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The synthesis of hydroxyapatite (HAp) with different shapes and sizes has attracted increasing attention because the applicability of this ceramic material depends on structure-properties relationships (i.e., the dimensions and morphology of HAp crystals determine properties such as the bioactivity and mechanical strength). Although different synthetic routes based on the addition of surfactants, organic modifiers, or dispersants have been proposed to control the growth of HAp crystals, many efforts are being devoted to simplify the whole process using simple parameters such as pH. However, the control of the morphology is still poor and shows low reproducibility. In this work, a new additive-free synthetic route, which is based on the hydrothermal method and the utilization of nonaqueous solvents, is proposed. The influence of the synthesis parameters such as pH, concentration of starting solutions, and the solvent on relevant features such as phase purity, crystallinity, crystallite size, and morphology has been examined using spectroscopic techniques, X-ray diffraction, and scanning electron microscopy. As a consequence, this work presents an easy and robust method based only on the use of organic solvent and the control of the pH that produces pure and crystalline HAp with a controlled shape and size. This method has been used to elucidate some of the key aspects of the crystal growth mechanism and to synthesize HAp crystals with different and well-defined shapes (e.g., belts, rods, flakes needle-like, or polymorph) and sizes, in a reproducible way.

Cellulose-based supercapacitors display important advantages in comparison with devices fabricated with other materials, regarding environmental friendliness, flexibility, cost and versatility. Recent progress in the field has been mainly focused on the utilization of cellulose fibres as: structural mechanical reinforcement of electrodes; precursors of electrically active carbon-based materials; or primary electrolytes that act as reservoirs of secondary electrolytes. In this work, a flexible, lightweight, robust, portable and manageable all-carboxymethyl cellulose symmetric supercapacitor has been obtained by assembling two electrodes based on carboxymethyl cellulose hydrogels to a solid electrolytic medium formulated with the same material. Hydrogels, which were made by cross-linking carboxymethyl cellulose paste with citric acid in water, rendered not only effective solid electrolytic media by simply loading NaCl but also electroactive electrodes. For the latter, conducting polymer microparticles, which were loaded into the hydrogel network during the physical cross-linking step, were appropriately connected through the in situ anodic polymerization of a similar conducting polymer in aqueous medium, thus creating conduction paths. The performance of the assembled supercapacitors has been proved by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. This design opens a new window for the green and mass production of flexible cellulose-based supercapacitors

Waterborne polyurethane-urea dispersions (WPUD), which are based on 100% bio-based semi-crystalline polyester polyol and isophorone diisocyanate, have been successfully synthesized and doped with single-walled carbon nanotubes (SWCNT) to obtain a finishing agent that provides textiles with multifunctional properties. The chemical structure of WPUD has been characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The thermal properties have been evaluated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). Mechanical properties have been studied by tensile stress–strain analysis. Moreover, the particle size, particle size distribution (PSD), and stability of developed waterborne dispersions have been assessed by dynamic light scattering (DLS), Z-potential, and accelerated aging tests (analytical centrifugation). Subsequently, selected fabrics have been face-coated by the WPUD using knife coating method and their properties have been assessed by measuring water contact angle (WCA), water column, fabric stiffness, and air permeability. The electrical conductivity of textiles coated with SWCNT-doped WPUD has been evaluated by EN 1149 standard. Finally, the surface morphologies of uncoated and coated fabrics have been studied by scanning electron microscopy (SEM). All of the synthesized polyurethane-ureas provide the coated substrates with remarkable water-repellency and water column, being therefore a more sustainable alternative to waterproof coatings based on fluoropolymers, such as PTFE. The additivation of the polymeric matrices with SWCNT has led to textile coatings with excellent electrical conductivity, maintaining water column properties, giving rise to multifunctional coatings that are highly demanded in protective workwear and technical textiles. Peer Reviewed Objectius de Desenvolupament Sostenible::12 - Producció i Consum Responsables::12.4 - Per a 2020, aconseguir la gestió ecològicament racional dels productes químics i de tots els residus al llarg del seu cicle de vida, de conformitat amb els marcs internacionals convinguts, i reduir-ne de manera significativa l’alliberament a l’atmosfera, a l’aigua i al sòl a fi de minimitzar-ne els efectes adversos sobre la salut humana i el medi ambient Objectius de Desenvolupament Sostenible::12 - Producció i Consum Responsables

Porous biodegradable scaffolds provide a physical substrate for cells allowing them to attach, proliferate and guide the formation of new tissues. A variety of techniques have been developed to fabricate tissue engineering (TE) scaffolds, among them the most relevant is the thermally-induced phase separation (TIPS). This technique has been widely used in recent years to fabricate three-dimensional (3D) TE scaffolds. Low production cost, simple experimental procedure and easy processability together with the capability to produce highly porous scaffolds with controllable architecture justify the popularity of TIPS. This paper provides a general overview of the TIPS methodology applied for the preparation of 3D porous TE scaffolds. The recent advances in the fabrication of porous scaffolds through this technique, in terms of technology and material selection, have been reviewed. In addition, how properties can be effectively modified to serve as ideal substrates for specific target cells has been specifically addressed. Additionally, examples are offered with respect to changes of TIPS procedure parameters, the combination of TIPS with other techniques and innovations in polymer or filler selection.

