Polymers, Volume 13, Issue 5 (March-1 2021) – 172 articles

This study seeks to render residues from banana plants into a useful byproduct with possible applications in wound dressings and food packaging. Films based on cellulose extracted from banana plant pseudostem and doped with phenolic compounds extracted from banana plant leaves were developed. The phenolic compounds were extracted using batch solid-liquid and Soxhlet methods, with different drying temperatures and periods of time. The total phenolic content and antioxidant activity were quantified. The optimum values were obtained using a three-day period batch-solid extraction at 40 °C (791.74 ± 43.75 mg/L). SEM analysis indicates that the pseudostem (PS) films have a porous structure, as opposed to hydroxyethyl cellulose (HEC) films which presented a homogeneous and dense surface. Mechanical properties confirmed the poor robustness of PS films. By contrast HEC films manifested improved tensile strength at low levels of water activity. FTIR spectroscopy reinforced the need to improve the cellulose extraction process, the success of lignin and hemicellulose removal, and the presence of phenolic compounds. XRD, TGA and contact angle analysis showed similar results for both films, with an amorphous structure, thermal stability and hydrophilic behavior. Full article

Achieving multiple physical properties from a single material through three-dimensional (3D) printing is important for manufacturing applications. In addition, industrial-level durability and reliability is necessary for realizing individualized manufacturing of devices using 3D printers. We investigated the properties of architected materials composed of ultraviolet (UV)-cured urethane elastomers for use as insoles. The durability and reliability of microlattice and metafoam architected materials were compared with those composed of various foamed materials currently used in medical insoles. The hardness of the architected materials was able to be continuously adjusted by controlling the design parameters, and the combination of the two materials was effective in controlling rebound resilience. In particular, the features of the architected materials were helpful for customizing the insole properties, such as hardness, propulsive force, and shock absorption, according to the user’s needs. Further, using elastomer as a component led to better results in fatigue testing and UV resistance compared with the plastic foam currently used for medical purposes. Specifically, polyethylene and ethylene vinyl acetate were deformed in the fatigue test, and polyurethane was mechanically deteriorated by UV rays. Therefore, these architected materials are expected to be reliable for long-term use in insoles. Full article

We report the effect of an iodine filler on photoisomerization kinetics of photo-switchable PEO-BDK-MR thin films. The kinetics of photoisomerization and time progression of PEO-BDK-MR/I₂ nanocomposite thin films are investigated using UV-Vis, FTIR spectroscopies, and modified mathematical models developed using new analytical methods. Incorporating iodine filler into the PEO-BDK-MR polymeric matrix enhances the isomerization energy barrier and considerably increases the processing time. Our outcomes propose that enhanced photoisomerized and time processed (PEO-BDK-MR)/I₂ thin films could be potential candidates for a variety of applications involving molecular solar thermal energy storage media. Full article

Self-healing anticorrosion composite coatings containing isophorone diisocyanate-loaded polyurethane microcapsules were developed, and comprehensive research on prepolymer and microcapsules synthesis, as well as functional composite coatings preparation and characterization, was performed. The influence of the prepolymer type and the concentration of the stabilizing agent used in the synthesis procedure on the properties of the microcapsules was studied in detail. For this purpose, three different prepolymers were prepared from toluene-2,4-diisocyanate (TDI) and either glycerol, 1,4-butanediol, or 1,6-hexanediol, and their chemical properties were investigated. Microcapsules were synthesized from the obtained prepolymers, according to the oil-in-water polymerization method, where 1,6-hexanediol was used as a chain extender, while the concentration of the stabilizing agent in the synthesis procedure was varied. Microcapsules prepared from TDI-glycerol prepolymer, synthesized in the presence of 10 wt% of the stabilizing agent, showed superior chemical, morphological, and thermo-gravimetrical properties; thus, they were incorporated into the coating in the concentration of 20 wt%. The prepared composite coatings demonstrated self-healing and anticorrosion properties, and thus the developed microcapsules show great potential for the incorporation into the composite anticorrosion coatings at critical points where damage can easily occur, providing longer and more efficient anticorrosion protection. Full article

