Grupos Investigadores

Líneas de Investigación

  • Valorización de residuos
  • Tratamiento de aguas residuales
  • Nanocomposites termoplásticos y nanocomposites blandos
  • Matrices de hidrogel para la sorción y liberación de moléculas modelo. Liberación de fármacos
  • Interacciones supramoleculares de sustancias de interés farmacéutico, biológico o medioambiental con ciclodextrinas, tensioactivos y polímeros
  • Estudio químico y material del patrimonio histórico-artístico
  • Estructura de fase y propiedades de materiales coloidales y poliméricos
  • Degradación fotocatalítica de contaminantes emergentes
  • Biometanización de residuos orgánicos

Palabras Clave

  • Valorización de residuos
  • Tratamiento de aguas
  • Química Supramolecular
  • Matrices poliméricas
  • Digestión anaerobia
  • Ciclodextrinas

Publicaciones Científicas desde 2018

  • Autores: Lorente, M. A.; González Gaitano, Gustavo; González-Benito, J. (Autor de correspondencia)
    Revista: POLYMERS
    ISSN 2073-4360 Vol.14 N° 7 2022 págs. 1299
    The relationship between processing conditions, structure and morphology are key issues to understanding the final properties of materials. For instance, in the case of polymers to be used as scaffolds in tissue engineering, wound dressings and membranes, morphology tuning is essential to control mechanical and wettability behaviors. In this work, the relationship between the processing conditions of the solution blow spinning process (SBS) used to prepare nonwoven mats of polyethylene oxide (PEO), and the structure and morphology of the resulting materials are studied systematically, to account for the thermal and mechanical behaviors and dissolution in water. After finding the optimal SBS processing conditions (air pressure, feed rate, working distance and polymer concentration), the effect of the solvent composition has been considered. The structure and morphology of the blow spun fibers are studied as well as their thermal, mechanical behaviors and dissolution in water. We demonstrate that the morphology of the fibers (size and porosity) changes with the solvent composition, which is reflected in different thermal and mechanical responses and in the dissolution rates of the materials in water.
  • Autores: Guembe-Michel, N.; Durán Benito, Adrián; Sirera Bejarano, Rafael; et al.
    ISSN 1422-0067 Vol.23 N° 2 2022 págs. 685
    Pseudopolyrotaxanes (PPRs) are supramolecular structures consisting of macrocycles able to thread on a linear polymer chain in a reversible, non-covalent way, often referred to in the literature as "molecular necklaces". While the synthesis and reaction mechanisms of these structures in solution have been widely described, their solvent-free production has received little attention, despite the advantages that this route may offer. We propose in this work a kinetic mechanism that describes the PPR formation in the solid phase as a process occurring in two consecutive stages. This mechanism has been used to investigate the spontaneous formation of a PPR that occurs when grinding alpha-Cyclodextrin (alpha-CD) with polyethylene glycol (PEG). In the threading stage, the inclusion of the polymer and subsequent release of the water molecules lodged in the cavity of the macrocycle cause vibrational changes that are reflected in the time-dependence of the FTIR-ATR spectra, while the further assembly of PPRs to form crystals produces characteristic reflections in the XRD patterns, due to the channel-like arrangement of CDs, that can be used to track the formation of the adduct in crystalline form. The effects that working variables have on the kinetics of the reaction, such as temperature, feed ratio, molar mass of the polymer and the introduction of an amorphous block in the polymer structure, have been investigated. The rate constants of the threading step increase with the temperature and the activation energy of the process increases at lower proportions of CD to PEG. This is attributed to the lower degree of covering of the polymer chain with CDs that reduces the hydrogen-bonding driven stabilization between adjacent macrocycles. The formation of crystalline PPR, which takes place slowly at room temperature, is markedly promoted at higher temperatures, with lower proportions of CD favoring both the formation and the growth of the crystals. The molar mass of the polymer does not modify the typical channel-like arrangement of packed PPRs but the conversion into crystalline PPR diminishes when using PEG1000 instead of PEG400. At a microscopic level, the crystals arrange into lamellar structures, in the order of hundreds of nm, embedded in an amorphous-like matrix. The introduction of a polypropylene oxide block in the structure of the polymer (Pluronic L62) renders poorer yields and a considerable loss of crystallinity of the product of the reaction. The methodology here proposed can be applied to the general case of inclusion complexes of CDs with drugs in the solid phase, or to multicomponent systems that contain polymers as excipients in pharmaceutical formulations along with CDs.
  • Autores: Pérez-Rodríguez, J. L. (Autor de correspondencia); Robador, M. D.; Durán Benito, Adrián (Autor de correspondencia)
    ISSN 2190-5444 Vol.137 N° 4 2022 págs. 469
    The walls of the Alcazar Palace in Seville have been covered with ceramic tiles of different styles that were manufactured with different techniques. Several studies have been carried out on these ceramics, but no interest has been paid to the tiles manufactured by the workshop of the Valladares family, one of the most productive ceramic workshops in Triana (Seville). In this work, tiles that were made in the Valladares workshop are studied for the first time. The tiles from the Cenador del Leon built in 1645-1646 were chosen. The experimental studies suggest that the ceramic body was manufactured with silico-calcareous clay. This raw material was heated to a temperature of ca. 900 degrees C. A nondestructive and on-site analytical procedure was applied first. Microsamples were also taken and studied through microanalytical techniques. The maiolica style was used by Benito de Valladares for tile manufacture. The glaze phases were constituted by two layers. The pigments and doping elements used to obtain different colors were characterized. Valladares' work is considered as a continuation of Augusta's work; therefore, a comparison between both ceramists has been realized to better understand the ceramics production in southern Spain during the sixteenth to seventeenth centuries.
  • Autores: Durán Benito, Adrián (Autor de correspondencia); Pérez-Rodríguez, J. L.
    ISSN 2190-5444 Vol.137 N° 1 2022 págs. 79
    This manuscript provided one of the first scientific studies performed on ancient Spanish liturgical vestments by using a multitechnical physicochemical approach. The interlining and lining fabrics were done by cotton and the core of threads by silk. Silver, gold and little amounts of copper were detected. The highest values of gold were found in the metal threads of the cope and the gallon of the chasuble. Two layers were identified: the internal composed by silver and the external by silver and gold. The fibers were proved to be degraded and also the surface of the metal, where scratches and silver-based compounds were detected due to environmental and anthropogenic actions. Indigo was employed as dye in the blue and green fabrics. Wax was detected in the yellow fibers, although other dyes could not be discarded. The materials used in the restoration processes were of minor quality.
  • Autores: Peñas Esteban, Francisco Javier (Autor de correspondencia); Romo Hualde, Ana; Isasi Allica, José Ramón
    ISSN 1566-2543 Vol.30 2022 págs. 1189 - 1198
    A cyclodextrin-based polymer was prepared by crosslinking beta-cyclodextrin with epichlorohydrin to be assessed as a sorbent material for cresols in packed-bed columns. Both Langmuir and Freundlich isotherms were appropriate to describe the sorption equilibrium in the conditions tested, and the thermodynamic parameters obtained for this process confirmed its exothermic nature with similar enthalpies (between - 6.8 and - 8.3 kJ/mol) for the three isomers. The removal of cresols from water was carried out in nine cycles of sorption-desorption in fixed-column experiments with the cyclodextrin hydrogel, achieving sorption capacities of 6.2, 11.6, and 15.1 mg/g for o-, m-, p-cresol, respectively. These differences in sorption capacities are due to the different chemical structures of cresols, that is, the relative position of the methyl and hydroxyl groups. However, similar sorption rates were observed for each isomer, with a mean value of 0.10 mg-cresol g-CDP-1 min(-1) in all cases. The experimental data for the breakthrough and the elution curves have been successfully modeled by two effective two-parameter equations, a dose-response model for the sorption step and a pulse-peak model for the regeneration step. The cyclodextrin polymer matrix has been proven to be an effective a good sorbent material for removing cresols from water, exhibiting remarkable reusability performance and structural stability throughout the successive elution steps carried out with methanol.
  • Autores: Etxebeste Mitxeltorena, Mikel; Durán Benito, Adrián; Sanmartín Grijalba, Carmen (Autor de correspondencia); et al.
    ISSN 1388-6150 Vol.147 N° 4 2022 págs. 3127 - 3139
    In this study, the thermal behavior of a series of leishmanicidal selenocyanate and diselenide biological active compounds has been studied by means of differential scanning calorimetry, X-ray diffraction and thermogravimetry in order to establish thermal stability criteria and investigate their polymorphism. Moreover, stability under acid, alkaline and oxidative media was tested using high-performance liquid chromatography with fluorescence detection. The results of the experiments show that there are five types of polymorphic behaviors for the studied compounds. In addition, relationship is found among stability and a series of structural effects and stress conditions of compounds.