Polydopamine–ethylene glycol dimethacrylate copolymer is a biocompatible coating with cell adhesion promotion and antibiofilm properties. This copolymer has been successfully applied on metallic implants, such as stainless steel and titanium implants, using several deposition techniques (e.g. layer-by-layer, silane activation, chemical vapor deposition, or liquid-assisted plasma polymerization). However, its application in zirconia ceramic materials, which are widely used in dentistry and medicine, has never been described. In this work, polydopamine–ethylene glycol dimethacrylate copolymer has been deposited on ultra-smooth surfaces of yttria-stabilized zirconia discs (average roughness = 2.08 ± 0.08 nm) by using liquid-assisted atmospheric-pressure plasma-induced polymerization (LA-APPiP). After the polymerization, the nanometric coating (250 nm, measured by ellipsometry) had an average roughness of 79.85 ± 13.71 nm and water contact angle of 57.8 ± 2.2 degrees, consistent with the highly hydrophilic nature of the biocompatible copolymer, if compared to the pristine zirconia (72.7 ± 2.0 degrees). The successful covalent bonding of the copolymer with the zirconia surface, thanks to the previous activation of the substrate with oxygen plasma, was proved by X-ray photoelectron spectroscopy (XPS). The polymer composition has been investigated by XPS and Raman spectroscopies. The LA-APPiP technique has been proved to be an excellent method to produce homogenous films without the need to employ solvents and further purification steps. The new copolymer film allows the uniform growth of human osteoblast-like MG-63 cells, after 7 days of cell culture, as observed by fluorescence microscopy.

Pharmacological chaperones (PCs) are low-molecular weight chemical molecules used in patients for the treatment of some rare diseases caused primarily by protein instability. A controlled and on-demand release of PCs via nanoparticles is an alternative for cases in which long treatments are needed and prolonged oral administration could have adverse effects. In this work, pyrimethamine (PYR), which is a potent PC consisting of pyrimidine-2,4-diamine substituted at position 5 by a p-chlorophenyl group and at position 6 by an ethyl group, was successfully loaded in electroresponsive poly(3,4-ethylenedioxythiophene) nanoparticles (PEDOT NPs). The PYR-loading capacity was 11.4 ± 1.5%, with both loaded and unloaded PEDOT NPs exhibiting similar sizes (215 ± 3 and 203 ± 1 nm, respectively) and net surface charges (-26 ± 7 and -29 ± 6 mV, respectively). In the absence of electrical stimulus, the release of PC from loaded NPs is very low (1.6% in 24 h and 18% in 80 days) in aqueous environments. Instead, electrical stimuli that sustained for 30 min enhanced the release of PYR, which was ~50% when the voltage was scanned from –0.5 V to 0.5 V (cyclic voltammetry) and ~35% when a constant voltage of 1.0 V was applied (chronoamperometry).

International audience; Chemical derivatization and amorphization are two possible strategies to improve the solubility and bioavailability of drugs, which is a key issue for the pharmaceutical industry. In this contribution, we explore whether both strategies can be combined by studying how small differences in the molecular structure of three related pharmaceutical compounds affect their crystalline structure and melting point (Tm), the relaxation dynamics in the amorphous phase, and the glass transition temperature (Tg), as well as the tendency toward recrystallization. Three benzodiazepine derivatives of almost same molecular mass and structure (Diazepam, Nordazepam and Tetrazepam) were chosen as model compounds. Nordazepam is the only one that displays N–H···O hydrogen bonds both in crystalline and amorphous phases, which leads to a significantly higher Tm (by 70–80 K) and Tg (by 30–40 K) compared to those of Tetrazepam and Diazepam (which display similar values of characteristic temperatures). The relaxation dynamics in the amorphous phase, as determined experimentally using broadband dielectric spectroscopy, is dominated by a structural relaxation and a Johari–Goldstein secondary relaxation, both of which scale with the reduced temperature T/Tg. The kinetic fragility index is very low and virtually the same (mp ≈ 32) in all three compounds. Two more secondary relaxations are observed in the glass state: the slower of the two has virtually the same relaxation time and activation energy in all three compounds, and is assigned to the inter-enantiomer conversion dynamics of the flexible diazepine heterocycle between isoenergetic P and M conformations. We tentatively assign the fastest secondary relaxation, present only in Diazepam and Tetrazepam, to the rigid rotation of the fused diazepine–benzene double ring relative to the six-membered carbon ring. Such motion appears to be largely hindered in glassy Nordazepam, possibly due to the presence of the hydrogen bonds. Supercooled liquid Tetrazepam and Nordazepam are observed to crystallize into their stable crystalline form with an Avrami exponent close to unity indicating unidimensional growth with only sporadic nucleation, which allows a direct assessment of the crystal growth rate. Despite the very similar growth mode, the two derivatives exhibit very different kinetics for a fixed value of the reduced temperature and thus of the structural relaxation time, with Nordazepam displaying slower growth kinetics. Diazepam does not instead display any tendency toward recrystallization over short periods of time (even close to Tm). Both these observations in three very similar diazepine derivatives provide direct evidence that the kinetics of recrystallization of amorphous pharmaceuticals is not a universal function, at least in the supercooled liquid phase, of the structural or the conformational relaxation dynamics, and it is not simply correlated with related parameters such as the kinetic fragility or activation barrier of the structural relaxation. Only the crystal growth rate, and not the nucleation rate, shows a correlation with the presence or absence of hydrogen bonding.

