Editor’s Choice Articles

To date, PTFE, PFA, and FEP-based fluoropolymer coatings have proven unbeatable in many services due to their excellent chemical inertness, very low wettability, thermal resistance, high non-stick properties, and good applicability. In use, these coatings usually suffer service cycles with consequent deterioration, and it is of great interest to determine the intensity and type of wear caused in addition to the deterioration that occurs in their properties. In this work, the response of three polymeric coatings of interest applied to aluminum substrates, after being subjected to the action of abrasive particles of aluminum corundum, glass, and plastic projected under pressure, has been studied. During the application of a given wear cycle, the hardness, surface roughness, surface texture, and thickness of the coating have been measured, in addition to the slip angle and surface transmittance to analyze the evolution of each type of coating. The results allowed a concise evaluation of the performance of three fluoropolymeric coatings of great interest, differentiating the induced erosive wear phenomena and contributing complete information to facilitate the correct selection for users with practical application purposes and as a basis for future research work focused on advancements in this field. Full article

An environmentally friendly hydrogel based on gelatin has been investigated as a gel polymer electrolyte in a symmetric carbon-based supercapacitor. To guarantee the complete sustainability of the devices, biomaterials from renewable resources (such as chitosan, casein and carboxymethyl cellulose) and activated carbon (from coconut shells) have been used as a binder and filler within the electrode, respectively. The electrochemical properties of the devices have been compared by using cyclic voltammetry, galvanostatic charge/discharge curves and impedance spectroscopy. Compared to the liquid electrolyte, the hydrogel supercapacitors show similar energy performance with an enhancement of stability up to 12,000 cycles (e.g., chitosan as a binder). The most performant device can deliver ca. 5.2 Wh/kg of energy at a high power density of 1256 W/kg. A correlation between the electrochemical performances and charge storage mechanisms (involving faradaic and non-faradaic processes) at the interface electrode/hydrogel has been discussed. Full article

Modern biomedical technologies predict the application of materials and devices that not only can comply effectively with specific requirements, but also enable remote control of their functions. One of the most prospective materials for these advanced biomedical applications are materials based on temperature-responsive polymer brush coatings (TRPBCs). In this review, methods for the fabrication and characterization of TRPBCs are summarized, and possibilities for their application, as well as the advantages and disadvantages of the TRPBCs, are presented in detail. Special attention is paid to the mechanisms of thermo-responsibility of the TRPBCs. Applications of TRPBCs for temperature-switchable bacteria killing, temperature-controlled protein adsorption, cell culture, and temperature-controlled adhesion/detachment of cells and tissues are considered. The specific criteria required for the desired biomedical applications of TRPBCs are presented and discussed. Full article

New oligo- and polyenaminones with M_w ~ 7–50 KDa were prepared in high yields by transaminative amino-enaminone polymerization of regioisomeric bis[(dimethylamino)methylidene]cyclohexanediones with alkylene and phenylenediamines. The polymers obtained are practically insoluble in aqueous and organic solvents and exhibit film-forming properties, UV light absorption at wavelengths below 500 nm, and redox activity. These properties indicate a promising application potential of these polymers, which could find use in optical and optoelectronic applications and in energy storage devices. Full article

In this study, the synthesis of a Michael donor compound from cellulose production by-products—tall oil fatty acids—was developed. The developed Michael donor compounds can be further used to obtain polymeric materials after nucleophilic polymerization through the Michael reaction. It can be a promising alternative method for conventional polyurethane materials, and the Michael addition polymerization reaction takes place under milder conditions than non-isocyanate polyurethane production technology, which requires high pressure, high temperature and a long reaction time. Different polyols, the precursors for Michael donor components, were synthesized from epoxidized tall oil fatty acids by an oxirane ring-opening and esterification reaction with different alcohols (trimethylolpropane and 1,4-butanediol). The addition of functional groups necessary for the Michael reaction was carried out by a transesterification reaction of polyol hydroxyl groups with tert-butyl acetoacetate ester. The following properties of the developed polyols and their acetoacetates were analyzed: hydroxyl value, acid value, moisture content and viscosity. The chemical structure was analyzed using Fourier transform infrared spectroscopy, gel permeation chromatography, size-exclusion chromatography and nuclear magnetic resonance. Matrix-assisted laser desorption/ionization analysis was used for structure identification for this type of acetoacetate for the first time. Full article

Within the era of battery technology, the urgent demand for improved and safer electrolytes is immanent. In this work, novel electrolytes, based on pyrrolidinium-bistrifluoromethanesulfonyl-imide polymeric ionic liquids (POILs), equipped with quadrupolar hydrogen-bonding moieties of ureido-pyrimidinone (UPy) to mediate self-healing properties were synthesized. Reversible addition–fragmentation chain-transfer (RAFT) polymerization was employed using S,S-dibenzyl trithiocarbonate as the chain transfer agent to produce precise POILs with a defined amount of UPy and POIL-moieties. Kinetic studies revealed an excellent control over molecular weight and polydispersity in all polymerizations, with a preferable incorporation of UPy monomers in the copolymerizations together with the ionic monomers. Thermogravimetric analysis proved an excellent thermal stability of the polymeric ionic liquids up to 360 °C. By combining the results from differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS), and rheology, a decoupled conductivity of the POILs from glass transition was revealed. While the molecular weight was found to exert the main influence on ionic conductivity, the ultimate strength and the self-healing efficiency (of up to 88%) were also affected, as quantified by tensile tests for both pristine and self-healed samples, evidencing a rational design of self-healing electrolytes bearing both hydrogen bonding moieties and low-molecular-weight polymeric ionic liquids. Full article

