Polymers, Volume 12, Issue 4 (April 2020) – 265 articles

The enzymatic ring-opening copolymerization (eROP) of globalide (Gl) and pentadecalactone (PDL) was performed in solution from mixtures of the two macrolactones at ratios covering the whole range of comonomeric compositions. The resulting P(Gl_x-r-PDL_y) random copolyesters were aminofunctionalized by thiol-ene reaction with aminoethanethiol. ROP of γ-benzyl-l-glutamate N-carboxyanhydride initiated by P(Gl_x-r-PDL_y)-NH₂ provided neutral poly(γ-benzyl-l-glutamate)-grafted copolyesters, which were converted by hydrolysis into negatively charged hybrid copolymers. Both water-soluble and nonsoluble copolymers were produced depending on copolymer charge and their grafting degree, and their capacity for self-assembling in nano-objects were comparatively examined. The emulsion solvent-evaporation technique applied to the chloroform-soluble copolymers grafted with benzyl glutamate rendered well-delineated spherical nanoparticles with an average diameter of 200–300 nm. Conversely, micellar solutions in water were produced from copolyesters bearing grafted chains composed of at least 10 units of glutamic acid in the free form. The copolymer micelles were shown to be able to load doxorubicin (DOX) efficiently through electrostatic interactions and also to release the drug at a rate that was markedly pH dependent. Full article

Mineral trioxide aggregate (MTA) is widely used in various dental endodontic applications such as root-end filling, furcal perforation repair, and vital pulp therapy. In spite of many attempts to improve handling properties and reduce the discoloration of MTA, the ideal root canal filling material has yet to be fully developed. The objective of this study was to investigate the setting time, mechanical properties, and biocompatibility of MTA set by a silk fibroin solution. A 5 wt% silk fibroin (SF) solution (a novel hydration accelerant) was used to set SavDen^® MTA and ProRoot^® white MTA (WMTA). Changes in setting time, diametral tensile strength (DTS), material crystallization, in vitro cell viability, and cell morphology were assessed by Vicat needle measurement, a universal testing machine, scanning electron microscopy (SEM), and WST-1 assay, respectively. The initial setting time of ProRoot^® MTA and SavDen^® MTA experienced a drastic decrease of 83.9% and 42.1% when deionized water was replaced by 5 wt% SF solution as the liquid phase. The DTS of SavDen^® MTA showed a significant increase after set by the SF solution in 24 h. A human osteoblast-like cell (MG-63)-based WST-1 assay revealed that both ProRoot^® MTA and SavDen^® MTA hydrated using SF solution did not significantly differ (p > 0.05) in cell viability. MG-63 cells with pseudopodia attachments and nuclear protrusions represent a healthier and more adherent status on the surface of MTA when set with SF solution. The results suggest that the 5 wt% SF solution may be used as an alternative hydration accelerant for MTA in endodontic applications. Full article

Aberrations and the image quality of holographic lenses were evaluated by a Hartmann–Shack (HS) wavefront sensor. Two lenses, one recorded with a symmetrical configuration and the other with an asymmetrical one, were stored in a photopolymer called Biophotopol. Each was reconstructed with two different wavelengths, 473 nm and 633 nm. Different metrics were applied to determine and quantify the aberration of the lenses (Zernike coefficients, Seidel coefficients, Marechal tolerances, root-mean-square (RMS), peak to valley, critical fraction of the pupil), and the quality of the image they provided (Strehl ratio, entropy, cutoff frequency, modulation transfer function (MTF), and area under the MTF). Good agreement between the metrics related to optical quality was obtained. The negative asymmetric holographic lenses had less aberration than the positive symmetric ones. Full article