Silver nanoparticles (Ag NPs) appeared as promising antimicrobial candidates to face the development of antibiotic resistance. Although reported as toxic towards mammalian cells, their combination with biomolecules have shown reduced toxicity, while maintaining the antimicrobial function. Herein, hyaluronic acid (HA) with low (40 kDa), medium (200 and 600 kDa) and high (2 MDa) molecular weight (Mw) was modified with adipic acid dihydrazide (ADH) and used as reducing and capping agents to synthesise antimicrobial hybrid Ag NPs. The Mw of the polymer played a crucial role in the morphology, size and antibacterial activity of the Ag NPs. The 600 and 200 kDa HA-ADH-Ag NPs were able to reduce the Escherichia coli and Staphylococcus aureus concentration by more than 3 logs, while the 40 kDa NPs reached ~2 logs reduction. The 2 MDa HA-ADH failed to form homogenous NPs with strong bactericidal activity. A mechanistic study of the interaction with a model bacterial membrane using Langmuir isotherms confirmed the greater interaction between bacteria and higher Mw polymers and the effect of the NP’s morphology. The nanocomposites low toxicity to human skin cells was demonstrated in vitro, showing more than 90% cell viability after incubation with the NPs.

When an amorphous polymer is cooled under pressure from above its glass transition temperature to room temperature, and then the pressure is released, this results in a densified state of the glass. This procedure applied to an epoxy composite system filled with boron nitride (BN) particles has been shown to increase the density of the composite, reduce its enthalpy, and, most importantly, significantly enhance its thermal conductivity. An epoxy-BN composite with 58 wt% BN platelets of average size 30 &micro, m has been densified by curing under pressures of up to 2.0 MPa and then cooling the cured sample to room temperature before releasing the pressure. It is found that the thermal conductivity is increased from approximately 3 W/mK for a sample cured at ambient pressure to approximately 7 W/mK, in parallel, the density increases from 1.55 to 1.72 &plusmn, 0.01 g/cm3. This densification process is much more effective in enhancing the thermal conductivity than is either simply applying pressure to consolidate the epoxy composite mixture before curing or applying pressure during cure but then removing the pressure before cooling to room temperature, this last procedure results in a thermal conductivity of approximately 5 W/mK. Furthermore, it has been shown that the densification and corresponding effect on the thermal conductivity is reversible, it can be removed by heating above the glass transition temperature and then cooling without pressure and can be reinstated by again heating above the glass transition temperature and then cooling under pressure. This implies that a densified state and an enhanced thermal conductivity can be induced even in a composite prepared without the use of pressure.

Conducting polymers have been increasingly used as biologically interfacing electrodes for biomedical applications due to their excellent and fast electrochemical response, reversible doping–dedoping characteristics, high stability, easy processability, and biocompatibility. These advantageous properties can be used for the rapid detection and eradication of infections associated to bacterial growth since these are a tremendous burden for individual patients as well as the global healthcare system. Herein, a smart nanotheranostic electroresponsive platform, which consists of chloramphenicol (CAM)-loaded in poly(3,4-ethylendioxythiophene) nanoparticles (PEDOT/CAM NPs) for concurrent release of the antibiotic and real-time monitoring of bacterial growth is presented. PEDOT/CAM NPs, with an antibiotic loading content of 11.9 ± 1.3% w/w, are proved to inhibit the growth of Escherichia coli and Streptococcus sanguinis due to the antibiotic release by cyclic voltammetry. Furthermore, in situ monitoring of bacterial activity is achieved through the electrochemical detection of ß-nicotinamide adenine dinucleotide, a redox active specie produced by the microbial metabolism that diffuse to the extracellular medium. According to these results, the proposed nanotheranostic platform has great potential for real-time monitoring of the response of bacteria to the released antibiotic, contributing to the evolution of the personalized medicine.

Thermally induced phase separation followed by freeze drying has been used to prepare biodegradable and biocompatible scaffolds with interconnected 3D microporous structures from poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) copolymers containing 5 and 12 wt % of 3-hydroxyvalerate (HV). Solutions of PHBV in 1,4-dioxane, underwent phase separation by cooling under two different thermal gradients (at &minus, 25 &deg, C and &minus, 5 &deg, C). The cloud point and crystallization temperature of the polymer solutions were determined by turbidimetry and differential scanning calorimetry, respectively. Parameters affecting the phase separation mechanism such as variation of both the cooling process and the composition of the PHBV copolymer were investigated. Afterwards, the influence of these variables on the morphology of the porous structure and the final mechanical properties (i.e., rigidity and damping) was evaluated via scanning electron microscopy and dynamic mechanical thermal analysis, respectively. While the morphology of the scaffolds was considerably affected by polymer crystallization upon a slow cooling rate, the effect of solvent crystallization was more evident at either high hydroxyvalerate content (i.e., 12 wt % of HV) or high cooling rate. The decrease in the HV content gave rise to scaffolds with greater stiffness because of their higher degree of crystallinity, being also noticeable the greater consistency of the structure attained when the cooling rate was higher. Scaffolds were fully biocompatible supports for cell adhesion and proliferation in 3D cultures and show potential application as a tool for tissue regeneration.

