Eco-Friendly Blends of Recycled PET Copolymers with PLLA and Their Composites with Chopped Flax Fibres.

The structure and properties of blends of a novel polyethylene terephthalate copolymer (COPET) obtained by chemical recycling of commercial PET with high-molar-mass poly-L-lactide (PLLA) are investigated and compared to corresponding composites with chopped flax fibres. The focus is on the morphology at nano- and micro-scales, on the thermal characteristics and on the mechanical behaviour. The blends are immiscible, as evidenced by virtually unchanged glass transition temperatures of the blend components compared to the neat polymers (49 °C for COPET and 63 °C for PLLA by DSC). At low PLLA content, the blends display a sea-island morphology with sub-micron to micron droplet sizes. As the composition approaches 50/50, the morphology transitions to a coarser co-continuous elongated structure. The blends and composites show strongly improved stiffness compared to COPET above its glass transition temperature, e.g., from melt behaviour at 60 °C for COPET alone to almost 600 MPa for the 50/50 blend and 500 MPa for the 20% flax composite of the 80/20 COPET/PLLA blend. The flax fibres increase the crystallisation rate of PLLA in blends with dispersed PLLA morphology. The evidence of cavitation on the fracture surfaces of blends shows that despite the immiscibility of the components, the interfacial adhesion between the phases is excellent. This is attributed to the presence of aliphatic ester spacers in COPET. The tensile strength of the 80/20 blend is around 50 MPa with a Young's modulus of 2250 MPa. The corresponding 20% flax composite has similar tensile strength but a high Young's modulus equal to 6400 MPa, which results from the individual dispersion and strong adhesion of the flax fibres and leads close to the maximum possible reinforcement of the composite, as demonstrated by tensile tests and nano-indentation. The Ashby approach to eco-selection relying on the embodied energy (EE) further clarifies the eco-friendliness of the blends and their composites, which are even better positioned than PLLA in a stiffness versus EE chart.

Poly-ɛ-caprolactone nanocapsules loaded with copaiba essential oil reduce inflammation and pain in mice.

Diverse drugs have been used for the management of inflammation disorders and pain. However, they present many side effects and stimulate the search for new pharmacotherapeutic alternatives. Plant-derived products such as copaiba essential oil (CO) offer beneficial pharmacological effects. On the other hand, essential oil's low water solubility and physical instability hinder its in vivo application. Thus, poly-ɛ-caprolactone (PCL)-based nanocarriers have been used to increase their stability and efficacy. This work aimed to encapsulate CO in PCL nanocapsules and evaluate their effect on inflammation models and pain. The polymeric nanocapsules loading CO (CO-NC) were prepared by nanoprecipitation technique, characterized, and analyzed for their anti-inflammatory effect in vitro and in vivo. The results showed that CO-NC presented a spherical shape, 229.3 ± 1.5 nm diameter, and a negative zeta potential (approximately -23 mV). CO and CO-NC presented anti-inflammatory and antioxidant effects by LPS-activated macrophages (J774 cells). In addition, CO-NC significantly reduced TNF-α secretion (3-fold) compared to CO. In vivo, pre-treatment with CO or CO-NC (50, 100, 200 mg/kg, intraperitoneal; i.p) reduced the mechanical allodynia, paw edema, and pro-inflammatory cytokines induced by intraplantar (i.pl) injection of carrageenan in mice. Specifically, CO-NC (200 mg/kg; i.p.) reduced the production of TNF-α similar to the control group. Our results support using polymeric nanocapsules for CO delivery in inflammatory conditions.

Quantifying the local mechanical properties of twisted double bilayer graphene.

Nanomechanical measurements of minimally twisted van der Waals materials remained elusive despite their fundamental importance for device realisation. Here, we use Ultrasonic Force Microscopy (UFM) to locally quantify the variation of out-of-plane Young's modulus in minimally twisted double bilayer graphene (TDBG). We reveal a softening of the Young's modulus by 7% and 17% along single and double domain walls, respectively. Our experimental results are confirmed by force-field relaxation models. This study highlights the strong tunability of nanomechanical properties in engineered twisted materials, and paves the way for future applications of designer 2D nanomechanical systems.