Organic solar cells (OSCs) are promising renewable energy sources for replacing fossil fuels. The power conversion efficiency (PCE) of OSCs has increased based on tremendous effort in material and device engineering. Still, the stability of OSC, such as long lifetime, negative temperature coefficient, must be enhanced for commercialization. In this study, we investigated OSC performance at a high operating temperature near 300–420 K, which are typical temperature regions in photovoltaic applications, with a different hole-extraction layer (HEL). The metal oxide-based HEL, MoO₃, exhibited stable operating properties with a PCE drop rate of −0.13%/°C, as compared to polymeric HEL, PEDOT:PSS (−0.20%/°C). This performance reduction of polymeric HEL originated from the degradation of the interface in contact with PEDOT:PSS, as compared to the robust inorganic metal oxide HEL. Full article

One of the most successfully procedures used to increase the production of t-resveratrol in Vitis vinifera suspension-cultured cells is the application of cyclodextrins (CDs) and methyl jasmonate (MJ) as elicitors. In particular, β-CDs are characterized by their chemical structure which makes them special, not only by acting as elicitors, but also because they are compounds capable of trapping high added-value hydrophobic molecules such as t-resveratrol. However, the use of β-CDs as elicitors increases the production costs of this compound, making their industrial exploitation economically unfeasible. Therefore, the development of β-CDs recovery strategies is necessary to provide a viable solution to their industrial use. In this work, carboxymethylated and hydroxypropylated β-CDs have been used to form polymers using epichlorohydrin (EPI) as a cross-linking agent. The polymers were coated to Fe₃O₄ nanoparticles and were jointly used with MJ to elicit V. vinifera suspension-cultured cells. Once elicitation experiments were finished, a magnet easily allowed the recovery of polymers, and t-resveratrol was extracted from them by using ethyl acetate. The results indicated that the production of t-resveratrol in the presence of free carboxymethyl-β-CDs was much lower than that found in the presence of carboxymethyl-β-cyclodextrins-EPI polymer coated magnetic nanoparticles. In addition, the maximal levels of t-resveratrol were found at 168 h of elicitation in the presence of 15 g/L hydroxypropyl-β-CDs polymer coated magnetic nanoparticles and MJ, and non-t-resveratrol was found in the extracellular medium, indicating that all the t-resveratrol produced by the cells and secreted into the culture medium was trapped by the polymer and extracted from it. This work also showed that polymers can be regenerated and reused during three cycles of continuous elicitation since the induction and adsorption capacity of hydroxypropyl-β-CDs polymer-coated magnetic nanoparticles after these cycles of elicitation remained high, allowing high concentrations of t-resveratrol to be obtained. Full article

Oriental lacquer is a natural polymeric coating with a satiny texture and excellent characteristics, such as chemical resistance and durability. However, the poor lightfastness resulted in the natural aromatic structures of the urushiol structures limited its suitability for outdoor application. This study aimed at the improvement of the lightfastness by adding the different hindered amine light stafbilizers (HALS) with 2 phr addition as well as the effects on the coating and film property of the refined oriental lacquers (RL). The Cryptomeria japonica plate, glass sheets, and the other substrates were used for finishing. The results showed that the lightfastness of RL film was obviously improved by adding 2 phr HALS of Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (H90) containing -NH group and Bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethyl ethyl) -4-hydroxyphenyl] methyl] butylmalonate (H60) containing -NCH₃ groups. The HALS additions increased the pH value of RL and improved the activities of laccase-catalyzed reaction. Meanwhile, the oxidative polymerization of the side chains of RL was inhibited, caused by a radical scavenging ability of HALS. The changes in the drying process affected not only the curing time, but also the film properties. Among the 2 phr additions of different HALS, the film containing H90 had the best lightfastness. Meanwhile, it kept the most similar properties with RL and shortened the drying time of RL, and it was selected as the best HALS addition under 2 phr in this study. Full article