  • Autores: Petitjean, Max Renaud; Lamberto, N.; Zornoza Cebeiro, Arantza; et al.
    ISSN 0144-8617 Vol.288 2022 págs. 119387
    Polysaccharides such as xanthan, locust bean gum or chitosan are easily crosslinked and purified using citric acid in an ecofriendly process. In order to achieve an improved sorption capability towards hydrophobic solutes, B-cyclodextrin, a cyclic oligosaccharide, and lignin, a natural aromatic polymer, are incorporated in the same process. Once crosslinked, the influence of these on the sorption capacities towards model solutes has been assessed by comparing the sorption isotherms of matrices with or without the hydrophobic modifications. The sorption capacities of these materials for different phenolic compounds have also been tested to ascertain their efficiencies as a function of their affinities to B-cyclodextrin cavities and/or their partition coefficients. In addition, these functionalized carbohydrate matrices were successfully characterized by principal component analysis, which is a useful tool to select the most appropriate polymers to interact with a specific molecule.
  • Autores: Petitjean, Max Renaud; García-Zubiri, I. X.; Isasi Allica, José Ramón (Autor de correspondencia)
    ISSN 1610-3653 Vol.19 N° 4 2021 págs. 3465 - 3476
    Cyclodextrins are glucose macrocycles whose inclusional capabilities towards non-polar solutes can be modulated with the help of other macrostructures. The incorporation of cyclodextrin moieties into larger structures produces five types of new materials: crosslinked networks, functionalized chains, amphiphilic cyclodextrins, polyrotaxanes and nanocomposites. This review presents crosslinking and grafting to prepare covalently-attached cyclodextrins, and applications in the food and pharmaceutical sectors, from an historical point of view. In food science, applications include debittering of juices, retention of aromas and release of preservatives from packaging. In biomedical science, cyclodextrin polymers are applied classically to drug release, and more recently to gene delivery and regenerative medicine. The remarkable points are: 1) epichlorohydrin and diisocyanates have been extensively used as crosslinkers since the 1960s, but during the last two decades more complex cyclodextrin polymeric structures have been designed. 2) The evolution of cyclodextrin polymers matches that of macromolecular materials with regard to complexity, functionality and capabilities. 3) The use of cyclodextrin polymers as sorbents in the food sector came first, but smart packaging is now an active challenge. Cyclodextrins have also been recently used to design treatments against the coronavirus disease 2019 (COVID-19).
  • Autores: Shahrour, Hawraa; Dandache, I.; Martínez López, Ana Luisa (Autor de correspondencia); et al.
    ISSN 0928-4931 Vol.121 2021 págs. 111876
    Device-Associated Healthcare-Associated Infections (DA-HAI) are a major threat to public health worldwide since they are associated with increased hospital stays, morbidity, mortality, financial burden, and hospital overload. A strategy to combat DA-HAI involves the use of medical devices endowed with surfaces that can kill or repel pathogens and prevent biofilm formation. We aimed to develop low-toxic protease-resistant anti-biofilm surfaces that can sensitize drug-resistant bacteria to sub-inhibitory concentrations of antibiotics. To this end, we hypothesized that polymyxin B nonapeptide (PMBN) could retain its antibiotic-enhancing potential upon immobilization on a biocompatible polymer, such as silicone. The ability of PMBN-coated silicone to sensitize a multidrug-resistant clinical isolate of Pseudomonas aeruginosa (strain Ps4) to antibiotics and block biofilm formation was assessed by viable counting, confocal microscopy and safranin uptake. These assays demonstrated that covalently immobilized PMBN enhances not only antibiotics added exogenously but also those incorporated into the functionalized coating. As a result, the functionalized surface exerted a potent bactericidal activity that precluded biofilm formation. PMBN-coated silicone displayed a high level of stability and very low cytotoxicity and hemolytic activity in the presence of antibiotics. We demonstrated for the first time that an antibiotic enhancer can retain its activity when covalently attached to a so
  • Autores: Petitjean, Max Renaud; Isasi Allica, José Ramón (Autor de correspondencia)
    ISSN 0141-8130 Vol.180 2021 págs. 570 - 577
    Three different polysaccharides, xanthan gum, chitosan and locust bean gum, were crosslinked with or without ß-cyclodextrin, using citric acid in different ratios, to create "green" hydrogel matrices. The crosslinking of these polysaccharides was produced through an inexpensive and innocuous solvent-free synthesis process. A favorable swelling behavior of the hydrophilic matrices facilitates the sorption of the solutes tested. Interestingly, the amount of ß-cyclodextrin groups is not the only factor to yield the best sorption capability for hydrophobic model molecules: polysaccharides themselves also influence the sorption depending on their characteristic functional groups, the conformation of their chains and, as mentioned above, their degrees of swelling. In order to ascertain the effect of the polysaccharides on the sorption capabilities of a model sorbate (1-naphthol), isotherms using a wide range of solute concentrations were analyzed, and the Hill equation yielded the best fitting results and provided some insight into the mechanisms of interaction.
  • Autores: Ruiz Ardanaz, I.; Lasheras Adot, María Esther; Durán Benito, Adrián (Autor de correspondencia)
    Revista: MINERALS
    ISSN 2075-163X Vol.11 N° 2 2021 págs. 153
    Several medieval tiles from Tiebas Castle in Navarre, classified as carreaux de pavement, were mineralogically analyzed. The aim was to add information to the very scarce analytical data available for carreaux de pavement in order to provide a quality primary work, mainly descriptive, in this topic. The characterization techniques applied were: optical microscopy (OM), colorimetry, Fourier transform infrared (FT-IR) spectroscopy, differential thermal analysis and thermogravimetry (DTA-TG), X-ray fluorescence (XRF) spectroscopy, petrographic microscopy (PM), X-ray diffraction (XRD), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDS). The tiles comprised three layers: a top glaze with mainly silicon and lead-based compounds; a thin layer of silicoaluminate (very possibly kaolinite) called engobe under it; and the pastes, composed of quartz, hematite, potassium feldspars and calcite. Honey glazes were richer in iron, being copper-based compounds responsible for dark green glazes. The orangish-reddish color of the pastes was provided by hematite. Although the tiles were found in three different locations within the castle, no significant differences were detected among them. The carreaux de pavement from Tiebas had similarities with that from the Bordeaux region. According to the composition data and thickness of tiles from other French carreaux de pavement, the Tiebas artifacts were dated to the 13th century.
  • Autores: De Diego Díaz, Beatriz; Peñas Esteban, Francisco Javier; Fernández Rodríguez, Juana (Autor de correspondencia)
    ISSN 0959-6526 Vol.280 N° P2 2021 págs. 124479
    Lignocellulosic residues are a widely available energy resource, but their conversion into biogas through biomethanation may be hindered by a chemical structure with strong bonds. A strategy based on temperature-phased anaerobic digestion (TPAD) is here applied to optimize anaerobic digestion of artichoke as a representative lignocellulosic waste. The experiments consist of a first thermophilic stage conducted at 55 °C (7 and 5 days), followed by a second mesophilic stage at 35 °C. In addition, for comparison, single-stage temperature trials are carried out within the most common conditions for biomethanation (mesophilic at 35 °C, and thermophilic at 55 °C), as well as at the intermediate range (42 °C). In general, biomethanation of artichoke residues under TPAD configuration provides better performance than single-stage systems. Particularly, the best performance is observed for the TPAD arrangement using a thermophilic phase of 7 days. Thus, at this optimal configuration, volatile solids (VS) removal of 54%, and biogas and methane yields of 442 mL/g-VS and 375 mL-CH4/g-VS were reached, respectively. Moreover, a kinetic model coupling biogas generation and substrate consumption has been applied. Good agreement is found for both variables in each system tested. The calculated non-biodegradable substrate (S¿) is lower in TPAD systems (mean 49.6%) compared with that of single-stages (average 53.9%).
  • Autores: Pérez-Rodríguez, J. L. (Autor de correspondencia); Franquelo, M. L. ; Durán Benito, Adrián
    ISSN 1388-6150 Vol.143 N° 4 2021 págs. 3257 - 3265
    In this work, it is reported that thermal analysis techniques such as TG, DTA and X-ray thermodiffraction, performed in air or nitrogen atmosphere, are very useful for evaluating and characterizing the pigments and the supports used for the manufacture of wall paintings from the San Isidoro del Campo Monastery (fifteenth century) in which different scenes from the life of San Jeronimo are represented. The use of thermal techniques has allowed for collecting information on the technology and raw materials used in the manufacture of these wall paintings. The composition of the different colours forming the wall paintings is the following: blue by azurite, green by atacamite, red by iron oxide (hematite), cinnabar and ochre by iron oxyhydroxides (goethite), black by carbon and white by calcite. In all the colours, calcite and quartz were also identified. The paintings were performed by using the fresco technique. The support mortars are constituted of calcite, quartz and straw.