Four new conjugated polymers alternating benzothiadiazole units and thiophene moieties functionalized with ionic phosphonium or sulfonic acid salts in the side chains were synthesized by a postfunctionalization approach of polymeric precursors. The introduction of ionic groups makes the conjugated polymers soluble in water and/or polar solvents, allowing for the fabrication of bulk heterojunction (BHJ) solar cells using environmentally friendly conditions. All polymers were fully characterized by spectroscopic, thermal, electrochemical, X-ray diffraction, scanning electron, and atomic force techniques. BHJ solar cells were obtained from halogen-free solvents (i.e., ethanol and/or anisole) by blending the synthesized ionic push–pull polymers with a serinol-fullerene derivative or an ionic homopolymer acting as electron-acceptor (EA) or electron-donor (ED) counterparts, respectively. The device with the highest optical density and the smoothest surface of the active layer was the best-performing, showing a 4.76% photoconversion efficiency. Full article

The quantitative relationship between the fraction of UV exposure energy and the retention fraction of tensile strength was investigated on the m-Aramid/p-Aramid blend ratio of spun yarn. An exponential equation to calculate tensile strength from an arbitrary UV exposure energy is evaluated for yarns and fabrics. The spun yarns were exposed to UV light using a xenon-arc weathering meter. The retention fraction of tensile strength decreased exponentially with increasing the fraction of UV exposure energy. Curve fitting of the retention fraction of tensile strength to the fraction of UV exposure energy revealed two groups of degradation coefficients based on the blending ratio of m-Aramid/p-Aramid. The correlation between the degradation coefficients (${\alpha }_y$ and ${\alpha }_f$) of spun yarn and fabrics can be linearly regressed. The constant of proportionality in linear regression is considered to be the gap between the structure and the breaking mechanism of the fabric relative to yarn breakage. Based on the correlation between the degradation coefficients of spun yarn and fabrics and a mathematical model of the tensile strength of the spun yarn, the tensile strength of fabrics at a given UV exposure energy can be estimated from the tensile strength of the yarn. Full article

This study synthesized a series of new biobased copolyamides (co-PAs), namely PA56/PA66 with various comonomer ratios, by using in situ polycondensation. The structures, compositions, behaviors, and crystallization kinetics of the co-PAs were investigated through proton nuclear magnetic resonance (¹H NMR) spectroscopy, gel permeation chromatography (GPC), Fourier transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X-ray diffraction (XRD). The influence of the composition of co-PAs on their mechanical properties and thermal stability was investigated. The co-PAs exhibited a eutectic melting point when the PA56 content was 50 mol%, with the crystallization temperature decreasing from 229 to a minimum 188 °C and the melting temperature from 253 to a minimum 218 °C. The results indicated that the tensile strength and flexural modulus first decreased and then increased as the PA66 content increased. The nonisothermal crystallization kinetics of the PA56/PA66 co-PAs were analyzed using both the Avrami equation modifications presented by Jeziorny and Mo. The results also indicated that the crystallization rate of the PA56/PA66 co-PAs was higher than that of PA56. Full article

There is a growing demand for bone graft substitutes that mimic the extracellular matrix properties of the native bone tissue to enhance stem cell osteogenesis. Composite hydrogels containing human bone allograft particles are particularly interesting due to inherent bioactivity of the allograft tissue. Here, we report a novel photocurable composite hydrogel bioink for bone tissue engineering. Our composite bioink is formulated by incorporating human allograft bone particles in a methacrylated alginate formulation to enhance adult human mesenchymal stem cell (hMSC) osteogenesis. Detailed rheology and printability studies confirm suitability of our composite bioinks for extrusion-based 3D bioprinting technology. In vitro studies reveal high cell viability (~90%) for hMSCs up to 28 days of culture within 3D bioprinted composite scaffolds. When cultured within bioprinted composite scaffolds, hMSCs show significantly enhanced osteogenic differentiation as compared to neat scaffolds based on alkaline phosphatase activity, calcium deposition, and osteocalcin expression. Full article

Due to their good material properties (e.g., corrosion and wear resistance, biocompatibility), thermoplastic materials like polyamide 12 (PA12) are interesting for functional coatings on metallic components. To ensure a spatially resolved coating and to shorten the process chain, directed energy deposition of polymer powders by means of a laser beam (DED-LB/P) offers a promising approach. Due to characteristic absorption bands, the use of a thulium fiber laser with a wavelength of 1.94 μm is investigated in a DED-LB/P setup to generate PA12 coatings on stainless steel substrates without the need to add any absorbing additives. The influence of the energy density and powder mass flow was analyzed by infrared thermography. Furthermore, the coatings were characterized by differential scanning calorimetry, laser-scanning-microscopy, optical microscopy and cross-cutting tests. The results in this study demonstrate for the first time the basic feasibility of an absorber-free DED-LB/P process by using a thulium fiber laser. PA12 coatings with a low porosity and good adhesion are achievable. Depending on the application-specific requirements, a trade-off must be made between the density and surface quality of the PA12 coatings. The use of infrared thermography is appropriate for in-situ detection of process instabilities caused by an excessive energy input. Full article