3D printing has exponentially grown in popularity due to the personalization of each printed part it offers, making it extremely beneficial for the very demanding biomedical industry. This technique has been extensively developed and optimized and the advances that now reside in the development of new materials suitable for 3D printing, which may open the door to new applications. Fused deposition modeling (FDM) is the most commonly used 3D printing technique. However, filaments suitable for FDM must meet certain criteria for a successful printing process and thus the optimization of their properties in often necessary. The aim of this work was to prepare a flexible and printable polyurethane filament parting from a biocompatible waterborne polyurethane, which shows potential for biomedical applications. In order to improve filament properties and printability, cellulose nanofibers and graphene were employed to prepare polyurethane based nanocomposites. Prepared nanocomposite filaments showed altered properties which directly impacted their printability. Graphene containing nanocomposites presented sound enough thermal and mechanical properties for a good printing process. Moreover, these filaments were employed in FDM to obtained 3D printed parts, which showed good shape fidelity. Properties exhibited by polyurethane and graphene filaments show potential to be used in biomedical applications. Full article

Soluble heterocomplexes consisting of sodium hydride in combination with trialkylaluminum derivatives have been used as anionic initiating systems at 100 °C in toluene for convenient homo-, co- and ter-polymerization of myrcene with styrene and isoprene. In this way it has been possible to obtain elastomeric materials in a wide range of compositions with interesting thermal profiles and different polymeric architectures by simply modulating the alimentation feed and the (monomers)/(initiator systems) ratio. Especially, a complete study of the myrcene-styrene copolymers (PMS) was carried out, highlighting their tapered microstructures with high molecular weights (up to 159.8 KDa) and a single glass transition temperature. For PMS copolymer reactivity ratios, r_myr = 0.12 ± 0.003 and r_sty = 3.18 ± 0.65 and r_myr = 0.10 ± 0.004 and r_sty = 3.32 ± 0.68 were determined according to the Kelen–Tudos (KT) and extended Kelen–Tudos (exKT) methods, respectively. Finally, this study showed an easy accessible approach for the production of various elastomers by anionic copolymerization of renewable terpenes, such as myrcene, with commodities. Full article

In this work, hierarchical MoS₂/C quasi-hollow microspheres are prepared by a one-pot hydrothermal process with the addition of glucose. The glucose is not only inclined to form the roundish sphere in the completion of the synthesis of MoS₂, but at the same time the microspheres formed by the glucose can act as the nuclei on which the MoS₂ grows. Glucose, acting as a nucleating agent, has the advantages of being low-cost and environmentally friendly, which can simplify the fabrication process. The interiors of the MoS₂/C samples are multi-hole and quasi-hollow, which is beneficial for the insertion and extraction of lithium ions. For the first time, we demonstrate that hierarchical-structured MoS₂/C quasi-hollow microspheres exhibit an excellent cycling stability and rate capability in lithium ion batteries (LIBs) and are significantly superior to the bulk MoS₂. The method presented in this article may provide a simple, clean. and economical strategy for the preparation of MoS₂/C microspheres as a feasible and promising anode material for LIBs. Full article

Linseed oil was graft modified with maleic anhydride and introduced into alginate by co-extrusion, producing alginate hybrid filaments. A straightforward grafting of maleic anhydride onto the oil backbone produced the modified oil. Additional esterification with n-dodecanol was also investigated. The structures of the modified oils were verified with 2D-NMR. The modified oil was mixed with alginate and extruded into CaCl₂, forming thin filaments with diameters in the 130–260 μm range. The impact of oil integration into the alginate filaments was assessed, with special emphasis on stress-at-break, and compared to values predicted by an empirical model relating the “stress to alginate concentration” ratio to prevailing conditions during filament drawing. Analogous alginate filaments were prepared with hydrochloric-, oxalic- and phytic acid calcium salts for comparison with alginate–oil hybrids to reveal the induced impact, with respect to the composition and charge, on the tensile performance. Full article

Persistent organic pollutant inhibition in the combustion process of polyvinyl chloride (PVC) by prior addition of an inhibitor is currently being studied, reducing the emission of pollutants, and thus reducing the large amount of waste PVC destined for landfill. In this work, the use of sewage sludge (SS) as an alternative to chemical inhibitors to improve the quality emissions of the incineration of polyvinyl chloride waste (PVC e-waste) was studied and optimized. Different combustion runs were carried out at 850 °C in a laboratory tubular reactor, varying both the molar ratio R_i (0.25, 0.50, 0.75) between inhibitors (N + S) and chlorine (Cl) and the oxygen ratio λ (0.15, 0.50) between actual oxygen and stoichiometric oxygen. The emissions of several semivolatile compounds families such as polycyclic aromatic hydrocarbons (PAHs), polychlorobenzenes (ClBzs), and polychlorophenols (ClPhs), with special interest in the emissions of the most toxic compounds, i.e., polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs), were analyzed. A notable decrease in PCDD/F and dl-PCB formation was achieved in most of the experiments, especially for those runs performed under an oxygen-rich atmosphere (λ = 0.50), where the addition of sludge was beneficial with inhibition ratios Ri ≥ 0.25. An inhibition ratio of 0.75 showed the best results with almost a 100% reduction in PCDD/F formation and a 95% reduction in dl-PCB formation. Full article

