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Weak polyelectrolyte chains are versatile polymeric materials due to the large number of functional groups that can be used in different environmental applications. Herein, one weak polycation (polyethyleneimine, PEI) and two polyanions (poly(acrylic acid), PAA, and poly(sodium methacrylate), PMAA) were directly deposited through precipitation of an inter-polyelectrolyte coacervate onto the silica surface (IS), followed by glutaraldehyde (GA) crosslinking and extraction of polyanions chains. Four core-shell composites based on silica were synthesized and tested for adsorption of lead (Pb 2+ ) and nickel (Ni 2+ ) as model pollutants in batch sorption experiments on the laboratory scale. The sorbed/desorbed amounts depended on the crosslinking degree of the composite shell, as well as on the type of anionic polyelectrolyte. After multiple loading/release cycles of the heavy metal ions, the maximum sorption capacities were situated between 5-10 mg Pb 2+ /g composite and 1-6 mg Ni 2+ /g composite. The strong crosslinked composites (r = 1.0) exhibited higher amounts of heavy metal ions (Me 2+ ) sorbed than the less crosslinked ones, with less PEI on the surface but with more flexible chains being more efficient than more PEI with less flexible chains. Core-shell composites based on silica and weak polyelectrolytes could act as sorbent materials, which may be used in water or wastewater treatment.

This study continues the discussion on the surface modification of polymers using an atmospheric pressure plasma (APP) reactor in air. These results complement prior research focusing on nonpolar polymers. Polymers, such as polyethylene terephthalate, polyetheretherketone, and polymethyl methacrylate, containing structurally bonded oxygen are studied, representing a range of properties such as oxygen content, crystalline/amorphous structure, polarity, functionality, and aliphatic/aromatic structure. APP induces superior wetting properties on the hydrophilic polymer surfaces with rapid and uniform modification within 0.5 s of exposure. The amorphous structures undergo additional modification for longer exposure. Moreover, the aliphatic chain structures require longer plasma exposure to reach surface modification equilibrium. The polar polymers reach a limit level of modification corresponding to a minimum water contact angle of about 50°. The surface polarity increases on average by a factor of approximately two. The equilibrium values of the adhesion work attained after post-processing recovery fall within a limited range of about 100-120 mJ/m 2 . The enhancement of surface functionality through the creation of oxidized groups primarily depends on the initial oxygen content and reaches a limit of about 40 at.% oxygen. The surface properties of the treated polar surfaces exhibit good stability, comparable to that of the previously tested nonpolar polymers.

Pharmaceuticals and heavy metals pose significant risks to human health and aquatic ecosystems, necessitating their removal from water and wastewater. A promising alternative for this purpose involves their removal by adsorption on composite sorbents prepared using a conventional layer-by-layer (LbL) method or an innovative coacervate direct deposition approach. In this study, four novel composite materials based on a silica core (IS) and a polyelectrolyte coacervate shell were used for the investigation of dynamic adsorption of three heavy metals (lead, nickel and cadmium) and an organic drug model (diclofenac sodium salt, DCF-Na). The four types of composite sorbents were tested for the first time in dynamic conditions (columns with continuous flow), and the column conditions were similar to those used in wastewater treatment plants. The influence of the polyanion nature (poly(acrylic acid) (PAA) vs. poly(sodium methacrylate) (PMAA)), maintaining a constant poly(ethyleneimine) (PEI), and the cross-linking degree (r = 0.1 and r = 1.0) of PEI chains on the immobilization of these pollutants (inorganic vs. organic) on the same type of composite was also studied. The experiments involved both single- and multi-component aqueous solutions. The kinetics of the dynamic adsorption process were examined using two non-linear models: the Thomas and Yoon-Nelson models. The tested sorbents demonstrated good adsorption capacities with affinities for the metal ions in the following order: Pb 2+ > Cd 2+ > Ni 2+ . An increase in the initial diclofenac sodium concentration led to an enhanced adsorption capacity of the IS/(PEI-PAA) c-r1 sorbent. The calculated sorption capacities were in good agreement with the adsorption capacity predicted by the Thomas and Yoon-Nelson models. The substantial affinity observed between DCF-Na and a column containing composite microparticles saturated with heavy metal ions was explained., Competing Interests: The authors declare no conflict of interest.