Lecithin-based nanocapsule loading sucupira (Pterodon emarginatus) oil effects in experimental mucositis.

Intestinal mucositis (IM) is a frequent adverse effect in anticancer therapy without standard treatment. The oil obtained from sucupira (Pterodon emarginatus) has anti-inflammatory properties, and the soybean lecithin reduces the intestinal toxicity of several xenobiotics. However, their water insolubility impairs the in vivo application. For this reason, we evaluated if the nanoencapsulation of sucupira oil (SO) in lecithin-based nanocapsules (SO-NC) could be a therapeutically effective system for the treatment of IM in murine cisplatin (CDDP)-induced intestinal mucositis model. SO was analyzed by LC-HRMS/MS and HPLC. SO-NC was prepared by nanoprecipitation and characterized using DLS, HPLC, and AFM. Mice body weight and food consumption were assessed daily during experimental mucositis induced by CDDP. The animals were euthanized, and intestinal permeability, inflammatory mediators, and intestinal histology were performed. SO-NC demonstrated adequate characteristics for oral administration as size under 300 nm, IP < 0.3, high EE, and spherical shape. In vitro cytotoxicity performed against RAW 264.7 cell lines resulted in cell viability above 80 % confirming the non-cytotoxic profile of SO (IC50 268 µg/mL) and SO-NC (IC50 118.5 µg/mL) up to 117.2 µg/mL. The untreated mice showed intestinal toxicity after i.p. of CDDP, principally weight loss, increased intestinal permeability, and MPO and TNF-α levels. Surprisingly, the administration of SO to CDDP-mucositis animals did not circumvent the CDDP effects and increased intestinal permeability. However, SO-NC proved efficient in mitigating the experimental intestinal mucositis by improving intestinal epithelium architecture, reducing intestinal permeability, and improving the MPO levels. In conclusion, SO-NC can positively impact intestinal mucositis by promoting mucosal recovery. This is a promising strategy for developing a new treatment for intestinal mucositis.

Integrated Approach to Eco-Friendly Thermoplastic Composites Based on Chemically Recycled PET Co-Polymers Reinforced with Treated Banana Fibres.

A major societal issue of disposal and environmental pollution is raised by the enormous and fast-growing production of single-use polyethylene terephthalate (PET) bottles, especially in developing countries. To contribute to the problem solution, an original route to recycle PET in the form of value-added environmentally friendly thermoplastic composites with banana fibres (Musa acuminata) has been developed at the laboratory scale. Banana fibres are a so far undervalued by-product of banana crops with great potential as polymer reinforcement. The melt-processing constraints of commercial PET, including used bottles, being incompatible with the thermal stability limits use of natural fibres; PET has been modified with bio-sourced reactants to produce co-polymers with moderate processing temperatures below 200 °C. First, commercial PET were partially glycolyzed with 1.3-propanediol to produce co-oligomers of about 20 repeating units, which were next chain extended with succinic anhydride and post-treated in a very unusual "soft solid state" process at temperatures in the vicinity of the melting point to generate co-polymers with excellent ductility. The molar mass build-up reaction is dominated by esterification of the chain ends and benefits from the addition of succinic anhydride to rebalance the acid-to-hydroxyl end-group ratio. Infra-red spectroscopy and intrinsic viscosity were extensively used to quantify the concentration of chain ends and the average molar mass of the co-polymers at all stages of the process. The best co-polymers are crystallisable, though at slow kinetics, with a Tg of 48 °C and a melting point strongly dependent upon thermal history. The composites show high stiffness (4.8 GPa at 20% fibres), consistent with the excellent dispersion of the fibres and a very high interfacial cohesion. The strong adhesion can be tentatively explained by covalent bonding involving unreacted succinic anhydride in excess during solid stating. A first approach to quantify the sustainable benefits of this PET recycling route, based on a rational eco-selection method, gives promising results since the composites come close to low-end wood materials in terms of the stiffness/embodied energy balance. Moreover, this approach can easily be extended to many other natural fibres. The present study is limited to a proof of concept at the laboratory scale but is encouraging enough to warrant a follow-up study toward scale-up and application development.