The application of fiber-reinforced plastic (FRP) composite materials instead of metals, due to the low density of FRP materials, results in weight savings in the base plates of aircraft pallets. Lower weight leads to lower fuel consumption of the aircraft and thereby less environmental damage. The study aimed to investigate replacing the currently used aluminum base plates of aircraft pallets with composite sandwich plates to reduce the weight of the pallets, thereby the weight of the unit loads transported by aircraft. The newly constructed sandwich base plate consists of an aluminum honeycomb core and FRP composite face-sheets. First, we made experimental tests and numerical calculations for the investigated FRP sandwich panel to validate the applicability of the calculation method. Next, the mechanical properties of 40 different layer-combinations of 4 different FRP face-sheet materials (phenolic woven glass fiber; epoxy woven glass fiber; epoxy woven carbon fiber; and hybrid layers) were investigated using the Digimat-HC modeling program in order to find the appropriate face-sheet construction. Face-sheets were built up in 1, 2, 4, 6 or 8 layers with sets of fiber orientations including cross-ply (0°, 90°) and/or angle-ply (±45°). The weight optimization method was elaborated considering 9 design constraints: stiffness, deflection, skin stress, core shear stress, facing stress, overall buckling, shear crimping, skin wrinkling, and intracell buckling. A case study for the base plate of an aircraft pallet was introduced to validate the optimization procedure carried out using the Matlab (Interior Point Algorithm) and Excel Solver (Generalized Reduced Gradient Nonlinear Algorithm) programs. In the case study, the weight of the optimal structure (epoxy woven carbon fiber face-sheets) was 27 kg, which provides weight savings of 66% compared to the standard aluminum pallet. The article’s main added value is the elaboration and implementation of an optimization method that results in significant weight savings and thus lower fuel consumption of aircraft. Full article

A series of well-defined (polyisoprene)₂(polystyrene), I₂S, single graft copolymers with similar total molecular weights but different compositions, f_PS, were blended with a low molecular weight polyisoprene homopolymer matrix at a constant concentration 2 wt%, and the micellar characteristics were studied by small-angle x-ray scattering. To investigate the effect of macromolecular architecture on the formation and characteristics of micelles, the results on the single graft copolymers were compared with those of the corresponding linear polystyrene-b-polyisoprene diblock copolymers, SI. The comparison reveals that the polystyrene core chains are more stretched in the case of graft copolymer micelles. Stretching turned out to be purely a result of the architecture due to the second polyisoprene block in the corona. The micellization of a (polystyrene)₂(polyisoprene), S₂I, graft copolymer was also studied, and the comparison with the results of the corresponding I₂S and SI copolymers emphasizes the need for a critical core volume rather than a critical length of the core-forming block, in order to have stable micelles. Finally, the absence of micellization in the case of the I₂S copolymer with the highest polystyrene volume fraction is discussed. For this sample, macrophase separation occurs, with polyisoprene cylinders formed in the copolymer-rich domains of the phase-separated blends. Full article

Starch is the second most abundantly available natural polymer in the world, after cellulose. If we add its biodegradability and non-toxicity to the natural environment, it becomes a raw material very attractive for the food and non-food industries. However, in the latter case, mainly due to the high hydrophilicity of starch, it is necessary to carry out many more or less complex operations and processes. One of the fastest growing industries in the last decade is the processing of biodegradable materials for packaging purposes. This is mainly due to awareness of producers and consumers about the dangers of unlimited production and the use of non-degradable petroleum polymers. Therefore, in the present review, an attempt was made to show the possibilities and limitations of using starch as a packaging material. The most important physicochemical features of this biopolymer are discussed, and special attention is paid to more or less environmentally friendly methods of improving its processing properties. Full article

Chitosan nanofibrous membranes are prepared via an electrospinning technique and explored as potential wound healing patches. In particular, the effect of a physical or chemical crosslinking treatment on the mat morphological, mechanical, water-related, and biological properties is deeply evaluated. The use of phosphate ions (i.e., physical crosslinking) allows us to obtain smooth and highly homogenous nanofibers with an average size of 190 nm, whereas the use of ethylene glycol diglycidyl ether (i.e., chemical crosslinking) leads to rougher, partially coalesced, and bigger nanofibers with an average dimension of 270 nm. Additionally, the physically crosslinked mats show enhanced mechanical performances, as well as greater water vapour permeability and hydrophilicity, with respect to the chemically crosslinked ones. Above all, cell adhesion and cytotoxicity experiments demonstrate that the use of phosphate ions as crosslinkers significantly improves the capability of chitosan mats to promote cell viability owing to their higher biocompatibility. Moreover, tuneable drug delivery properties are achieved for the physically crosslinked mats by a simple post-processing impregnation methodology, thereby indicating the possibility to enrich the prepared membranes with unique features. The results prove that the proposed approach may lead to the preparation of cheap, biocompatible, and efficient chitosan-based nanofibers for biomedical and pharmaceutical applications. Full article