Currently, the epoxy resin market is expressing concerns about epoxy resins' non-recyclability, which can hinder their widespread use. Moreover, epoxy monomers are synthesized via petroleum-based raw materials, which also limits their use. So, it is crucial to find more environmentally friendly alternative solution for their formulation. Within this context, the aim of this paper is to exploit a Cradle-to-Cradle approach, which consists of remodeling and reshaping the productive cycle of consumer products to make sure that they can be infinitely reused rather than just being recycled with a downgrading of their properties or uses, according to the principle of the complete circular economy. Indeed, after starting with a fully-recyclable bio-based epoxy formulation and assessing its recyclability as having a process yield of 99%, we obtained a recycled polymer that could be reused, mixing with the same bio-based epoxy formulation with percentages varying from 15 wt% to 27 wt%. The formulation obtained was thoroughly characterized by a dynamic-mechanical analysis, differential scanning calorimetry, and flexural tests. This approach had two advantages: (1) it represented a sustainable disposal route for the epoxy resin, with nearly all the epoxy resin recovered, and (2) the obtained recycled polymer could be used as a green component of the primary bio-based epoxy matrix. In the end, by using replicated general factorial designs (as statistical tools) combined with a proper optimization process, after carrying out a complete thermo-mechanical characterization of the developed epoxy formulations, the right percentage of recycled polymer content was selected with the aim of identifying the most performing epoxy matrix formulation in terms of its thermo-mechanical properties.

Intrathecal pseudodelivery of drugs is a novel route to administer medications to treat neurodegenerative diseases based on the CSF-sink therapeutic strategy by means of implantable devices. While the development of this therapy is still in the preclinical stage, it offers promising advantages over traditional routes of drug delivery. In this paper, we describe the rationale of this system and provide a technical report on the mechanism of action, that relies on the use of nanoporous membranes enabling selective molecular permeability. On one side, the membranes do not permit the crossing of certain drugs; whereas, on the other side, they permit the crossing of target molecules present in the CSF. Target molecules, by binding drugs inside the system, are retained or cleaved and subsequently eliminated from the central nervous system. Finally, we provide a list of potential indications, the respective molecular targets, and the proposed therapeutic agents.

This life cycle assessment (LCA) study focused on comparing the environmental performances of two types of synthesis strategies for polyethyleneimine (PEI) coated silica particles (organic/inorganic composites). The classic layer-by-layer and the new approach (one-pot coacervate deposition) were the two synthesis routes that were tested for cadmium ions removal from aqueous solutions by adsorption in equilibrium conditions. Data from the laboratory scale experiments for materials synthesis, testing, and regeneration, were then fed into a life cycle assessment study so that the types and values of environmental impacts associated with these processes could be calculated. Additionally, three eco-design strategies based on material substitution were investigated. The results point out that the one-pot coacervate synthesis route has considerably lower environmental impacts than the layer-by-layer technique. From an LCA methodology point of view, it is important to consider material technical performances when defining the functional unit. From a wider perspective, this research is important as it demonstrates the usefulness of LCA and scenario analysis as environmental support tools for material developers because they highlight environmental hotspots and point out the environmental improvement possibilities from the very early stages of material development.