Inspired by the growing demand for smart and environmentally friendly polymer materials, we employed 2,2′-disulfanediyldianiline (22DTDA) as a chain extender to synthesize a waterborne polyurethane (WPUR). Due to the ortho-substituted structure of the aromatic disulfide, the urea moieties formed a unique microphase structure in the WPUR, its mechanical strength was enhanced more 180 times relative to that of the material prepared without 22DTDA, and excellent self-healing abilities at body temperature in air or under ultrasound in water were obtained. If the self-healing process was carried out at 37 °C, 50 °C or under ultrasound, the ultimate tensile strength and elongation at break of the healed film could reach 13.8 MPa and 1150%, 15.4 MPa and 1215%, or 16 MPa and 1056%, respectively. Moreover, the WPUR films could be re-healed at the same fracture location over three cutting–healing cycles, and the recovery rates of the tensile strength and elongation at break remained almost constant throughout these cycles. Full article

Carbon fiber significantly enhances the mechanical, thermal and electrical properties of rubber composites, which are widely used in aerospace, military, national defense and other cutting-edge fields. The preparation of a high-performance carbon fiber rubber composite has been a research hotspot, because the surface of carbon fiber is smooth, reactive inert and has a poor adhesion with rubber. In this paper, a high-performance rubber composite is prepared by mixing dopamine-modified staple carbon fiber with natural latex, and the mechanisms of modified carbon fiber-reinforced natural latex composite are explored. The experimental results show that the surface-modified staple carbon fiber forms uniform and widely covered polydopamine coatings, which significantly improve the interface adhesion between the carbon fiber and the rubber matrix. Meanwhile, when the concentration of dopamine is 1.5 g/L and the staple carbon fiber is modified for 6h, the carbon fiber rubber composite shows excellent conductivity, thermal conductivity, and dynamic mechanical properties, and its tensile strength is 10.6% higher than that of the unmodified sample. Full article

The effect of crosslinking on vapor permeation behavior of polyelectrolyte membranes was studied. Poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) membranes were crosslinked by using crosslinkers with different lengths between the reactive ends. Crosslinked membranes with a longer crosslinking length showed lower water vapor permeability due to the lower sorption coefficient. It was also shown that the permeation behavior of PAMPS membranes was more affected by sorption than diffusion. For chemical protection applications, the ratio of water over chemical warfare agent permeability (i.e., selectivity) was measured. Due to the high water solubility of polyelectrolytes, crosslinked PAMPS allowed for the selective permeation of water over harmful chemical vapor, showing a selectivity of 20. The addition of electrospun nylon nanofibers in the membranes significantly improved the selectivity to 80, since the embedded nanofibers effectively reduced both diffusion and sorption coefficients of chemical warfare agents. Full article

The combination of topology and CO₂ switchability could provide new options for amphiphilic copolymers. Cyclic molecules supply novel topologies, and CO₂ switching provides stimulus responsiveness. Cyclic poly(2–(diethylamino)ethyl methacrylate)–b–poly(ethylene oxide) and their corresponding block copolymers were prepared from poly(ethylene oxide) and 2–(diethylamino)ethyl methacrylate via atom transfer radical polymerization and Keck allylation with a Hoveyda–Grubbs catalyst. Changes in conductivity, surface activity, and hydrodynamic size were examined to illustrate the switchability of the produced amphiphilic copolymers upon contact with CO₂ in the presence of water. The reversible emulsification and switchable viscosity behaviors of the copolymers were also demonstrated. Full article

Drug delivery constitutes the formulations, technologies, and systems for the transport of pharmaceutical compounds to specific areas in the body to exert safe therapeutic effects. The main criteria for selecting the correct medium for drug delivery are the quantity of the drug being carried and the amount of time required to release the drug. Hence, this research aimed to improve the aforementioned criteria by synthesizing a medium based on calcium carbonate-nanocellulose composite and evaluating its efficiency as a medium for drug delivery. Specifically, the efficiency was assessed in terms of the rates of uptake and release of 5-fluorouracil. Through the evaluation of the morphological and chemical properties of the synthesized composite, the established 3D printing profiles of nanocellulose and CaCO₃ took place following the layer-by-layer films. The 3D printed double laminated CaCO₃-nanocellulose managed to release the 5-fluorouracil as an effective single composition and in a time-controlled manner. Full article