Blends with different ratios of polylactide and polyamide 6,10 (PA610) have been prepared by melt-mixing using a Brabender mixer equipment. Previously, a rheologically modified polylactide (PLAREx) was obtained through reactive extrusion using a multifunctional epoxide agent. It was expected that unreacted epoxy groups of PLAREx were able to improve the compatibility between the two polymers. SEM observations revealed a logical dependence of the morphology of immiscible phases with composition, and more interestingly a co-continuity at relatively low PA content (around 50%) was detected. This result contrasts with previous observations performed with non-modified PLA. Confined PA domains increased with the PA content and hardly crystallized at the typical crystallization temperature of the pure PA (195 °C). Synchrotron X-ray diffraction studies indicated that a PA crystallization at a lower temperature close to 120 °C was enhanced and led to a pseudohexagonal ¿ phase that differs from the characteristic layered structure of PA610. SAXS data revealed also that well differentiated lamellar entities could be assigned at both immiscible polymer phases. Clear differences were observed in the spherulitic morphologies attained under isothermal melt crystallization experiments. Results indicated that the texture of PLAREx spherulites was modified by the presence of PA. Compatibilization of PA molecules on the crystal lamellar boundaries of PLAREx led to an enhancement of the lamellar twisting frequency. Optical microscopy results also indicated that the crystal growth rate of PLAREx increased by the incorporation of PA, but in contrast this had an adverse effect on the nucleation process

Epoxy resin composites filled with thermally conductive but electrically insulating particles play an important role in the thermal management of modern electronic devices. Although many types of particles are used for this purpose, including oxides, carbides and nitrides, one of the most widely used fillers is boron nitride (BN). In this review we concentrate specifically on epoxy-BN composites for high thermal conductivity applications. First, the cure kinetics of epoxy composites in general, and of epoxy-BN composites in particular, are discussed separately in terms of the effects of the filler particles on cure parameters and the cured composite. Then, several fundamental aspects of epoxy-BN composites are discussed in terms of their effect on thermal conductivity. These aspects include the following: the filler content; the type of epoxy system used for the matrix; the morphology of the filler particles (platelets, agglomerates) and their size and concentration; the use of surface treatments of the filler particles or of coupling agents; and the composite preparation procedures, for example whether or not solvents are used for dispersion of the filler in the matrix. The dependence of thermal conductivity on filler content, obtained from over one hundred reports in the literature, is examined in detail, and an attempt is made to categorise the effects of the variables and to compare the results obtained by different procedures.

Simultaneous drug release and monitoring using a single polymeric platform represents a significant advance in the utilization of biomaterials for therapeutic use. Tracking drug release by real-time electrochemical detection using the same platform is a simple way to guide the dosage of the drug, improve the desired therapeutic effect, and reduce the adverse side effects. The platform developed in this work takes advantage of the flexibility and loading capacity of hydrogels, the mechanical strength of microfibers, and the capacity of conducting polymers to detect the redox properties of drugs. The engineered platform is prepared by assembling two spin-coated layers of poly-¿-glutamic acid hydrogel, loaded with poly(3,4-ethylenedioxythiophene) (PEDOT) microparticles, and separated by a electrospun layer of poly-e-caprolactone microfibers. Loaded PEDOT microparticles are used as reaction nuclei for the polymerization of poly(hydroxymethyl-3,4-ethylenedioxythiophene) (PHMeDOT), that semi-interpenetrate the whole three layered system while forming a dense network of electrical conduction paths. After demonstrating its properties, the platform is loaded with levofloxacin and its release monitored externally by UV–vis spectroscopy and in situ by using the PHMeDOT network. In situ real-time electrochemical monitoring of the drug release from the engineered platform holds great promise for the development of multi-functional devices for advanced biomedical applications.

Ultrasound micromolding technology has been applied to get microporous polylactide scaffolds from the subsequent leaching of incorporated NaCl salts. A small amount of water-soluble polyethylene glycol (PEG) was required in order to improve the leaching process and get compact pieces with interconnected pores. Distribution of polymers in the processed specimens was quite homogeneous due to the small PEG content, although it was more concentrated in the regions close to the feeding channels due to its higher viscosity. Hydrophobic drugs like triclosan could be incorporated causing a minimum degradation during ultrasound processing and suffering an insignificant solubilization during the leaching step. Final scaffolds showed clear bactericide or bacteriostatic effects before and after 10 h of exposure. Cell proliferation of MDCK epithelial cells was higher for TCS loaded porous scaffolds (200%) than for unloaded samples (170%) and non-porous polylactide (PLA) specimens (100%, control). Micrographs showed the absence of non-inhibition areas in both the specimens and the container, confirming the biocompatibility of PLA specimens.

Transmission electron microscopy, temperature-modulated differential scanning calorimetry, and broadband dielectric spectroscopy were employed to characterize ternary nanocomposites consisting of carboxylated carbon nanotubes (CNT) dispersed in a blend of two immiscible polymers, poly(L,lactide) (PLLA) and thermoplastic polyurethane (TPU). The nanocomposite blends were obtained by melt-compounding of PLLA and TPU in the presence of 0.2 wt-% CNT, either in the presence or absence of a Joncryl® ADR chain extender for PLLA, leading to reactive and non-reactive melt mixed samples. In both cases, the binary PLLA/TPU blend is characterized by phase separation into submicron TPU droplets dispersed in the PLLA matrix, and displays two separate glass transition temperatures. The carbon nanotubes are present either inside the TPU phase (samples obtained without chain extender), or at their boundaries (reactive-melt mixed samples). The effect of the sub-micron confinement of the TPU component is to decrease the cooperativity length of the primary segmental relaxation of this polymer, which is accentuated by the presence of the CNT fillers. Depending on the type of sample, five or six distinct relaxations are observed by means of dielectric spectroscopy, which we are able to assign to different dielectric phenomena. Our dielectric data show that the CNT fillers do not contribute directly to the long-range charge transport in the nanocomposite blends, consistent with the nanocomposites morphology, but rather result in a shift of the Maxwell-Wagner-Sillars space-charge frequency associated with charge accumulation at the PLLA/TPU boundary. Such shift testifies to a selective conductivity enhancement of the TPU phase due to the filler.

