Nanofibrous polysulfone/TiO2 nanocomposites: surface properties and their relation with E. coli adhesion

Solution blow spinning, SBS, was used to prepare fibrous films of thermoplastic nanocomposites with potential antibacterial properties based on polysulfone, PSF, filled with well dispersed TiO2 nanoparticles. The PSF/TiO2 nanocomposites were produced with different nanoparticles content up to 10% by weight. A wide characterization was carried out focusing on the morphology at the nanoscale, roughness, contact angles, and surface free energy. Cell adhesion was studied by inspection by scanning electron microscopy (SEM). A uniform dispersion of the nanofiller was achieved, with the nanoparticles evenly embedded in the polymer along the fibers when they were created during the blow spinning process. TiO2 content influenced the topography of the films, most likely due to a direct effect on the solvent evaporation rate. The results obtained pointed out that an increase of the surface hydrophobicity as a result of the increased roughness induced by the presence of TiO2 nanoparticles was the main contribution to the reduction of DH5α Escherichia coli cells adhesion.This work was financially supported by the Projects MAT2014-59116-C2 (Ministerio de Economía y Competitividad); 2012/00130/004 (Fondos de Investigación de Fco. Javier Gonzalez Benito, política de reinversión de costes generales, Universidad Carlos III de Madrid) and 2011/00287/002 (Acción Estratégica en Materiales Compuestos poliméricos e Interfases, Universidad Carlos III de Madrid)

Effect of a silica nanofiller on the structure, dynamics and thermostability of LDPE in LDPE/silica nanocomposites

The effect of the presence of silica nanoparticles on the structure, thermal stability and dynamics of low density polyethylene, LDPE, has been studied. Different loads of nanoparticles were dispersed within a LDPE matrix using high energy ball milling (HEBM) as a preliminary processing step to ensure a uniform dispersion of nanofiller to obtain nanocomposites in the form of films by hot pressing. The monitoring of the FTIR-ATR spectra of the samples as a function of the temperature has proven as a convenient method to study the interactions at a molecular scale between the polyethylene chains and the nanofiller. Band splitting observed in the bending and rocking modes of the ethylene groups indicated formation of crystalline phases whereas the analysis of absorbance band ratios from the stretching vibrations of PE accounted for the behavior of the polymer bulk. No evidence of strong polymer–filler interactions were found with the exception of a thermal relaxation process observed at 55 °C. Structural, morphological and thermal characterization of the nanocomposites did not reveal remarkable changes at low loads of filler, indicating that in the case of LDPE–silica nanocomposites, where weak interactions between the polymer and filler occur, the volume fraction of nanoparticles must be relatively high in order to produce changes in the bulk properties.The authors acknowledge financial support from projects MAT2007-65752 and MAT2010-16815, and the assistance of S. Martínez with the TGA and FTIR-ATR experiments

Poly (ethylene-co-vinyl acetate) films prepared by solution blow spinning: surface characterization and its relation with E.coli adhesion

Solution blow spinning, SBS, a quite novel processing method, was used to obtain poly (ethylene-co-vinyl acetate), EVA, films with controlled surface properties. The influence of the surface characteristics of EVA films on the adhesion of DH5α Escherichia coli was studied. In particular, the initial concentration of the EVA solution to be blow spun was varied in order to get different surface topographies. Considering the potential use of EVA based materials in applications such as food packaging or scaffolds for tissue engineering all factors affecting proliferation of microorganisms on their surfaces should be studied and understood. Structural, morphological and surface characterizations based on the use of infrared spectroscopy, FTIR, scanning electron microscopy, SEM, and contact angle measurements were performed to ascertain the main factor influencing the E. coli adhesion on the EVA films. Roughness data were determined at different scales from 3D surfaces obtained using a stereoscopic reconstruction of SEM images. It was concluded that, depending on the conditions of the SBS process, only variations of topography were found on the EVA films, being therefore the unique cause of different adhesion capacity of E. coli cells. A correlation between roughness and the number of attached E. coli cells showed that the higher the roughness at microscale level the higher the biofilm development, demonstrating that, apart from specific interactions at nanoscale surface, heterogeneity at microscale can greatly modify the antibacterial action.Authors gratefully acknowledge financial support from the Project MAT2014-59116-C2 (Ministerio de Economía y Competitividad). We also greatly appreciate the technical support from the Tissue Engineering and Regenerative Group (Department of Bioengeneering and Aerospace Engeneering) of the Carlos III University of Madrid, particularly to Angélica Corral and José Luis Jorcano