The ion partition detected in homeopathically manufactured medicine cuprum metallicum and controls

Homeopathy is highly controversial. The main reason for this is its use of very highly dilute medicines (high homeopathic potencies, HHP), diluted beyond the Avogadro/Loschmidt limit. Research using Nano Tracking Analysis has demonstrated the presence of particles in HHPs. This study aims to verify the results of a previous publication that identified the ionic composition of these particles in all dilutions. We used Scanning Electron Microscopy & Energy Dispersive X-Ray Spectroscopy (SEM-EDX) to examine dilutions of a commonly used homeopathic medicine, an insoluble metal, Cuprum metallicum, for the presence of particles (NPs). The homeopathic medicines tested were specially prepared according to the European pharmacopoeia standards. We compared the homeopathic dilutions/dynamizations of copper with simple dilutions and dynamized lactose controls. We observed an ionic diversity common to all preparations including HHPs but also significant differences in the relative quantity of each ion between manufacturing lines of homeopathic copper and lactose controls. The probability that the observed differences could have occurred chance alone (especially above Avogadro limit) can be rejected at p < 0.001. The essential component of these homeopathic medicines is sodium hydrogen carbonate, modulated by some other elements and by its quantity, size and shape. Homeopathic medicines made of Cuprum metallicum do contain material with a specific ionic composition even in HHPs diluted beyond the Avogadro/Loschmidt limit. This specificity can be attributed to the manufacturing process. This material demonstrates that the step-by-step process (dynamized or not) does not match the theoretical expectations of a dilution process. The starting material and dilution/dynamization method influences the nature of these NPs. Further measurements are needed on other raw materials using the same controls (solvent and simply diluted manufacturing lines) to support these findings. The role of sodium bicarbonate must be carefully studied in the future.

One-Step Aqueous Spraying Process for the Fabrication of Omniphobic Fabrics Free of Long Perfluoroalkyl Chains.

We report on a simple and versatile method for the preparation in one-step of omniphobic textiles, using only aqueous suspensions of silica particles and polyurethane devoid of long perfluoroalkyl chains (C8) that are now legally-banned because of severe environmental concerns. The omniphobic coatings can be applied on different substrates including fabrics, can resist acidic and basic conditions and a moderate number of washing cycles, and repel liquids such as n-octane, dodecane, hexadecane, ethylene glycol, glycerol, olive oil, and water. Analysis of the wetting properties of coated fabrics indicates that the liquid repellence results from the trapping of air in the re-entrant roughness created by aggregates of silica particles, together with the low surface tension of the polyurethane which bears legally accepted short perfluoroalkyl chains (C4). Our study is a significant step forward toward achieving more environmentally-friendly and robust omniphobic textiles.

Layer-by-layer assembly of enzyme-loaded halloysite nanotubes for the fabrication of highly active coatings.

The development of sturdy enzyme-containing hydrophilic coatings is important for applications such as water purification or biological sensing. Here, we investigate the encapsulation of a model enzyme (beta-lactamase, BlaP) into aluminosilicate halloysite nanotubes (HNTs), and their subsequent use for the fabrication of enzymatic coatings by layer-by-layer (LbL) assembly. Highly stable suspensions of enzymatically-active halloysite nanotubes were obtained by alkaline treatment of HNTs, followed by enzyme adsorption into the lumen of the nanotubes and of poly(ethylene imine) (PEI) onto their outer surface. Bioactive thin films based on the LbL-assembly of these modified nanotubes with negatively-charged alginate provided coatings with a significantly higher enzymatic activity compared to films in which the enzyme is not incorporated in the nanotubes. The obtained results show that the encapsulation of an enzyme in halloysite nanotubes is a viable route towards stable bioactive coatings, which could be easily adapted to entrap other types of biomacromolecules with the aim of preparing thin films for air or effluent decontamination.

Environmentally Friendly Super-Water-Repellent Fabrics Prepared from Water-Based Suspensions.

We report on a facile, versatile, and environmentally friendly method to prepare superhydrophobic fabrics by a simple dip-coating method in water-based suspensions and emulsions. All the materials used are fluorine-free and commercially available at a large scale. The method can be easily integrated into standard textile industrial processes and has a strong potential for the mass production of environmentally friendly superwater-repellent fabrics. The produced fabrics show good resistance to machine washing and acidic or alkaline treatments. In addition, it is shown that superhydrophobicity can be quantitatively predicted based on the combination of the roughness of the fabric and of the fiber coating.