Segmental dynamics in unentangled isotactic, syndiotactic, and atactic poly(methyl methacrylate) (i-, a-, and s-PMMA) melts confined between pristine graphene, reduced graphene oxide, RGO, or graphene oxide, GO, sheets is studied at various temperatures, well above glass transition temperature, via atomistic molecular dynamics simulations. The model RGO and GO sheets have different degrees of oxidization. The segmental dynamics is studied through the analysis of backbone torsional motions. In the vicinity of the model nanosheets (distances less than ≈2 nm), the dynamics slows down; the effect becomes significantly stronger with increasing the concentration of the surface functional groups, and hence increasing polymer/surface specific interactions. Upon decreasing temperature, the ratios of the interfacial segmental relaxation times to the respective bulk relaxation times increase, revealing the stronger temperature dependence of the interfacial segmental dynamics relative to the bulk dynamics. This heterogeneity in temperature dependence leads to the shortcoming of the time-temperature superposition principle for describing the segmental dynamics of the model confined melts. The alteration of the segmental dynamics at different distances, d, from the surfaces is described by a temperature shift, $\Delta T_{\mathrm{seg}}\left(d\right)$ (roughly speaking, shift of a characteristic temperature). Next, to a given nanosheet, i-PMMA has a larger value of $\Delta T_{\mathrm{seg}}$ than a-PMMA and s-PMMA. This trend correlates with the better interfacial packing and longer trains of i-PMMA chains. The backbone torsional autocorrelation functions are shown in the frequency domain and are qualitatively compared to the experimental dielectric loss spectra for the segmental $\alpha$-relaxation in polymer nanocomposites. The ${\epsilon }_{\mathrm{T}}^{{}^{″}}\left(f\right)$ (analogous of dielectric loss, ${\epsilon }^{{}^{″}}\left(f\right)$, for torsional motion) curves of the model confined melts are broader (toward lower frequencies) and have lower amplitudes relative to the corresponding bulk curves; however, the peak frequencies of the ${\epsilon }_{\mathrm{T}}^{{}^{″}}\left(f\right)$ curves are only slightly affected. Full article

New coordination oligomers and polymers of Sn(IV)-tetra(4-sulfonatophenyl)porphyrin have been constructed by the chelation reaction of its diaxialphenolates with Cu²⁺. The structure and properties of the synthesized polyporphyrin arrays were investigated by ¹H Nuclear Magnetic Resonance (¹H NMR), Infra Red (IR), Ultra Violet - Visible (UV-Vis) and fluorescence spectroscopy, mass spectrometry, Powder X-Rays Diffraction (PXRD), Electron Paramagnetic Resonance (EPR), thermal gravimetric, elemental analysis, and quantum chemical calculations. The results show that the diaxial coordination of bidentate organic ligands (L-tyrazine and diaminohydroquinone) leads to the quenching of the tetrapyrrole chromophore fluorescence, while the chelation of the porphyrinate diaxial complexes with Cu²⁺ is accompanied by an increase in the fluorescence in the organo-inorganic hybrid polymers formed. The obtained results are of particular interest to those involved in creating new ‘chemo-responsive’ (i.e., selectively interacting with other chemical species as receptors, sensors, or photocatalysts) materials, the optoelectronic properties of which can be controlled by varying the number and connection type of monomeric fragments in the polyporphyrin arrays. Full article

The incidence of dental caries, especially root caries, has risen in elderly populations in recent years. Specialized restorative materials are needed due to the specific site of root caries and the age-related changes in general and oral health in the elderly. Unfortunately, the restorative materials commonly used clinically cannot fully meet the requirements in this population. Specifically, the antibacterial, adhesive, remineralization, mechanical, and anti-aging properties of the materials need to be significantly improved for dental caries in the elderly. This review mainly discusses the strengths and weaknesses of currently available materials, including amalgam, glass ionomer cement, and light-cured composite resin, for root caries. It also reviews the studies on novel anti-caries materials divided into three groups, antimicrobial, remineralization, and self-healing materials, and explores their potential in the clinical use for caries in the elderly. Therefore, specific restorative materials for caries in the elderly, especially for root caries, need to be further developed and applied in clinical practice. Full article