The widespread concerns about the environmental problems caused by conventional plastic food packaging and food waste led to a growing effort to develop active and intelligent systems produced from renewable biodegradable polymers for food packaging applications. Among intelligent systems, the most widely used are pH indicators, which are generally based on a pH-sensitive dye incorporated into a solid support. The objective of this study was to develop new intelligent systems based on renewable biodegradable polymers and a new bio-inspired pH-sensitive dye. The structure of the dye was elucidated through FT-IR and 1D and 2D NMR spectroscopic analyses. UV-VIS measurements of the dye solutions at various pH values proved their halochromic properties. Their toxicity was evaluated through theoretical calculations, and no toxicity risks were found. The new anthocyanidin was used for the development of biodegradable intelligent systems based on chitosan blends. The obtained polymeric films were characterized through UV-VIS and FT-IR spectroscopy. Their thermal properties were assessed through a thermogravimetric analysis, which showed a better stability of chitosan–PVA–dye and chitosan–starch–dye films compared to those of chitosan–cellulose–dye films and the dye itself. The films’ sensitivity to pH variations was evaluated through immersion in buffer solutions with pH values ranging from 2 to 12, and visible color changes were observed. Full article

Cellulose nanofibers (CNF) are sustainable nanomaterials, obtained by the mechanical disintegration of cellulose, whose properties make them an interesting adsorbent material due to their high specific area and active groups. CNF are easily functionalized to optimize the performance for different uses. The hypothesis of this work is that hydrophobization can be used to improve their ability as adsorbents. Therefore, hydrophobic CNF was applied to adsorb hexavalent chromium from wastewater. CNF was synthetized by TEMPO-mediated oxidation, followed by mechanical disintegration. Hydrophobization was performed using methyl trimetoxysilane (MTMS) as a hydrophobic coating agent. The adsorption treatment of hexavalent chromium with hydrophobic CNF was optimized by studying the influence of contact time, MTMS dosage (0–3 mmol·g⁻¹ CNF), initial pH of the wastewater (3–9), initial chromium concentration (0.10–50 mg·L⁻¹), and adsorbent dosage (250–1000 mg CNF·L⁻¹). Furthermore, the corresponding adsorption mechanism was identified. Complete adsorption of hexavalent chromium was achieved with CNF hydrophobized with 1.5 mmol MTMS·g⁻¹ CNF with the faster adsorption kinetic, which proved the initial hypothesis that hydrophobic CNF improves the adsorption capacity of hydrophilic CNF. The optimal adsorption conditions were pH 3 and the adsorbent dosage was over 500 mg·L⁻¹. The maximum removal was found for the initial concentrations of hexavalent chromium below 1 mg·L⁻¹ and a maximum adsorption capacity of 70.38 mg·g⁻¹ was achieved. The kinetic study revealed that pseudo-second order kinetics was the best fitting model at a low concentration while the intraparticle diffusion model fit better for higher concentrations, describing a multi-step mechanism of hexavalent chromium onto the adsorbent surface. The Freundlich isotherm was the best adjustment model. Full article

Biosorbtive removal of the antibacterial drug, ethacridine lactate (EL), from aqueous solutions was investigated using as biosorbent Saccharomyces pastorianus residual biomass immobilized in calcium alginate. The aim of this work was to optimize the biosorption process and to evaluate the biosorption capacity in the batch system. Response surface methodology, based on a Box–Behnken design, was used to optimize the EL biosorption parameters. Two response functions (removal efficiency and biosorption capacity) were maximized dependent on three factors: initial concentration of EL solution, contact time, and agitation speed. The highest values for the studied functions (89.49%, 26.04 mg/g) were obtained in the following operational conditions: EL initial concentration: 59.73 mg/L; contact time: 94.26 min; agitation speed: 297.57 rpm. A number of nonlinear kinetic models, including pseudo-first-order, pseudo-second-order, Elovich, and Avrami, were utilized to validate the biosorption kinetic behavior of EL in the optimized conditions. The kinetic data fitted the pseudo-first-order and Avrami models. The experimental results demonstrated that the optimized parameters (especially the agitation speed) significantly affect biosorption and should be considered important in such studies. Full article

The present work aims to enhance the use of agricultural byproducts for the production of bio-composites by melt extrusion. It is well known that in the production of such bio-composites, the weak point is the filler-matrix interface, for this reason the adhesion between a polylactic acid (PLA)/poly(butylene succinate)(PBSA) blend and rice and wheat bran platelets was enhanced by a treatment method applied on the fillers using a suitable beeswax. Moreover, the coupling action of beeswax and inorganic fillers (such as talc and calcium carbonate) were investigated to improve the thermo-mechanical properties of the final composites. Through rheological (MFI), morphological (SEM), thermal (TGA, DSC), mechanical (Tensile, Impact), thermomechanical (HDT) characterizations and the application of analytical models, the optimum among the tested formulations was then selected. Full article

