Preparation and characterisation of biodegradable starch-based nanocomposite materials

Different formulations of biodegradable starch-polyester blend nanocomposite materials have been film blown on a pilot scale film blowing tower. The physical properties of different films have been examined by thermal and mechanical analysis and X-ray diffraction. The results show that the addition of an organoclay (from 0 to 5 wt%) significantly improves both the processing and tensile properties over the original starch blends. Wide angle X-ray diffraction (WAXD) results indicate that the best results were obtained for 30wt% starch blends, and the level of delamination depends on the ratio of starch to polyester and amount of organoclay added. The crystallisation temperature of the nanocomposite blends is significantly lower than the base blend. This is probably due to the platelets inhibiting order, and hence crystallisation, of the starch and polyester. The mechanical and thermal properties of the blends are also sensitive to the way the clay particles are dispersed. (C) 2003 Society of Chemical Industry.

Anomalous water absorption in porous materials

The absorption of fluid by unsaturated, rigid porous materials may be characterized by the sorptivity. This is a simple parameter to determine and is increasingly being used as a measure of a material's resistance to exposure to fluids (especially moisture and reactive solutes) in aggressive environments. The complete isothermal absorption process is described by a nonlinear diffusion equation, with the hydraulic diffusivity being a strongly nonlinear function of the degree of saturation of the material. This diffusivity can be estimated from the sorptivity test. In a typical test the cumulative absorption is proportional to the square root of time. However, a number of researchers have observed deviation from this behaviour when the infiltrating fluid is water and there is some potential for chemo-mechanical interaction with the material. In that case the current interpretation of the test and estimation of the hydraulic diffusivity is no longer appropriate. Kuntz and Lavallee (2001) discuss the anomalous behaviour and propose a non-Darcian model as a more appropriate physical description. We present an alternative Darcian explanation and theory that retrieves the earlier advantages of the simple sorptivity test in providing parametric information about the material's hydraulic properties and allowing simple predictive formulae for the wetting profile to be generated.

Influence of shapes of selected vegetable materials on drying kinetics during fluidized bed drying

Three different particular geometrical shapes of parallelepiped, cylinder and sphere were taken from cut green beans (length:diameter = 1:1, 2:1 and 3:1) and potatoes (aspect ratio = 1:1, 2:1 and 3:1) and peas, respectively. Their drying behaviour in a fluidised bed was studied at three different drying temperatures of 30, 40 and 50 degreesC (RH = 15%). Drying curves were constructed using non-dimensional moisture ratio (MR) and time and their behaviour was modelled using exponential (MR = exp(-kt)) and Page (MR = exp(-kt(n))) models. The effective diffusion coefficient of moisture transfer was determined by Fickian method using uni- and three-dimensional moisture movements. The diffusion coefficient was least affected by the size when the moisture movement was considered three-dimensional, whereas the drying temperature had a significative effect on diffusivity as expected. The drying constant and diffusivity coefficients were on the descending order for potato, beans and peas. The Arrhenius activation energy for the peas was also highest, indicating a strong barrier to moisture movement in peas as compared to beans and skinless cut potato pieces. (C) 2003 Elsevier Science Ltd. All rights reserved.

Prediction of multilayer adsorption and capillary condensation phenomena in cylindrical mesopores

MCM-41 periodic mesoporous silicates with a high degree of structural ordering are synthesized and used as model adsorbents to study the isotherm prediction of nitrogen adsorption. The nitrogen adsorption isotherm at 77 K for a macroporous silica is measured and used in high-resolution alpha(s)-plot comparative analysis to determine the external surface area, total surface area and primary mesopore volume of the MCM-41 materials. Adsorption equilibrium data of nitrogen on the different pore size MCM-41 samples (pore diameters from 2.40 to 4.92 nm) are also obtained. Based on the Broekhoff and de Boer' thermodynamic analysis, the nitrogen adsorption isotherms for the different pore size MCM-41 samples are interpreted using a novel strategy, in which the parameters of an empirical expression, used to represent the potential of interaction between the adsorbate and adsorbent, are obtained by fitting only the multilayer region prior to capillary condensation for C-16 MCM-41. Subsequently the entire isotherm, including the phase transition, is predicted for all the different pore size MCM-41 samples without any fitting. The results show that the prediction of multilayer adsorption and total adsorbed amount are in good agreement with the experimental isotherms. The predictions of the relative pressure corresponding to capillary equilibrium (coexistence) transition agree remarkably with experimental data on the adsorption branch even for hysteretic isotherms, confirming that this is the branch appropriate for pore size distribution analysis. The impact of pore radius on the adsorption film thickness and capillary coexistence pressure is also investigated, and found to agree with the experimental data. (C) 2003 Elsevier Inc. All rights reserved.