Short fiber reinforced rubber composites have been widely used in rubber products attributed to their excellent wear resistance. However, there are still some serious problems in the processing of short fiber reinforced rubber composites, such as Mooney viscosity increasing, temperature and extrusion pressure rising, and unstable extrusion quality. In particular, short fibers need to be extruded in a specific direction during the molding process, and the problems in this process are particularly prominent. In this manuscript, the influence of gear pump assisted extrusion on the properties of short fiber rubber composites is studied. The experimental results show that the application of a gear pump to assist extrusion could significantly increase the die pressure, reduce the extrusion temperature of the blend, and improve the extrusion efficiency and stability of the blend. Furthermore, it could improve the vulcanization efficiency, increase the tensile strength and tear strength of the compound, reduce wear, and guarantee the quality of extrusion products. Full article

Dynamic crosslinking networks based on Diels–Alder (DA) chemistry and ionic interactions were introduced to maleic anhydride modified ethylene-vinyl acetate copolymer (mEVA) via in situ melt processing. The dual dynamic crosslinking networks were characterized by temperature-dependent FTIR, and the effects on the shape memory properties of mEVA were evaluated with dynamic mechanical thermal analysis and cyclic tensile testing. A crosslinking density was achieved at 2.36 × 10⁻⁴ mol·cm⁻³ for DA-crosslinked mEVA; as a result, the stress at 100% extension was increased from 3.8 to 5.6 MPa, and tensile strength and elongation at break were kept as high as 30.3 MPa and 486%, respectively. The further introduction of 10 wt % zinc methacrylate increased the dynamic crosslinking density to 3.74 × 10⁻⁴ mol·cm⁻³ and the stress at 100% extension to 9.0 MPa, while providing a tensile strength of 28.4 MPa and strain at break of 308%. The combination of reversible DA covalent crosslinking and ionic network in mEVA enabled a fixing ratio of 76.4% and recovery ratio of 99.4%, exhibiting an enhanced shape memory performance, especially at higher temperatures. The enhanced shape memory and mechanical performance of the dual crosslinked mEVA showed promising reprocessing and recycling abilities of the end-of-life products in comparison to traditional peroxide initiated covalent crosslinked counterparts. Full article

Humic acids (HA) exhibit fascinating multifunctional features, yet degradation phenomena as well as poor stability in aqueous environments strongly limit their use. Inorganic nanoparticles are emerging as a powerful interface for the development of robust HA bio-hybrid materials with enhanced chemical stability and tunable properties. Hybrid organic-inorganic SiO₂/HA nanostructures were synthesized via an in-situ sol-gel route, exploiting both physical entrapment and chemical coupling. The latter was achieved through amide bond formation between carboxyl groups of HA and the amino group of 3-aminopropyltriethoxysilane (APTS), as confirmed by Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. Monodisperse hybrid nanoparticles about 90 nm in diameter were obtained in both cases, yet Electron Paramagnetic Resonance (EPR) spectroscopy highlighted the different supramolecular organization of HA. The altered HA conformation was reflected in different antioxidant properties of the conjugated nanoparticles that, however, resulted in being higher than for pure HA. Our findings proved the key role of both components in defining the morphology of the final system, as well as the efficacy of the ceramic component in templating the HA supramolecular organization and consequently tuning their functional features, thus defining a green strategy for bio-waste valorization. Full article