Solution casting of cellulose acetate films: influence of surface substrate and humidity on wettability, morphology and optical properties

Variations on the processing conditions of conventional methods for polymeric film preparation may allow tuning certain properties. In this work, different casting surfaces and humidity are presented as variables to consider for cellulose acetate (CA) film preparation using conventional solution casting method. Specifically, borosilicate glass, soda-lime glass and Teflon (PTFE) dishes have been used for casting and their influence on various properties on CA films assessed. The surfaces of glass dishes are smooth, while PTFE surface has a pattern constituted by concentric channels of micro dimensions (as seen by optical microscope), which is adopted by cast films upon drying. The resulting patterned films are translucent while films produced using smooth surfaces are transparent. The effect of the environment humidity (35%, 55% and 75% RH) in the properties of the CA films during the evaporation of solvent from solution has been evaluated. Higher humidity produces smoother surfaces and increased crystallinity as shown by XRD and DSC; however, the wettability of the films does not seem to be influenced by this variable. Due to the specific morphology of the patterned films, changes in material opacity upon wetting are detected, from translucent to transparent, while the removal of water from the surface restores the translucency. This micropatterning effect that causes different visual appearance of the material can find use as a humidity sensor in food packaging applications.Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This work was financially supported by CONEX-Plus program of Universidad Carlos III de Madrid (UC3M) and the European Commission through the Marie-Sklodowska Curie COFUND Action (Grant Agreement No 801538). Authors also appreciate the financial support received from AEI (Ministerio de Ciencia e Innovación of Spain, PID2020-112713RB-C22 and -C21); the Universidad Carlos III de Madrid, Fondos de Investigación of Fco. Javier González Benito (2012/00130/004) and the strategic Action in Multifunctional Nanocomposite Materials (2011/00287/003)

Nanomorphology and nanomechanical characteristics of solution-blow-spun PVDF-based fibers filled with carbon nanotubes

Fibers of poly(vinylidene fluoride) (PVDF) filled with multiwalled carbon nanotubes (MWCNTs) were prepared by solution blow spinning (SBS). The influence of the MWCNTs on the surface morphology and mechanical behavior of single fibers was studied. The morphology of the materials prepared and the dispersion of the MWCNTs within the polymer were studied by optical microscopy (OM) and transmission electron microscopy (TEM), while atomic force microscopy (AFM) was used to inspect the topography of single fibers and to perform nanoindentation tests. OM and TEM images indicated a good dispersion of the MWCNTs within the PVDF. AFM images evidenced clear changes in the topography of the blow-spun fibers when the MWCNTs were present in the polymer. A greater amount of MWCNTs in the PVDF led to more heterogeneous fiber surfaces. The nanoindentation force curves revealed that the stiffness was practically constant along the fibers, which indicated that the mechanical response was homogeneous and, in turn, an even distribution of the MWCNTs. The incorporation of the MWCNTs produced a mechanical reinforcement of the PVDF fibers, showing increases of 31% and 49% in the elastic modulus when 1% and 5% by weight of MWCNTs were added to the polymer, respectively.This work was financially supported by the projects MAT2014-59116-C2 (Ministerio de Economía y Competitividad), 2012/00130/004 (Fondos de Investigación de Fco. Javier Gonzalez Benito, Política de Reinversión de Costes Generales, Universidad Carlos III de Madrid), and 2011/00287/002 (Acción Estratégica en Materiales Compuestos Poliméricos e Interfases, Universidad Carlos III de Madrid). TEM characterization was done at LABMET, which is associated with the Red de Laboratorios de la Comunidad de Madrid. Finally, we would like to express appreciation for the technical support given by Carmen Ballesteros and Beatriz Galiana to perform the TEM tests

Cyclodextrin-Grafted TiO2 Nanoparticles: Synthesis, Complexation Capacity, and Dispersion in Polymeric Matrices