The outbreak of the worrisome coronavirus disease in 2019 has caused great concern among the global public, especially regarding the need for personal protective equipment with applied antiviral agents to reduce the spread and transmission of the virus. Thus, in our research, chitosan-based bioactive polymers as potential antiviral agents were first evaluated as colloidal macromolecular solutions by elemental analysis and charge. Three different types of low and high molecular weight chitosan (LMW Ch, HMW Ch) and a LMW Ch derivative, i.e., quaternary chitosan (quart-LMW Ch), were used. To explore their antiviral activity for subsequent use in the form of coatings, the macromolecular Chs dispersions were incubated with the model virus phi6 (surrogate for SARS-CoV-2), and the success of virus inactivation was determined. Inactivation of phi6 with some chitosan-based compounds was very successful (>6 log), and the mechanisms behind this were explored. The changes in viral morphology after incubation were observed and the changes in infrared bands position were determined. In addition, dynamic and electrophoretic light scattering studies were performed to better understand the interaction between Chs and phi6. The results allowed us to better understand the antiviral mode of action of Chs agents as a function of their physicochemical properties. Full article

Bone tissue attracts cancer cell homing biologically, mechanically, or chemically. It is difficult and time consuming to identify their complex cross-talk using existed methods. In this study, a multi-component bone matrix was fabricated using gelatin, hydroxyapatite (HAp), and epidermal growth factor (EGF) as raw materials to investigate how “acellular” bone matrix affects cancer cell homing in bone. Then, EGF-responsive cancer cells were cultured with the scaffold in a dynamical bioreactor. For different culture periods, the effects of HAp, gelatin, and EGF on the cell adhesion, proliferation, 3D growth, and migration of cancer were evaluated. The results indicated that a small amount of calcium ion released from the scaffolds accelerated cancer MDA-MB-231 adhesion on the surface of inner pores. Moreover, degradable gelatin key caused cancer cell growth on the scaffold surface to turn into a 3D aggregation. Despite this, the formation of cancer spheroids was slow, and required 14 days of dynamic culture. Thankfully, EGF promoted cancer cell adhesion, proliferation, and migration, and cancer spheroids were observed only after 3-day culture. We concluded that the combination of the multiple components in this scaffold allows cancer cells to meet multiple requirements of cancer dynamic progression. Full article

Soft robotic modules have potential use for therapeutic and educational purposes. To do so, they need to be safe, soft, smart, and customizable to serve individuals’ different preferences and personalities. A safe modular robotic product made of soft materials, particularly silicon, programmed by artificial intelligence algorithms and developed via additive manufacturing would be promising. This study focuses on the safe tactile interaction between humans and robots by means of soft material characteristics for translating physical communication to auditory. The embedded vibratory sensors used to stimulate touch senses transmitted through soft materials are presented. The soft module was developed and verified successfully to react to three different patterns of human–robot contact, particularly users’ touches, and then communicate the type of contact with sound. The study develops and verifies a model that can classify different tactile gestures via machine learning algorithms for safe human–robot physical interaction. The system accurately recognizes the gestures and shapes of three-dimensional (3D) printed soft modules. The gestures used for the experiment are the three most common, including slapping, squeezing, and tickling. The model builds on the concept of how safe human–robot physical interactions could help with cognitive and behavioral communication. In this context, the ability to measure, classify, and reflect the behavior of soft materials in robotic modules represents a prerequisite for endowing robotic materials in additive manufacturing for safe interaction with humans. Full article

This study presents the production, characterization, and application of celandine (Chelidonium majus L.) extracts (aqueous, acidic, alcoholic, and ultrasound) on wool fibers and their characterization. The study aims to obtain an ecologically dyed wool support that possesses biocompatible and antimicrobial activities. The plant extracts were characterized based on pH, total polyphenol content, and berberine content. Ecologically dyed wool supports were characterized based on scanning electron microscopy, levelness index, color measurements, contact angle indirect biocompatibility, and antibacterial analysis. According to the obtained results, celandine extract can be considered a potential candidate for the sustainable dyeing and functionalization of wool fibers. Full article

In the context of sustainable and circular economy, the recovery of biowaste for sustainable biocomposites formulation is a challenging issue. The aim of this work is to give a new life to agricultural carob waste after glucose extraction carried out by a local factory for carob candy production. A pyrolysis process was carried out on bio-waste to produce biofuel and, later, the solid residual fraction of pyrolysis process was used as interesting filler for biocomposites production. In this work, biochar particles (BC) as a pyrolysis product, after fuels recovery of organic biowaste, specifically, pyrolyzed carobs after glucose extraction, were added on poly(butylene-adipate-co-terephthalate), (PBAT), at two different concentrations, i.e., 10 and 20 wt%. The BC have been produced using three pyrolysis processing temperatures (i.e., 280, 340 and 400 °C) to optimize the compositions of produced solid fractions and biofuels. The resulting particles from the pyrolysis process (BC280, BC340 and BC400) were considered as suitable fillers for PBAT. Firstly, the BC particles properties were characterized by elemental composition and spectroscopy analysis, particle size measurements and evaluation of radical scavenging activity and efficiency. Moreover, PBAT/BC composites were subjected to analysis of their rheological and thermal behavior, morphologies and mechanical properties. In addition, accelerated weathering, monitored by both tensile test and spectroscopic analysis, was carried out, and obtained results show that the biochar particles can exert a beneficial effect on photo-oxidation delay of PBAT matrix. Full article

