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We employ fast scanning calorimetry to monitor the isothermal aging kinetics in glassy polymers, complemented with measurements on other glasses. Apart from following the time evolution of the glass enthalpic state, we monitor the aging kinetics of the devitrification width on heating, ΔT_{dev}. We find that significantly below the glass transition temperature, T_{g}, the glass enthalpy attains equilibrium earlier than ΔT_{dev}, which evolves at long aging times toward enhanced heterogeneity. Hence, our results indicate that the description of time dependent evolution in glassy materials requires information beyond the mere description of its enthalpic state.
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Polymer glasses attain thermodynamic equilibrium owing to structural relaxation at various length scales. Herein, calorimetry experiments were conducted to trace the macroscopic relaxation of slow-cooled (SC) and hyperquenched (HQ) polystyrene (PS) glasses and based on detailed comparisons with molecular dynamics probed by dye reorientation, we discussed the possible molecular process governing the equilibration of PS glasses near the glass transition temperatures (Tg). Both SC and HQ glasses equilibrate owing to the cooperative segment motion above a characteristic temperature (Tc) slightly lower than the Tg. In contrast, below the Tc, the localized backbone motion with an apparent activation energy of 290 ± 20 kJ/mol, involving approximately six repeating units, assists equilibrium recovery of PS glasses on the experimentally accessible time scales. The results possibly indicate the presence of an alternative mechanism other than the α-cooperative process controlling physical aging of materials in their deep glassy states.
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Introduction: Once dispersed in water, plastic materials become promptly colonized by biofilm-forming microorganisms, commonly known as plastisphere. Methods: By combining DNA sequencing and Confocal Laser Scanning Microscopy (CLSM), we investigated the plastisphere colonization patterns following exposure to natural lake waters (up to 77 days) of either petrochemical or biodegradable plastic materials (low density polyethylene - LDPE, polyethylene terephthalate - PET, polylactic acid - PLA, and the starch-based MaterBi® - Mb) in comparison to planktonic community composition. Chemical composition, water wettability, and morphology of plastic surfaces were evaluated, through Transform Infrared Spectroscopy (ATR-FTIR), Scanning Electron Microscopy (SEM), and static contact angle analysis, to assess the possible effects of microbial colonization and biodegradation activity. Results and Discussion: The phylogenetic composition of plastisphere and planktonic communities was notably different. Pioneering microbial colonisers, likely selected from lake waters, were found associated with all plastic materials, along with a core of more than 30 abundant bacterial families associated with all polymers. The different plastic materials, either derived from petrochemical hydrocarbons (i.e., LDPE and PET) or biodegradable (PLA and Mb), were used by opportunistic aquatic microorganisms as adhesion surfaces rather than carbon sources. The Mb-associated microorganisms (i.e. mostly members of the family Burkholderiaceae) were likely able to degrade the starch residues on the polymer surfaces, although the Mb matrix maintained its original chemical structure and morphology. Overall, our findings provide insights into the complex interactions between aquatic microorganisms and plastic materials found in lake waters, highlighting the importance of understanding the plastisphere dynamics to better manage the fate of plastic debris in the environment.
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The description of kinetics of physical aging, namely the slow evolution of a glass thermodynamic state toward equilibrium, generally relies on the exclusive role of the main α relaxation. Here, we study the kinetics of physical aging over a wide temperature range in five small molecules interacting via van der Waals forces monitoring the time evolution of the glass enthalpic state. To this aim, we employ fast scanning calorimetry, which permits exploring a wide range of aging times. To challenge the role of the α relaxation in the description of physical aging, we employ a model-independent approach, based on the time to reach equilibrium, and a modified version of the single parameter aging model. The latter accounts for the non-linearity of aging making use of the so-called density scaling approach to describe the dependence of the α relaxation time on the glass thermodynamic state. We show that the α relaxation is generally adequate to describe aging at temperatures close to the glass transition and, for lower temperatures, the latest stages of equilibration. In contrast, at low aging temperatures, it fails to catch a wide portion of the time-dependent evolution of the glass thermodynamic state, which is found to be much faster than predicted considering only the α relaxation. Hence, our results and analysis provide compelling arguments that the description of glass equilibration under a wide range of aging conditions is conveyed by different molecular mechanisms, beyond the mere role of the α relaxation.