The modification of the surface of titanium dioxide nanoparticles (TiO2 NPs) by the incorporation of cyclodextrins (CDs), cyclic oligosaccharides with a hydrophobic cavity, can largely improve the functionality of TiO2 by lodging molecules of interest in the CD to act directly on the surface of the nanoparticles or for further release. With this aim, we have synthesized betaCD-modified nanoparticles (betaCDTiO2 NPs) by a two-step reaction that involves the incorporation of a spacer and then the linking of the macrocycle, and characterized them by thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The capacity of the functionalized structures to trap model compounds (Rhodamine and 1-naphthol) has been compared to that of bare TiO2 NPs by fluorescence and Ultraviolet-visible (UV-visible) spectroscopy. The presence of the CDs on the surface of the TiO2 avoids the photo-degradation of the guest, which is of interest in order to combine the photocatalytic activity of TiO2, one of its most interesting features for practical purposes, with the delivery of compounds susceptible of being photo-degraded. The betaCDTiO2 NPs have been dispersed in polymeric matrices of frequently used polymers, polyethylene (LDPE) and polyethylene oxide (PEO), by cryogenic high energy ball milling to produce nanocomposites in the form of films. The surface modification of the nanoparticles favors the homogenization of the filler in the matrix, while the nanoparticles, either in bare or functionalized form, do not seem to alter the crystallization properties of the polymer at least up to a 5% (w/w) load of filler.This research was funded by Ministerio de Ciencia e Innovación, project MAT2014-59116-C2-2-R

Cyclodextrin-grafted barium titanate nanoparticles for improved dispersion and stabilization in water-based systems

Ceramic nanoparticles with piezoelectric properties, such as BaTiO3 (BT), constitute a promising approach in the fields of nanocomposite materials and biomaterials. In the latter case, to be successful in their preparation, the drawback of their fast aggregation and practically null stability in water has to be overcome. The objective of this investigation has been the surface functionalization of BaTiO3 nanoparticles with cyclodextrins (CDs) as a way to break the aggregation and improve the stability of the nanoparticles in water solution, preventing and minimizing their fast precipitation. As a secondary goal, we have achieved extra-functionality of the nanoparticles, bestowed from the hydrophobic cavity of the macrocycle, which is able to lodge guest molecules that can form inclusion complexes with the oligosaccharide. The nanoparticle functionalization has been fully tracked and characterized, and the cytotoxicity of the modified nanoparticles with fibroblasts and pre-osteoblasts cell lines has been assessed with excellent results in a wide range of concentrations. The modified nanoparticles were found to be suitable for the easy preparation of nanocomposite hydrogels, via dispersion in hydrophilic polymers of typical use in biomedical applications (PEG, Pluronics, and PEO), and further processed in the form of films via water casting, showing very good results in terms of homogeneity in the dispersion of the filler. Likewise, as examples of application and with the aim of exploring a different range of nanocomposites, rhodamine B was included in the macrocycles as a model molecule, and films prepared from a thermoplastic matrix (EVA) via high-energy ball milling have been tested by impedance spectroscopy to discuss their dielectric properties, which indicated that even small modifications in the surface of the nanoparticles generate a different kind of interaction with the polymeric matrix. The CD-modified nanoparticles are thus suitable for easy preparation of the water-based nanocomposites either as hydrogels or as nanocomposites based on thermoplastic matrices.Financial supports from Asociación de Amigos of the University of Navarra for the PhD scholarship of R. Serra-Gómez as well as the Ministerio de Economia y Competitividad in the form of funding under projects. MAT2010-16815 and MAT2014-59116, are greatfully acknowledged

PVDF/TiO2 nanocomposites prepared by solution blow spinning: surface properties and their relation with S. Mutans adhesion