  • Autores: Puig Rigall, Joan; Blanco Prieto, María; Aydillo Miguel, Carlos; et al.
    ISSN 0167-7322 Vol.324 2021
    The combination of polymeric surfactants with different features into mixed micelles give access to properties that may be superior to the single-component micelles. In this work, we investigated synergistic effects in mixtures of D-alpha-Tocopheryl polyethylene glycol succinate (TPGS) with poloxamines (also known as Tetronic), pH-responsive and thermogelling polyethylene oxide (PEO)-polypropylene oxide (PPO) 4-arm block copolymers. We examined the morphology of the self-assembled micelles of TPGS with Tetronic 1107 (T1107) and 908 (T908) in the presence of naproxen (NA), used as a model drug, and assessed the capacity of the single and mixed micelles to trap the guest, using a combination of small-angle neutron scattering (SANS) and NMR spectroscopy (1D, 2D-NOESY and diffusion NMR), over a range of compositions and temperatures, in the dilute regime and gel state. NA did not interact with T1107 or T908 in their unimer form, but it was incorporated into the hydrophobic core of the micelles above the critical micellar temperature (CMT). In contrast, TPGS dissolved NA at any temperature, mainly in the tocopherol core, with some partitioning in the PEG-shell. The micellar structure was not altered by the presence of NA, except for an expansion of the core size, a result of the preferential accumulation of NA in that compartment. The solubility of the drug in single component micelles increased markedly with temperature, while mixed micelles produced an intermediate enhancement o
  • Autores: Goñi Ciaurriz, Leire; Senosiain, M.; Vélaz Rivas, Itziar (Autor de correspondencia)
    ISSN 1422-0067 Vol.22 N° 5 2021 págs. 2257
    Polymeric materials, such as polyvinyl alcohol (PVA) and ethylene-PVA copolymers (EVOH) are widely used in the food sector as packaging materials because of their excellent properties. TiO2 nanoparticles (NPs) show photocatalytic activity; when added to the aforementioned polymers, on the one hand, they are expected to provide bactericidal capacity, whereas on the other hand, they could favor nanocomposite degradation. These types of nanoparticles can be derivatized with cyclodextrin macromolecules (CDs), which can act as food preservative carriers, increasing the packaging food protective properties. In this work, films containing beta-Cyclodextrin (beta CD)-grafted TiO2 nanoparticles and PVA or EVOH were prepared. Regarding the photocatalytic activity of the nanoparticles and the possible environmental protection, accelerated aging tests for PVA, EVOH, and their composites with cyclodextrin-grafted TiO2 nanoparticle (NP) films were performed by two methods, namely, stability chamber experiments at different conditions of temperature and relative humidity and UV light irradiation at different intensities. After analyzing the systems color changes (CIELAB) and Fourier transform infrared spectroscopy (FTIR) spectra, it was observed that the film degradation became more evident when increasing the temperature (25-80 degrees C) and relative humidity percentage (28-80%). There was no significant influence of the presence of CDs during the degradation process. When irradiating the films with UV light, the largest color variation was observed in the nanocomposite films, as expected. Moreover, the color change was more relevant with increasing NP percentages (1-5%) due to the high photocatalytic activity of TiO2. In addition, films were characterized by FTIR spectroscopy and variation in the signal intensities was observed, suggesting the increase of the material degradation in the presence of TiO2 NPs.
  • Autores: Puig Rigall, Joan; Blanco Prieto, María (Autor de correspondencia); Radulescu, A.; et al.
    ISSN 0021-9797 Vol.582 2021 págs. 353-363
    Hypothesis: The combination of polymeric surfactants into mixed micelles is expected to improve properties relevant to their use in drug delivery, such as micellar size, gelation, and toxicity. We investigated synergistic effects in mixtures of D-¿-Tocopheryl polyethylene glycol succinate (TPGS), an FDA-approved PEGylated derivative of vitamin E, and Tetronic surfactants, pH-responsive and thermogelling polyethylene oxide (PEO)-polypropylene oxide (PPO) 4-arm block copolymers. We hypothesized that mixed micelles would form under specific conditions and provide a handle to tune formulation characteristics. Experiments: We examined the morphology of the self-assembled structures in mixtures of TPGS with two Tetronic: T1107 and T908, using a combination of dynamic light scattering (DLS), small-angle neutron scattering (SANS), NMR spectroscopy (NOESY and diffusion NMR) and oscillatory rheology, over a range of compositions, temperatures and pH. Cell viability was assessed in NIH/3T3 fibroblasts. Findings: The combination of TPGS with either of the two Tetronic produces spherical core-shell micelles that comprise both surfactants in their structure (mixed micelles). T1107 unimers incorporate into TPGS aggregates below the critical micelle temperature of the poloxamine, while mixed micelles only form under limited conditions with T908. At high concentration/temperature, small proportions of TPGS extend the gel phase, more markedly with T1107, with similar elastic moduli (30-50 kPa) and a BCC crystalline structure. Cell viability of NIH/3T3 fibroblasts grown in the hydrogels increases significantly when the poloxamine gels are doped with TPGS, making the combination of poloxamines and TPGS a promising platform for drug delivery.
  • Autores: Puig Rigall, Joan; Fernández Rubio, Celia; González-Benito, J.; et al.
    ISSN 0378-5173 Vol.578 2020 págs. 119057
    Miltefosine (MF), an alkylphospholipid originally developed for breast cancer treatment, is a highly active drug for the treatment against leishmaniasis, a neglected tropical disease considered the world's second leading cause of death by a parasitic agent after malaria. MF exhibits dose-limiting gastrointestinal side effects in patients and its penetration through lipophilic barriers is reduced. In this work we propose a reformulation of MF by incorporating the drug to poly(ethylene)oxide (PEO)-based polymeric micelles, specifically, D-alpha-tocopheryl polyethylene glycol succinate (TPGS) and Tetronic block copolymers (T904 and T1107). A full structural characterization of the aggregates has been carried out by SANS (small-angle neutron scattering) and dynamic light scattering (DLS), in combination with proton 1D and 2D nuclear magnetic resonance (NMR) spectroscopy, to determine the precise location of the drug. The structure of MF micelles has been characterized as a function of the temperature and concentration. In the presence of the block-copolymers, MF forms mixed micelles in a wide range of temperatures, TPGS being the co-surfactant that incorporates more MF unimers. The hydrophobic tail of MF and those of the block copolymers are in close contact within the micelles, which present a core-shell structure with a hydrophilic corona formed by the PEG blocks of the TPGS and the zwitterion head group of the MF. In order to identify the best carrier, the antileishmanicidal activity of MF in the different formulations has been tested on macrophages, promastigotes and intracellular amastigotes. The combination of the three vehicles with MF makes the formulated drug more active than MF alone against L. major promastigotes, however, only the combination with T904 increases the MF activity against intracellular amastigotes. With the aim of exploring gel-based formulations of the drug, the combination of MF and T1107 under gelation conditions has also been investigated.
  • Autores: Goñi Ciaurriz, Leire; González Gaitano, Gustavo; Vélaz Rivas, Itziar (Autor de correspondencia)
    ISSN 0378-5173 Vol.588 2020 págs. 119664
    Photocatalytic properties of titanium dioxide nanoparticles (TiO2 NPs) have encouraged their use as fillers in polymer-based nanocomposites for application in food packaging. The surface modification of TiO2 NPs with cyclodextrins (CDs) can improve their functionality in a large extent. With this purpose, sorbic acid (SA) and benzoic acid (BA), commonly used as antifungal and antibacterial food preservatives, respectively, have been encapsulated in CD-grafted NPs. Inclusion complex formation of SA and BA with a and beta CDs in water has been assessed first by means of H-1 NMR and UV-Vis spectroscopy to determine the affinity of the preservatives for the macrocycles and the stoichiometry of the complexes. The association constants of both preservatives were found to be lower for beta CD, however, the loading efficiency in beta CD-grafted NPs was higher than that exhibited by alpha CD-NPs. Release kinetics from the CD-grafted NPs have been carried out. In the case of SA, the alpha CD-grafted NPs showed a prolonged and sustained release profile, suggesting its application as microbial growth inhibition system if incorporated into packaging materials.
  • Autores: Ziolek, R.M.; Omar, J.; Hu, W.; et al.