Nowadays, there are still numerous challenges for well-known biomedical applications, such as tissue engineering (TE), wound healing and controlled drug delivery, which must be faced and solved. Hydrogels have been proposed as excellent candidates for these applications, as they have promising properties for the mentioned applications, including biocompatibility, biodegradability, great absorption capacity and tunable mechanical properties. However, depending on the material or the manufacturing method, the resulting hydrogel may not be up to the specific task for which it is designed, thus there are different approaches proposed to enhance hydrogel performance for the requirements of the application in question. The main purpose of this review article was to summarize the most recent trends of hydrogel technology, going through the most used polymeric materials and the most popular hydrogel synthesis methods in recent years, including different strategies of enhancing hydrogels’ properties, such as cross-linking and the manufacture of composite hydrogels. In addition, the secondary objective of this review was to briefly discuss other novel applications of hydrogels that have been proposed in the past few years which have drawn a lot of attention. Full article

Glass fiber-reinforced phenolic resins are well suited to substitute aluminum die-cast materials. They meet the high thermomechanical and chemical demands that are typically found in combustion engine and electric drive train applications. An injection molding process development for further improving their mechanical properties by increasing the glass fiber length in the molded part was conducted. A novel screw mixing element was developed to improve the homogenization of the long fibers in the phenolic resin. The process operation with the mixing element is a balance between the desired mixing action, an undesired preliminary curing of the phenolic resin, and the reduction of the fiber length. The highest mixing energy input leads to a reduction of the initial fiber length L₀ = 5000 μm to a weighted average fiber length of L_p = 571 μm in the molded part. This is an improvement over L_p = 285 μm for a short fiber-reinforced resin under comparable processing conditions. The mechanical characterization shows that for the long fiber-reinforced materials, the benefit of the increased homogeneity outweighs the disadvantages of the reduced fiber length. This is evident from the increase in tensile strength from σ_m = 21 MPa to σ_m = 57 MPa between the lowest and the highest mixing energy input parameter settings. Full article

Powder bed fusion (PBF) is an additive manufacturing (AM) technique which offers efficient part-production, light-weighting, and the ability to create complex geometries. However, during a build cycle, multiple aging and degradation processes occur which may affect the reusability of the Polyamide 12 (PA-12) powder. Limited understanding of these phenomena can result in discarding re-usable powder unnecessarily, or the production of parts with insufficient properties, both of which lead to significant amounts of waste. This paper examines the thermal, chemical, and mechanical characteristics of PA-12 via an oven storage experiment that simulates multi jet fusion (MJF) conditions. Changes in the properties of PA-12 powder during oven storage showed two separate, time-dependent trends. Initially, differential scanning calorimetry showed a 4.2 °C increase in melting temperature (T_m) and a rise in crystallinity (X_c). This suggests that secondary crystallisation is occurring instead of, or in addition to, the more commonly reported further polycondensation process. However, with extended storage time, there were substantial reductions in T_m and X_c, whilst an 11.6 °C decrease in crystallisation temperature was observed. Fourier transform infrared spectroscopy, a technique rarely used in PBF literature, shows an increased presence of imide bonds—a key marker of thermo-oxidative degradation. Discolouration of samples, an 81% reduction in strength and severe material embrittlement provided further evidence that thermo-oxidative degradation becomes the dominant process following extended storage times beyond 100 h. An additional pre-drying experiment showed how moisture present within PA-12 can also accelerate degradation via hydrolysis. Full article

Bioplastics may solve environmental issues related to the current linear plastic economy, but they need improvement to be viable alternatives. To achieve this, we aimed to add chitin nanocrystals (ChNC) to polylactic acid (PLA), which is known to alter material properties while maintaining a fully bio-based character. However, ChNC are not particularly compatible with PLA, and surface modification with fatty acids was used to improve this. We used fatty acids that are different in carbon chain length (C4–C18) and degree of saturation (C18:2). We successfully used Steglich esterification and confirmed covalent attachment of fatty acids to the ChNC with FTIR and solid-state ¹³C NMR. The morphology of the ChNC remained intact after surface modification, as observed by TEM. ChNC modified with C4 and C8 showed higher degrees of substitution compared to fatty acids with a longer aliphatic tail, while particles modified with the longest fatty acid showed the highest hydrophobicity. The addition of ChNC to the PLA matrix resulted in brown color formation that was reduced when using modified particles, leading to higher transparency, most probably as a result of better dispersibility of modified ChNC, as observed by SEM. In general, addition of ChNC provided high UV-protection to the base polymer material, which is an additional feature that can be created through the addition of ChNC, which is not at the expense of the barrier properties, or the mechanical strength. Full article

Fused deposition modelling (FDM)-printed parts can be treated with various post-processes to improve their mechanical properties, dimensional accuracy and surface finish. Samples of polylactic acid (PLA) and acrylonitrile butadiene styrene (ABS) parts are treated with annealing to study a ceramic powder mould’s effectiveness in order to avoid dimensional part deformation. The variables chosen are annealing temperatures and the usage of a ceramic powder mould to avoid part deformations. A flexural strength test was carried out to evaluate the mould’s influence on the mechanical properties of the part. The effectiveness of the mould has been evaluated mainly attending to the length of the part, because this is the dimension most affected by deformation. A polynomial approximation to a deformation’s length and the effectiveness of the mould allows for their prediction. Results obtained show that effectiveness increases with the annealing temperature. Nevertheless, mould effectiveness decreases when parts are fabricated with PLA, because it is a semi-crystalline thermoplastic, and it suffers a lower shrinkage during thermal post-process than amorphous polymers such as ABS. Attending to the flexural strength test, mould has no significant influence on the mechanical properties of the treated parts in both materials studied. Full article

