Removal of paracetamol on biomass-derived activated carbon: Modeling the fixed bed breakthrough curves using batch adsorption experiments

The remediation of paracetamol (PA), an emerging contaminant frequently found in wastewater treatment plants, has been studied in the low concentration range (0.3–10 mg L−1) using as adsorbent a biomass-derived activated carbon. PA uptake of up to 100 mg g−1 over the activated carbon has been obtained, with the adsorption isotherms being fairly explained by the Langmuir model. The application of Reichemberg and the Vermeulen equations to the batch kinetics experiments allowed estimating homogeneous and heterogeneous diffusion coefficients, reflecting the dependence of diffusion with the surface coverage of PA. A series of rapid small-scale column tests were carried out to determine the breakthrough curves under different operational conditions (temperature, PA concentration, flow rate, bed length). The suitability of the proposed adsorbent for the remediation of PA in fixed-bed adsorption was proven by the high PA adsorption capacity along with the fast adsorption and the reduced height of the mass transfer zone of the columns. We have demonstrated that, thanks to the use of the heterogeneous diffusion coefficient, the proposed mathematical approach for the numerical solution to the mass balance of the column provides a reliable description of the breakthrough profiles and the design parameters, being much more accurate than models based in the classical linear driving force.

Removal Of Glyphosate Herbicide From Water Using Biopolymer Membranes.

Enormous amounts of pesticides are manufactured and used worldwide, some of which reach soils and aquatic systems. Glyphosate is a non-selective herbicide that is effective against all types of weeds and has been used for many years. It can therefore be found as a contaminant in water, and procedures are required for its removal. This work investigates the use of biopolymeric membranes prepared with chitosan (CS), alginate (AG), and a chitosan/alginate combination (CS/AG) for the adsorption of glyphosate present in water samples. The adsorption of glyphosate by the different membranes was investigated using the pseudo-first order and pseudo-second order kinetic models, as well as the Langmuir and Freundlich isotherm models. The membranes were characterized regarding membrane solubility, swelling, mechanical, chemical and morphological properties. The results of kinetics experiments showed that adsorption equilibrium was reached within 4 h and that the CS membrane presented the best adsorption (10.88 mg of glyphosate/g of membrane), followed by the CS/AG bilayer (8.70 mg of glyphosate/g of membrane). The AG membrane did not show any adsorption capacity for this herbicide. The pseudo-second order model provided good fits to the glyphosate adsorption data on CS and CS/AG membranes, with high correlation coefficient values. Glyphosate adsorption by the membranes could be fitted by the Freundlich isotherm model. There was a high affinity between glyphosate and the CS membrane and moderate affinity in the case of the CS/AG membrane. Physico-chemical characterization of the membranes showed low values of solubility in water, indicating that the membranes are stable and not soluble in water. The SEM and AFM analysis showed evidence of the presence of glyphosate on CS membranes and on chitosan face on CS/AG membranes. The results showed that the glyphosate herbicide can be adsorbed by chitosan membranes and the proposed membrane-based methodology was successfully used to treat a water sample contaminated with glyphosate. Biopolymer membranes therefore potentially offer a versatile method to eliminate agricultural chemicals from water supplies.

Detection of catechol using mixed Langmuir-Blodgett films of a phospholipid and phthalocyanines as voltammetric sensors

The combination of metallic phthalocyanines (MPcs) and biomolecules has been explored in the literature either as mimetic systems to investigate molecular interactions or as supporting layers to immobilize biomolecules. Here, Langmuir-Blodgett (LB) films containing the phospholipid dimyristoyl phosphatidic acid (DMPA) mixed either with iron phthalocyanine (FePc) or with lutetium bisphthalocyanine (LuPc(2)) were applied as ITO modified-electrodes in the detection of catechol using cyclic voltammetry. The mixed Langmuir films of FePc + DMPA and LuPc(2) + DMPA displayed surface-pressure isotherms with no evidence of molecular-level interactions. The Fourier Transform Infrared (FTIR) spectra of the multilayer LB films confirmed the lack of interaction between the components. The DMPA and the FePc molecules were found to be oriented perpendicularly to the substrate, while LuPc(2) molecules were randomly organized. The phospholipid matrix induced a remarkable electrocatalytic effect on the phthalocyanines; as a result the mixed LB films deposited on ITO could be used to detect catechol with detection limits of 4.30 x 10(-7) and 3.34 x 10(-7) M for FePc + DMPA and LuPc(2) + DMPA, respectively. Results from kinetics experiments revealed that ion diffusion dominated the response of the modified electrodes. The sensitivity was comparable to that of other non-enzymatic sensors, which is sufficient to detect catechol in the food industry. The higher stability of the electrochemical response of the LB films and the ability to control the molecular architecture are promising for further studies with incorporation of biomolecules.