While cationic microgels are potentially useful for the transfection or transformation of cells, their synthesis has certain drawbacks regarding size, polydispersity, yield, and incorporation of the cationic comonomers. In this work, a range of poly(N-isopropylacrylamide) (PNIPAM) microgels with different amounts of the primary amine N-(3-aminopropyl)methacrylamide hydrochloride (APMH) as the cationic comonomer were synthesized. Moreover, the pH-value during reaction was varied for the synthesis of microgels with 10 mol% APMH-feed. The microgels were analyzed by means of their size, thermoresponsive swelling behavior, synthesis yield, polydispersity and APMH-incorporation. The copolymerization of APMH leads to a strong decrease in size and yield of the microgels, while less than one third of the nominal APMH monomer feed is incorporated into the microgels. With an increase of the reaction pH up to $9.5$, the negative effects of APMH copolymerization were significantly reduced. Above this pH, synthesis was not feasible due to aggregation. The results show that the reaction pH has a strong influence on the synthesis of pH-responsive cationic microgels and therefore it can be used to tailor the microgel properties. Full article

Retinol has been widely used as an anti-wrinkle active ingredient in cosmetic fields. However, the oxidation of retinol by air was one of the critical problems for application in the skincare field. In this study, Retinol-loaded lipid nanocarriers were prepared via the vacuum emulsification method to increase the stability of retinol vulnerable to air and optimized encapsulation conditions and to increase the penetration efficiency into skin. Optimizing the components of lipid nanocarriers, gradients of carbon chain C8-22 using various lipid species which made the amorphous structure and enough spaces to load retinol inside the capsules were estimated from the lower enthalpy change and peak shift in DSC analysis. The vacuum-assisted lipid nanocarriers (VLN) could help suppress oxidation, which could have advantages to increase the thermal stability of retinol. The retinol-loaded VLN (VLN-ROL) had narrow size distribution under 0.3 PDI value, under 200 nm scaled particle size, and fully negative surface charge of about -50 mV for the electrostatic repulsion to avoid aggregation phenomenon among the lipid nanoparticles. It maintained 90% or more retinol concentration after 4 weeks of storage at 25, 40 and 50 °C and kept stable. The VLN-ROL-containing cream showed improved penetration efficiency applied to porcine skins compared to the commercial retinol 10S from BASF. The total amount of retinol into the skin of VLN-ROL (0.1% of retinol) was enhanced by about 2.2-fold (2.86 ± 0.23 μg) higher than that in 0.1% of bare retinol (about 1.29 ± 0.09 μg). In addition, applied on a 3D Human skin model, the epidermal thickness and the relative percentage of dermal collagen area effectively increased compared to the control and retinol, respectively. Additionally, the level of secreted IL-1α was lower and epidermal damage was weaker than commercial product A. This retinol-loaded lipid nanocarrier could be a potentially superior material for cosmetics and biomedical research. Full article

Increasing machine learning methods are being applied to infrared non-destructive assessment for internal defects assessment of composite materials. However, most of them extract only linear features, which is not in accord with the nonlinear characteristics of infrared data. Moreover, limited infrared images tend to restrict the data analysis capabilities of machine learning methods. In this work, a novel generative kernel principal component thermography (GKPCT) method is proposed for defect detection of carbon fiber reinforced polymer (CFRP) composites. Specifically, the spectral normalization generative adversarial network is proposed to augment the thermograms for model construction. Sequentially, the KPCT method is used by feature mapping of all thermogram data using kernel principal component analysis, which allows for differentiation of defects and background in the dimensionality-reduced data. Additionally, a defect-background separation metric is designed to help the performance evaluation of data analysis methods. Experimental results on CFRP demonstrate the feasibility and advantages of the proposed GKPCT method. Full article

Highly flexible and compressible porous polyurethane (PU) structures have effectively been applied in capacitive pressure sensors because of the good elastic properties of the PU structures. However, PU porous structure-based pressure sensors have been limited in practical applications owing to their low durability during pressure cycling. Herein, we report a flexible pressure sensor based on a three-dimensional porous structure with notable durability at a compressive pressure of 500 kPa facilitated by the use of a shape memory polymer (SMP). The SMP porous structure was fabricated using a sugar templating process and capillary effect. The use of the SMP resulted in the maintenance of the sensing performance for 100 cycles at 500 kPa; the SMP can restore its original shape within 30 s of heating at 80 °C. The pressure sensor based on the SMP exhibited a higher sensitivity of 0.0223 kPa⁻¹ than a typical PU-based sensor and displayed excellent sensing performance in terms of stability, response time, and hysteresis. Additionally, the proposed sensor was used to detect shoe insole pressures in real time and exhibited remarkable durability and motion differentiation. Full article