The use of soil conditioners in conjunction with brackish water irrigation is critical for the efficient development and use of brackish water as well as the enhancement of the structure of saline soil and stimulating crop growth. This study investigated the effects of different polyacrylamide (PAM) dosages (0, 0.02%, 0.04%, and 0.06%) on the water flow properties of sandy loam during brackish water infiltration using one-dimensional vertical and horizontal soil column infiltration experiments. The results showed that: (1) PAM could lower the soil infiltration rate and increase soil water retention performance under brackish water infiltration conditions. (2) PAM had a significant effect on the parameters of the Philip and Kostiakov infiltration models. The soil sorption rate S and the empirical coefficient λ were the smallest, and the empirical index β was the largest when the PAM dosage was 0.04%. (3) PAM dosage displayed a quadratic polynomial connection with the soil saturated water content and the saturated hydraulic conductivity. The soil saturated water content was highest when the PAM dosage was 0.04%, the intake suction h_d of the Brooks-Corey model increased by 15.30%, and the soil water holding capacity was greatly improved. (4) Soil treated with PAM could absorb more water under the same soil water suction, whereas the soil unsaturated hydraulic conductivity and its growth rate decreased. The soil saturated diffusion rate D_s, as well as the soil water diffusion threshold, rose. Finally, the 0.04% PAM dosage could improve soil hydrodynamic characteristics under brackish water infiltration, which is beneficial for the efficient utilization of brackish water. Full article

Polylactides (PLAs) are thermoplastic materials known for their wide range of applications. Moreover, the equimolar mixtures of poly(L-Lactide) (PLLA) and poly(D-Lactide) (PDLA) can form stereocomplexes (SCs), which leads to the formation of new non-covalent complex macromolecular architectures. In this work, we report the synthesis and characterization of non-covalent triblock terpolymers of polystyrene-b-stereocomplex PLA-b-poly(2-vinylpyridine) (PS-b-SC-b-P2VP). Well-defined ω-hydroxy-PS and P2VP were synthesized by “living” anionic polymerization high-vacuum techniques with sec-BuLi as initiator, followed by termination with ethylene oxide. The resulting PS-OH and P2VP-OH were used as macroinitiators for the ring-opening polymerization (ROP) of DLA and LLA with Sn(Oct)₂ as a catalyst to afford PS-b-PDLA and P2VP-b-PLLA, respectively. SC formation was achieved by mixing PS-b-PDLA and P2VP-b-PLLA chloroform solutions containing equimolar PLAs segments, followed by precipitation into n-hexane. The molecular characteristics of the resulting block copolymers (BCPs) were determined by ¹H NMR, size exclusion chromatography, and Fourier-transform infrared spectroscopy. The formation of PS-b-SC-b-P2VP and the effect of molecular weight variation of PLA blocks on the resulting polymers, were investigated by differential scanning calorimetry, X-ray powder diffraction, and circular dichroism spectroscopies. Full article

In this research, ethyl cellulose films were prepared by a simple, easy, controlled one-pot method using either ethanol or ethyl lactate as solvents, the films being formed at 6 °C. Titanium dioxide nanoparticles were incorporated to improve the oxygen transmission and water vapour transmission rates of the obtained films. This method used no plasticizers, and flexible materials with good mechanical properties were obtained. The resulting solvent-free and transparent ethyl cellulose films exhibited good mechanical properties and unique free-shapable properties. The obtained materials had similar properties to those reported in the literature, where plasticizers were incorporated into ethyl cellulose films with an elastic modulus of 528 MPa. Contact angles showed the hydrophobic nature of all the prepared materials, with contact angles between 80 and 108°. Micrographs showed the smooth surfaces of the prepared samples and porous intersections with honeycomb-like structures. The oxygen and water vapor transmission rates were the lowest for the ethyl cellulose films prepared in ethyl lactate, these being 615 cm³·m⁻²·day⁻¹ and 7.8 gm⁻²·day⁻¹, respectively, showing that the films have promise for food packaging applications. Full article

Plantation-grown Eucalyptus nitens (E. nitens) has been grown predominantly for the pulp and paper industry. In this study, the suitability of E. nitens as a structural material is examined using static tensile tests in a universal testing machine. The anisotropic tensile behaviour of 240 Eucalyptus nitens small clear wood samples with a diversity of grain angles was examined in both dry and wet conditions. The samples had a highly anisotropic tensile characterisation in the context of both a low moisture content (MC = 12%) and a high moisture content (MC > its fibre saturation point, FSP). The results showed that, in a high moisture content condition, the wood showed a lower failure strength and more ductility at all grain angles than in a low moisture content condition. The underlying failure mechanism of Eucalyptusnitens timber in tension was determined in detail from the perspective of the microstructure of wood cellulose polymer composites. The mean tensile failure strengths perpendicular and parallel to the fibre direction were, respectively, 5.6 and 91.6 MPa for the low MC and 3.8 and 62.1 MPa for the high MC condition. This research provides a basis for using E. nitens as a potential structural tensile member. The moisture modification factors of Eucalyptus timber at a mean level are higher than those of the traditional construction material, Pinus radiata, implying that E. nitens is promising as a material to be used for tensile members in water saturated conditions. Full article