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Reducing the sample size can profoundly impact properties of bulk metallic glasses. Here, we systematically reduce the length scale of Au and Pt-based metallic glasses and study their vitrification behavior and atomic mobility. For this purpose, we exploit fast scanning calorimetry (FSC) allowing to study glassy dynamics in an exceptionally wide range of cooling rates and frequencies. We show that the main α relaxation process remains size independent and bulk-like. In contrast, we observe pronounced size dependent vitrification kinetics in micrometer-sized glasses, which is more evident for the smallest samples and at low cooling rates, resulting in more than 40 K decrease in fictive temperature, Tf, with respect to the bulk. We discuss the deep implications on how this outcome can be used to convey glasses to low energy states.
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In the last decade, the application of dynamic covalent chemistry in the field of polymeric materials has become the subject of an increasing number of studies, gaining applicative relevance. This is due to the fact that polymers containing dynamic functions possess a structure that affords reprocessability, recyclability and peculiar self-healing properties inconceivable for "classic" polymer networks. Consequently, the synthesis of a dynamic covalent chemistry-based polymer and its chemical, thermal, and mechanical characterizations are reported in the present research. In particular, oleic acid has been used as starting material to follow the founding principles of the circular economy system and, thanks to the aromatic disulfide component, which is the foundation of the material dynamic characteristics, the obtained polymer resulted as being reprocessable and self-healable. Moreover, the polymer can strongly interact with copper surfaces through the formation of stable Cu-S bonds. Then, the application of the polymer as a solvent-free reusable adhesive for copper was investigated by lap joint shear tests and comparisons with the properties of an analogous material, devoid of the disulfide bonds, were conducted.
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Here, we present a one-pot procedure for the preparation of hyaluronic acid (HA) sulfonated hydrogels in aqueous alkaline medium. The HA hydrogels were crosslinked using 1,4-butanedioldiglycidyl ether (BDDE) alone, or together with N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (Bes), as a safe sulfonating agent. Conditions for the simultaneous reaction of HA with BDDE and Bes were optimized and the resulting hydrogels were characterized under different reaction times (24, 72, and 96 h). The incorporation of sulfonic groups into the HA network was proven by elemental analysis and FTIR spectroscopy and its effect on water uptake was evaluated. Compared with the non-sulfonated sample, sulfonated gels showed improved mechanical properties, with their compressive modulus increased from 15 to 70 kPa, higher stability towards hyaluronidase, and better biocompatibility to 10T1/2 fibroblasts, especially after the absorption of collagen. As main advantages, the procedure described represents an easy and reproducible methodology for the fabrication of sulfonated hydrogels, which does not require toxic chemicals and/or solvents.
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Polylactides (PLAs) are a class of polymers that are very appealing in biomedical applications due to their degradability in nontoxic products, tunable structural, and mechanical properties. However, they have some drawbacks related to their high hydrophobicity, lack of functional groups able to graft bioactive molecules, and solubility in unsafe solvents. To circumvent these shortcomings, porous scaffolds for tissue engineering were prepared by vigorously mixing a solution of isotactic and atactic PLA in nontoxic ethyl acetate at 70 °C with a water solution of choline taurinate. The partial aminolysis of the polymer ester bonds by taurine -NH2 brought about the formation of PLA oligomers with surfactant activity that stabilized the water-in-oil emulsion. Upon drying, a negligible shrinking occurred, and mechanically stable porous scaffolds were obtained. By varying the polymer composition and choline taurinate concentration, it was possible to modulate the pore dimensions (30-50 µm) and mechanical properties (Young's moduli: 1-6 MPa) of the samples. Furthermore, the grafted choline taurinate made the surface of the PLA films hydrophilic, as observed by contact angle measurements (advancing contact angle: 76°; receding contact angle: 40°-13°). The preparation method was very simple because it was based on a one-pot mild reaction that did not require an additional purification step, as all the employed chemicals were nontoxic.