In this paper, a new pH-responsive nanosystem based on mesoporous silica nanoparticles (MSNs) was developed for cancer therapy. Poly(2-(diethylamino) ethyl methacrylate) (PDEAEMA) was grafted on their outer surface and acts as a gatekeeper, followed by subsequent modification of the polymer by cysteine (MSN-PDEAEMA-Cys) and poly(oligo(ethylene glycol) methyl ether methacrylate) (MSN-PDEAEMA-Cys-POEGMEMA). The physicochemical properties of these nanocarriers were characterized using scanning and transmission electron microscopies (SEM and TEM), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and dynamic light scattering (DLS). The synthesized nanoparticles were well-dispersed with a diameter of ca. 200 nm. The obtained XPS results confirm the successful modification of MSN-PDEAEMA with Cys and POEGMEMA by increasing the peak intensity of C–O and C=O groups at 286.5 and 288.5 eV, respectively. An anti-cancer drug, doxorubicin (DOX), was encapsulated into the fabricated nanoplatform. The DOX release amount at physiological pH of 7.4 was limited (10%), while an accumulation drug release of ca. 35% was accomplished after 30 h in acidic media. The MTT cell line was used to assess the cytotoxicity of the unloaded and DOX-loaded fabricated nanoplatforms. Upon loading of DOX on these nanomaterials, they showed significant toxicity to human liver cancer cells. These results suggest that the prepared nano-structured materials showed good biocompatibility as well, and they can serve as nanocarriers for the delivery of anti-cancer drugs. Full article

In this study, five urethane acrylates (UAs), namely aliphatic urethane hexa-acrylate (87A), aromatic urethane hexa-acrylate (88A), aliphatic UA (588), aliphatic urethane triacrylate diluted in 15% HDD (594), and high-functional aliphatic UA (5812), were selected to formulate five UA-based photopolymer resins for digital light processing (DLP)-based 3D printing. Each UA (40 wt%) was added and blended homogenously with ethoxylated pentaerythritol tetraacrylate (40 wt%), isobornyl acrylate (12 wt%), diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (3 wt%), and a pink acrylic (5 wt%). Each UA-based resin specimen was designed using CAD software and fabricated using a DLP 3D printer to specific dimensions. Characteristics, mechanical properties, and cytotoxicity levels of these designed UA-based resins were investigated and compared with a commercial 3D printing denture base acrylic resin (BB base) control group at different UV exposure times. Shore hardness-measurement data and MTT assays were analyzed using a one-way analysis of variance with Bonferroni’s post hoc test, whereas viscosity, maximum strength, and modulus were analyzed using the Kruskal–Wallis test (α = 0.05). UA-based photopolymer resins with tunable mechanical properties were successfully prepared by replacing the UA materials and the UV exposure times. After 15 min of UV exposure, the 5812 and 594 groups exhibited higher viscosities, whereas the 88A and 87A groups exhibited lower viscosities compared with the BB base group. Maximum flexural strength, flexural modulus, and Shore hardness values also revealed significant differences among materials (p < 0.001). Based on MTT assay results, the UA-based photopolymer resins were nontoxic. In the present study, mechanical properties of the designed photopolymer resins could be adjusted by changing the UA or UV exposure time, suggesting that aliphatic urethane acrylate has good potential for use in the design of printable resins for DLP-type 3D printing in dental applications. Full article

The outstanding properties of carbon nanotubes (CNTs) present some limitations when introduced into rubber matrices, especially when these nano-particles are applied in high-performance tire tread compounds. Their tendency to agglomerate into bundles due to van der Waals interactions, the strong influence of CNT on the vulcanization process, and the adsorptive nature of filler–rubber interactions contribute to increase the energy dissipation phenomena on rubber–CNT compounds. Consequently, their expected performance in terms of rolling resistance is limited. To overcome these three important issues, the CNT have been surface-modified with oxygen-bearing groups and sulfur, resulting in an improvement in the key properties of these rubber compounds for their use in tire tread applications. A deep characterization of these new materials using functionalized CNT as filler was carried out by using a combination of mechanical, equilibrium swelling and low-field NMR experiments. The outcome of this research revealed that the formation of covalent bonds between the rubber matrix and the nano-particles by the introduction of sulfur at the CNT surface has positive effects on the viscoelastic behavior and the network structure of the rubber compounds, by a decrease of both the loss factor at 60 °C (rolling resistance) and the non-elastic defects, while increasing the crosslink density of the new compounds. Full article