Osteoblast, fibroblast and in vivo biological response to poly(vinylidene fluoride) based composite materials

Electroactivematerials can be taken to advantage for the development of sensors and actuators as well as for novel tissue engineering strategies. Composites based on poly(vinylidenefluoride),PVDF,have been evaluated with respect to their biological response. Cell viability and proliferation were performed in vitro both with Mesenchymal Stem Cells differentiated to osteoblasts and Human Fibroblast Foreskin 1. In vivo tests were also performed using 6-week-old C57Bl/6 mice. It was concluded that zeolite and clay composites are biocompatible materials promoting cell response and not showing in vivo pro-inflammatory effects which renders both of them attractive for biological applications and tissue engineering, opening interesting perspectives to development of scaffolds from these composites. Ferrite and silver nanoparticle composites decrease osteoblast cell viability and carbon nanotubes decrease fibroblast viability. Further, carbon nanotube composites result in a significant increase in local vascularization accompanied an increase of inflammatory markers after implantation.

Multi-scale modeling of the mechanical behavior of polymer-based materials

Polymers have become the reference material for high reliability and performance applications. In this work, a multi-scale approach is proposed to investigate the mechanical properties of polymeric based material under strain. To achieve a better understanding of phenomena occurring at the smaller scales, a coupling of a Finite Element Method (FEM) and Molecular Dynamics (MD) modeling in an iterative procedure was employed, enabling the prediction of the macroscopic constitutive response. As the mechanical response can be related to the local microstructure, which in turn depends on the nano-scale structure, the previous described multi-scale method computes the stress-strain relationship at every analysis point of the macro-structure by detailed modeling of the underlying micro- and meso-scale deformation phenomena. The proposed multi-scale approach can enable prediction of properties at the macroscale while taking into consideration phenomena that occur at the mesoscale, thus offering an increased potential accuracy compared to traditional methods.

Predicting the mechanical behavior of amorphous polymeric materials under strain through multi-scale simulation

Polymeric materials have become the reference material for high reliability and performance applications. However, their performance in service conditions is difficult to predict, due in large part to their inherent complex morphology, which leads to non-linear and anisotropic behavior, highly dependent on the thermomechanical environment under which it is processed. In this work, a multiscale approach is proposed to investigate the mechanical properties of polymeric-based material under strain. To achieve a better understanding of phenomena occurring at the smaller scales, the coupling of a finite element method (FEM) and molecular dynamics (MD) modeling, in an iterative procedure, was employed, enabling the prediction of the macroscopic constitutive response. As the mechanical response can be related to the local microstructure, which in turn depends on the nano-scale structure, this multiscale approach computes the stress-strain relationship at every analysis point of the macro-structure by detailed modeling of the underlying micro- and meso-scale deformation phenomena. The proposed multiscale approach can enable prediction of properties at the macroscale while taking into consideration phenomena that occur at the mesoscale, thus offering an increased potential accuracy compared to traditional methods.