The utilization of hydrogels derived from biopolymers as solid electrolyte (SE) of electrochemical supercapacitors (ESCs) is a topic of increasing interest because of their promising applications in biomedicine (e.g. for energy storage in autonomous implantable devices). In this work an unsaturated polyesteramide that contains phenylalanine, butenediol and fumarate as building blocks has been photo-crosslinked to obtain a hydrogel (UPEA-h). The structure of UPEA-h, which is characterized by a network of open interconnected pores surrounded by regions with compact morphology, favors ion transport, while the biodegradability and biocompatibility conferred by the α-amino acid unit and the ester group are appropriated for its usage in the biomedical field. Voltammetric and galvanostatic assays have been conducted to evaluate the behavior of UPEA-h when used as SE in ESCs with poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes. Hence, PEDOT/UPEA-h devices displayed supercapacitor response of up 179 F/g and capacitance retention higher than 90%. Moreover, the long-term stability, leakage-current, and self-discharging response of PEDOT/UPEA-h ESCs reflect the great potential of UPEA-h as ion-conductive electrolyte. Indeed, the performance of PEDOT/UPEA-h is higher than found in analogous devices constructed using other biohydrogels as SE (e.g. κ-carrageenan, poly-γ-glutamic acid and cellulose hydrogels).

A fresco painting has a calcium carbonate binder produced as result of the carbonation process of a lime paste. The reaction environmental conditions are similar to those of bio-mineral formation where an amorphous calcium carbonate (ACC) phase has been found to be the precursor of other CaCO3 polymorphs following the sequence: hydrated ACC, anhydrous ACC, vaterite, aragonite, and, finally, stable calcite. In order to determine whether ACC is also formed during the fresco drying process, as well as, the final surface calcium carbonate phases present, a series of laboratory mock-ups, replicating as close as possible each of the paint strata and submitted to the same atmospheric conditions have been designed and studied. The results indicate that the continuous supply of water and reagents by the lime and sand mortar promote the ACC formation even at the completion of water evaporation and that the high pH of the medium does not favour the formation of calcium carbonate polymorphs other than calcite. In fact, the results demonstrate that the presence of an ACC layer in the mural painting surface confirms that the original painting technique used was fresco. Finally, the presence of an ACC layer is important for stablishing adequate cleaning (the solubility of hydrated ACC is superior to those of calcite) and conservation protocols (ACC is susceptible to suffer dehydration) for the fresco paintings. The project received financial support from MINECO (Spain), grant MAT2016-77753-R and Generalitat de Catalunya, grant 2017 SGR 0042. The µSR-XRD experiments were performed at BL13 XALOC beamline at ALBA Synchrotron Facillity with the collaboration of ALBA staff (proposal 2017092488). We acknowledge the collaboration of Mireia Mestre, chief of Restoration Department of MNAC.

Lightweight materials and components have gained remarkable scientific and technological importance in the recent times as the main drivers of innovation. They are finding widespread use across all industry sectors to reduce the production cost and enhance materials quality and functionality, while maintaining the strength of the final material. In particular, antimicrobial lightweight materials have been garnering increased interest for management of resistant pathogens that are mainly responsible for the food spoilage and the occurrence of severe foodborne and hospital acquired infections. Research initiatives have been devoted to engineering various innovative materials as nanoparticles, hydrogels, foams and surface coatings with improved antimicrobial properties. In this chapter we summarize the recent advances in development of antimicrobial nano-enabled lightweight solutions using polymers, biopolymers, and different types of highly effective than their bulk counterparts nanoparticles with low probability for resistance development, showing the way forward to limit the spread and emergence of antimicrobial resistance. This work was supported by the European project ReInvent - "Novel Products for Constrution and Automotive Industries Based on Bio Materials and Nature Fibers" (H2020-BIBI-JTI-2017, Grant Agreement number 792049) and the European project PROTECT - "Pre-commercial lines for the production of surface nanostructured antimicrobial and antibiofilm textiles, medical devices, and water treatment membranes" (H2020-720851). The autors would like to acknowledge the European Regional Development Fund (FEDER). A.G.M. would like to thank Generalitat the Catalunya for providing her the Ph.D. grant (2019FI_B 01004) and G.F. acknowledges Universitat Politècnica de Catalunya and Banco Santander for his Ph.D. grant (113 FPI-UPC 2018)

The processes related to the fixation of nitrogen in a catalyst able to produce glycine and alanine from a N2, CO2 and CH4 gas mixture at mild reaction conditions have been studied by combining experimental and theoretical investigations. Results have allowed to understand the role of different elements of the catalyst, which is constituted by permanently polarized hydroxyapatite (p-HAp), zirconia, and aminotris(methylenephosphonic acid) (ATMP). ATMP attracts N2 molecules towards the surface, maintaining them close to the zirconia and p-HAp components that are the most active from a catalytic point of view. On the other hand, the associative mechanism is thermodynamically favoured under mild reaction conditions with respect to the dissociative one, which is limited by the barrier associated to the N N bond cleavage. Because this reaction mechanism is similar to that employed in the nitrogen fixation by nitrogenase enzymes, these findings provide an opportunity to design new bioinspired catalysts.