This article's objective is the synthesis of new composites based on thermoplastic polyurethane (TPU) and TiO 2 nanowires (NWs) as free-standing films, highlighting their structural and optical properties. The free-standing TPU-TiO 2 NW films were prepared by a wet chemical method accompanied by a thermal treatment at 100 °C for 1 h, followed by air-drying for 2 h. X-ray diffraction (XRD) studies indicated that the starting commercial TiO 2 NW sample contains TiO 2 tetragonal anatase (A), cubic Ti 0.91 O (C), and orthorhombic Ti 2 O 3 (OR), as well as monoclinic H 2 Ti 3 O 7 (M). In the presence of TPU, an increase in the ratio between the intensities of the diffraction peaks at 43.4° and 48° belonging to the C and A phases of titanium dioxide, respectively, is reported. The increase in the intensity of the peak at 43.4° is explained to be a consequence of the interaction of TiO 2 NWs with PTU, which occurs when the formation of suboxides takes place. The variation in the ratio of the absorbance of the IR bands peaked at 765-771 cm -1 and 3304-3315 cm -1 from 4.68 to 4.21 and 3.83 for TPU and the TPU-TiO 2 NW composites, respectively, with TiO 2 NW concentration equal to 2 wt.% and 17 wt.%, indicated a decrease in the higher-order aggregates of TPU with a simultaneous increase in the hydrogen bonds established between the amide groups of TPU and the oxygen atoms of TiO 2 NWs. The decrease in the ratio of the intensity of the Raman lines peaked at 658 cm -1 and 635 cm -1 , which were assigned to the vibrational modes E g in TiO 2 A and E g in H 2 Ti 3 O 7 (I TiO2-A /I H2Ti3O7 ), respectively, from 3.45 in TiO 2 NWs to 0.94-0.96 in the TPU-TiO 2 NW composites, which indicates that the adsorption of TPU onto TiO 2 NWs involves an exchange reaction of TPU in the presence of TiO 2 NWs, followed by the formation of new hydrogen bonds between the -NH- of the amide group and the oxygen atoms of Ti x O 2x-mn , Ti 2 O 3 , and Ti 0.91 O. Photoluminescence (PL) studies highlighted a gradual decrease in the intensity of the TPU emission band, which is situated in the spectral range 380-650 nm, in the presence of TiO 2 NW. After increasing the TiO 2 NW concentration in the TPU-TiO 2 NW composite mass from 0 wt.% to 2 wt.% and 17 wt.%, respectively, a change in the binding angle of the TPU onto the TiO 2 NW surface from 12.6° to 32° and 45.9°, respectively, took place.

Fused filament fabrication is a technology of additive manufacturing that uses molten thermoplastics for building parts. Due to the convenient shape of the raw material, a simple filament, the market offers a great variety of materials from simple to blends of compatible materials. However, finding a material with the desired properties can be difficult. Making it in-house or using a material manufacturer can be costly and time-consuming, especially when the optimum blend ratios are unknown or new design perspectives are tested. This paper presents an accessible method of producing core-shell filaments using material extrusion 3D printing. The printed filaments are characterised by a polycarbonate (PC) core and acryl butadiene styrene (ABS) shell with three material ratios. Their performance was investigated through printed samples. Additionally, the material mixing degree was studied by varying the extrusion temperature, nozzle feeding geometry, and layer thickness. The influence of all four factors was evaluated using a graphical representation of the main effects. The results showed that a core-shell filament can be processed using a 3D printer with a dual extrusion configuration and that the mechanical properties of the samples can be improved by varying the PC-ABS ratio. This research provides an accessible method for developing new hybrid filaments with a predesigned structure using a 3D printer.

Advanced wastewater treatment processes are required to implement wastewater reuse in agriculture or industry, the efficient removal of targeted priority and emerging organic & inorganic pollutants being compulsory (due to their eco-toxicological and human health effects, bio-accumulative, and degradation characteristics). Various processes such as membrane separations, adsorption, advanced oxidation, filtration, disinfection may be used in combination with one or more conventional treatment stages, but technical and environmental criteria are important to assess their application. Natural and synthetic polyelectrolytes combined with some inorganic materials or other organic or inorganic polymers create new materials (composites) that are currently used in sorption of toxic pollutants. The recent developments on the synthesis and characterization of composites based on polyelectrolytes, divided according to their macroscopic shape-beads, core-shell, gels, nanofibers, membranes-are discussed, and a correlation of their actual structure and properties with the adsorption mechanisms and removal efficiencies of various pollutants in aqueous media (priority and emerging pollutants or other model pollutants) are presented.

Composites of magnetite (Fe 3 O 4 ) nanoparticles dispersed in a polydimethylsiloxane (PDMS) matrix were prepared by a molding process. Two types of samples were obtained by free polymerization with randomly dispersed particles and by polymerization in an applied magnetic field. The magnetite nanoparticles were obtained from magnetic micrograins of acicular goethite (α-FeOOH) and spherical hematite (α-Fe 2 O 3 ), as demonstrated by XRD measurements. The evaluation of morphological and compositional properties of the PDMS:Fe 3 O 4 composites, performed by SEM and EDX, showed that the magnetic particles were uniformly distributed in the polymer matrix. Addition of magnetic dispersions promotes an increase of thermal conductivity compared with pristine PDMS, while further orienting the powders in a magnetic field during the polymerization process induces a decrease of the thermal conductivity compared with the un-oriented samples. The shape of the magnetic dispersions is an important factor, acicular dispersions providing a higher value for thermal conductivity compared with classic commercial powders with almost spherical shapes.