    ISSN 0024-9297 Vol.53 N° 24 2020 págs. 11065 - 11076
    We investigated the pH-directed self-assembly of Tetronic 304 (T304), an amphiphilic four-arm block copolymer of interest for application in drug delivery systems. While T304 and its analogues have been investigated regarding their pharmaceutical and therapeutic applications, a fundamental understanding of their pH-directed self-assembly is lacking. Integrating unbiased molecular dynamics simulations with small-angle neutron scattering and dynamic light scattering experiments provided an unprecedentedly detailed interpretation of our experimental findings and also directed the selection of suitable models for experimental data analysis. We subsequently probed the interactions that drive and hinder the self-assembly of T304 at the atomistic level of detail. pH-driven conformation changes in the central ethylenediamine group of T304, and subsequent interactions with water, ultimately drive the self-assembly of T304 and the structure of the resulting polymeric micelles. Our work provides detailed mechanistic understanding of pH-directed polymer self-assembly and supports the rational design of new pH-responsive functional polymer materials.
  • Autores: Puig Rigall, Joan; Serra Gómez, Rafael; Guembe-Michel, N.; et al.
    ISSN 0024-9297 Vol.53 N° 8 2020 págs. 3166 - 3174
    Pseudopolyrotaxanes (PPRs) are supramolecular host-guest complexes constituted by the reversible threading of macrocycles along a polymer chain. We report the formation of hybrid PPRs (hPPRs), where two types of cyclodextrins (CDs) thread either simultaneously or sequentially on four-arm poly-(ethylene oxide)-poly(propylene oxide) (PEO-PPO) block copolymers (Tetronic): native alpha-CD (CD) (with higher affinity for PEO) and dimethylated beta-CD (DIMEB, with higher affinity for PPO). The competitive complexation along the chains is examined with three Tetronics, differing mainly in the length of their PEO blocks: T904, T1107, and T1307. While PPRs formed with alpha-CD are insoluble, due to the hydrogen-bond network formed between adjacent alpha-CDs, the presence of DIMEB leads to soluble hybrid PPRs, slows down the kinetics of complexation, and increases the number of alpha-CDs threaded per arm. The morphology of the constructs in solution over time is followed by time-resolved small-angle neutron scattering (TR-SANS), while their crystalline structure is studied by X-ray diffraction. Whereas the complexation of the polymeric surfactant with DIMEB shifts the unimer-micelle equilibrium toward unimers, the presence of alpha-CD slows down demicellization and reduces its extent. Overall, the co-threading of two cyclodextrins on the same polymer provides a handle to tune the complexation process and the final properties of the PPR, including solubility, kinetics of complexation, and composition of the complexes.
  • Autores: Petitjean, Max Renaud; Aussant, F.; Vergara, A.; et al.
    Revista: GELS
    ISSN 2310-2861 Vol.6 N° 4 2020 págs. 51
    The incorporation of cyclodextrins into polymeric crosslinked gels of hydrophilic nature can be useful for promoting the sorption of hydrophobic molecules and/or modulating the release of active principles. The covalent addition of these excipients to the matrix integrates their solubilizing effect that can contribute to increase the capacity of retention of hydrophobic substances. In this study, three diverse polysaccharides, chitosan, xanthan gum, and locust bean gum, were crosslinked with or without beta-cyclodextrin, using citric acid in different ratios, to create hydrogel matrices. Through a green synthetic path, the efficient production of soluble and insoluble (hydrogel) networks functionalized with beta-cyclodextrin was achieved by means of a solventless procedure. The characterization of their chemical composition, swelling in water, and their sorption and release behavior were also carried out in this work.
  • Autores: Vandera, K. K. A. ; Picconi, P. ; Valero, M.; et al.
    ISSN 1543-8384 Vol.17 N° 7 2020 págs. 2354 - 2369
    Gram-negative bacteria possess numerous defenses against antibiotics, due to the intrinsic permeability barrier of their outer membrane (OM), explaining the recalcitrance of some common and life-threatening infections. We report the formulation of a new drug, PPA148, which shows promising activity against all Gram-negative bacteria included in the ESKAPEE pathogens. PPA148 was solubilized by inclusion complexation with cyclodextrin followed by encapsulation in liposomes. The complex and liposomal formulation presented increased activity against E. coli compared to the pure drug when assessed with the Kirby Bauer assay. The novel formulation containing 1 mu g PPA148 reached similar efficacy levels equivalent to those of 30 mu g of pure rifampicin. A range of biophysical techniques was used to explore the mechanism of drug uptake. Langmuir trough (LT) and neutron reflectivity (NR) techniques were employed to monitor the interactions between the drug and the formulation with model membranes. We found evidence for liposome fusion with the model Gram-negative outer membrane and for cyclodextrins acting as inner membrane (IM) permeation enhancers without presenting intrinsic antimicrobial activity. An antibiotic-in-cyclodextrin-in-liposomes (ACL) formulation was developed, which targets both the bacterial OM and IM, and offers promise as a means to breach the Gram-negative cell envelope.
  • Autores: Figueroa Pizano, MD; Vélaz Rivas, Itziar (Autor de correspondencia); Martínez Barbosa, ME (Autor de correspondencia)
    ISSN 1940-087X Vol.155 N° e59636 2020
  • Autores: Durán Benito, Adrián (Autor de correspondencia); Perez-Rodriguez, J. L.
    ISSN 0924-2031 Vol.111 2020 págs. 103153
    The mainly use of infrared spectroscopy and colorimetry allowed the characterization of the pigments and compounds of the wall paintings from the Monastery of San Isidoro del Campo in Seville, dated on the 15th century. Calcite, quartz and albite were detected in the ground mortar layers. As pigments, red ochre, yellow ochre, paratacamite, atacamite, azurite and carbon black were used, and also lime as the binder, therefore the fresco technique was employed. Both FTIR-ATR and FTIR (in transmission) experiments were performed. Comparison between materials used in some of the wall paintings from Seville in this period was performed. The article revealed important information about wall paintings within a historical context related to the 15th century Catholic Reformation.
  • Autores: Gonzalez-Benito, J.; Olmos, D.; Teno, J.; et al.
    ISSN 0021-8995 Vol.136 N° 10 2019 págs. 47115
    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.
  • Autores: Franquelo, M.L. (Autor de correspondencia); Durán Benito, Adrián; Perez-Rodriguez, J.L.
    ISSN 1386-1425 Vol.218 2019 págs. 331 - 341
    This work comprises an exhaustive study of Spanish decorative leathers dating from the 12th to 14th centuries. These paintings are considered a key example of a crucible of artistic styles: Gothic, Islamic and Florentine Trecento. The goal of this work was to use the scientific information provided by a number of experimental techniques - namely EDX, micro-FTIR, micro-Raman and micro-XRD - to assess the dating of the wooden vault, leather preparation and filling fibres. Another goal was to assess the artistic technique based on the characterization of pigments and the differentiation between original materials and those added throughout its history. Gypsum was the original preparation layer extended over the leather. A new preparation stratum was added in further interventions with the artwork. The original pictorial materials and those used during refurbishments have been identified. Original pigments were: red lead, Mars red, red lake, cinnabar, lapis lazuli, red ochres, raw sienna, white lead and charcoal black. Gilding was also found. Pigments added during restoration were: barite, emerald green, rutile, anatase, Mars red, cadmium red, lithopone, cadmium yellow, charcoal black and orpiment.
  • Autores: Zornoza Cebeiro, Arantza; Moreno, L. ; Puig Rigall, Joan; et al.
    ISSN 0167-7322 Vol.282 2019 págs. 205 - 212
    The solubilisation of methylparaben (MP), an antimicrobial agent used as a food preservative and in cosmetics and personal-care products, in two poloxamines of different Hydrophilic-Lipophilic Balance (HLB), namely Tetronic 904 (T904) and 1107 (T1107), has been studied. The influence of the preservative on the aggregation behaviour of both Tetronics has been analysed by dynamic light scattering (DLS) and small-angle neutron scattering (SANS), while the precise location of the molecule in the aggregates as well as the effects of the micellar solubilisation on the reactivity of the preservative have been elucidated by NMR and UV spectroscopies. The presence of MP reduces the critical micelle temperature (CMT) of any of the poloxamines and induces the formation of larger micelles at room temperature compared to the plain poloxamines; in addition, a remarkable temperature dependent effect on the structure of the micelles has been detected, which progressively evolve from core-shell spheres to rods as the temperature increases. The incorporation of the preservative into the micelles modifies its reactivity against alkaline hydrolysis, resulting in a decrease of its reaction rate constant in which the dominant factor for the reduction in the hydrolysis rate is the incorporation into the micelle core, with a little effect of the length of the hydrophilic polyethylene oxide (PEO) blocks.
  • Autores: Peñas Esteban, Francisco Javier (Autor de correspondencia); Sevillano Vaca, Xabier; Peñas, M. I.