Production of surfactants from bio-materials

Este trabalho foi desenvolvido no âmbito de um projecto europeu, BIOPRODUCTION, tendo em vista o desenvolvimento de dois tipos de biomaterias funcionais: ésteres de açúcares com ácidos gordos (SFAE) e metacrilatos funcionais. A síntese laboratorial do biosurfactante SFAE foi efectuada utilizando como matérias-primas diferentes sacáridos, nomeadamente sacarose, glucose e melaço de cana-de-açúcar (mistura de polissacáridos), e ésteres metílicos de ácidos gordos (FAME) de óleos vegetais, tais como colza e coco. Esta síntese é constituída por dois passos: acilação dos açúcares com anidrido acético, e transesterificação do açúcar acilado com FAME, utilizando triflatos de lantanídeos como catalisador. Diferentes estequiometrias foram testadas, bem como diferentes processos de modo a evitar a degradação dos açúcares. Foram efectuados testes preliminares de emulsão e calculou-se, empiricamente, o respectivo HLB. Procedeu-se à caracterização do produto através de FTIR e RMN e também à optimização iterativa do processo de síntese. A modificação, à escala laboratorial, de metacrilatos de metilo (MMA) realizou-se recorrendo à sua transesterificação com polióis convencionais. Efectuaram-se testes de reticulação do produto com diferentes catalisadores e iniciadores para posterior aplicação em revestimentos de borracha. Por fim, para ambos os produtos serão necessários estudos adicionais de caracterização, nomeadamente tensão superficial para os biosurfactantes e propriedades mecânicas para polímeros modificados com MMA.

Biomimetic norfloxacin sensors made of molecularly-imprinted materials for potentiometric transduction

A biomimetic sensor for norfloxacin is presented that is based on host-guest interactions and potentiometric transduction. The artificial host was imprinted into polymers made from methacrylic acid and/or 2-vinyl pyridine. The resulting particles were entrapped in a plasticized poly(vinyl chloride) (PVC) matrix. The sensors exhibit near-Nernstian response in steady state evaluations, and detection limits range from 0.40 to 1.0 μgmL−1, respectively, and are independent of pH values at between 2 and 6, and 8 and 11, respectively. Good selectivity was observed over several potential interferents. In flowing media, the sensors exhibit fast response, a sensitivity of 68.2 mV per decade, a linear range from 79 μM to 2.5 mM, a detection limit of 20 μgmL−1, and a stable baseline. The sensors were successfully applied to field monitoring of norfloxacin in fish samples, biological samples, and pharmaceutical products

Benzo[c]thiophene chromophores linked to cationic Fe and Ru derivatives for NLO materials: synthesis characterization and quadratic hyperpolarizabilities

5-Monocyclopentadienyliron(II)/ruthenium(II) complexes of the general formula [M(5-C5H5)(PP)(L1)][PF6] {M = Fe, PP = dppe; M = Ru, PP = dppe or 2PPh3; L1 = 5-[3-(thiophen-2-yl)benzo[c]thiophenyl]thiophene-2-carbonitrile} have been synthesized and studied to evaluate their molecular quadratic hyperpolarizabilities. The compounds were fully characterized by NMR, FTIR and UV/Vis spectroscopy and their electrochemical behaviour studied by cyclic voltammetry. Quadratic hyperpolarizabilities () were determined by hyper-Rayleigh scattering measurements at a fundamental wavelength of 1500 nm. Density functional theory calculations were employed to rationalize the second-order non-linear optical properties of these complexes.

Nanohybrid materials as transducer surfaces for electrochemical sensing applications

A nanohybrid electrochemical transducer surface was developed using carbon and gold nanomaterials. The strategy relayed on casting multiwalled carbon nanotubes or carbon nanofibers onto a screen-printed carbon electrode surface, followed by in situ generation of gold nanoparticles by electrochemical deposition of ionic gold, in a reproducible manner. These transducers, so fabricated, were characterized using both electrochemical and microscopic techniques. Biofunctionality was evaluated using the streptavidin-biotin interaction system as the biological reaction model. These platforms allow to achieve low detection limits (in the order of pmoles), are reproducible and stable at least for a month after their preparation, being a perfect candidate to be used as transducer of different sensor devices.