To prepare a porous cellulose acetate (CA) for application as a battery separator, Cd(NO₃)₂·4H₂O was utilized with water-pressure as an external physical force. When the CA was complexed with Cd(NO₃)₂·4H₂O and exposed to external water-pressure, the water-flux through the CA was observed, indicating the generation of pores in the polymer. Furthermore, as the hydraulic pressure increased, the water-flux increased proportionally, indicating the possibility of control for the porosity and pore size. Surprisingly, the value above 250 LMH (L/m²h) observed at the ratio of 1:0.35 (mole ratio of CA: Cd(NO₃)₂·4H₂O) was of higher flux than those of CA/other metal nitrate salts (Ni(NO₃)₂ and Mg(NO₃)₂) complexes. The higher value indicated that the larger and abundant pores were generated in the cellulose acetate at the same water-pressure. Thus, it could be thought that the Cd(NO₃)₂·4H₂O salt played a role as a stronger plasticizer than the other metal nitrate salts such as Ni(NO₃)₂ and Mg(NO₃)₂. These results were attributable to the fact that the atomic radius and ionic radius of the Cd were largest among the three elements, resulting in the relatively larger Cd of the Cd(NO₃)₂ that could easily be dissociated into cations and NO₃⁻ ions. As a result, the free NO₃⁻ ions could be readily hydrated with water molecules, causing the plasticization effect on the chains of cellulose acetate. The coordinative interactions between the CA and Cd(NO₃)₂·4H₂O were investigated by IR spectroscopy. The change of ionic species in Cd(NO₃)₂·4H₂O was analyzed by Raman spectroscopy. Full article

In the field of polymer chemistry, tremendous efforts have been made over the last decade to replace petrochemical monomers with building blocks from renewable resources. In this respect, itaconic acid has been used as an alternative to acrylic acid or maleic acid in unsaturated polyesters for thermal or UV-curing applications. However, examples of poly(ester amide)s from itaconic acid are scarce. Under standard polycondensation reactions, the presence of free amines leads to aza-Michael addition reactions at the α,β-unsaturated double bond of the itaconic acid and isomerization reactions to mesaconic acid. Both reactions make the resulting materials useless as UV-curing polymer resins. To avoid these undesired side reactions, we herein report the use of preformed, well-defined diols containing internal amide bonds. The resulting unsaturated poly(ester amide) resins were analyzed before and after UV-induced crosslinking. Viscosity measurements revealed a strong thixotropic behavior induced by the amide groups, which is usually not detected in structurally similar polyester resins. Full article

In this work, we have used low-molecular-weight (PEG₁₂-b-PCL₆, PEG₁₂-b-PCL₉ or PEG₁₆-b-PLA₃₈; M_W, 1.25–3.45 kDa) biodegradable block co-polymers to construct nano- and micron-scaled hybrid (polymer/lipid) vesicles, by solvent dispersion and electroformation methods, respectively. The hybrid vesicles exhibit physical properties (size, bilayer thickness and small molecule encapsulation) of a vesicular boundary, confirmed by cryogenic transmission electron microscopy, calcein leakage assay and dynamic light scattering. Importantly, we find that these low M_W polymers, on their own, do not self-assemble into polymersomes at nano and micron scales. Using giant unilamellar vesicles (GUVs) model, their surface topographies are homogeneous, independent of cholesterol, suggesting more energetically favorable mixing of lipid and polymer. Despite this mixed topography with a bilayer thickness similar to that of a lipid bilayer, variation in surface topology is demonstrated using the interfacial sensitive phospholipase A₂ (sPLA₂). The biodegradable hybrid vesicles are less sensitive to the phospholipase digestion, reminiscent of PEGylated vesicles, and the degree of sensitivity is polymer-dependent, implying that the nano-scale surface topology can further be tuned by its chemical composition. Our results reveal and emphasize the role of phospholipids in promoting low M_W polymers for spontaneous vesicular self-assembly, generating a functional hybrid lipid-polymer interface. Full article

In the present paper, we investigate the effectiveness of nanocomposites (composed of ultra-high molecular weight polyethylene (UHMWPE) mixed with carbon nano-filler (CNF) and medical grade paraffin oil (PO), from the biological point of view. Wear measurements were carried out without (air) and with lubricant (distilled water, natural, and artificial lubricant), and antibacterial activity and cytotoxicity were evaluated. The results highlighted that the presence of CNF is important in the nanocomposite formulation because it reduces the wear rate and prevents oxidative degradation during its processing. An amount of 1.0 wt % of CNF is best because it reaches the optimal distribution within the polymeric matrix, resulting in the best wear resistant, bio-active, and anti-bacterial nanocomposite among all investigated samples. Full article