    ISSN 1369-703X Vol.151 2019 págs. 107308
    This work explores the behavior of a fluidized-bed bioreactor, packed with a hydrogel carrier of cyclodextrin-based polymer, under transient shock-loading events to evaluate its robustness and stability. Fourteen input rectangular pulses with different steps (6-24 times the baseline concentration) and duration (0.5-8 times the hydraulic residence time) were applied and the dynamic responses measured. A new shock-loading index is defined to quantify the combined effect of the influent concentration increase and the perturbation duration. The shock-loading index is directly proportional to the extra amount of phenol removed, to the additional oxygen consumed in the shock pulse, and to the time to return to baseline conditions. A simple model was developed to predict the effluent phenol concentration under pulsed shock-loading events. It assumes that a continuous-flow complete-mix system without diffusional mass transfer resistance in the biofilm. In addition, substrate adsorption is modeled using a simple concept based on the constant-pattern theory, while substrate biodegradation is described by the Haldane model. In spite of its conceptual simplicity, the model provides a pragmatic approach predicting a good match for data obtained during overload events (R-2 = 0.9810). The best-fitting parameters obtained were mu(M) = 0.166 +/- 0.007 d(-1), K-S = 8.62 +/- 0.46 mg/L, and K-I = 95.3 +/- 3.8 mg/L.
  • Autores: Fujiyoshi Tamae, Takeo; Carrez, O.; Imizcoz, M.; et al.
    ISSN 0144-8617 Vol.219 2019 págs. 105 - 112
    Interpenetrating polymer network (IPN) hydrogels were synthesised using beta-cyclodextrin (beta-CD) and N-vynil-2-pyrrolidone (NVP) crosslinked with epichlorohydrin and divinylbenzene, respectively, and prepared by four different procedures: simultaneous, sequential, hybrid and a novel one named hybrid-sequential. The IPNs prepared have been characterised by infrared spectroscopy and thermal analysis. The equilibrium swelling in water and the sorption of model substances into the IPNs have also been studied. The model sorbates (1-naphthol, 2-acetylnaphthalene and tannic acid) were selected according to the affinities towards each one of the two constituent polymers. Our studies reveal that these IPNs can be applied for the sorption of substances that can interact with the network by two mechanisms, i.e. inclusion within cyclodextrin cavities and/or via specific interactions with the functional groups present. Besides, due to the complementary character of their constituent polymers, these networks could also serve to retain two substances of different nature such as cetirizine and pseudoephedrine.
  • Autores: Puig Rigall, Joan; Serra Gómez, Rafael; Stead, I.; et al.
    ISSN 0024-9297 Vol.52 N° 4 2019 págs. 1458 - 1468
    Pseudo-polyrotaxanes (PPRs) are supramolecular host-guest complexes constituted by the reversible threading of a macrocycle along a polymer chain. The resuting dynamic "molecular necklaces" offer potential applications in nanotechnology, drug delivery, and biomaterials. We report the formation of PPRs by threading of cyclodextrins (CDs), cyclic oligosaccharides, onto X-shaped PEO-PPO block copolymers with two opposite presentation of their hydrophobic and hydrophilic blocks: Tetronic 904 (T904) and its reverse counterpart Tetronic 90R4 (T90R4). We assess the effects that relative block position on the polymeric surfactants and cavity size of CD have on the composition, morphology, thermodynamics, and kinetics of PPRs by using a combination of X-ray diffraction, scanning electron microscopy, NMR, UV-vis spectroscopy, and time-resolved small-angle neutron scattering (TR-SANS). Solid PPRs with lamellar microstructure and crystalline channel-like structures are obtained with native CDs and both Tetronics above a threshold concentration of the macrocycle, which varies with the type of CD and surfactant. While gamma-CD can form PPRs with both Tetronics, alpha-CD only forms a PPR with T90R4 at high concentrations. The results can be explained in terms of the preferential complexation of alpha-CD with EO and gamma-CD with PO monomers, which also has a direct impact on the kinetics of PPR formation.
  • Autores: Durán Benito, Adrián (Autor de correspondencia); Perez-Maqueda, R. ; Perez-Rodriguez, J. L.
    ISSN 1296-2074 Vol.36 2019 págs. 135 - 142
    The degradation processes that occurred on metal threads applied in the embroidery used for clothing and in the ornamentation of sculptures, the Sevillian Holy Week processions, and Portuguese and Spanish palace and museum are thoroughly analyzed. Some threads from the 14th and 18-19th centuries were considered. In the metal threads, sulphur- and chlorine-based compounds were detected either individually or together, depending on the degradation process. Basic silver carbonate, sodium bicarbonate and copper-based compounds were also observed. The different degradation processes were attributed to different factors, such as environmental contamination, degradation of the fibrous cores, and inadequate cleaning and/or mechanical treatments. (C) 2018 Elsevier Masson SAS. All rights reserved.
  • Autores: De Diego Díaz, Beatriz; Durán Benito, Adrián; Alvarez-Garcia, M. R.; et al.
    Revista: FUEL
    ISSN 0016-2361 Vol.245 2019 págs. 240 - 246
    In this paper, the use of techniques such as TGA, FTIR-ATR and XRD has provided valuable information about the lignocellulosic wastes in anaerobic digestion (AD) processes. A deep study of their break-down in solid state could improve the management of these recalcitrant substrates. Representative wastes (artichoke -ART-, asparagus -ASP-, the co-digestion of both -AcoD-and pure cellulose -CELL-) were assessed in batch. The main obtained results were related to biochemical parameters. As the biomethanization progressed, hemicellulose, cellulose and lignin were weakened as shown by TGA, and cellulose crystallinity decreased as demonstrated by XRD. Additionally, results from FTIR-ATR allowed hypothesizing that the formation of acetate in solid state did not always lead to its solubilisation, thus hindering biogas formation. AcoD and CELL were the most successful in releasing the newly formed acetate from the solid fraction to the aqueous medium, increasing its bioavailability, which was supported by the higher biogas production.
  • Autores: Peñas Esteban, Francisco Javier (Autor de correspondencia); Romo Hualde, Ana; Isasi Allica, José Ramón; et al.
    ISSN 1226-086X Vol.75 2019 págs. 93 - 99
    This paper examines the long-term application of a cyclodextrin hydrogel sorbent in multiple sorption-desorption cycles. Aqueous phenol was the target pollutant, whilst methanol, ethanol and isopropanol were chosen as eluents. The experimental results were well described by empirical models: the breakthrough curves by a two-parameter dose-response equation, and the elution curves by a pulse peak equation with two independent parameters. The differences in polarity of solvents produced sorbent fragmentation, particularly marked for isopropanol and considerably lower for methanol, and therefore a progressive increase in mass-transfer coefficients. In addition, a dual approach was developed from the proposed breakthrough model to address the mass transport of sorbate within the packed beds. The first one defines an average mass-transfer coefficient as representative for each complete sorption cycle, whereas a time-profile of this coefficient is deduced in the second method. A sorption capacity of 29.6 mg-phenol/g-sorbent was found in the working conditions.
  • Autores: Benigno, E.; Lorente, M. A.; Olmos, D.; et al.
    ISSN 0959-8103 Vol.68 N° 6 2019 págs. 1155 - 1163
    Low density polyethylene ( LDPE) based nanocomposites containing multi-walled carbon nanotubes ( MWCNTs) were prepared by a two-stepprocess consisting of apre-mixture using high energy ball milling ( HEBM) and subsequent hotpressing. The effects of ball milling and the presence of the MWCNTs on some physical properties of the materials and the antimicrobial efficiency against DH5.. 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 LDPEthermal behavior as a function of the type ofmaterial 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 theMWCNTs in the surface of the material as themain factor decreasing the polar contribution to the surface free energy. A correlation between hydrophobicity, biofilm development and the shape and size of DH5.. E. coli was observed, indicating that the presence of MWCNTs leads to a biocide effect by decreasing cell adhesion and changing itsmetabolism.
  • Autores: Carbajo-Gordillo, A. I.; Rodriguez-Lavado, J.; Jiménez-Blanco, J. L.; et al.
    ISSN 1359-7345 Vol.55 2019 págs. 8227 - 8230
    An original family of multivalent vectors encompassing gemini and facial amphiphilicity, namely cationic Siamese twin surfactants, has been prepared fromthe disaccharide trehalose; molecular engineering lets us modulate the self-assembling properties and the topology of the nanocomplexes with plasmid DNA for efficient gene delivery in vitro and in vivo.
  • Autores: Gonzalez-Benito, J. (Autor de correspondencia); Olmos, D.; Martinez-Tarifa, J. M.; et al.
    ISSN 0021-8995 Vol.136 N° 29 2019 págs. 47788
    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.
  • Autores: De Diego Díaz, Beatriz; Fernández Rodríguez, Juana (Autor de correspondencia); Vitas Pemán, Ana Isabel; et al.