Many natural exposure sites have been developed to ensure the reliability of materials intended for outdoor use. However, the effects of local climate on aging have not been completely understood. This study aimed to elucidate the regional characteristics of natural aging. Non-stabilized and stabilized polycarbonates were monitored in terms of their appearance (yellowing and loss of gloss) during natural weathering at five exposure sites (Tokyo, Kagoshima, Okinawa, Florida, and Arizona) in conjunction with climate fluctuation for up to 24 months. Three approaches were employed to characterize the natural aging behaviors: (i) modeling the rate function of degradation, (ii) evaluating the contribution ratio of individual degradational factors, and (iii) estimating the “synchronicity” by cross-correlation analysis with the climate dataset. The aging rates were the highest in Arizona and lowest in Kagoshima among the five exposure sites. First, prediction curves were constructed from the degradation rate function (variables: UV irradiation, temperature, and humidity), and these curves were found to agree well with the measured aging behaviors. Second, the exposure data in Arizona demonstrated strong temperature dependence, while those in Okinawa and Florida had stronger dependence on UV irradiation compared to other sites. Lastly, the synchronicity between UV irradiation and temperature was the highest in Arizona and lowest in Kagoshima, which can explain the significantly faster deterioration in Arizona and the slow deterioration in Kagoshima. Full article

This study demonstrates liquid crystal (LC) alignment behaviors on the surface of phytochemical-based and renewable chavicol-modified polystyrene (PCHA#, # = 20, 40, 60, 80, and 100, where # represent the molar content of chavicol moiety in the side group) via polymer modification reactions. Generally, a LC cell fabricated with a polymer film containing a high molar content of the chavicol side group exhibited a vertical LC alignment property. There is a correlation between the vertical alignment of LC molecules and the polar surface energy value of the polymer films. Therefore, vertical LC alignment was observed when the polar surface energy values of these polymer films were smaller than about 1.3 mJ/m², induced by the nonpolar chavicol moiety having long and bulky carbon groups. Aligning stability under harsh conditions such as ultraviolet (UV) irradiation of about 5 J/cm² was observed in the LC cells fabricated from PCHA100 film. Therefore, it was found that the plant-based chavicol-substituted polymer system can produce an eco-friendly and sustainable LC alignment layer for next-generation applications. Full article

Chitin has become a desirable raw material used in various areas of life. The black soldier fly (Hermetia illucens) can be a source of this substance. In the literature, there are many methods of obtaining chitin but there is no one universal method of isolating it. In this publication, we present various procedures for the isolation of chitin from H. illucens pupal exuviae. The obtained chitin variants were characterized using different techniques (optical and confocal microscopy, FTIR, XRD, EDX, thermogravimetric analysis). The tested chitin isolated with an efficiency of 5.69–7.95% was the α form with a crystallinity degree of 60% and maximum degradation temperature of 392 °C. Furthermore, we characterized the nickel ion biosorption process on chitin and proposed the mechanism of this process to be ion exchange and complexation. There have been no such studies thus far on the isolation of chitin from H. illucens exuviae or on the biosorption of nickel ions on this type of biosorbent. The conducted research can be used to develop the application of chitin as a metal biosorbent that can be obtained with relatively high efficiency and good sorption properties. Full article

In this study, we proved that micro/micro hierarchical structures are enough to achieve a superhydrophobic surface using polydimethylsiloxane (PDMS) dip-coating. Furthermore, the effect of fiber type and yarn diameter on superhydrophobicity and water spray resistance was investigated. Polyester fabrics with two types of fibers (staple fabric and filament) and three types of yarn diameters (177D, 314D, and 475D) were used. The changes in the surface properties and chemical composition were investigated. Static contact angles and shedding angles were measured for superhydrophobicity, and the self-cleaning test was conducted. Water spray repellency was also tested, as well as the water vapor transmission rate and air permeability. The PDMS-coated staple fabric showed better superhydrophobicity and oleophobicity than the PDMS-coated filament fabric, while the filament fabric showed good self-cleaning property and higher water spray repellency level. When the yarn diameter increased, the fabrics needed higher PDMS concentrations and longer coating durations for uniform coating. The water vapor transmission rate and air permeability did not change significantly after coating. Therefore, the superhydrophobic micro/micro hierarchical fabrics produced using the simple method of this study are more practical and have great potential for mass production than other superhydrophobic textiles prepared using the chemical methods. Full article