Estudis funcionals i de plegament dels dominis d'activació de les procarboxipeptidases

Els dominis d’activació (ADs) de les procarboxipeptidases de la subfamília A/B sempre han sorprès ja que representen una quarta part del proenzim. S’han realitzat alguns estudis per intentar descobrir-ne alguna possible funció alternativa, però no han estat fructífers. El descobriment de l’elevada velocitat de plegament del domini d’activació de la procarboxipeptidasa A2 humana, (ADA2h), emperò, va portar a proposar la possibilitat de que realitzessin una funció d’assistència al plegament del domini enzimàtic. Posteriorment, l’anàlisi del plegament d’ADA2h a pH baix va revelar la capacitat d’aquest domini per formar fibres amiloides, a més de demostrar que un increment de l’estabilitat proteica podia prevenir la formació d’aquests agregats. La profunda caracterització del plegament d’ADA2h va fer que aquesta proteïna fos un bon model amiloidogènic, de manera que es van proposar un seguit d’experiments que s’han desenvolupat en el present treball per tal de conèixer millor aquest procés. S’han dut a terme estudis cinètics d’agregació per tal de valorar la contribució dels diferents aminoàcids de la seqüència polipeptídica, utilitzant 29 variants puntuals d’ADA2h. Es va eliminar la contribució de l’estabilitat mitjançant la utilització d’urea, i per dicroïsme circular conjuntament amb un aparell de flux detingut, es van obtenir dues velocitats diferents, v1 i v2, que corresponen a la formació d’un intermediari i a la seva reorganització, respectivament. Experiments complementaris utilitzant espectroscòpia d’infraroig (IR) revelaren la reorganització de l’estat natiu (en aquest cas) per a donar la forma agregada. Les cinètiques d’IR van mostrar que ADA2h forma l’estructura _ típica de les fibres amiloides, previ desplegament les seves hèlixs-_. Finalment, s’han realitzat estudis de biocomputació per tal d’esbrinar possibles funcions alternatives dels ADs. Les superposicions estructurals semblen mostrar similaritat dels ADs amb dominis de reconeixement d’RNA (RRM). Aquesta hipòtesi s’ha comprovat experimentalment amb ADA4h, mostrant una dèbil, però existent, unió a RNA.

CD28/CTLA4-B7 interaction is dispensable for T cell stimulation by mouse mammary tumor virus superantigen but not for B cell differentiation and virus dissemination.

B cells are the primary targets of infection for mouse mammary tumor virus (MMTV). However, for productive retroviral infection, T cell stimulation through the virally-encoded superantigen (SAG) is necessary. It activates B cells and leads to cell division and differentiation. To characterize the role of B cell differentiation for the MMTV life cycle, we studied the course of infection in transgenic mice deficient for CD28/CTLA4-B7 interactions (mCTLA4-H gamma 1 transgenic mice). B cell infection occurred in CTLA4-H gamma 1 transgenic mice as integrated proviral DNA could be detected in draining lymph node cells early after infection by polymerase chain reaction analysis. In mice expressing I-E, B cells were able to present the viral SAG efficiently to V beta 6+ T cells. These cells expanded specifically and were triggered to express the activation marker CD69. Further stages of progression of infection appeared to be defective. Kinetics experiments indicated that T and B cell stimulation stopped more rapidly than in control mice. B cells acquired an activated CD69+ phenotype, were induced to produce IgM but only partially switched to IgG secretion. Finally, the dissemination of infected cells to other lymph nodes and spleen was reduced and the peripheral deletion of V beta 6+ T cells was minimal. In contrast, in mice lacking I-E, T cell stimulation was also impaired and B cell activation undetectable. These data implicate B7-dependent cellular interactions for superantigenic T cell stimulation by low-affinity TCR ligands and suggest a role of B cell differentiation in viral dissemination and peripheral T cell deletion.