Hydrogel materials with a gel-sol conversion due to external environmental changes have potential applications in a wide range of fields, including controlled drug delivery. Succinoglycans are anionic extracellular polysaccharides produced by various bacteria, including Sinorhizobium species, which have diverse applications. In this study, the rheological analysis confirmed that succinoglycan produced by Sinorhizobium meliloti Rm 1021 binds weakly to various metal ions, including Fe²⁺ cations, to maintain a sol form, and binds strongly to Fe³⁺ cations to maintain a gel form. The Fe³⁺-coordinated succinoglycan (Fe³⁺-SG) hydrogel was analyzed by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, circular dichroism (CD), and field-emission scanning electron microscopy (FE-SEM). Our results revealed that the Fe³⁺ cations that coordinated with succinoglycan were converted to Fe²⁺ by a reducing agent and visible light, promoting a gel-sol conversion. The Fe³⁺-SG hydrogel was then successfully used for controlled drug delivery based on gel-sol conversion in the presence of reducing agents and visible light. As succinoglycan is nontoxic, it is a potential material for controlled drug delivery. Full article

Thermoplastic resin transfer molding (T-RTM) is a cutting-edge manufacturing technique for high-volume production of composites with a recyclable thermoplastic matrix. Although a number of reactive thermoplastic matrices as well as industrial manufacturing equipment for T-RTM are commercially available today, the design of a T-RTM mold is still based on the skills and personal experience of the designer. This study summarizes the best knowledge and expertise in mold design and manufacturing and introduces an innovative mold for T-RTM. A concept and basic principles for designing a T-RTM mold are formulated in this study. The mold developed is manufactured and validated. Full article

Mechanical and strain sensing capabilities of carbon nanotube (CNT) reinforced composites manufactured by digital light processing (DLP) 3D printing technology have been studied. Both CNT content and a post-curing treatment effects have been analyzed. It has been observed that post-curing treatment has a significant influence on mechanical properties, with an increase of Young’s modulus and glass transition temperature whereas their effect in electrical properties is not so important. Furthermore, the strain sensing tests show a linear response of electrical resistance with applied strain, with higher values of sensitivity when decreasing CNT content due to a higher interparticle distance. Moreover, the electrical sensitivity of bending tests is significantly lower than in tensile ones due to the compression subjected face effect. Therefore, the good gauge factor values (around 2–3) and the high linear response proves the applicability of the proposed nanocomposites in structural health monitoring applications. Full article

The present work aims to combine the unique properties of cellulose nanofibers (CNF) with polyvinyl alcohol (PVA) to obtain high-performance nanocomposites. CNF were obtained by means of TEMPO-mediated ((2,2,6,6-Tetramethylpiperidin-1-yl)oxyl) oxidation, incorporated into the PVA matrix by means of compounding in a single-screw co-rotating internal mixer and then processed by means of injection molding. It was found that CNF were able to improve the tensile strength of PVA in 85% when 4.50 wt % of CNF were added. In addition, the incorporation of a 2.25 wt % of CNF enhanced the tensile strength to the same level that when 40 wt % of microsized fibers (stone groundwood pulp, SGW) were incorporated, which indicated that CNF possessed significantly higher intrinsic mechanical properties than microsized fibers. SGW was selected as reference for microsized fibers due to their extended use in wood plastic composites. Finally, a micromechanical analysis was performed, obtaining coupling factors near to 0.2, indicating good interphase between CNF and PVA. Overall, it was found that the use of CNF is clearly advantageous to the use of common cellulosic fibers if superior mechanical properties are desired, but there are still some limitations that are related to processing that restrict the reinforcement content at low contents. Full article