Room-Temperature Magnetic Switching of the Electric Polarization in Ferroelectric Nanopillars.

Magnetoelectric layers with a strong coupling between ferroelectricity and ferromagnetism offer attractive opportunities for the design of new device architectures such as dual-channel memory and multiresponsive sensors and actuators. However, materials in which a magnetic field can switch an electric polarization are extremely rare, work most often only at very low temperatures, and/or comprise complex materials difficult to integrate. Here, we show that magnetostriction and flexoelectricity can be harnessed to strongly couple electric polarization and magnetism in a regularly nanopatterned magnetic metal/ferroelectric polymer layer, to the point that full reversal of the electric polarization can occur at room temperature by the sole application of a magnetic field. Experiments supported by finite element simulations demonstrate that magnetostriction produces large strain gradients at the base of the ferroelectric nanopillars in the magnetoelectric hybrid layer, translating by flexoelectricity into equivalent electric fields larger than the coercive field of the ferroelectric polymer. Our study shows that flexoelectricity can be advantageously used to create a very strong magnetoelectric coupling in a nanopatterned hybrid layer.

Multiferroic Nanopatterned Hybrid Material with Room-Temperature Magnetic Switching of the Electric Polarization.

A nanopatterned hybrid layer is designed, wherein the electric polarization can be flipped at room temperature by a magnetic field aided by an electrical field. This is achieved by embedding ferromagnetic nanopillars in a continuous organic ferroelectric layer, and amplifying the magnetostriction-generated stress gradients by scaling down the supracrystalline cell of the material.

Growth and toxic gas sensing properties of poly(urethaneimide) thin films.

In this work we present a study on the growth and the gas sensing properties of poly(urethane imide) thin films. We first deeply characterized by atomic force microscopy (AFM) the nanostructuration of the poly(urethane imide) holding different amine groups. We further studied the interaction between highly toxic gases such as hexamethyleneimine (HMI) and pyridine and the polymer by using an unconventional method based on Quartz Crystal Microbalance (QCM) measurement. We showed for the first time that weak interactions, i.e. hydrogen bonding between the gas molecules and the polymer film allow the diffusion of the gas molecule deep in the polymeric film and the recovery of the film once the gas molecules leave the sensor. This first work paves a new way for the design of a completely recoverable sensor able to detect highly toxic gases for environmental concern.

Organic ferroelectric/semiconducting nanowire hybrid layer for memory storage.

Ferroelectric materials are important components of sensors, actuators and non-volatile memories. However, possible device configurations are limited due to the need to provide screening charges to ferroelectric interfaces to avoid depolarization. Here we show that, by alternating ferroelectric and semiconducting nanowires over an insulating substrate, the ferroelectric dipole moment can be stabilized by injected free charge carriers accumulating laterally in the neighboring semiconducting nanowires. This lateral electrostatic coupling between ferroelectric and semiconducting nanowires offers new opportunities to design new device architectures. As an example, we demonstrate the fabrication of an elementary non-volatile memory device in a transistor-like configuration, of which the source-drain current exhibits a typical hysteretic behavior with respect to the poling voltage. The potential for size reduction intrinsic to the nanostructured hybrid layer offers opportunities for the development of strongly miniaturized ferroelectric and piezoelectric devices.

Comparison of the density of proteins and peptides grafted on silane layers and polyelectrolyte multilayers.

Immobilized proteins or peptides are of critical importance for applications such as biosensing or cell culture. We analyze the structure of layers of a large variety of proteins and peptides, grafted on silicon substrates by different routes differing in the nature of the intermediate layer linking the biomolecules to the substrate, either a silane monolayer, or a polyelectrolyte multilayer made from synthetic or natural polymers. The structural analysis is essentially performed by X-ray reflectometry, which proves to be an efficient methodology not requiring the use of tagged biomolecules, capable of evaluating consistently the amount of grafted biomolecules per surface area with estimated precisions ranging from 10 to 20%. The study provides a quantitative basis for selecting one among a series of well-proofed and sturdy grafting methodologies and underlines the potential of XRR for assessing the amount of grafted biomacromolecules without requiring the expensive tagging of molecules. Our results also show that, for the coupling route resting on synthetic polyelectrolytes, the grafting density is significantly lower than for direct coupling over a silane layer. In contrast, when performed over a cushion based on polysaccharides, the grafting density is well above the values found for a dense layer grafted on a silane monolayer, indicating partial penetration and swelling of the polysaccharide cushion.

