leads to MWCNT arrays with lower Brunauer–Emmett–Teller (BET) surface area and total pore volume, though the effect is more pronounced for those arising from the iron-based compound. Despite this, precursor yields of individual nanotubes of larger diameter, higher BET area and total pore volume characterize the resulting arrays compared to those arising from cobalt phthalocyanine for the same temperatures. As evidenced by SEM and TEM images, the arrays synthesized from iron phthalocyanine at 880u2009°C show better vertical alignment and denser structures than those obtained from this compound at 950u2009°C, and also from cobalt phthalocyanine at both temperatures. Further ultrasonication of the arrays produced from the iron compound brings about a significant reduction in their adsorption capacity, attributable to the pronounced disarrangement of the resulting structures. The present results demonstrate that the alignment of MWCNT arrays plays a crucial role in their N2 adsorption characteristics.

Nitrate uptake improvement by modified activated carbons developed from two species of pine cones

Activated carbons from two species of pine cones (Pinus canariensis and Cupressus sempervirens) were prepared by phosphoric acid activation and tested for the removal of nitrate ions from aqueous solution. To investigate the feasibility of improving their nitrate adsorption capacity, two different post-treatments—a thermal treatment and a treatment with saturated urea solution—were also applied to the prepared activated carbons. Comparison of the treated and untreated activated carbons showed that both post-treatments improved the nitrate adsorption performance more than twice. The maximum adsorption capacity, as evaluated from determination of the adsorption isotherms for the P. canariensis based carbons, and their proper representation by the Langmuir model, demonstrated that the post-treatment with the urea solution led to activated carbons with increased nitrate removal effectiveness, even superior to other reported results. Enhancements in their adsorption capacity could be mainly ascribed to higher contents of nitrogen and basic functional groups, whereas porous structure of the activated carbons did not seem to play a key role in the nitrate uptake.

Graphene oxide/alginate beads as adsorbents: Influence of the load and the drying method on their physicochemical-mechanical properties and adsorptive performance

Graphene oxide/alginate beads were prepared from lab-synthesized graphene oxide, varying its content within the beads (0.05, 0.125, and 0.25wt.%). Ethanol-drying and lyophilization were compared as drying methods to obtain suitable adsorbents which were later tested to the removal of a model organic molecule (methylene blue). The morphological and textural properties of all the beads were characterized by scanning electron microscopy and N2 adsorption/desorption isotherms at -196°C, respectively. Limited porosity was obtained for all cases (SBET<60m2/g). Uniaxial compression tests were performed to assess the mechanical properties of the beads. Ethanol-dried ones exhibited higher Youngs elasticity modulus (E=192kPa) than the lyophilized samples (twice at 0.25wt.% graphene oxide loading), which disclosed breakage points at lower deformation percentages. Adsorption experiments were conducted and dye adsorption isotherms were obtained for the beads with the best removal performance. The experimental data were better fitted by the Langmuir model. The highest maximum adsorption capacity (4.25mmol/g) was obtained for the lyophilized beads with the highest graphene oxide content. Mechanical properties were found to be affected also by the dye adsorption.

Carbon nanotubes buckypapers for potential transdermal drug delivery.

Drug loaded buckypapers based on different types of carbon nanotubes (CNTs) were prepared and characterized in order to evaluate their potentialities for the design of novel transdermal drug delivery systems. Lab-synthesized CNTs as well as commercial samples were employed. Clonidine hydrochloride was used as model drug, and the influence of composition of the drug loaded buckypapers and processing variables on in vitro release profiles was investigated. To examine the influence of the drug nature the evaluation was further extended to buckypapers prepared with flurbiprofen and one type of CNTs, their selection being based on the results obtained with the former drug. Scanning electronic microscopy images indicated that the model drugs were finely dispersed on the CNTs. Differential scanning calorimetry, and X-ray diffraction pointed to an amorphous state of both drugs in the buckypapers. A higher degree of CNT-drug superficial interactions resulted in a slower release of the drug. These interactions were in turn affected by the type of CNTs employed (single wall or multiwall CNTs), their functionalization with hydroxyl or carboxyl groups, the chemical structure of the drug, and the CNT:drug mass ratio. Furthermore, the application of a second layer of drug free CNTs on the loaded buckypaper, led to decelerate the drug release and to reduce the burst effect.