    ISSN 1385-8947 Vol.334 2018 págs. 650 - 656
    Barley malt and sloe are two raw materials used in the production of beer and pacharan (a Spanish spirit drink), respectively. These organic wastes have been used as substrate of anaerobic digestion to assess the effect of temperature (35 degrees C and 55 degrees C) and thermal pretreatment (80 degrees C for 1.5 h). Viable microbiological isolates have also been identified through metabolic tests and a kinetic model which includes biogas generation and volatile solids (VS) removal has been proposed. Temperature studies on barley malt yielded higher productivities at 55 degrees C (the ratio of produced biogas volume per VS consumed was 119% higher than that at 35 degrees C), but similar VS removal (0.9% less elimination at 55 degrees C). On the other hand, sloe digestion was more effective at 35 degrees C (biogas/VS-consumed ratio 252% higher than that at 55 degrees C), while VS elimination can be considered the same. Attending to the effect of thermal pretreatment on productivity, barley malt showed no improvement while sloe was enhanced (144% at 35 degrees C and 160% at 55 degrees C). Kinetic modelling fits to the experimental results, showing differences in maximum specific growth rate of biomass according with the temperature conditions. In all cases the adjustment was good (R-2 > 0.96). Microbiological characterization identified bacterial population, both strict and facultative anaerobes.
  • Autores: Figueroa-Pizano, M. D.; Vélaz Rivas, Itziar (Autor de correspondencia); Peñas Esteban, Francisco Javier; et al.
    ISSN 0144-8617 Vol.195 2018 págs. 476 - 485
    The freezing-thawing is an advantageous method to produce hydrogels without crosslinking agents. In this study chitosan-poly(vinyl alcohol) (CS-PVA) hydrogels were prepared by varying the freezing conditions and composition, which affect the final characteristics of the products. The swelling degree, morphology, porosity, and diflunisal drug loading, as well as the drug release profiles were evaluated. The hydrogel swelling ratio was found to be mainly affected by the CS content, the number of freezing cycles and the temperature. SEM micrographs and porosity data confirm that pore size increases with the chitosan content. However, the use of either lower temperatures or longer freezing times, results in higher porosity and smaller pores. The drug release times of the CS-PVA hydrogels were as long as 30 h, and according to the mathematical fitting, a simple diffusion mechanism dominates the process. Moreover, a mathematical model predicting the hydrogels physical and structural behavior is proposed.
  • Autores: Olmos, D. ; Pontes-Quero, G. M. ; Corral, A. ; et al.
    ISSN 2079-4991 Vol.8 N° 2 2018 págs. 60
    In this work, the antimicrobial effect of silver nanoparticles in polyethylene based nanocomposites has been investigated using a non-conventional processing method to produce homogeneous materials. High energy ball milling under cryogenic conditions was used to achieve a powder of well-blended low-density polyethylene and commercial silver nanoparticles. The final composites in the form of films were obtained by hot pressing. The effect of various silver nanoparticles content (0, 0.5, 1 and 2 wt %) on the properties of low-density polyethylene and the antimicrobial effectiveness of the composite against DH5 ff Escherichia coli were studied. The presence of silver nanoparticles did not seem to affect the surface energy and thermal properties of the materials. Apart from the inhibition of bacterial growth, slight changes in the aspect ratio of the bacteria with the content of particles were observed, suggesting a direct relationship between the presence of silver nanoparticles and the proliferation of DH5 alpha ff E. coli (Escherichia coli) cells. Results indicate that these materials may be used to commercially produce antimicrobial polymers with potential applications in the food and health industries.
  • Autores: Iorio, M.; Santarelli, M. L.; González Gaitano, Gustavo; et al.
    ISSN 0169-4332 Vol.427 2018 págs. 1248 - 1256
    Basalt fibers were surface treated with silane coupling agents as a method to enhance the adhesion and durability of fiber-matrix interfaces in concrete based composite materials. In particular, this work has been focused on the study of basalt fibers chemical coatings with aminosilanes and their subsequent characterization. Surface treatments were carried out after removing the original sizing applied by manufacturer and pretreating them with an activation process of surface silanol regeneration. Different samples were considered to make convenient comparisons: as received fibers (commercial), calcinated fibers (without commercial sizing), activated samples (calcinated fibers subjected to an acid process for hydroxyl regeneration), and silanized fibers with ¿-aminopropiltriethoxysilane, ¿-aminopropilmethyldiethoxysilane and a mixture of 50% by weight of both silanes. A deep characterization was carried out in terms of structure using X-ray diffraction, XRD, and Fourier transform infrared spectroscopy, FTIR, thermal properties by thermogravimetric analysis, TGA, coupled with single differential thermal analysis, SDTA, and morphology by scanning electron microscopy, SEM, and atomic force microscopy, AFM.
  • Autores: Monreal-Perez, P.; Isasi Allica, José Ramón (Autor de correspondencia); Gonzalez-Benito, J.; et al.
    ISSN 2079-4991 Vol.8 N° 9 2018 págs. 642
    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 beta CD-modified nanoparticles (beta CDTiO2 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 beta CDTiO2 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.
  • Autores: Gonzalez, E. A. S.; Olmos, D. (Autor de correspondencia); Lorente, M. A. ; et al.
    Revista: POLYMERS
    ISSN 2073-4360 Vol.10 N° 12 2018 págs. 1365
    Polymer composite materials based on polylactic acid (PLA) filled with titanium dioxide (TiO2) nanoparticles were prepared. The aim of this work was to investigate the antibacterial action of TiO2 against a strain of E. coli (DH5) to obtain information on their potential uses in food and agro-alimentary industry. PLA/TiO2 systems were prepared by a two-step process: Solvent casting followed by a hot-pressing step. Characterization was done as a function of particle size (21 nm and <100 nm) and particle content (0%, 1%, 5%, 10%, and 20%, wt %). Structural characterization carried out by X-ray diffraction (XRD) and Fourier Transformed Infrared spectroscopy (FTIR) did not reveal significant changes in polymer structure due to the presence of TiO2 nanoparticles. Thermal characterization indicated that thermal transitions, measured by differential scanning calorimetry (DSC), did not vary, irrespective of size or content, whereas thermogravimetric analysis (TGA) revealed a slight increase in the temperature of degradation with particle content. Bacterial growth and biofilm formation on the surface of the composites against DH5 Escherichia coli was studied. Results suggested that the presence of TiO2 nanoparticles decreases the amount of extracellular polymeric substance (EPS) and limits bacterial growth.
  • Autores: Perez-Rodriguez, J. L. (Autor de correspondencia); Perez-Maqueda, R.; Franquelo, M. L.; et al.
    ISSN 1388-6150 Vol.134 N° 1 2018 págs. 15 - 22
    In this work, it is reported that thermal analysis techniques such as differential thermal analysis and thermogravimetric analysis are very useful for evaluating metals threads and fibres used in the manufacture of historical artifacts. Thermal analysis has been used to characterize the silk, cotton and linen employed as supports and the copper, silver and aluminium as the metallic components in the studied threads. Other organic compounds, mainly added for the conservation of the threads, have also been characterized.
  • Autores: Puig Rigall, Joan; Obregon-Gomez, I.; Monreal-Perez, P. ; et al.
    ISSN 0021-9797 Vol.524 2018 págs. 42 - 51
    Tetronics are X-shaped block-copolymers of polyethylene oxide and polypropylene oxide, which self-assemble into micelles and can undergo a sol-gel transition; these transitions are dependent on temperature, concentration but also pH, due to the central diamine group of the tetrablock. We report the nanoscale morphologies underlying these different phases and the rheology of the systems for a very large, highly hydrophilic block copolymer, Tetronic 908, through the combined use of oscillatory rheology, steadyblock-state and time-resolved fluorescence, small-angle neutron scattering (SANS), dynamic light scattering (DLS) and Fourier transform infrared attenuated total reflectance (FTIR-ATR). At low concentrations, SANS reveal core-shell micelles of ca. 10 nm radius, presenting a dehydrated core and a highly hydrated shell, with relatively small aggregation numbers (N-agg approximate to 13). The micelles are notably affected by the pH, due to the protonation of the central amine spacer at low pH (pH approximate to 2), which shifts micellization to higher temperature, with smaller micelles than at natural pH. In the intermediate concentration regime (10-15%), micelles become smaller (N-agg approximate to 5), and present a higher hydration of the core. In the high concentration regime, Tetronic 908 undergoes a sol-gel transition above a threshold temperature, which is fully inhibited at acidic pH. SANS data from the gel phase reveal a BCC order of tightly packed spheres. Temperature sweeps in oscillatory rheology show a shift of the onset of gelation towards lower temperatures as concentration increases, an increase in the elastic modulus G' and an expansion of gel region over a larger range of temperatures. SANS and rheology reveal that at pH below the natural pH (ca. 8), gelation is shifted to higher temperatures, but the morphology of the gels is similar, while under highly acidic conditions the gelation is fully suppresed. (C) 2018 Elsevier Inc. All rights reserved.