The pyrolysis behavior of corn stover and polypropylene during co-pyrolysis was studied using a tube furnace reactor. The effects of mixing ratio of corn stover and polypropylene, pyrolysis temperature, addition amount of catalyst (HZSM-5) and reaction atmosphere (N₂ and CO₂) on the properties of pyrolysis products were studied. The results showed that co-pyrolysis of corn stover and polypropylene can increase the yield of pyrolysis oil. When corn stover:polypropylene = 1:3, the yield of pyrolysis oil was as high as 52.1%, which was 4.5% higher than the theoretical value. With the increase of pyrolysis temperature, the yield of pyrolysis oil increased first and then decreased, and reached the optimal yield at 550 °C. The addition of catalyst (HZSM-5) reduced the proportion of oxygenates and promoted the generation of aromatic hydrocarbons. CO₂ has a certain oxidation effect on the components of pyrolysis oil, which promoted the increase of oxygen-containing aromatics and the reduction of deoxy-aromatic hydrocarbons. This study identified the theoretical basis for the comprehensive utilization of plastic and biomass energy. Full article

A series of well-defined antimicrobial polymers composed of comonomers bearing thiazole ring (2-(((2-(4-methylthiazol-5-yl)ethoxy)carbonyl)oxy)ethyl methacrylate monomer (MTZ)) and non-hemotoxic poly(ethylene glycol) side chains (poly(ethylene glycol) methyl ether methacrylate (PEGMA)) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. By post-polymerization functionalization strategy, polymers were quaternized with either butyl or octyl iodides to result in cationic amphiphilic copolymers incorporating thiazolium groups, thus with variable hydrophobic/hydrophilic balance associated to the length of the alkylating agent. Likewise, the molar percentage of PEGMA was modulated in the copolymers, also affecting the amphiphilicity. The antimicrobial activities of these cationic polymers were determined against Gram-positive and Gram-negative bacteria and fungi. Minimum inhibitory concentration (MIC) was found to be dependent on both length of the alkyl hydrophobic chain and the content of PEGMA in the copolymers. More hydrophobic octylated copolymers were found to be more effective against all tested microorganisms. The incorporation of non-ionic hydrophilic units, PEGMA, reduces the hydrophobicity of the system and the activity is markedly reduced. This effect is dramatic in the case of butylated copolymers, in which the hydrophobic/hydrophilic balance is highly affected. The hemolytic properties of polymers analyzed against human red blood cells were greatly affected by the hydrophobic/hydrophilic balance of the copolymers and the content of PEGMA, which drastically reduces the hemotoxicity. The copolymers containing longer hydrophobic chain, octyl, are much more hemotoxic than their corresponding butylated copolymers. Full article

Peripheral nerves are basic communication structures guiding motor and sensory information from the central nervous system to receptor units. Severed peripheral nerve injuries represent a large clinical problem with relevant challenges to successful synthetic nerve repair scaffolds as substitutes to autologous nerve grafting. Numerous studies reported the use of hollow tubes made of synthetic polymers sutured between severed nerve stumps to promote nerve regeneration while providing protection for external factors, such as scar tissue formation and inflammation. Few approaches have described the potential use of a lumen structure comprised of microchannels or microfibers to provide axon growth avoiding misdirection and fostering proper healing. Here, we report the use of a 3D porous microchannel-based structure made of a photocurable methacrylated polycaprolactone, whose mechanical properties are comparable to native nerves. The neuro-regenerative properties of the polymer were assessed in vitro, prior to the implantation of the 3D porous structure, in a 6-mm rat sciatic nerve gap injury. The manufactured implants were biocompatible and able to be resorbed by the host’s body at a suitable rate, allowing the complete healing of the nerve. The innovative design of the highly porous structure with the axon guiding microchannels, along with the observation of myelinated axons and Schwann cells in the in vivo tests, led to a significant progress towards the standardized use of synthetic 3D multichannel-based structures in peripheral nerve surgery. Full article