The aim of this study was to synthesize an intrinsically stretchable conductive polymer (CP) by atom transfer radical polymerization (ATRP). For this purpose, poly(3,4-ethyilenedioxythiophene) (PEDOT) was synthesized as a backbone, while poly(acrylate-urethane) (PAU) was grafted onto the PEDOT backbone to form graft polymers PEDOT-g-PAU. Different concentrations of acrylate-urethane (AU) were used to synthesize PAU side chains of different lengths. The successful synthesis of the obtained intermediates and products (PEDOT-g-PAU) was confirmed by infrared spectroscopy and nuclear magnetic resonance. Thermal properties were evaluated by differential scanning calorimetry and thermogravimetric analysis, while conductivity was determined by four-point probe measurement. A simple tensile test was performed to characterize the ductility of the samples. PEDOT-g-PAU has shown high stretchability of up to 500% and, therefore, could potentially be used in skin-worn flexible electronics, while additional subsequent doping is required to improve the deterioration of electrical properties after the addition of the insulating urethane layer. Full article

Faraday instability has great application value in the fields of controlling polymer processing, micromolding colloidal lattices on structured suspensions, organizing particle layers, and conducting cell culture. To regulate Faraday instability, in this article, we attempt to introduce an elastic polymer film covering the surface of a viscous fluid layer and theoretically study the behaviors of the Faraday instability phenomenon and the effect of the elastic polymer film. Based on hydrodynamic theory, the Floquet theory is utilized to formulate its stability criterion, and the critical acceleration amplitude and critical wave number are calculated numerically. The results show that the critical acceleration amplitude for Faraday instability increases with three increasing bending stiffness of the elastic polymer film, and the critical wave number decreases with increasing bending stiffness. In addition, surface tension and viscosity also have important effects on the critical acceleration amplitude and critical wave number. The strategy of controlling Faraday instability by covering an elastic polymer film proposed in this paper has great application potential in new photonic devices, metamaterials, alternative energy, biology, and other fields. Full article

Porous chitosan/saccharomycetes adsorption microspheres were successfully prepared by using silica gel as porogen. The morphology of porous chitosan/saccharomycetes microspheres was characterized by scanning electron microscopy, the interaction between molecules was characterized by Fourier transform infrared spectroscopy, and the crystallization property of the microspheres was characterized by X-ray diffraction. The results showed that the adsorption sites of amino and hydroxyl groups had been provided by the porous chitosan/saccharomycetes microspheres for the removal of preservatives, pigments, and other additives in food. The surface roughness of microspheres could be improved by increasing the mass ratio of saccharomycetes. The increase in silica gels could make the microsphere structure more compact. The porous chitosan/saccharomycetes microspheres could be used as adsorbents to adsorb doxycycline in wastewater. Full article

Ansa-zirconocene complexes are widely employed as precatalysts for olefin polymerization. Their synthesis generally leads to mixtures of their rac and meso isomers, whose separation is often problematic. In this contribution, we report on the synthesis of a novel silyl-bridged bis(indenyl)-based metallocene, and on the separation of its rac and meso isomers by simple recrystallization from toluene. The two complexes, activated by methylaluminoxane (MAO), have been used as precatalysts in ethylene/1-hexene copolymerization. Regardless of the reaction conditions, the meso complex outperformed its rac congener. A similar trend was observed by performing the process in the presence of the silica-supported versions of the complexes. This is remarkable, since meso metallocenes generally display lower activities than their rac analogues. Furthermore, the meso isomer generates polymer products that are more in line with the targets for the preparation of a bimodal PE grade made of a lower-MW high-density (HDPE) fraction and a higher-MW linear low-density (LLDPE) fraction. Full article

In this paper, a UV cross-linkable vitrimer-like polymer, ureidopyrimidinone functionalized telechelic polybutadiene, is reported. It is synthesized in two steps. First, 2(6-isocyanatohexylaminocarbonylamino)-6-methyl-4[1H]-pyrimidinone (UPy-NCO) reacts with hydroxy-functionalized polybutadiene (HTPB) to obtain UPy-HTPB-UPy, and then the resulted UPy-HTPB-UPy is cross-linked under 365 nm UV light (photo-initiator: bimethoxy-2-phenylacetophenone, DMPA). Further investigation reveals that the density of cross-linking and mechanical properties of the resulting polymers can be tailored via varying the amount of photo-initiator and UV exposure time. Before UV cross-linking, UPy-HTPB-UPy is found to be vitrimer-like due to the quadruple hydrogen-bonding interactions. The UPy groups at the end of the chain also enable for rapid solidification upon the evaporation of the solvent. The unsaturated double bonds in the HTPB chains enable UPy-HTPB-UPy to be UV cross-linkable in the solid state at room temperature. After cross-linking, the polymers have good shape memory effect (SME). Here, we demonstrate that this type of polymer can have many potential applications in additive manufacturing. In the cases of fused deposition modelling (FDM) and direct ink writing (DIW), not only the strength of the interlayer bonding but also the strength of the polymer itself can be enhanced via UV exposure (from thermoplastic to thermoset) either during printing or after printing. The SME after cross-linking further helps to achieve rapid volumetric additive manufacturing anytime and anywhere. Full article