The electrophotocatalytic synthesis of Glycine and Alanine from a simple gas mixture containing N2, CO2, CH4 and H2O under mild reaction conditions (95 °C and 6 bar) was recently developed using a catalyst formed by permanently polarized hydroxyapatite, which is achieved using a thermally stimulated polarization process, coated with two layers of aminotris(methylenephosphonic acid) (ATMP) separated by an intermediate layer of zirconyl chloride (ZC). This work reports the optimization of the ATMP- and ZC-coating content by examining the influence of their concentration of each component in each layer on the structural and electrochemical properties of the catalyst. After exhaustive analyses, such properties have been related with the efficiency of the catalysts prepared using different ATMP- and ZC-concentrations to yield Gly and Ala amino acids by fixing nitrogen from N2 and carbon from CO2 and CH4. Results show that, although the concentrations of ATMP and ZC in the first and the intermediate layers are important, the third layer plays a predominant role as is responsible of the apparition of supramolecular structures on the surface and the capacitive behavior of the coating.

Herein, a versatile bilayersystem, composed by a polypropylene(PP)mesh and a covalently bonded poly(N-isopropylacrylamide) (PNIPAAm) hydrogel, is reported. The cell adhesion mechanism was successfully modulated by controlling the architecture of the hydrogel in terms of duration of PNIPAAm graftingtime, crosslinker content, and temperature of material exposure in PBS solutions (belowandabove the LCST of PNIPAAm). The best in vitroresults with fibroblast (COS-1) and epithelial (MCF-7) cells was obtained with a mesh modified with porous iPP-g-PNIPAAm bilayer system, prepared via PNIPAAm grafting for 2 h at the lowest N,N'-methylene bis(acrylamide) (MBA)concentration (1 mM). Under these conditions, the detachment of the fibroblast-like cells was 50% lower than that of the control, after 7 days of cell incubation, which represents a high de-adhesionof cellsin a short period. Moreover, the whole system showed an excellent stability in dry or wet media, proving that the thermosensitive hydrogel was well adhered to the polymer surface, after PP fibreactivation by cold plasma. This study opens new insights on the development of anti-adherent meshes for abdominal hernia repairs.

Flexible and self-standing multilayered films made of nanoperforated poly(lactic acid) (PLA) layers separated by anodically polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) conducting layers have been prepared and used as electrodes for supercapacitors. The influence of the external layer has been evaluated by comparing the charge storage capacity of four- and five-layered films in which the external layer is made of PEDOT (PLA/PEDOT/PLA/PEDOT) and nanoperforated PLA (PLA/PEDOT/PLA/PEDOT/PLA), respectively. In spite of the amount of conducting polymer is the same for both four- and five-layered films, they exhibit significant differences. The electrochemical response in terms of electroactivity, areal specific capacitance, stability, and coulombic efficiency was greater for the four-layered electrodes than for the five-layered ones. Furthermore, the response in terms of leakage current and self-discharge was significantly better for the former electrodes than for the latter ones.

Two sets of ionically charged polypentadecalactone-polypeptide diblock copolymers (PPDLx-b-PAAy, with x= 15 or 20 and y ranging from 30 to 200), one containing alpha-L-glutamic acid (LGA) and the other containing epsilon-L-lysine (LL), were obtained from their respective precursors with the side groups of LGA and LL protected as gamma-O-benzyl and epsilon-N-carbobenzoxy, respectively. The copolymers were semicrystalline with the polyester block crystallized in the usual pseudo-rhombic lattice and the polypeptide in the alpha-helix or beta-sheet conformation depending on the amino acid and the length of the block. Copolymers with PAA blocks with y = 80 were water-soluble and they adopted the alpha-helix conformation in the aqueous medium when they are in the nonionized state. Both LGA and LL containing copolymers self-assembled in nanoparticles with a size between 150 and 180 nm in diameter. PPDL-b-PLGA nanoparticles were able to load DOX with an efficiency of ~70% whereas PPDL-b-PLL displayed a noticeable capacity for condensing DNA. In both cases hosting was based on the ionic complexation taking place between the ionized copolymer and the guest compound. Accordingly DOX release rate was found to be noticeably depending on pH.

Chloramphenicol (CAM) has been encapsulated into hydroxyapatite nanoparticles displaying different morphologies and crystallinities. The process was based on typical precipitation of solutions containing phosphate and calcium ions and the addition of CAM once the hydroxyapatite nuclei were formed. This procedure favored a disposition of the drug into the bulk parts of the nanoparticles and led to a fast release in aqueous media. Clear antibacterial activity was derived, being slightly higher for the amorphous samples due to their higher encapsulation efficiency. Polylactide (PLA) microfibers incorporating CAM encapsulated in hydroxyapatite nanoparticles were prepared by the electrospinning technique and under optimized conditions. Drug release experiments demonstrated that only a small percentage of the loaded CAM could be delivered to an aqueous PBS medium. This amount was enough to render an immediate bacteriostatic effect without causing a cytotoxic effect on osteoblast-like, fibroblasts, and epithelial cells. Therefore, the prepared scaffolds were able to retain CAM-loaded nanoparticles, being a reservoir that should allow a prolonged release depending on the polymer degradation rate. The studied system may have promising applications for the treatment of cancer since CAM has been proposed as a new antitumor drug.