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Water-in-salt systems, i.e., super-concentrated aqueous electrolytes, such as lithium bis(trifluoromethanesulfonyl)imide (21 mol/kgwater), have been recently discovered to exhibit unexpectedly large electrochemical windows and high lithium transference numbers, thus paving the way to safe and sustainable charge storage devices. The peculiar transport features in these electrolytes are influenced by their intrinsically nanoseparated morphology, stemming from the anion hydrophobic nature and manifesting as nanosegregation between anions and water domains. The underlying mechanism behind this structure-dynamics correlation is, however, still a matter of strong debate. Here, we enhance the apolar nature of the anions, exploring the properties of the aqueous electrolytes of lithium salts with a strongly asymmetric anion, namely, (trifluoromethylsulfonyl)(nonafluorobutylsulfonyl) imide. Using a synergy of experimental and computational tools, we detect a remarkable level of structural heterogeneity at a mesoscopic level between anion-rich and water-rich domains. Such a ubiquitous sponge-like, bicontinuous morphology develops across the whole concentration range, evolving from large fluorinated globules at high dilution to a percolating fluorous matrix intercalated by water nanowires at super-concentrated regimes. Even at extremely concentrated conditions, a large population of fully hydrated lithium ions, with no anion coordination, is detected. One can then derive that the concomitant coexistence of (i) a mesoscopically segregated structure and (ii) fully hydrated lithium clusters disentangled from anion coordination enables the peculiar lithium diffusion features that characterize water-in-salt systems.
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Simulación de Dinámica Molecular , Agua , Aniones , Electrólitos , LitioRESUMEN
The changes upon methanol (MeOH) addition in the structural arrangement of the highly eco-friendly deep eutectic solvent (DES) formed by choline chloride (ChCl) and sesamol in 1:3 molar ratio have been studied by means of attenuated total reflection Fourier transform infrared spectroscopy, small- and wide-angle X-ray scattering (SWAXS), and molecular dynamics simulations. The introduction of MeOH into the DES promotes the increase of the number of Cl-MeOH hydrogen bonds (HBs) through the replacement of sesamol and choline molecules from the chloride anion coordination sphere. This effect does not promote the sesamol-sesamol, choline-choline, and sesamol-choline interactions, which remain as negligible as in the pure DES. Differently, the displaced sesamol and choline molecules are solvated by MeOH, which also forms HBs with other MeOH molecules, so that the system arranges itself to keep the overall amount of HBs maximized. SWAXS measurements show that this mechanism is predominant up to MeOH/DES molar ratios of 20-24, while after this ratio value, the scattering profile is progressively diluted in the cosolvent background and decreases toward the signal of pure MeOH. The ability of MeOH to interplay with all of the DES components produces mixtures with neither segregation of the components at nanoscale lengths nor macroscopic phase separation even for high MeOH contents. These findings have important implications for application purposes since the understanding of the pseudophase aggregates formed by a DES with a dispersing cosolvent can help in addressing an efficient extraction procedure.
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The use of psychoactive substances is a serious problem in today's society and reliable methods of analysis are necessary to confirm their occurrence in biological matrices. In this work, a green sample preparation technique prior to HPLC-MS analysis was successfully applied to the extraction of 14 illicit drugs from urine samples. The isolation procedure was a dispersive liquid-liquid microextraction based on the use of a low transition temperature mixture (LTTM), composed of choline chloride and sesamol in a molar ratio 1:3 as the extracting solvent. This mixture was classified as LTTM after a thorough investigation carried out by FTIR and DSC, which recorded a glass transition temperature at -71 °C. The extraction procedure was optimized and validated according to the main Food and Drug Administration (FDA) guidelines for bioanalytical methods, obtaining good figures of merit for all parameters: the estimated lower limit of quantitation (LLOQ) values were between 0.01 µg L-1 (bk-MMBDB) and 0.37 µg L-1 (PMA); recoveries, evaluated at very low spike levels (in the ng-µg L-1 range), spanned from 55% (MBDB) to 100% (bk-MMBDB and MDPV); finally, both within-run and between-run precisions were lower than 20% (LLOQ) and 15% (10xLLOQ).
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Drogas Ilícitas/química , Microextracción en Fase Líquida/métodos , Frío , Humanos , Límite de Detección , Temperatura de TransiciónRESUMEN
We report on the thermodynamic, structural, and dynamic properties of a recently proposed deep eutectic solvent, formed by choline acetate (ChAc) and urea (U) at the stoichiometric ratio 1:2, hereinafter indicated as ChAc:U. Although the crystalline phase melts at 36-38 °C depending on the heating rate, ChAc:U can be easily supercooled at sub-ambient conditions, thus maintaining at the liquid state, with a glass-liquid transition at about -50 °C. Synchrotron high energy x-ray scattering experiments provide the experimental data for supporting a reverse Monte Carlo analysis to extract structural information at the atomistic level. This exploration of the liquid structure of ChAc:U reveals the major role played by hydrogen bonding in determining interspecies correlations: both acetate and urea are strong hydrogen bond acceptor sites, while both choline hydroxyl and urea act as HB donors. All ChAc:U moieties are involved in mutual interactions, with acetate and urea strongly interacting through hydrogen bonding, while choline being mostly involved in van der Waals mediated interactions. Such a structural situation is mirrored by the dynamic evidences obtained by means of 1H nuclear magnetic resonance techniques, which show how urea and acetate species experience higher translational activation energy than choline, fingerprinting their stronger commitments into the extended hydrogen bonding network established in ChAc:U.