Layers over layer-by-layer assemblies: silanization of polyelectrolyte multilayers.

The functionalization of poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) polyelectrolyte multilayers by silanes reacted from the gas phase is studied depending on reaction time and temperature, pH of multilayer assembly, and nature of the reacting silane group. Whereas monochlorosilanes only diffuse in the multilayer and graft in limited amount, trichloro- and triethoxysilanes form rapidly a continuous gel layer on the surface of the multilayer, with a thickness of ca. 10-20 nm. The reactivity is lower in the strongly paired regime of the multilayers (neutral assembly conditions) but otherwise is not affected by the pH of multilayer assembly. Silanization considerably broadens the range of possible functionalities for (PAH/PAA) multilayers: hydrophobicity, surface-initiated polymerization, and grafting of fluorescent probes by the formation of disulfide bridges are demonstrated. Conversely, our results also broaden the range of substrates that can be functionalized by silanes, using (PAH/PAA) multilayers as ubiquitous anchoring layers.

Nanoscale design of multifunctional organic layers for low-power high-density memory devices.

We demonstrate the design of a multifunctional organic layer by the rational combination of nanosized regions of two functional polymers. Instead of relying on a spontaneous and random phase separation process or on the tedious synthesis of block copolymers, the method involves the nanomolding of a first component, followed by the filling of the resulting open spaces by a second component. We apply this methodology to fabricate organic nonvolatile memory diodes of high density. These are built by first creating a regular array of ferroelectric nanodots by nanoimprint lithography, followed by the filling of the trenches separating the ferroelectric nanodots with a semiconducting polymer. The modulation of the current in the semiconductor by the polarization state of the ferroelectric material is demonstrated both at the scale of a single semiconductor channel and in a microscopic device measuring about 80,000 channels in parallel, for voltages below ca. 2 V. The fabrication process, which combines synergetically orthogonal functional properties with a fine control over their spatial distribution, is thus demonstrated to be efficient over large areas.

Supramolecular organization in organic-inorganic heterogeneous hybrid catalysts formed from polyoxometalate and poly(ampholyte) polymer.

Hybridization of polyoxometalates (POMs) via the formation of an organic-inorganic association constitutes a new route to develop a heterogeneous POM catalyst with tunable functionality imparted through supramolecular assembly. Herein, we report on strategies to obtain tunable well-defined supramolecular architectures of an organic-inorganic heterogeneous hybrid catalyst formed by the association of a hydrophobically substituted polyampholyte copolymer (poly N, N-diallyl-N-hexylamine-alt-maleic acid) and phosphotungstic acid (H3PW12O40) POMs. The self-assembling property of the initial polyampholyte copolymer matrix is modulated by controlling the pH of the hybridization solution. When deposited on a mica surface, isolated, long and extended polymer chains are formed under basic conditions (pH 7.9), while globular or coiled structures are formed under acidic conditions (pH 2). The supramolecular assembly of the POM-polymer hybrid is found to be directed by the type and quantities of charges present on the polyampholyte copolymer, which themselves depend on the pH conditions. The hypothesis is that the Keggin type [PW12O40](3-) anions, which have a size of ~1 nm, electrostatically bind to the positive charge sites of the polymer backbone. The hybrid material stabilized at pH 5.3 consists of POM-decorated polymer chains. Statistical analysis of distances between pairs of POM entities show narrow density distributions, suggesting that POM entities are attached to the polymer chains with a high level of order. Conversely, under acidic conditions (pH 2), the hybrid shows the formation of a core-shell type of structure. The strategies reported here, to tune the supramolecular assembly of organic-inorganic hybrid materials, are highly valuable for the design and a more rational utilization of POM heterogeneous catalysts in several chemical transformations.

Thicker is better? Synthesis and evaluation of well-defined polymer brushes with controllable catalytic loadings.