Natural waste materials containing chitin as adsorbents for textile dyestuffs: batch and continuous studies

In this work three natural waste materials containing chitin were used as adsorbents for textile dyestuffs, namely the Anodonta (Anodonta cygnea) shell, the Sepia (Sepia officinalis) and the Squid (Loligo vulgaris) pens. The selected dyestuffs were the Cibacron green T3G-E (CI reactive green 12), and the Solophenyl green BLE 155% (CI direct green 26), both from CIBA, commonly used in cellulosic fibres dyeing, the most used fibres in the textile industry. Batch equilibrium studies showed that the materials’ adsorption capacities increase after a simple and inexpensive chemical treatment, which increases their porosity and chitin relative content. Kinetic studies suggested the existence of a high internal resistance in both systems. Fixed bed column experiments performed showed an improvement in adsorbents’ behaviour after chemical treatment. However, in the column experiments, the biodegradation was the main mechanism of dyestuff removal, allowing the materials’ bioregeneration. The adsorption was strongly reduced by the pore clogging effect of the biomass. The deproteinised Squid pen (grain size 0.500–1.41 mm) is the adsorbent with highest adsorption capacity (0.27 and 0.037 g/g, respectively, for the reactive and direct dyestuffs, at 20ºC), followed by the demineralised Sepia pen and Anodonta shell, behaving like pure chitin in all experiments, but showing inferior performances than the granular activated carbon tested in the column experiments.

Molecularly-imprinted materials for potentiometric transduction: application to the antibiotic enrofloxacin

Enrofloxacin (ENR) is an antimicrobial used both in humans and in food producing species. Its control is required in farmed species and their surroundings in order to reduce the prevalence of antibiotic resistant bacteria. Thus, a new biomimetic sensor enrofloxacin is presented. An artificial host was imprinted in specific polymers. These were dispersed in 2-nitrophenyloctyl ether and entrapped in a poly(vinyl chloride) matrix. The potentiometric sensors exhibited a near-Nernstian response. Slopes expressing mVΔlog([ENR]/M) varied within 48–63. The detection limits ranged from 0.28 to 1.01 µg mL 1. Sensors were independent from the pH of test solutions within 4–7. Good selectivity was observed toward potassium, calcium, barium, magnesium, glycine, ascorbic acid, creatinine, norfloxacin, ciprofloxacin, and tetracycline. In flowing media, the biomimetic sensors presented good reproducibility (RSD of ±0.7%), fast response, good sensitivity (47 mV/Dlog([ENR]/ M), wide linear range (1.0×10-5–1.0×10-3 M), low detection limit (0.9 µg mL-1), and a stable baseline for a 5×10-2 M acetate buffer (pH 4.7) carrier. The sensors were used to analyze fish samples. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in vivo measurements of enrofloxacin or parent-drugs.

Selective recognition in potentiometric transduction of amoxicillin by molecularly imprinted materials

The indiscriminate use of antibiotics in foodproducing animals has received increasing attention as a contributory factor in the international emergence of antibiotic- resistant bacteria (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004). Numerous analytical methods for quantifying antibacterial residues in edible animal products have been developed over years (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004; Botsoglou and Fletouris in Handbook of food analysis, residues and other food component analysis, Marcel Dekker, Ghent, 2004). Being Amoxicillin (AMOX) one of those critical veterinary drugs, efforts have been made to develop simple and expeditious methods for its control in food samples. In literature, only one AMOX-selective electrode has been reported so far. In that work, phosphotungstate:amoxycillinium ion exchanger was used as electroactive material (Shoukry et al. in Electroanalysis 6:914–917, 1994). Designing new materials based on molecularly imprinted polymers (MIPs) which are complementary to the size and charge of AMOX could lead to very selective interactions, thus enhancing the selectivity of the sensing unit. AMOXselective electrodes used imprinted polymers as electroactive materials having AMOX as target molecule to design a biomimetic imprinted cavity. Poly(vinyl chloride), sensors of methacrylic acid displayed Nernstian slopes (60.7 mV/decade) and low detection limits (2.9×10-5 mol/L). The potentiometric responses were not affected by pH within 4–5 and showed good selectivity. The electrodes were applied successfully to the analysis of real samples.