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The structural properties of the deep eutectic solvent (DES) formed by choline chloride (ChCl) and sesamol in 1 : 3 ratio have been investigated and compared to those of reline (ChCl : urea 1 : 2). An integrated approach combining small and wide angle X-ray scattering with molecular dynamics simulations has been employed and the simulation protocol has been validated against the experimental data. In the ChCl : sesamol DES, strong hydrogen bonds (HBs) are formed between the chloride anion and the hydroxyl groups of the choline and of sesamol molecules. Conversely, choline-choline, choline-sesamol and sesamol-sesamol interactions are negligible. A more extended interplay between the constituents is observed in reline where, besides the HBs involving the chloride anion, the eutectic formation is favored also by strong choline-urea and urea-urea interactions. The three-dimensional arrangement around the individual components shows that, in the ChCl : sesamol DES, the cholinium cations and the sesamol molecules are packed in such a way to maximize the interactions with the chlorine anion. This structural arrangement may favor the π-π interactions between the sesamol molecules and the aromatic species mediated by the chloride ions, providing an interpretation for the high separation rates previously observed for phenolic DESs towards aromatic compounds.
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The composites based on basalt fibres and poly(lactic acid) (PLA) show promising applications in biomedical and automotive fields, but their mechanical performance is still largely hindered by poor interfacial properties. Zinc oxide nanorods have been successfully used to tune the PLA/basalt fibre interface by growing them on commercially available basalt fabrics. The hierarchical fibres significantly enhanced the mechanical properties of PLA-based composites, especially their flexural strength and stiffness. These values are 26% and 22% higher than those of unmodified basalt/PLA composites, and 24% and 34% higher than those of glass/PLA composites used as a baseline. The increase in tensile and flexural properties hinges on the mechanical interlocking action promoted by ZnO nanorods and on the creation of a compact transcrystallinity structure. A degradation of PLA matrix was detected but it was positively counteracted by the better interfacial stress transfer. This study offers a novel approach for modifying the fibre-matrix interface of biocomposites intended for high-performance applications.
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Nanopartículas del Metal/química , Nanotubos/química , Poliésteres/química , Óxido de Zinc/química , Materiales Biocompatibles/química , Rastreo Diferencial de Calorimetría , Cristalización , Vidrio , Calor , Cinética , Ensayo de Materiales , Microscopía Electrónica de Rastreo , Nanocompuestos/química , Nanopartículas , Polímeros/química , Silicatos/química , Estrés Mecánico , Temperatura , Resistencia a la Tracción , Difracción de Rayos X , Zinc/químicaRESUMEN
Scaffolds are three-dimensional porous structures that must have specific requirements to be applied in tissue engineering. Therefore, the study of factors affecting scaffold performance is of great importance. In this work, the optimal conditions for cross-linking preformed chitosan (CS) scaffolds by the tripolyphosphate polyanion (TPP) were investigated. The effect on scaffold physico-chemical properties of different concentrations of chitosan (1 and 2% w/v) and tripolyphosphate (1 and 2% w/v) as well as of cross-linking reaction times (2, 4, or 8 h) were studied. It was evidenced that a low CS concentration favored the formation of three-dimensional porous structures with a good pore interconnection while the use of more severe conditions in the cross-linking reaction (high TPP concentration and crosslinking reaction time) led to scaffolds with a suitable pore homogeneity, thermal stability, swelling behavior, and mechanical properties, but having a low pore interconnectivity. Preliminary biocompatibility tests showed a good osteoblasts' viability when cultured on the scaffold obtained by CS 1%, TPP 1%, and an 8-h crosslinking time. These findings suggest how modulation of scaffold cross-linking conditions may permit to obtain chitosan scaffold with properly tuned morphological, mechanical and biological properties for application in the tissue regeneration field.