In this work, new films containing composite materials based on blends of thermoplastic polymers of the polyurethane (TPU) and polyolefin (TPO) type, in the absence and presence of BaTiO 3 nanoparticles (NPs) with the size smaller 100 nm, were prepared. The vibrational properties of the free films depending on the weight ratio of the two thermoplastic polymers were studied. Our results demonstrate that these films are optically active, with strong, broad, and adjustable photoluminescence by varying the amount of TPU. The crystalline structure of BaTiO 3 and the influence of thermoplastic polymers on the crystallization process of these inorganic NPs were determined by X-ray diffraction (XRD) studies. The vibrational changes induced in the thermoplastic polymer's matrix of the BaTiO 3 NPs were showcased by Raman scattering and FTIR spectroscopy. The incorporation of BaTiO 3 NPs in the matrix of thermoplastic elastomers revealed the shift dependence of the photoluminescence (PL) band depending on the BaTiO 3 NP concentration, which was capable of covering a wide visible spectral range. The dependencies of the dielectric relaxation phenomena with the weight of BaTiO 3 NPs in thermoplastic polymers blends were also demonstrated.

The Terahertz's wavelength is located between the microwave and the infrared region of the electromagnetic spectrum. Because it is non-ionizing and non-invasive, Terahertz (THz)-based detection represents a very attractive tool for repeated assessments, patient monitoring, and follow-up. Cancer acts as the second leading cause of death in many regions, and current predictions estimate a continuous increasing trend. Of all types of tumors, digestive cancers represent an important percentage and their incidence is expected to increase more rapidly than other tumor types due to unhealthy lifestyle habits. Because it can precisely differentiate between different types of molecules, depending on water content, the information obtained through THz-based scanning could have several uses in the management of cancer patients and, more importantly, in the early detection of different solid tumors. The purpose of this manuscript is to offer a comprehensive overview of current data available on THz-based detection for digestive cancers. It summarizes the characteristics of THz waves and their interaction with tissues and subsequently presents available THz-based technologies (THz spectroscopy, THz-tomography, and THZ-endoscope) and their potential for future clinical use. The third part of the review is focused on highlighting current in vitro and in vivo research progress in the field, for identifying specific digestive cancers known as oral, esophageal, gastric, colonic, hepatic, and pancreatic tumors.

Vasopressin (VP) is one of the principal transmitters in the suprachiasmatic nucleus (SCN). Approximately 20% of neurones in the dorsomedial division of the SCN synthesize the peptide and a high proportion of SCN neurones (> 40%) are excited by VP acting through the V1 receptor. This suggests that VP may act as a feedback regulator of electrical activity within the nucleus. Such an intrinsic excitatory signal can be demonstrated by perifusion with a V1 antagonist which reduces spontaneous neural activity. As the synthesis and release of VP occurs in a circadian manner, this leads to a variable feedback excitation which may contribute to the circadian pattern of activity of the neural clock. This role in amplifying rhythmicity is supported by observations that animals deficient in VP show a reduced circadian amplitude of behavioural rhythms (e.g. locomotor and cortical electroencephalographic rhythms). VP expression declines during ageing and although aged animals show no change in the proportion of SCN neurones excited by VP, the rhythm of spontaneous electrical activity shows a progressive decline, consistent with the reduced endogenous excitatory feedback. However, the homozygous Brattleboro rat which lacks any VP expression still maintains rhythms of electrical activity, indicating that VP is not the sole factor generating circadian activity. The generation of this rhythmicity may depend upon the interaction of VP with other transmitter systems, such as the inhibitory transmitters somatostatin and GABA which show a circadian variation in efficacy. In addition to its role in feedback amplification of the endogenous rhythm of electrical activity, VP also functions as part of the efferent signal to the rest of the CNS where it potentially regulates a number of behavioural and physiological rhythms, including the circadian activity of the hypothalamo-pituitary-adrenal axis. Thus, the combined amplification and signalling functions makes VP an important component of the neuronal clock function in mammals.