Polymer brushes (PBs) have been used as supports for the immobilization of palladium complexes on silicon surfaces. The polymers were grown by surface-initiated atom-transfer radical polymerization (SI-ATRP) and postdecorated with dipyridylamine (dpa) ligands. The pendant dpa units were in turn complexed with [Pd(OAc)(2)] to afford hybrid catalytic surfaces. A series of catalytic samples of various thicknesses (ca. 20-160 nm) and associated palladium loadings (ca. 10-45 nmol cm(-2)) were obtained by adjusting the SI-ATRP reaction time and characterized by ellipsometry, X-ray reflectivity, X-ray photoelectron spectroscopy, and inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS revealed a near-linear relationship between thickness of the polymer brush and palladium content, which confirmed the robustness of the preparation and postmodification sequence presented herein, rendering possible the creation of functional architectures with predefined catalytic potential. The activities of the catalytic PBs were determined by systematically exploring a full range of substrate-to-catalyst ratios in a model palladium(0)-catalyzed reaction. Quantitative transformations were observed for loadings down to 0.03 mol % and a maximum turnover number (TON) of around 3500 was established for the system. Comparison of the catalytic performances evidenced a singular influence of the thickness on conversions and TONs. The limited recyclability of the hairy catalysts has been attributed to palladium leaching.

Grafting control of mainstay terpyridine self-assembled monolayers for the preparation of planar silicon surfaces with variable catalytic loadings.

Monolayers of terpyridine-derivatized silanes were self-assembled, with accurately controlled grafting densities, on single-crystal silicon surfaces. Complexation of the resulting terpyridine monolayers with Pd(OAc)(2) afforded a series of catalytic surfaces covering a full range of Pd loadings (0.14-0.85 nmol.cm(-2)) in the aim to explore their impact on catalysis methodically. X-ray reflectivity (XRR), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma mass spectrometry (ICP-MS) were combined to afford a precise picture of the grafting density, chemical composition, and catalyst loadings of the surfaces investigated here. We report that the control of the terpyridine density and thus the control of catalytic loadings can be achieved through a fine modification of silanization concentrations, which affords surfaces with tunable catalytic activity.

New insight into the "depth of cure" of dimethacrylate-based dental composites.

OBJECTIVES: To demonstrate that determination of the depth of cure of resin-based composites needs to take into account the depth at which the transition between glassy and rubbery states of the resin matrix occurs. METHODS: A commercially available nano-hybrid composite (Grandio) in a thick layer was light cured from one side for 10 or 40 s. Samples were analyzed by Vickers indentation, Raman spectroscopy, atomic force microscopy, electron paramagnetic imaging and differential scanning calorimetry to measure the evolution of the following properties with depth: microhardness, degree of conversion, elastic modulus of the resin matrix, trapped free radical concentration and glass transition temperature. These measurements were compared to the composite thickness remaining after scraping off the uncured, soft composite. RESULTS: There was a progressive decrease in the degree of conversion and microhardness with depth as both properties still exhibited 80% of their upper surface values at 4 and 3.8 mm, respectively, for 10 s samples, and 5.6 and 4.8 mm, respectively, for 40 s samples. In contrast, there was a rapid decrease in elastic modulus at around 2.4 mm for the 10 s samples and 3.0 mm for the 40 s samples. A similar decrease was observed for concentrations of propagating radicals at 2 mm, but not for concentrations of allylic radicals, which decreased progressively. Whereas the upper composite layers presented a glass transition temperature - for 10 s, 55°C (±4) at 1 mm, 56.3°C (±2.3) at 2 mm; for 40 s, 62.3°C (±0.6) at 1 mm, 62°C (±1) at 2 mm, 62°C (±1.7) at 3 mm - the deeper layers did not display any glass transition. The thickness remaining after scraping off the soft composite was 7.01 (±0.07 mm) for 10 s samples and 9.48 (±0.22 mm) for 40 s samples. SIGNIFICANCE: Appropriate methods show that the organic matrix of resin-based composite shifts from a glassy to a gel state at a certain depth. Hence, we propose a new definition for the "depth of cure" as the depth at which the resin matrix switches from a glassy to a rubbery state. Properties currently used to evaluate depth of cure (microhardness, degree of conversion or scraping methods) fail to detect this transition, which results in overestimation of the depth of cure.