  • Autores: Uriz, A.; Sanmartín Grijalba, Carmen; Plano Amatriain, Daniel; et al.
    ISSN 0927-7765 Vol.170 2018 págs. 463 - 469
    Selenium (Se) incorporated into organic frameworks has demonstrated anticancer activity against several cancer types. One of the drawbacks of most of these constructs is their poor solubility and bioavailability, which can be overcome with the use of suitable nanocarriers. We have synthesized a series of 5-substituted amide selenodiazoles, based on the parent structure of ebselen, an organoselenium drug with proven cytoprotective activity, and solubilized them in polymeric micelles of poloxamines, poly(ethylene oxide)-poly(propylene oxide) X-shaped tetrablock-copolymers. Scattering methods (SANS and DLS) were employed to characterize the micellar nanocarriers. MTT biological evaluation highlights the selectivity of the Se-compounds towards cancer cells, with MCF-7 standing as the most responsive line. The alkylation of the heterocycle with a 12-carbon hydrophobic tail displays the highest activity, showing a 100-fold increase with respect to ebselen. This compound also exhibits the greatest increase in solubility in poloxamine micelles, overall resulting in a one-fold increase in activity with respect to the non-formulated form, making it a hit compound for further optimization.
  • Autores: Gallego-Yerga, L.; Benito, J. M.; Blanco Fernández, Laura; et al.
    ISSN 0947-6539 Vol.24 N° 15 2018 págs. 3825 - 3835
    Engineering self-assembled superstructures through complexation of plasmid DNA (pDNA) and single-isomer nanometric size macromolecules (molecular nanoparticles) is a promising strategy for gene delivery. Notably, the functionality and overall architecture of the vector can be precisely molded at the atomic level by chemical tailoring, thereby enabling unprecedented opportunities for structure/self-assembling/pDNA delivery relationship studies. Beyond this notion, by judiciously preorganizing the functional elements in cyclodextrin (CD)-based molecular nanoparticles through covalent dimerization, here we demonstrate that the morphology of the resulting nanocomplexes (CDplexes) can be tuned, from spherical to ellipsoidal, rod-type, or worm-like nanoparticles, which makes it possible to gain understanding of their shape-dependent transfection properties. The experimental findings are in agreement with a shift from chelate to cross-linking interactions on going from primary-face- to secondary-face-linked CD dimers, the pDNA partner acting as an active payload and as a template. Most interestingly, the transfection efficiency in different cells was shown to be differently impacted by modifications of the CDplex morphology, which has led to the identification of an optimal prototype for tissue-selective DNA delivery to the spleen in vivo.
  • Autores: Rochin-Wong, S.; Rosas-Durazo, A. ; Zavala-Rivera, P. ; et al.
    Revista: POLYMERS
    ISSN 2073-4360 Vol.10 N° 7 2018 págs. 760
    Engineering of multifunctional drug nanocarriers combining stability and good release properties remains a great challenge. In this work, natural polymers kappa-carrageenan (kappa-CAR) and chitosan (CS) were deposited onto olive oil nanoemulsion droplets (NE) via layer-by-layer (LbL) self-assembly to study the release mechanisms of the anti-inflammatory diflunisal (DF) as a lipophilic drug model. The nano-systems were characterized by dynamic light scattering (DLS), zeta potential (zeta-potential) measurements, transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (XEDS) and Fourier transform infrared spectroscopy (FTIR) to confirm the NE-coating with polymer layers. In addition, kinetic release studies of DF were developed by the dialysis diffusion bag technique. Mathematical models were applied to investigate the release mechanisms. The results showed that stable and suitably sized nanocapsules (similar to 300 nm) were formed. Also, the consecutive adsorption of polyelectrolytes by charge reversal was evidenced. More interestingly, the drug release mechanism varied depending on the number of layers deposited. The nanosized systems containing up to two layers showed anomalous transport and first order kinetics. Formulations with three and four layers exhibited Case II transport releasing diflunisal with zero order kinetics.
  • Autores: Treu, L. ; Kougias, P. G. (Autor de correspondencia); De Diego Díaz, Beatriz; et al.
    ISSN 0960-8524 Vol.264 2018 págs. 140 - 147
    Microbial dynamics in an upgrading biogas reactor system undergoing a more than two years-period at stable operating conditions were explored. The carbon dioxide generated during biomass degradation in the first reactor of the system was converted to methane into the secondary reactor by addition of external hydrogen. Considering the overall efficiency, the long-term operation period resulted in an improved biogas upgrading performance (99% methane content). However, a remarkable accumulation of acetate was revealed, indicating the enhancement of homoacetogenic activity. For this reason, a shift in the anaerobic digestion microbiome was expected and evaluated by 16S rRNA amplicon analysis. Results demonstrated that the most abundant archaeal species identified in the first time point, Candidatus Methanoculleus thermohydrogenotrophicum, was replaced by Methanothermobacter thermautotrophicus, becoming dominant after the community adaptation. The most interesting taxonomic units were clustered by relative abundance and six main long-term adaptation trends were found, characterizing functionally related microbes (e.g. homoacetogens).
  • Autores: Perez-Rodriguez, J. L.; Robador, M. D.; Albardonedo, A. ; et al.
    ISSN 1296-2074 Vol.31 2018 págs. 112 - 121
    The majority of the studied artworks were altarpieces, sculptures and/or wood-based works from different periods. Non-traditional gilding techniques have been first described in this paper, such as those that employ materials as oil in the gilding on bole, glue and bole with lead white in mordant gilding, vermilion in the preparation layers; and brass gilding or those with aluminium, lead chromate, mica or corla trying to imitate the golden hue in restoration or repaint processes. For the determination of the composition of the different gilded layers, spectroscopic techniques, such as FTIR and micro-Raman, and SEM-EDX elemental chemical analyses were successfully used. (C) 2017 Elsevier Masson SAS. All rights reserved.
  • Autores: De Diego Díaz, Beatriz; Cerdan, J. M. A.; Peñas Esteban, Francisco Javier; et al.
    ISSN 0960-3085 Vol.110 2018 págs. 120 - 125
    Different wastes treated together can be the supplement of nutritional deficiencies for the microorganisms involved in anaerobic codigestion (AcoD). In this study, the presence of macromolecules and trace elements on AcoD of agricultural waste was assessed. An extra nutrients solution that plays a key role in the microbiological metabolism was used at three different conditions: mesophilic (35 degrees C), intermediate (42 degrees C) and thermophilic (55 degrees C). The main results showed that at 35 degrees C in the presence of nutrients, biogas production reached 1.5-fold the production of biogas without them. Additionally, productivity was 1.9 times higher than that for the process without nutrients. Also, 42 degrees C without nutrients posed an interesting approach due to the uncommon use of this intermediate temperature, which has been demonstrated to be worth considering (55% of VS removal and 7.4 L-biogas). The AcoD at 55 degrees C showed that biogas production also surpassed 10.2 L with nutrients and that mL-CH4/g-VS were 1.2-fold of that obtained for the process without extra solution. Results for each temperature indicate that the nutrients solution contributes to AcoD. Furthermore, 35 degrees C, the most widespread temperature range at industrial scale, was the temperature at which the impact of nutrients was more remarkable. A deeper knowledge of AD nutritional limitations according to temperatures can optimize the industrial process in order to get better biogas yields and biomass removal. (C) 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
  • Autores: Perez-Rodriguez, J. L.; Albardonedo, A. ; Robador, M. D.; et al.
    ISSN 1431-9276 Vol.24 N° 5 2018 págs. 574 - 590
    Gilding threads collected from Spanish and Portuguese palaces and from the embroideries and adornments of sculptures of the Virgin and Christ that form part of Sevillian Holy Week were analyzed and compared (20 artifacts were evaluated). The study covered a broad time period with examples from the 13th to 14th centuries, 18th to 20th centuries, and also including modern embroideries. A combination of scanning electron microscopy and energy-dispersive X-ray spectroscopy was used. The knowledge of the layered structures of the threads has provided very valuable information regarding the manufacturing techniques. The different metal threads found in the embroidery studied consisted of gold, silver, copper, and alloys of these metals and aluminium. The fabrication procedures often differed in the different workshops and changed with time. In the modern embroideries, a decrease of precious metal concentration was detected. The threads were wound around a core of silk threads.
  • Autores: Iorio, M.; Teno, J.; Nicolás, M.; et al.
