Novel approach over template molecule elimination in molecularly imprinted polymers by using heat activated persulfate.

This study proposes a new alternative for template removal from molecularly imprinted polymers by heat activated persulfate. It is known that trace amounts of template molecule remains in the polymer network after extraction by current methodologies leading to bleeding and incomplete removal of template which could compromise final determination of target analytes especially in trace analysis. A previously developed molecularly imprinted polymer specially designed for Coenzyme Q10 (CoQ10) extraction was employed as a model to test this template elimination approach. This polymer is based on methacrylic acid and ethylene glycol dimethylacrylate as monomers and Coenzyme Q0 as template. This coenzyme has the same quinone group as the CoQ10. Selectivity was analyzed comparing the recovery of CoQ10 and ubichromenol, a CoQ10 related substance. Chemical degradation using heat-activated persulfate allows the elimination of the template molecule with a high level of efficiency, being a simple and ecological methodology, yielding a polymer that exhibits comparable selectivity and imprinting effect with respect to traditional extraction methods.

Mathematical analysis of the effect of process conditions on the porous structure development of activated carbons derived from Pine cones.

This paper presents the results of a study on the influence of the degree of impregnation and activation temperature on the formation of the porous structure of activated carbons (ACs) obtained from Pine cones by the chemical activation process using potassium hydroxide as an activator. The advanced new numerical clustering based adsorption analysis (LBET) method, together with the implemented unique numerical procedure for the fast multivariant identification were applied to nitrogen and carbon dioxide adsorption isotherms determined for porous structure characterization of the ACs. Moreover, the Quenched Solid Density Functional Theory (QSDFT) method was chosen to determine pore size distributions. The results showed a significant influence of the primary structure of Pine cones on the formation of the porous structure of the developed ACs. Among others, it was evidenced by a very high degree of surface heterogeneity of all the obtained ACs, irrespective of the degree of impregnation with potassium hydroxide and the activation temperature. Moreover, the analysis of carbon dioxide adsorption isotherms showed, that the porous structure of the studied ACs samples contains micropores accessible only to carbon dioxide molecules. The results also showed a significant advantage of the LBET method over those conventionally used for porous structure analysis based on Brunauer-Emmett-Teller (BET) and Dubinin-Raduskevich (DR) equations, because it takes into account surface heterogeneities. The novel analyses methods were more fully validated as a reliable characterization tool, by extending their application to the isotherms for ACs developed from the same precursor by phosphoric acid activation, and for samples arising from these ACs, further subjected to additional post-treatments. The effect of the raw material used as precursor was moreover analysed by comparison with previous reported results for other ACs. The complementarity of the results obtained with the LBET and QSDFT methods is also noteworthy, resulting in a more complete and reliable picture of the analyzed porous structures.

Tailoring activated carbons from Pinus canariensis cones for post-combustion CO2 capture.

Activated carbons (ACs) from Pinus canariensis cones were developed by KOH chemical activation. The effect of the impregnation KOH/carbonized cones ratio (IR = 1, 2, or 3) and temperature (873, 973, 1073 K) on main chemical, textural, and morphological characteristics of the resulting ACs was systematically examined. CO2 adsorption capacity from gaseous streams was evaluated by gravimetric adsorption tests, and the analysis of breakthrough curves was determined in a packed-bed column at 303 K and atmospheric pressure. Comparison of CO2 adsorption capacities of the ACs at 273 K and 303 K at equilibrium showed that those samples developed at 973 K with IR = 3 (BET surface area ~ 1900 m2 g-1) attained the highest values (6.4 mmol g-1 and 1.9 mmol g-1, respectively), even though the ACs obtained at 1073 K with the same IR exhibited the largest surface area (2200 m2 g-1). Thermodynamic parameters evaluated from CO2 adsorption isotherms determined in the range 273-333 K for the former sample pointed to a physisorption, spontaneous, and exothermic process; isosteric heat of adsorption was also estimated for the range of surface coverage of the equilibrium isotherms. The kinetics of CO2 adsorption onto all the ACs was successfully described by the linear driving force model. The breakthrough curves were properly represented by the Thomas' model, the longest breakthrough time and highest adsorption capacity being also attained for the bed packed with the ACs developed at 973 K with IR = 3. Higher CO2 adsorption capacities of the ACs were directly related to the presence of narrow micropores (< 0.9 nm) induced by the stronger activation conditions. However, an excessively severe combination of the IR and activation temperature exerted a negative influence on CO2 adsorption onto the ACs, likely due to micropores widening.