Preparação e caracterização físico-química de complexos de inclusão entre anestésicos locais e hidroxipropil-beta-ciclodextrina

S(-) Bupivacaine (S(-)BVC) and Lidocaine (LDC) are widely used local anesthetics (LA). Hydroxypropyl beta-cyclodextrin (HP-beta-CD) is used as a drug-carrier system. The aim of this work was to characterize inclusion complexes between LA and HP-beta-CD. The affinity constants determined at different pHs show favourable complexation. The release kinetics experiments showed that S(-)BVC and LDC changed the released profiles in the presence of HP-beta-CD. Nuclear magnetic resonance experiments gave information about the interaction between LA and the cyclodextrin cavity. This study focused on the physicochemical characterization of drug-delivery formulations that come out as potentially new therapeutic options for pain treatment.

Determinação de parâmetros cinéticos em fluxo com câmara de gradiente e deteção espectrofotométrica: aplicação à reação entre o violeta de cristal e o ião hidróxido

A didactic experiment is proposed aimed to extend the Flow Injection Analysis (FIA) based methodology to the area of physical chemistry/chemical reactors for undergraduate labs. Our prime objective was to describe the use of a gradient chamber for determination of the rate constant for the reaction between crystal violet and the hydroxide ion. The study was complemented by determining the effect of temperature on the rate constant. The kinetic parameters, activation energy and reaction rate constant are determined based on an assumption of rate orders. The main didactic advantages of the proposed experimental set-up are the use of less reagents, contributing to a more environmental friendly experiment. The experiment illustrates also the reduction of associated errors and time by using automated analysis owing to decreased operator manipulation.

Poly(epsilon-caprolactone)nanocapsules as carrier systems for herbicides: Physico-chemical characterization and genotoxicity evaluation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Preparação e caracterização físico-química de complexos de inclusão entre anestésicos locais e hidroxipropil-beta-ciclodextrina

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Supercritical fluid extraction from fennel (Foeniculum vulgare): global yield, composition and kinetic data

Supercritical fluid extraction (SFE) from solids has proven to be technically feasible for almost any system; nonetheless, its economical viability has been proven for a restricted number of systems. A common practice is to compare the cost of manufacturing of vegetable extracts by a variety of techniques without deeply considering the huge differences in composition and functional properties among the various types of extracts obtained; under this circumstance, the cost of manufacturing do not favor SFE. Additionally, the influence of external parameters such as the agronomic conditions and the SFE system geometry are not considered. In the present work, these factors were studied for the system fennel seeds + CO2. The effects of the harvesting season and the degree of maturation on the global yields for the system fennel seeds + CO2 were analyzed at 300 bar and 40 degrees C. The effects of the pressure on the global yields were determined for the temperatures of 30 and 40 degrees C. Kinetics experiments were done for various ratios of bed height to bed diameter. Fennel extracts were also obtained by hydrodistillation and low-pressure solvent extraction. The chemical composition of the fennel extracts were determined by gas chromatography. The SFE maximum global yield (12.5%, dry basis) was obtained with dry harvested fennel seeds. Anethole and fenchone were the major constituents of the extract; the following fat acids palmitic (C16H32O2), palmitoleic stearic (C18H36O2), oleic (C18H34O2), linoleic (C18H32O2) and linolenic (C18H30O2) were also detected in the extracts. A relation between amounts of feed and solvent, bed height and diameter, and solvent flow rate was proposed. The models of Sovova, Goto et al. and Tan and Lion were capable of describing the mass transfer kinetics. (c) 2005 Elsevier B.V. All rights reserved.