    ISSN 0303-402X Vol.296 N° 3 2018 págs. 461-469
    Poly(methyl methacrylate) (PMMA) films filled with titanium oxide (TiO2) nanoparticles were prepared by solution blow spinning (SBS). The influence of the presence of nanoparticles (up to 10% by weight) in the physicochemical properties of the material was studied, focusing on the morphology, structure, and thermal properties, by scanning electron microscopy (SEM), Fourier-transformed infrared spectroscopy (FTIR), thermogravimetry (TGA), and differential scanning calorimetry (DSC). It was demonstrated that SBS allows obtaining PMMA/TiO2 nanocomposites with a relatively high amount of nanoparticles uniformly dispersed within the polymeric matrix, varying the surface characteristics of the films according to the amount of TiO2. The results indicate that the flow of the macromolecules is somewhat forced by the SBS process, and that specific interactions between the ester group of the MMA and the surface of the nanoparticles induce a preferential conformation of the functional group with respect to the PMMA backbone, at least at low loads of nanopartciles, conditions in which the self-aggregation of the nanofiller takes place in a lesser extent.
  • Autores: Serres-Gomez, M.; González Gaitano, Gustavo; Kaldybekov, D. B. ; et al.
    Revista: LANGMUIR
    ISSN 0743-7463 Vol.34 N° 36 2018 págs. 10591 - 10602
    Polypseudorotaxanes are polymer chains threaded by molecular rings that are free to unthread; these "pearl-necklace" can self-assemble further, leading to higher-order supramolecular structures with interesting functionalities. In this work, the complexation between alpha-cyclodextrin (alpha-CD), a cyclic oligosaccharide of glucopyranose units, and poly(ethylene glycol) (PEG) grafted to silica nanoparticles was studied. The threading of alpha-CD onto the polymeric chains leads to their aggregation into bundles, followed by either the precipitation of the inclusion complex or the formation of a gel phase, in which silica nanoparticles are incorporated. The kinetics of threading, followed by turbidimetry, revealed a dependence of the rate of complexation on the following parameters: the concentration of alpha-CD, temperature, PEG length (750, 4000, and 5000 g mol(-1)), whether the polymer is grafted or free in solution, and the density of grafting. Complexation is slower, and temperature has a higher impact on PEG grafted on silica nanoparticles compared to PEG free in solution. Thermodynamic parameters extracted from the transition-state theory showed that inclusion complex formation is favored with grafted PEG compared to free PEG and establishes a ratio of complexation of five to six ethylene oxide units per cyclodextrin. The complexation yields, determined by gravimetry, revealed that much higher yields are obtained with longer chains and higher grafting density.
  • Autores: Rochín-Wong, S.; Vélaz Rivas, Itziar
    Libro: Drug carriers
    ISSN 978-1-80355-832-5 2022 págs. 1 - 33
    In recent years, innovative drug nanocarriers have been developed to enhance stability, bioavailability, and provide sustained release. In this chapter, systems based on natural macromolecules, lipids, or polymeric/polyelectrolyte nanocapsules and their principal chemical and functional characteristics are described. Nano-vesicular systems are especially relevant in different fields. Particularly, a promising potential is offered by systems based on colloidal nanocapsules, that exhibit a typical core-shell structure in which the drug can be confined into the cavity or in the polymeric coating that surrounds it. Both the cavity and the active substance can be lipophilic or hydrophilic and in solid or liquid form depending on the materials and methods used, making these nanocapsules attractive carriers for drug delivery. In addition, a compilation of different methods and materials employed in the preparation of these nanosystems and a recent review of applications of lipid and polymeric nanocapsules have been made, focussing on the encapsulation of drugs.
  • Autores: Fernández Rodríguez, Juana; De Diego Díaz, Beatriz; Tapia-Martin, M. E.
    Libro: Clean energy and resources recovery: biomass waste based biorefineries
    ISSN 978-0323852234 Vol.1 2021 págs. 155 - 202
    Agricultural lignocellulosic waste can generate serious environmental problems if not properly managed. Biodegradation, through anaerobic digestion (AD), is a cost-effective strategy for biogas production. However, studies on the biodegradation of lignocellulose show that the substrate is recalcitrant to microbiological hydrolysis, which reduces the efficiency of converting organic matter into biogas. The main reasons are its complex structure and slow biodegradation. The appropriate performance of biomethanization suggests a deep knowledge of substrate composition. Typically, the composition is about 10% to 25% lignin, 20% to 30% hemicellulose, and 40% to 50% cellulose. This book chapter will summarize the AD process and rate-limiting steps, compositional properties (focusing especially on pretreatment strategies applied to lignocellulosic biomass to improve methane yield), and overall AD performance. The most common pretreatments applied to organic substrates will be studied: physical, chemical, biological, and a combination of them. Additionally, the new trends in pretreatments will be exposed.
  • Autores: Petitjean, Max Renaud; García-Zubiri, I; Isasi Allica, José Ramón
    Libro: The History of Cyclodextrins. Environmental Chemistry for a Sustainable World
    ISSN 978-3-030-49307-3 Vol.52 2020 págs. 281-304
  • Autores: Durán Benito, Adrián; Jimenez de Haro, M.C
    Libro: La colección de documentos árabes del Archivo Histórico Provincial de Granada. Estudio, edición y facsímil digital
    ISSN 978-84-9959-352-4 2020 págs. 14-31

Proyectos desde 2018

  • Título: Incorporación de fármacos en fibras poliméricas para liberación dérmica: aplicación al tratamiento de leishmaniasis cutánea e infecciones de la piel
    Código de expediente: PID2020-112713RB-C21
    Convocatoria: 2020 AEI PROYECTOS I+D+i (incluye Generación del conocimiento y Retos investigación)
    Fecha de inicio: 01-01-2021
    Fecha fin: 31-12-2023
    Importe concedido: 84.700,00 €
    Fondos FEDER: NO
  • Título: La maleta periodica
    Código de expediente: FCT-18-13809
    Investigador principal: CRISTINA SOLA LARRAÑAGA.
    Convocatoria: 2019 FECYT Fomento de la cultura científica
    Fecha de inicio: 01-04-2019
    Fecha fin: 31-12-2020
    Importe concedido: 11.000,00 €
    Fondos FEDER: NO
  • Título: Optimización del desarrollo y gestión de envases con materiales nanoparticulados sostenibles para uso alimentario
    Código de expediente: 0011-1383-2019-000005 PI017
    Investigador principal: MARIA ICIAR VELAZ RIVAS.
    Financiador: GOBIERNO DE NAVARRA
    Convocatoria: 2019 GN Centros
    Fecha de inicio: 01-12-2018
    Fecha fin: 30-11-2019
    Importe concedido: 61.120,00 €
    Fondos FEDER: NO
  • Título: Funcionalización de envases con nuevos materiales nanoparticulados para uso alimentario
    Código de expediente: 0011-1383-2018-000005 PI039 ENMATNAN
    Investigador principal: MARIA ICIAR VELAZ RIVAS.
    Financiador: GOBIERNO DE NAVARRA
    Convocatoria: 2018 GN Centros
    Fecha de inicio: 01-02-2018
    Fecha fin: 30-11-2018
    Importe concedido: 46.223,74 €
    Fondos FEDER: NO
  • Título: Diseño, desarrollo y evaluación de nuevos sistemas dendriméricos y glicodendriméricos de aplicación a terapia génica antitumoral
    Código de expediente: CTQ2015-64425-C2-2-R
    Fecha de inicio: 01-01-2016
    Fecha fin: 31-12-2019
    Importe concedido: 60.500,00 €
    Fondos FEDER: SI
  • Título: Materiales nanocompuestos termoplásticos con propiedades antimicrobianas con potenciales aplicaciones en la industria agroalimentaria
    Código de expediente: MAT2014-59116-C2-2-R
    Investigador principal: GUSTAVO GONZALEZ GAITANO.
    Convocatoria: 2014-MINECO Retos Investigación
    Fecha de inicio: 01-01-2015
    Fecha fin: 31-12-2018
    Importe concedido: 72.600,00 €
    Fondos FEDER: SI
  • Título: Aplicaciones de matrices poliméricas de ciclodextrinas sintetizadas mediante procesos sostenibles
    Convocatoria: 2020 Convocatoria PIUNA, 2019 Convocatoria PIUNA, 2018 Convocatoria PIUNA
    Fecha de inicio: 01-09-2018
    Fecha fin: 31-08-2021
    Importe concedido: 23.530,00 €
  • Título: Diseño y desarrollo preclínico de nuevas moléculas híbridas de selenio como agentes antitumorales
    Convocatoria: 2020 Convocatoria PIUNA, 2019 Convocatoria PIUNA, 2018 Convocatoria PIUNA
    Fecha de inicio: 01-09-2018
    Fecha fin: 31-08-2021
    Importe concedido: 51.500,00 €