Skin aging is caused by exposure to various external factors. Ultraviolet B (UVB) irradiation induces oxidative stress, photoaging, and inflammation in skin cells. Pinus densiflora Sieb. et Zucc. (red pine) has various antimicrobial and antioxidant activities. However, the anti-inflammatory effects of red pine on skin have rarely been reported. The protective effects of malonic acid (MA) isolated from Pinus densiflora were investigated against UVB-induced damage in an immortalized human keratinocyte cell line (HaCaT). MA increased levels of the antioxidant enzymes superoxide dismutase 1 (SOD-1) and heme oxygenase 1 (HO-1) via activation of nuclear factor-erythroid 2-related factor-2 (Nrf2), resulting in a reduction in UVB-induced reactive oxygen species (ROS) levels. Additionally, the inhibition of ROS increased HaCaT cell survival rate. Thus, MA downregulated the expression of ROS-induced nuclear factor-κB, as well as inflammation-related cytokines (interleukin-6, cyclooxygenase-2, and tumor necrosis factor-α). Furthermore, MA significantly suppressed the mitogen-activated protein kinase/activator protein 1 signaling pathway and reduced the expression of matrix metalloproteinases (MMPs; MMP-1, MMP-3, and MMP-9). In contrast, MA treatment increased the expression of collagen synthesis regulatory genes (COL1A1 and COL3A1) via regulation of Smad2/3 signal induction through transforming growth factor-β. In conclusion, MA protected against UVB-induced photoaging via suppression of skin inflammation and induction of collagen biosynthesis. Full article

Bacteria produce a variety of multifunctional polysaccharides, including structural, intracellular, and extracellular polysaccharides. They are attractive for the industrial sector due to their natural origin, sustainability, biodegradability, low toxicity, stability, unique viscoelastic properties, stable cost, and supply. When incorporated into different matrices, they may control emulsification, stabilization, crystallization, water release, and encapsulation. Acetan is an important extracellular water-soluble polysaccharide produced mainly by bacterial species of the genera Komagataeibacter and Acetobacter. Since its original description in Komagataeibacter xylinus, acetan-like polysaccharides have also been described in other species of acetic acid bacteria. Our knowledge on chemical composition of different acetan-like polysaccharides, their viscoelasticity, and the genetic basis for their production has expanded during the last years. Here, we review data on acetan biosynthesis, its molecular structure, genetic organization, and mechanical properties. In addition, we have performed an extended bioinformatic analysis on acetan-like polysaccharide genetic clusters in the genomes of Komagataeibacter and Acetobacter species. The analysis revealed for the first time a second acetan-like polysaccharide genetic cluster, that is widespread in both genera. All species of the Komagataeibacter possess at least one acetan genetic cluster, while it is present in only one third of the Acetobacter species surveyed. Full article

Currently, the availability of a wide variety of universal adhesives makes it difficult for clinicians to choose the correct system for specific bonding situations to dentin substrate. This study aimed to determine whether there are any alternative techniques or additional strategies available to enhance the bond strength of universal adhesives to dentin through a systematic review and meta-analysis. Two reviewers executed a literature search up to September 2020 in four electronic databases: PubMed, ISI Web of Science, Scopus, and EMBASE. Only in vitro studies that reported the dentin bond strength of universal adhesives using additional strategies were included. An analysis was carried out using Review Manager Software version 5.3.5 (The Nordic Cochrane Centre, The Cochrane Collaboration, Copenhagen, Denmark). The methodological quality of each in vitro study was assessed according to the parameters of a previous systematic. A total of 5671 potentially relevant studies were identified. After title and abstract examination, 74 studies remained in systematic review. From these, a total of 61 studies were included in the meta-analysis. The bond strength of universal adhesives to dentin was improved by the use of one of the following techniques: Previous application of matrix metalloproteinases (MMP) inhibitors (p < 0.001), prolonged application time (p = 0.007), scrubbing technique (p < 0.001), selective dentin etching (p < 0.001), non-atmospheric plasma (p = 0.01), ethanol-wet bonding (p < 0.01), prolonged blowing time (p = 0.02), multiple layer application (p = 0.005), prolonged curing time (p = 0.006), and hydrophobic layer coating (p < 0.001). On the other hand, the use of a shortened application time (p = 0.006), and dentin desensitizers (p = 0.01) impaired the bond strength of universal adhesives to dentin. Most of the analyses performed showed a high heterogenicity. The in vitro evidence suggests that the application of universal adhesives using some alternative techniques or additional strategies may be beneficial for improving their bonding performance to dentin. This research received no external funding. Considering that this systematic review was carried out only with in vitro studies, registration was not performed. Full article