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.

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 Young's 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.

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).

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.

Cationization of kappa- and iota-carrageenan--Characterization and properties of amphoteric polysaccharides.

Commercial kappa- and iota carrageenans were cationized with 3-chloro-2-hydroxypropyltrimethylammonium chloride in aqueous sodium hydroxide solution. For kappa-carrageenan three derivatives with different degrees of substitution were obtained. Native and amphoteric kappa-carrageenans were characterized by NMR and infrared spectroscopy, scanning electron and atomic force microscopy; methanolysis products were studied by electrospray ionization mass spectrometry. Young moduli and the strain at break of films, differential scanning calorimetry, rheological and flocculation behavior were also evaluated; the native and the amphoteric derivatives showed different and interesting properties. Cationization of iota-carrageenan was more difficult, indicating as it was previously observed for agarose, that substitution starts preferentially on the 2-position of 3,6-anhydrogalactose residues; in iota-carrageenan this latter unit is sulfated.

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.

Batch and dynamic sorption of Ni(II) ions by activated carbon based on a native lignocellulosic precursor.

Vinal-derived Activated Carbon (VAC) developed by phosphoric acid activation of sawdust from Prosopis ruscifolia native wood was tested for the adsorption of Ni(II) ions from dilute solutions in both batch and dynamic modes, comparing it with a Commercial Activated Carbon (CAC). Batch experiments were performed to determine adsorption kinetics and equilibrium isotherms for both carbons. It was possible to remove near 6.55 mg Ni g(-1) VAC and 7.65 mg Ni g(-1) CAC after 5 h and 10 h contact time, respectively. A pseudo second order equation fitted well with the kinetics of the process, and Langmuir adsorption model was used to adjust the experimental results concerning the adsorption isotherm. The parameters obtained indicate a stronger interaction between sorbent and sorbate for VAC (K = 26.56 L mmol(-1)) than for CAC (K = 19.54 L mmol(-1)). Continuous experiments were performed in a fixed-bed column packed with the investigated carbons, evaluating the influence of operational parameters such as flow rate, bed height and feed concentration on the breakthrough curves obtained. The breakthrough occurred more slowly for low concentrations of the metal ion in the feed, low flow rates and high bed height. The breakthrough curves were properly represented by Hall's model for both carbon types. Regeneration of the vinal activated carbon in column was tested, obtaining the same breakthrough curve in a new cycle of use. Finally, vinal-derived activated carbon can effectively be used to treat wastewater having until 30 ppm Ni(II).

Studies on the cationization of agarose.

Cationized agaroses with different degrees of substitution (0.04-0.77) were synthesized, employing 3-chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC). The influence of different reaction parameters on the substitution degree and molecular weight was evaluated. The investigated parameters were concentration of reagents, temperature, time, and addition of NaBH(4). The products were characterized by means of scanning electronic microscopy, infrared spectroscopy, viscosimetry, and NMR spectroscopy. Methanolysis products were studied by electrospray ionization mass spectrometry. The higher the concentration of CHPTAC employed, a higher degree of substitution was obtained, if the optimum concentration of NaOH in each case was employed. Insufficient quantities of NaOH reduced epoxide formation and the reacting alkoxides of the polysaccharide, whereas an excess of NaOH favored degradation of the epoxide and decrease in the molecular weight of the product. A reaction time of 2h was sufficient to obtain products with the maximum degree of substitution for each case. The addition of NaBH(4) gave products with a slightly higher molecular weight, but the extra cost involved should not justify its use for large-scale application.

Preparation and characterization of a novel starch-based interpolyelectrolyte complex as matrix for controlled drug release.

