Concepción Abrusci

Anion effects on kinetics and thermodynamics of CO2 absorption in ionic liquids

A thermogravimetric technique based on a magnetic suspension balance operating in dynamic mode was used to study the thermodynamics (in terms of solubility and Henrys law constants) and kinetics (i.e., diffusion coefficients) of CO2 in the ionic liquids [bmim][PF6], [bmim][NTf2], and [bmim][FAP] at temperatures of 298.15, 308.15, and 323.15 K and pressures up to 20 bar. The experimental technique employed was shown to be a fast, accurate, and low-solvent-consuming method to evaluate the suitability of the ionic liquids (ILs) to be used as CO2 absorbents. Thermodynamic results confirmed that the solubility of CO2 in the ILs followed the order [bmim][FAP] > [bmim][NTf2] > [bmim][PF6], increasing with decreasing temperatures and increasing pressures. Kinetic data showed that the diffusion coefficients of CO2 in the ILs followed a different order, [bmim][NTf2] > [bmim][FAP] > [bmim][PF6], increasing with increasing temperatures and pressures. These results evidenced the different influence of the IL structure and operating conditions on the solubility and absorption rate of CO2, illustrating the importance of considering both thermodynamic and kinetic aspects to select adequate ILs for CO2 absorption. On the other hand, the empirical Wilke-Chang correlation was successfully applied to estimate the diffusion coefficients of the systems, with results indicating the suitability of this approach to foresee the kinetic performance of ILs to absorb CO2. The research methodology proposed herein might be helpful in the selection of efficient absorption solvents based on ILs for postcombustion CO2 capture.

Efficient biodegradation of common ionic liquids by Sphingomonas paucimobilis bacterium

The biodegradation of ionic liquids (ILs) was evaluated by an indirect impedance technique, through which carbon dioxide production was measured during bioassay time. The biodegradation study was focused on finding a microorganism able to efficiently degrade common IL compounds. For the first time, a bacteria strain of Sphingomonas paucimobilis was employed in biodegradability tests of ILs, carried out for 37 commercial imidazolium-, pyridinium-, pyrrolidinium-, ammonium- and phosphonium-based ILs, including in the sample 12 different anions and 14 different cations. Remarkably, more than half of ILs studied (54% of the sample) exhibited a biodegradation percentage ≥60% after a 28-day incubation period with S. paucimobilis at 45 °C; therefore, they behave as easily biodegradable compounds from the indirect impedance test. In summary, current results suggested the possibility of biotreatment for the rapid and ultimate mineralisation of widely used ILs, such as BmimNTf2, BmimPF6, etc., which were noted as recalcitrant to biodegradation in previous standard tests with other microorganisms.

In Vitro Biocompatibility and Antimicrobial Activity of Poly(ε-caprolactone)/Montmorillonite Nanocomposites

A triblock copolymer based on poly(ε-caprolactone) (PCL) and 2-(N,N-diethylamino)ethyl methacrylate (DEAEMA)/2-(methyl-7-nitrobenzofurazan)amino ethyl acrylate (NBD-NAcri), was synthesized via atom transfer radical polymerization (ATRP). The corresponding chlorohydrated copolymer, named as PCL-b-DEAEMA, was prepared and anchored via cationic exchange on montmorillonite (MMT) surface. (PCL)/layered silicate nanocomposites were prepared through melt intercalation, and XRD and TEM analysis showed an exfoliated/intercalated morphology for organomodified clay. The surface characterization of the nanocomposites was undertaken by using contact angle and AFM. An increase in the contact angle was observed in the PCL/MMT(PCL-b-DEAEMA) nanocomposites with respect to PCL. The AFM analysis showed that the surface of the nanocomposites became rougher with respect to the PCL when MMTk10 or MMT(PCL-b-DEAEMA) was incorporated, and the value increased with the clay content. The antimicrobial activity of the nanocomposites against B. subtilis and P. putida was tested. It is remarkable that the biodegradation of PCL/MMT(PCL-b-DEAEMA) nanocomposites, monitored by the production of carbon dioxide and by chemiluminescence emission, was inhibited or retarded with respect to the PCL and PCL/1-MMTk10. It would indicate that nature of organomodifier in the clay play an important role in B. subtilis and P. putida adhesion processes. Biocompatibility studies demonstrate that both PCL and PCL/MMT materials allow the culture of murine L929 fibroblasts on its surface with high viability, very low apoptosis, and without plasma membrane damage, making these materials very adequate for tissue engineering.