Thermoplastic nanocomposite materials with potential bactericide properties were prepared and their surface properties and adhesion to Streptococcus mutans, S. mutans, were characterized. Solution blow spinning was successfully used to prepare films with a fiber-like structure on the surface of nanocomposites based on Polyvinylidene fluoride, PVDF, filled with well dispersed TiO2 nanoparticles. PVDF/TiO2 nanocomposites were prepared varying the nanoparticles content (0%, 1%, 2%, 5% and 10% by weight). In order to understand the influence of the presence of TiO2 nanoparticles and the final surface properties on the adhesion of S. mutans to the materials, a deep characterization was carried out focusing on the morphology, roughness, surface free energy from contact angle measurements and cell adhesion by single cell force spectroscopy. It was observed that the uniform dispersion of the nanofiller arose from nanoparticles embedded in the polymer when fibers were created during the blow spinning process. TiO2 content influenced the topography of the films probably due to a direct effect on the solvent evaporation rate. Although this factor greatly conditioned the roughness of the samples and therefore the surface free energy, S. mutant adhesion on the substrates under study was concluded to be more dependent on the specific interactions with the surface polar groups of the material.Authors gratefully acknowledge financial support of Ministerio de Economía y Competitividad (grant number MAT2014-59116-C2). Furthermore, the authors greatly appreciate The Ministerio de Educación Cultura y Deporte of Spain in the frame of "Modalidad A del Programa de estancias de movilidad de profesores e investigadores en centros extranjeros de enseñanza superior e investigación" for granting the research proposal of Javier González-Benito (Ref.: PR2015-00018) to do short stay at the National Institute of Standards and Technology, NIST (USA)

PVDF/BaTiO3/carbon nanotubes ternary nanocomposites prepared by ball milling: Piezo and dielectric responses

Nanocomposites based on poly(vinylidene fluoride) (PVDF) filled with barium titanate, BaTiO3, (BT) particles, and multiwalled carbon nanotubes (MWCNTs) were prepared by high-energy ball milling (HEBM) and subsequent hot pressing. This method of materials preparation allowed obtaining uniform dispersions of the nanofillers. The influence of the particles on the polymer structure and morphology was studied. To understand the origin of changes in the PVDF properties, thermal and electrical behaviors of the PVDF/BT/MWCNT nanocomposites were studied as a function of composition. The addition of BT, MWCNT, or its mixture had not any influence on the PVDF polymorphism. However, calorimetric results pointed out that the presence of the nanofillers exerted nucleation mainly ascribed to the surface to volume ratio of the nanoparticles. The capacitance of the composites increased as the nanofiller content increased, being the effect mainly dependent on the surface to volume ratio of the nanoparticles. The dielectric behavior of the materials as a function of frequency was modeled by a Debye equivalent circuit only below the percolation threshold respect to the amount of MWCNT. The piezoelectric behavior of the ternary nanocomposites was highly affected by the incorporation of the nanofillers only when high dielectric losses occurred above the percolation threshold.The authors gratefully acknowledge the financial support from the Ministerio de Ciencia e Innovacion (MAT2010-16815) and the Ministerio de Asuntos Exteriores y de Cooperacion and the Agencia Espanola de Cooperacion Internacional para el Desarrollo for supporting the Ph.D. thesis of F.A.S

Nanocomposites based on low density polyethylene filled with carbon nanotubes prepared by high energy ball milling and their potential antibacterial activity

Low density polyethylene (LDPE) based nanocomposites containing multi-walled carbon nanotubes (MWCNTs) were prepared by a two-step process consisting of a pre-mixture using high energy ball milling (HEBM) and subsequent hot pressing. The effects of ball milling and the presence of the MWCNTs on some physical properties of the materials and the antimicrobial efficiency against DH5α Escherichia coli were studied. Fourier transform infrared spectroscopy revealed that the polymer structure did not change in the final materials after the addition of MWCNTs and mixing. Differential scanning calorimetry showed small differences in the LDPE thermal behavior as a function of the type of material due to small changes in the polymer crystallization. This result was mainly ascribed to the milling process rather than to the incorporation of the MWCNTs. The presence of 1% by weight of the nanofiller increased the rigidity and hydrophobicity of the nanocomposites with respect to neat LDPE. This effect was explained by the preferential location of the MWCNTs in the surface of the material as the main factor decreasing the polar contribution to the surface free energy. A correlation between hydrophobicity, biofilm development and the shape and size of DH5α E. coli was observed, indicating that the presence of MWCNTs leads to a biocide effect by decreasing cell adhesion and changing its metabolism