A novel cationized starch-based interpolyelectrolyte complex (IPEC) was formed using kappa-carrageenan as the counter polyion. Characterization of the product by turbidity measurements and elemental analyses indicated a 1:1 interaction of the repeating units. FT-IR spectra for the IPEC showed some differences in comparison with either IPEC constituents or physical mixture. The swelling of tablets obtained by direct compression was independent of pH, and a maximum value of 742% was attained after 24h. The performance of the IPEC as matrix for controlled release of ibuprofen indicates that drug delivery takes place in a zero-order manner. Experimental dissolution data in the buffer stage were properly represented by a model accounting for contributions of Fickian diffusion and relaxation phenomena; this model suggests that the former predominates over the latter, for the modeled range.

Early tracheostomy versus late tracheostomy in the surgical intensive care unit.

BACKGROUND: This study's purpose was to determine if early tracheostomy (ET) of severely injured patients reduces days of ventilatory support, the frequency of ventilator-associated pneumonia (VAP), and surgical intensive care unit (SICU) length of stay (LOS). METHODS: This 2-year retrospective review included 185 SICU patients with acute injuries requiring mechanical ventilation and tracheostomy. ET was defined as 7 days or less, and late tracheostomy (LT) as more than 7 days. RESULTS: The incidence of VAP was significantly higher in the LT group, relative to the ET group (42.3% vs. 27.2%, respectively; P <.05). Acute Physiology and Chronic Health Evaluation II scores, hospital and SICU LOS, and the number of ventilator days were significantly higher in the LT group. CONCLUSIONS: In patients who required prolonged mechanical ventilation, there was significant decreased incidence of VAP, less ventilator time, and lower ICU LOS when tracheostomy was performed within 7 days after admission to the SICU.

Biodigestores anaeróbicos de flujo ascendente para la depuración de líquido cloacal

El trabajo permitió verificar la aplicabilidad del tratamiento anaerobio a la depuración de líquido cloacal sin utilizar calefacción en clima templado. Compara el comportamiento de reactores de lecho fijo (filtro anaerobio) con manto de barro de flujo ascendente (UASB) operados en condiciones similares durante el período de 450 días y a escala semipiloto. Los tiempos de residencia hidráulica utilizados entre 24 y 6 horas, alcanzándose remociones medias del orden de 65 por ciento para DQO y 70 por ciento para DBO

Biodigestores anaeróbicos de flujo ascendente para la depuración de líquido cloacal

El trabajo permitió verificar la aplicabilidad del tratamiento anaerobio a la depuración de líquido cloacal sin utilizar calefacción en clima templado. Compara el comportamiento de reactores de lecho fijo (filtro anaerobio) con manto de barro de flujo ascendente (UASB) operados en condiciones similares durante el período de 450 días y a escala semipiloto. Los tiempos de residencia hidráulica utilizados entre 24 y 6 horas, alcanzándose remociones medias del orden de 65 por ciento para DQO y 70 por ciento para DBO

Tratamiento anaeróbico de líquido cloacal en clima templado

El trabajo tiene como objetivo verificar la aplicabilidad de reactores anaerobios no calefaccionados para el tratamiento de líquido cloacal en clima templado. Se construyeron dos unidades de lecho fijo y dos de manto, se pusieron en marcha utilizando unicamente barro cloacal primario y, luego, se operaron en paralelo. Durante la primera etapa el tiempo de residencia hidráulica se fijó en 24 hs. y la carga orgánica promedio fue de 0,4 g. DQO/1.día, siendo la temperatura media de las unidades no calefaccionadas 25ºC. En estas condiciones se alcanzaron remociones del 65 por ciento para DQO y 81 por ciento para DBO en el reactor de lecho fijo sin calefacción

Tratamiento anaeróbico de líquido cloacal en clima templado

El trabajo tiene como objetivo verificar la aplicabilidad de reactores anaerobios no calefaccionados para el tratamiento de líquido cloacal en clima templado. Se construyeron dos unidades de lecho fijo y dos de manto, se pusieron en marcha utilizando unicamente barro cloacal primario y, luego, se operaron en paralelo. Durante la primera etapa el tiempo de residencia hidráulica se fijó en 24 hs. y la carga orgánica promedio fue de 0,4 g. DQO/1.día, siendo la temperatura media de las unidades no calefaccionadas 25ºC. En estas condiciones se alcanzaron remociones del 65 por ciento para DQO y 81 por ciento para DBO en el reactor de lecho fijo sin calefacción