Enzyme-induced graft polymerization for preparation of hydrogels: synergetic effect of laccase-immobilized-cryogels for pollutants adsorption

The use of polyethylene oxide-polypropylene oxide-polyethylene oxide block-copolymers as a mediator in the laccase-induced graft polymerization of diacrylic derivate of polyethylene glycols resulted in the formation of PEG-g-F68 hydrogels. The proper oxygen content in the reaction medium to obtain reasonable polymerization conversions (i.e., on one hand, laccase needs oxygen as substrate whereas, on the other, oxygen is a strong inhibitor of radical polymerizations) was achieved by the use of an enzymatic scavenging system consisting of glucose oxidase and glucose. Eventually, laccase was immobilized within the resulting PEG-g-F68 hydrogel with full preservation of enzyme activity. Laccases have been used for bioremediation purposes because of their ability to degrade phenolic compounds. Thus, laccase-immobilized PEG-g-F68 hydrogels were submitted to the ISISA (ice segregation induced self-assembly) process for preparation of laccase-immobilized PEG-g-F68 cryogels which exhibited a macroporous structure where immobilized laccase preserved almost total activity (ca. 90%) for a period exceeding three months after preparation. Synergy between macroporous structure (deriving from the ISISA process), amphiphilic domains (deriving from graft copolymer) and activity of the immobilized enzyme provided outstanding adsorption capabilities to the cryogels (up to 235 mg g−1).

Submicro foaming in biopolymers by UV pulsed laser irradiation

Microstructuring of polymers and biopolymers is of application in medical technology and biotechnology. Using different fabrication techniques three-dimensionally shaped and micro structured constructs can be developed for drug release and tissue engineering. As an alternative method, laser microstructuring offers a series of advantages including high resolution capability, low heat deposition in the substrate and high level of flexibility. In this work we present evidence of laser microfoam formation in collagen and gelatine by nanosecond pulsed laser irradiation in the UV at 248 and 266 nm. Irradiation at 355 nm produces melting followed by resolidification of the substrate, whereas irradiation at 532 and 1064 nm induces the formation of craters of irregular contours. Single pulse irradiation of a collagen film with an homogenized KrF microbeam yields a 20 μm thick expanded layer, which displays the interesting features of a nanofibrous 3-dimensional network with open cells. In gelatine, irradiation at 248 and 266 nm produces similar morphological modifications. The effect of the structural properties of the substrate on the laser induced microfoam is studied by comparing gelatines differing in gel strength (Bloom values 225 and 75) and in crosslinking degree. While results are discussed on the basis of thermal and photomechanical mechanisms and of the role played by the water content of the substrates, it is thought that such structures could have a biomimic function in future 3D cell culture devices for research.

New blends of ethylene-butyl acrylate copolymers with thermoplastic starch. Characterization and bacterial biodegradation.

Ethylene-butyl acrylate copolymer (EBA) with 13% of butyl acrylate content was used to produce blends with 10, 30 and 60% of thermoplastic starch (TPS) plasticized with glycerol. Ethylene-acrylic acid copolymer (EAA) was used as compatibilizer at 20% content with respect to EBA. The blends were characterized by X-ray diffraction, ATR-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (SEM), water-Contact Angle measurements (CA), Differential Scanning Calorimetry (DSC) and Stress-strain mechanical tests. Initiated autoxidation of the polymer blends was studied by chemiluminescence (CL) confirming that the presence of the polyolefin-TPS interphase did not substantially affect the oxidative thermostability of the materials. Three bacterial species have been isolated from the blend films buried in soil and identified as Bacillus subtilis, Bacillus borstelensis and Bacillus licheniformis. Biodegradation of the blends (28days at 45°C) was evaluated by carbon dioxide measurement using the indirect impedance technique.

Combinatorial Approach for Fabrication of Coatings to Control Bacterial Adhesion

Abstract Due to the high importance of bacterial infections in medical devices there is an increasing interest in the design of anti-fouling coatings. The application of substrates with controlled chemical gradients to prevent microbial adhesion is presented. We describe here the co-polymerization of poly(ethylene glycol) dimethacrylate with a hyperbranched multimethacrylate (H30MA) using a chemical gradient generator; and the resulting films were characterized with respect to their ability to serve as coating for biomedical devices. The photo-polymerized materials present special surface properties due to the hyperbranched structure of H30MA and phase separation at specific concentrations in the PEGDM matrix. This approach affords the investigation of cell response to a large range of different chemistries on a single sample. Two bacterial strains commonly associated with surgical site infections, Escherichia coli and Pseudomonas aeruginosa, have been cultured on these substrates to study their attachment behaviour. These gradient-coated samples demonstrate less bacterial adhesion at higher concentrations of H30MA, and the adhesion is substantially affected by the extent of surface phase segregation.