Detection of catechol using mixed Langmuir-Blodgett films of a phospholipid and phthalocyanines as voltammetric sensors

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Removal of glyphosate herbicide from water using biopolymer membranes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Production of biogenic silica during the EBENE cruise, Equatorial Pacific

During the EBENE cruise (November 1996), distributions of biogenic silica concentration and production rates were investigated in the surface waters of the equatorial Pacific (180°W, from 8°S to 8°N), with particular emphasis on the limitation of the biogenic silica production by ambient silicic acid concentrations. Integrated over the depth of the euphotic layer, concentrations of biogenic silica and production rates were maximum at the Equator (8.0 and 2.6 mmol/m**2/d) and decreased more or less symmetrically polewards. Contribution of diatoms to the new production was estimated indirectly, comparing biogenic silica production rates and available data of new and export production in the same area. This comparison shows that new production in the equatorial area could mostly be sustained by diatoms, accounting for the major part of the exported flux of organic carbon. Kinetics experiments of silicic acid enrichment were performed. Half saturation constants were 1.57 µM at 3°S and 2.42 µM at the Equator close to the ambient concentrations. The corresponding Vmax values for Si uptake were 0.028/h at 3°S and 0.052/h at the equator. Experiments also show that in situ rates were restricted to 13-78% of Vmax, depending on ambient silicic acid concentrations. This work provides the first direct evidence that the rate of Si uptake by diatom populations of the equatorial Pacific is limited by the ambient concentration of silicic acid. However, such Si limitation might not be sufficient in itself to explain the low diatom growth rates observed, and additional limitation is suggested. One hypothesis that is consistent with the results of Fe limitation studies is that Fe and Si limitations may interact, rather than just being a mutually exclusive explanation for the HNLC character of the system.

Poly(epsilon-caprolactone)nanocapsules as carrier systems for herbicides: Physico-chemical characterization and genotoxicity evaluation

The toxicity of herbicides used in agriculture is influenced by their chemical stability, solubility, bioavailability, photodecomposition, and soil sorption. Possible solutions designed to minimize toxicity include the development of carrier systems able to modify the properties of the compounds and allow their controlled release. Polymeric poly(epsilon-caprolactone) (PCL) nanocapsules containing three triazine herbicides (ametryn, atrazine, and simazine) were prepared and characterized in order to assess their suitability as controlled release systems that could reduce environmental impacts. The association efficiencies of the herbicides in the nanocapsules were better than 84%. Assessment of stability (considering particle diameter, zeta potential, polydispersity, and pH) was conducted over a period of 270 days, and the particles were found to be stable in solution. In vitro release kinetics experiments revealed controlled release of the herbicides from the nanocapsules, governed mainly by relaxation of the polymer chains. Microscopy analyses showed that the nanocapsules were spherical, dense, and without aggregates. In the infrared spectra of the PCL nanocapsules containing herbicides, there were no bands related to the herbicides, indicating that interactions between the compounds had occurred. Genotoxicity tests showed that formulations of nanocapsules containing the herbicides were less toxic than the free herbicides. The results indicate that the use of PCL nanocapsules is a promising technique that could improve the behavior of herbicides in environmental systems. (C) 2012 Elsevier B.V. All rights reserved.

Effect of addition of maltodextrin on drying kinetics and stickiness of sugar and acid-rich foods during convective drying: experiments and modelling

The effect of addition of maltodextrin on drying kinetics of drops containing fructose, glucose, sucrose and citric acid individually and in mixtures was studied experimentally using single drop drying experiments and numerically by solving appropriate mass and heat transfer equations. The numerical predictions agreed with the experimental moisture and temperature histories within 5-6% average relative (absolute) errors and average differences of +/- 1degreesC, respectively. The stickiness of these drops was determined using the glass transition temperature (T-g) of the drops' surface layer as an indicator. The experimental stickiness histories followed the model predictions with reasonable accuracy. A safe drying (non-sticky) regime in a spray drying environment has been proposed, and used to estimate the optimum amount of addition of maltodextrin for successful spray drying of 120 micron diameter droplets of fruit juices. (C) 2003 Elsevier Ltd. All rights reserved.