Biomass pellets provide a pivotal opportunity in promising energy transition scenarios as a renewable source of energy. A large share of the current utilization of pellets is facilitated by intensive global trade operations. Considering the long distance between the production site and the end-user locations, pellets may face fluctuating storage conditions, resulting in their physical and chemical degradation. We tested the effect of different storage conditions, from freezing temperatures (−19 °C) to high temperature (40 °C) and humidity conditions (85% relative humidity), on the physicochemical properties of untreated and torrefied biomass pellets. Moreover, the effect of sudden changes in the storage conditions on pellet properties was studied by moving the pellets from the freezing to the high temperature and relative humidity conditions and vice versa. The results show that, although storage at one controlled temperature and RH may degrade the pellets, a change in the temperature and relative humidity results in higher degradation in terms of higher moisture uptake and lower mechanical strength. Full article

Poly(vinyl chloride) is a common plastic that is widely used in many industrial applications. Poly(vinyl chloride) is mixed with additives to improve its mechanical and physical properties and to enable its use in harsh environments. Herein, to protect poly(vinyl chloride) films against photoirradiation with ultraviolet light, a number of tin complexes containing valsartan were synthesized and their chemical structures were established. Fourier-transform infrared spectroscopy, weight loss, and molecular weight determination showed that the non-desirable changes were lower in the films containing the tin complexes than for the blank polymeric films. Analysis of the surface morphology of the irradiated polymeric materials showed that the films containing additives were less rough than the irradiated blank film. The tin complexes protected the poly(vinyl chloride) films against irradiation, where the complexes with high aromaticity were particularly effective. The additives act as primary and secondary stabilizers that absorb the incident radiation and slowly remit it to the polymeric chain as heat energy over time at a harmless level. Full article

A functional polyurethane based on the heterocyclic group was synthesized and its self-healing and mechanical properties were examined. To synthesize a heterocyclic polyurethane, a polyol and a heterocyclic compound with di-hydroxyl groups at both ends were blended and the blended solution was reacted with a crosslinker containing multiple isocyanate groups. The heterocyclic polyurethane demonstrates better self-healing efficiency than the conventional polyurethane with no heterocyclic groups. Furthermore, unlike the conventional self-healing materials, the heterocyclic polyurethane examined in this study shows an outstanding recovery of the mechanical properties after the self-healing process. These results are attributed to the unique supramolecular network resulting from the strong hydrogen bonding interaction between the urethane group and the heterocyclic group in the heterocyclic polyurethane matrix. Full article

Subtropical natural exposure may significantly affect the bonding behavior of fiber reinforced polymer (FRP) externally bonded to concrete. To study the effect of subtropical natural climates on the FRP-concrete interface, natural exposure tests and an analytical approach were carried out on specimens externally bonded with carbon fiber reinforced polymer (CFRP) and basalt fiber reinforced polymer (BFRP). The bilinear bond stress-slip relationships for different exposure periods were derived from the experimental results of the strengthened reinforced concrete (RC) beams. Based on these bond-slip relationships, the full-range behavior of shear stress along the bond length and debonding load can be obtained through the analytical solution. The testing and numerical results showed that subtropical natural exposure can greatly affect the bond behavior of CFRP-concrete and BFRP-concrete interfaces in the early exposure period. In the late exposure period, the bond behavior was basically stable. With the increase of exposure time, the position of maximum shear stress tended to move backward, which indicated that the behavior of the FRP-concrete interface was weakened by natural exposure. Compared to the CFRP-concrete interface, subtropical natural exposure has greater influence on the bond behavior of the BFRP-concrete interface. Full article

Gradient hydrogels refer to hydrogel materials with a gradual or abrupt change in one or some of their properties. They represent examples of more sophisticated gel materials in comparison to simple, native gel networks. Here, we review techniques used to prepare gradient hydrogels which have been reported in literature over the last few years. A variety of simple preparation methods are available, most of which can be relatively easily utilized in standard laboratories Full article