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Wound healing is a dynamic process that can be seriously delayed by many factors including infectious complications. The development of dressings with intrinsic wound healing activity and/or releasing bioactive compounds may help with addressing such an issue. In this study, hyaluronic acid (HA) at different percentages (1-35%) was used to modify chitosan (CS) biological and physico-chemical properties in order to obtain 2D-matrices able to promote healing and protect from infection. HA incorporation in the CS matrix decreased film transparency and homogeneity, but improved film water uptake and surface wettability. The water vapor transmission rate (WVTR) increased up to a 5% HA content, where it reached the highest value (672 g/m2 day), and decreased for higher HA contents. At all of the tested HA concentrations, HA affected mechanical properties providing matrices more flexible than pure CS with benefit for wound care. Pure CS films permitted S. epidermidis adhesion and biofilm formation. That was not true for CS/HA matrices, where HA at concentrations equal to or greater than 5% was able to avoid S. epidermidis adhesion. Fibroblasts adhesion also took benefit from the HA presence in the film, especially at 5% content, where the best adhesion and proliferation was found.
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Vendajes , Quitosano , Fibroblastos/metabolismo , Ácido Hialurónico , Membranas Artificiales , Staphylococcus epidermidis/crecimiento & desarrollo , Adhesión Bacteriana , Adhesión Celular , Células Cultivadas , Fibroblastos/microbiología , Fibroblastos/patología , Humanos , MasculinoRESUMEN
This paper illustrates the development of a procedure based on the use of a low transition temperature mixture (LTTM) for the dispersive liquid-liquid microextraction (DLLME) of fungicides, insecticides and acaricides from surface waters. The LTTM preparation involves the heat-mixing of choline chloride and acetylsalicylic acid in a molar ratio 1:2 (ChCl(ASA)2). The resulting mixture appears as a clear viscous liquid at room-temperature, denser than water (1.20⯱â¯0.01â¯g mL-1). For its characterization, differential scanning calorimetry (DSC) provided crucial evidence to classify it as a LTTM rather than as a deep eutectic solvent (DES) since it revealed an intense glass transition at -37⯰C. Large-angle X-ray scattering (LAXS) confirmed the lack of any long-distance order. Due to the LTTM immiscibility with water, an evaluation study was carried out to test ChCl(ASA)2 as an effective alternative to the conventional chlorinated solvents for DLLME. To this end, 24 pesticides were used as model compounds, extracted from surface water samples (5â¯mL) and analyzed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The definitive procedure required the optimization of some key parameters such as volume of extracting solvent, type and volume of dispersing solvent, volume of the aqueous sample, LTTM dispersion procedure, and extraction time. Depending on pKa and logP values, recoveries ranged from 18 (for very polar compounds) to 96%, revealing that the ideal candidates for the extraction with ChCl(ASA)2 are neutral compounds with logP >2. After complete validation, the method was applied to analyze water samples from the River Tiber where dodine and dimetomorph were found at low µg L-1 concentration levels.
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Monitoreo del Ambiente/métodos , Microextracción en Fase Líquida , Plaguicidas/aislamiento & purificación , Temperatura de Transición , Contaminantes Químicos del Agua/aislamiento & purificación , Agua/química , Cromatografía Líquida de Alta Presión , Hormonas Juveniles , Plaguicidas/análisis , Solventes/química , Espectrometría de Masas en Tándem , Contaminantes Químicos del Agua/análisisRESUMEN
Despite advances in material sciences and clinical procedures for surgical hygiene, medical device implantation still exposes patients to the risk of developing local or systemic infections. The development of efficacious antimicrobial/antifouling materials may help with addressing such an issue. In this framework, polyethylene glycol (PEG)-grafted segmented polyurethanes were synthesized, physico-chemically characterized, and evaluated with respect to their bacterial fouling-resistance properties. PEG grafting significantly altered the polymer bulk and surface properties. Specifically, the PEG-grafted polyurethanes possessed a more pronounced hard/soft phase segregated microstructure, which contributed to improving the mechanical resistance of the polymers. The better flexibility of the soft phase in the PEG-functionalized polyurethanes compared to the pristine polyurethane (PU) was presumably also responsible for the higher ability of the polymer to uptake water. Additionally, dynamic contact angle measurements evidenced phenomena of surface reorganization of the PEG-functionalized polyurethanes, presumably involving the exposition of the polar PEG chains towards water. As a consequence, Staphylococcus epidermidis initial adhesion onto the surface of the PEG-functionalized PU was essentially inhibited. That was not true for the pristine PU. Biofilm formation was also strongly reduced.