Preparation and characterization of controlled release matrices based on novel seaweed interpolyelectrolyte complexes

Novel interpolyelectrolyte complexes (IPECs) between naturally sulfated polysaccharides of the seaweed Polysiphonia nigrescens (PN) and cationized agaroses (CAG) and Eudragit E (EE) were prepared using an organic solvent free process, characterized, and explored for controlled drug release. Tablets containing model drug ibuprofen and IPECs were prepared by direct compression. Drug release in acid medium was low owing to the low solubility of ibuprofen in that condition and to the matrix action. Zero order drug release was determined in the buffer stage (pH=6.8), with Fickian diffusion predominating over relaxation during the initial phases. Relaxation appears to increase along the release process and even overcomes diffusion for some systems. Drug release profiles could be controlled by varying the content of IPECs in the tablets. Also, the change in molecular weight and the degree of substitution of the components allowed altering the release profiles.

Synthesis and characterization of molecularly imprinted polymer nanoparticles for coenzyme Q10 dispersive micro solid phase extraction.

Molecularly imprinted polymer nanoparticles (MIPNPs) with the ability to recognize coenzyme Q10 (CoQ10) were synthesised in order to be employed as sorbent in a dispersive micro-solid phase extraction (DMSPE) for the determination of CoQ10 in a liver extract. CoQ10 is a redox-active, lipophilic substance integrated in the mitochondrial respiratory chain which acts as an electron carrier, shuttling electrons from complex I (NADH-ubiquinone oxidoreductase) and II (succinate-ubiquinone oxidoreductase) to complex III (ubiquinol-cytochrome c reductase), for the production of cellular energy. The MIPNPs were synthesised by precipitation polymerization using coenzyme Q0 as the dummy template, methacrylic acid as the functional monomer, an acetonitrile: water mixture as the porogen, ethylene glycol dimethacrylate as the crosslinker and potassium persulfate as initiator. The nanoparticles were characterized by microscopy, capillary electrophoresis, dynamic light scattering, N2 adsorption-desorption isotherms, and infrared spectroscopy. The MIPNPs demonstrated the presence of selective cavities complementary to the quinone nucleus of CoQ10, leading to a specific recognition of CoQ10 compared with related compounds. In the liver extract the relative CoQ10 peak area (CoQ10 area/total peak area) increased from 4.6% to 25.4% after the DMSPE procedure. The recovery percentage of CoQ10 from the liver matrix was between 70.5% and 83.7% quantified against CoQ10 standard processed under the same conditions. The DMSPE procedure allows the elution of almost all the CoQ10 retained (99.4%) in a small volume (200μL), allowing the sample to be concentrated 2.5 times (LOD: 1.1μgg(-1) and LOQ: 3.7μgg(-1) of tissue). The resulted clean up of the sample, the improvement in peak shape and baseline and the reduction of interferences, evidence that the MIPNPs could potentially be applied as sorbent in a DMSPE with satisfactory results and with a minimum amount of sorbent (1mg).

Development and in vitro evaluation of potential electromodulated transdermal drug delivery systems based on carbon nanotube buckypapers

Buckypapers based on different types of carbon nanotubes with and without the addition of four model drugs, two of basic nature (clonidine hydrochloride, selegiline hydrochloride) and the others of acidic character (flurbiprofen, ketorolac tromethamine) were prepared and characterized. The influence of the conditions employed in the preparation of the buckypapers (dispersion time and solvents used in the preparation, as well as the type of carbon nanotubes used and the characteristics of the drug involved) on their conductivity was especially examined. The in vitro performance of the drug loaded buckypapers as passive and active transdermal drug release systems, the latter being modulated by means of the application of electric voltages, was studied. Passive drug loaded buckypapers presented characteristic release profiles, also depending on the drug used, which indicate differences in the drug-carbon nanotubes non-covalent interactions. Application of electrical biases of appropriate polarities enabled the modulation of the drug release profiles in any desired direction. Different mathematical models were fitted to passive and electromodulated experimental release data for the four model drugs. Among these models, the most appropriate for data description was a two-compartment pseudo-second-order one.