Given that the copolymers of complex topology and composition are at the forefront of multifunctional materials research, this work reports aboutan amphiphilic random, heterografted copolymer of (A-g-B)m-ran-(A-g-C)ntype, which was designed to work as an efficient and biocompatible electronic interface. The copolymer (henceforth denoted as PTh-g-(PEG-r-PCL) for simplification) was synthesized in hierarchical fashion, having ¿-conjugated polythiophene (PTh) as main chain and polarunits, polyethylene glycol (PEG) and oligo-¿-caprolactone as side chains. Theproperties of the newcopolymer,in solution and in solid state,were evaluated. The applied investigations showed that, due to its amphiphilic character and incompatibility of the side chains, PTh-g-(PEG-r-PCL) experiences microphase separation in solutionand film states. By electronicmicroscopy techniques were evidenced two types of supramolecular structures: (a) porous spherical particles and (b) rod-like structures. When deposited on carbon electrodes,the copolymerpresented a good electroactivity and electrostability.Copolymer's biocompatibility studies, performed by using Cos-1 and Vero cell lines,demonstrated an excellent adhesion when comparing with bare steel electrode while a slight decrease of proliferation was registered, more pronounced for Vero cells, in spite of cells normal growth and morphology. Thanks to its excellent capability for electrochemically interfacing with aqueous electrolytes, the voltammetric oxidation ofNADH coenzyme at PTh-g-(PEG-r-PCL) film-modified carbon electrode revealed that it can be used as selective biosensor of this biomolecule, as well.

Polyglobalide (PGl) with number average polymerization degree of ~20 was prepared by enzymatic ROP and then polyfunctionalized at 60% with aminothioethylene groups. The PGl 20 -(NH 2 ) 12 copolymer was used as macroinitiator for the ROP of NCAs of BLG (γ-benzyl L-glutamate) and ZLL ( e N -carbobenzoxy- l -lysine) protected amino acids to produce neutral polypeptide- graft ed polyglobalides poly[Gl 20 - graft -(AA) z ] with z = 5 and 12, which upon deprotection, afforded anionic and cationic copolymers, respectively. Both protected and deprotected graft copolymers were characterized in full detail by NMR, and their thermal properties were evaluated by TGA and DSC. The structure of these copolymers in the solid-state was examined by FTIR and XRD using synchrotron radiation. All grafted polyglobalides were amorphous but the polypeptide side chains were arranged in either alpha-helix or beta-sheet conformation, and reliable indications on the occurrence of supramolecular structures were frequently found. The capacity of poly[Gl 20 - graft -(AA) z ] copolymers to self-assemble in aqueous medium was evidenced by the preparation of well-shaped spheroidal nanoparticles with a diversity of sizes depending on copolymer composition and charge. Loading and release of doxorubicin (DOX) from nanoparticles made of negatively charged poly[Gl 20 - graft -(LGA) 12 ] as well as DNA complexation with cationic poly[Gl 20 - graft -(LL) 5 ] were explored to appraise the potential of these copolymers for building drug delivery systems.

The dynamics in highly asymmetric mixtures with large difference in Tg of the two components are complex. At low values of the lower-Tg2 component only the a1-relaxation and its Tga1 were found together with a fast relaxation. Three different interpretations of the fast relaxation were given. The first one interpreted the fast relaxation as the JG ß-relaxation, and the a2-relaxation is present but not resolved. The second one interpreted it as localized and noncooperative a'-relaxation of the low-Tg2 component totally confined by the frozen high-Tg1 component. The third one interpreted it also as the confined a2-relaxation, but it is liquid-like and cooperative. We review exhaustively the experimental data of many highly asymmetric mixtures and polymer blends to show unequivocally that the observed fast relaxation is the JG ß-relaxation. Notwithstanding, the confined-but-cooperative a2-relaxation exists, albeit not resolved. Experimental data are exclusively considered and objectively utilized to arrive at the conclusions.

Conducting polymers typically exhibit different oxidation states, which are easily interchangeable among them by means of the application of an electrical potential. In this work, we present a theoretical and experimental study to regulate the pore size of poly(3,4-ethylenedioxythiophene) (PEDOT) films doped with ClO4- ions by controlling their oxidation state. More specifically, different bulk and surface PEDOT models have been evaluated applying 2D- and 3-D periodic boundary conditions to density functional theory calculations. In highly oxidized PEDOT films, calculations predict that the incorporation of dopant ions increases the separation between neighboring chains, causing a structural re-organization. Thus, the calculated average pore size, which has been modeled as a structural defect in 2D surface models, increases by 15.1%. This increment is consistent with experimental measures of the nanopore size in PEDOT films with enhanced porosity, which reflect a difference of 25.2% between the oxidized and reduced forms. This superficial phenomenon could easily be used to retain and release controlled drugs through the application of different electric potentials

In the present work, the results of a computational study aimed at assessing the conformational profile of bombesin are reported. The conformational space of the peptide was sampled by means of a 4 μs accelerated molecular dynamics simulation in water, using an explicit solvent model. The results were analyzed using Principal Component Analysis to get essential information on peptide fluctuations, along with cluster analysis to characterize different conformations in the sample. Analysis of the results suggests that the peptide adopts helical structures at the C-terminus that tend to unwind at the end of the peptide chain, since there are many structures exhibiting only two turns of a helix at the central segment of the peptide. In addition, the peptide also adopts hairpin turn structures at the N-terminus. Results of the simulation were confronted with available NMR results in a 2,2,2-trifluoroethanol/water (30% v/v) solution. Distances deduced form NOEs experiments only provide support to the presence of helical conformations that represent the most populated structures in the simulation. The absence of other conformations in the NMR experiments can be explained to be due to the α-helix enhancing nature of the solvent used in the experiments.

“This is a post-peer-review, pre-copyedit version of an article published in Cellulose. The final authenticated version is available online at: https://doi.org/10.1007/s10570-019-02678-5 Bacterial cellulose (BC) was functionalized applying the Laccase/TEMPO oxidative treatment, leading to a five-fold increase of the concentration of carboxyl groups. Paper produced with this cellulose showed improved mechanical properties while maintaining barrier function against water and greases as compared to paper produced with non-oxidized BC. Also, the negative charge provided by the carboxyl groups on functionalized BC was used to generate silver nanoparticles (AgNPs), obtaining a BC paper and Ag composite. The presence of AgNPs in the composites was validated by SEM, EDS and ICP analysis, showing spherical, uniformly sized particles stabilized in the BC nanofibers matrix. Additionally, antimicrobial property of composites containing AgNPs was tested. The results showed the strong antimicrobial activity of the composites against Gram-positive and Gram-negative bacteria and fungi. The generation of Ag nanoparticles in a matrix that combine the physical characteristics of the BC nanofibers with the stiffness and the mechanical properties of paper produced composites that may have applicability in technological and biomedical uses

Understanding the glass transition requires getting the picture of the dynamical processes that intervene in it. Glass-forming liquids show a characteristic decoupling of relaxation processes when they are cooled down towards the glassy state. The faster (βJG) process is still under scrutiny, and its full explanation necessitates information at the microscopic scale. To this aim, nuclear γ-resonance time-domain interferometry (TDI) has been utilized to investigate 5-methyl-2-hexanol, a hydrogen-bonded liquid with a pronounced βJG process as measured by dielectric spectroscopy. TDI probes in fact the center-of-mass, molecular dynamics at scattering-vectors corresponding to both inter- and intra-molecular distances. Our measurements demonstrate that, in the undercooled liquid phase, the βJG relaxation can be visualized as a spatially-restricted rearrangement of molecules within the cage of their closest neighbours accompanied by larger excursions which reach out at least the inter-molecular scale and are related to cage-breaking events. In-cage rattling and cage-breaking processes therefore coexist in the βJG relaxation.

Semipermanently polarized hydroxyapatite, named SP/HAp(w), is obtained by applying a constant dc electric field of 1–10 kV/cm at 300–850 °C to the samples previously sintered in water vapor, while permanently polarized hydroxyapatite, PP/HAp(a), is produced by applying a dc electric field of 3 kV/cm at 1000 °C to the samples sintered in air. SP/HAp(w) has been used for biomedical applications, while PP/HAp(a) has been proved to be a valuable catalyst for N2 and CO2 fixation. In this work, structural differences between SP/HAp(w) and PP/HAp(a) have been ascertained using Raman microscopy, wide-angle X-ray diffraction, scanning electronic microscopy, high-resolution transmission electron microscopy, and grazing incidence X-ray diffraction. Results prove the existence of crystal distortion in the form of amorphous calcium phosphate and ß-tricalcium phosphate (ß-TCP) phases close to the surface because of the atmosphere used in the sintering process. The existence of an amorphous layer in the surface and the phase transition through ß-TCP of SP/HAp(w) are the structural factors responsible for the differences with respect to PP/HAp(a). Moreover, a superstructure has been identified in PP/HAp(a) samples, which could be another structural factor associated with enhanced conductivity, permanent polarization, and catalytic activity of this material

The electro-chemo-mechanical response of robust and flexible free-standing films made of three nanoperforated poly(lactic acid) (pPLA) layers separated by two anodically polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) layers has been demonstrated. The mechanical and electrochemical properties of these films, which are provided by pPLA and PEDOT, respectively, have been studied by nanoindentation, cyclic voltammetry, and galvanostatic charge–discharge assays. The unprecedented combination of properties obtained for this system is appropriated for its utilization as a Faradaic motor, also named artificial muscle. Application of square potential waves has shown important bending movements in the films, which can be repeated for more than 500 cycles without damaging its mechanical integrity. Furthermore, the actuator is able to push a huge amount of mass, as it has been proved by increasing the mass of the passive pPLA up to 328% while keeping the mass of electroactive PEDOT unaltered.

When a liquid is cooled to produce a glass its dynamics, dominated by the structural relaxation, become very slow, and at the glass-transition temperature Tg its characteristic relaxation time is about 100 s. At slightly elevated temperatures (~1.2 Tg) however, a second process known as the Johari-Goldstein relaxation, βJG, decouples from the structural one and remains much faster than it down to Tg. While it is known that the βJG-process is strongly coupled to the structural relaxation, its dedicated role in the glass-transition remains under debate. Here we use an experimental technique that permits us to investigate the spatial and temporal properties of the βJG relaxation, and give evidence that the molecules participating in it are highly mobile and spatially connected in a system-spanning, percolating cluster. This correlation of structural and dynamical properties provides strong experimental support for a picture, drawn from theoretical studies, of an intermittent mosaic structure in the deeply supercooled liquid phase., The Johari-Goldstein relaxation is a precursor of the glass transition in liquids. Caporaletti et al. use time-dependent interferometry data to substantiate its suggested structural appearance as a globally percolating, fluctuating mosaic.