This paper reports the manipulation of elastic instability of the viscoelastic fluid in a rhombus cross microchannel (RCM) structure. The bistable instability and unsteady instability of the flow is firstly demonstrated in a standard cross microchannel (SCM) for reference. We then keep the bi-stable instability over a much wider injection rate range in the RCM, which is attributed to the stabilizing effect of the rhombus structure. A semi-bistable instability was also established in the RCM at a high enough injection rate. In addition, the unsteady elastic instability is realized in the RCM through an asymmetric injection rate condition. Full article

This attempt aims at assessing heat generation in thermal conductive polymer (TCP) composites widely used in aerospace sectors. Temperature histories were investigated in both nonreinforced and glass-fiber-reinforced TCPs during abrasive milling. Glass/epoxy and glass/polyester composites with 30% unidirectional glass fiber content were prepared according to appropriate curing cycles. Type K thermocouples connected to a data acquisition system ensured the recording of temperature history along the trim plan during milling. Unexpectedly, when milling TCP composites parallel to fibers, peak temperature was found to be slightly lower than that recorded in nonreinforced polymers. The lateral surface of fibers acts to favor sliding friction, which limits heat generation at interfaces, while relatively low specific heat capacity and thermal conductivity of glass fiber disadvantage heat transfer. However, when milling perpendicular to fibers, the contact area between the tool and the transverse failure area of fibers increases drastically, hence involving severe friction at interfaces. This yields peak temperatures sensitively higher than those obtained in nonreinforced polymers. SEM inspections highlighted the failure modes dominating the material removal process in both nonreinforced and glass-fiber-reinforced polymers. The microcracks and debris observed at the trim plan explain, in part, the heat generation detected on temperature rate plots. Thus, heat conduction between phases governs sensitive surface finish integrity and tool lifetime and, hence, has great economic impact on the manufacturing steps. Full article

Spider silks exhibit excellent mechanical properties and have promising application prospects in engineering fields. Because natural spider silk fibers cannot be manufactured on a large scale, researchers have attempted to fabricate bio-inspired spider silks. However, the fabrication of bio-inspired spider silks with dynamically tunable mechanical properties and stimulation–response characteristics remains a challenge. Herein, the 4D printing of shape memory polyurethane is employed to produce dynamic bio-inspired spider silks. The bio-inspired spider silks have two types of energy-absorbing units that can be adjusted, one by means of 4D printing with predefined nodes, and the other through different stimulation methods to make the bio-inspired spider silks contract and undergo spiral deformation. The shape morphing behaviors of bio-inspired spider silks are programmed via pre-stress assemblies enabled by 4D printing. The energy-absorbing units of bio-inspired spider silks can be dynamically adjusted owing to stress release generated with the stimuli of temperature or humidity. Therefore, the mechanical properties of bio-inspired spider silks can be controlled to change dynamically. This can further help in developing applications of bio-inspired spider silks in engineering fields with dynamic changes of environment. Full article

Compared with polyolefins that are used as single-use plastics, polylactic acid (PLA) has a lower tear strength in films. The relationship between the tear strength and the higher-order structure of films was investigated using PLA films that absorbed moisture at 30 °C and 95% relative humidity (RH) or that had been annealed under reduced pressure conditions. Although the mobile amorphous (MAm) amount did not change under high humidity, the film became brittle due to enthalpy relaxation. The crystallization by annealing also caused embrittlement, and the MAm amount decreased to 10%. The displacement until tearing is lowered from 2.5 to 0.5 mm in both cases. However, in situ retardation measurements revealed that there was a significant difference in the fracture morphology of the torn tip. When crystallized, the molecular chains and crystals are oriented in the tensile direction of the film, and a fragmented structure is observed in the ligament. Embrittlement due to enthalpy relaxation caused a weak orientation perpendicular to the tensile direction of the film, and cracks occurs along with this orientation. Full article

The alignment of cellulose by an electric field is an interesting subject for cellulose material processing and its applications. This paper reports an atomistic molecular dynamics simulation of the crystalline cellulose nanofiber (CNF) model in varying electric field directions and strengths. GROMACS software was used to study crystalline cellulose 1β consisting of 18 chains in an aqueous environment at room temperature, and an electric field was applied along the cellulose chain direction and the perpendicular direction with varying field strength. The root-mean-square displacement, radius of gyration, end-to-end length, and hydrogen bond population of the crystalline CNF model were analyzed to determine the effects of the applied electric field on the structure of the CNF model. The results suggest that the nanosecond electric field can induce the orientation of the CNF along the applied electric field direction. The alignment rate and ability to maintain the alignment depend on the electric field strength. Analysis of the radius of gyration, end-to-end length, and bond lengths for intrachain and interchain hydrogen bonds revealed no significant effect on the cellulose structure. Cellulose alignment in an electric field has the potential to broaden the design of electric field-induced processing techniques for cellulose filaments, thin films, and electro-active cellulose composites. Full article

A diblock copolymer (P(VBTAC/NaSS)₁₇-b-PAPTAC₅₀; P(VS)₁₇A₅₀) composed of amphoteric random copolymer, poly(vinylbenzyl trimethylammonium chloride-co-sodium p-styrensunfonate) (P(VBTAC/NaSS); P(VS)) and cationic poly(3-(acrylamidopropyl) trimethylammonium chloride) (PAPTAC; A) block, and poly(acrylic acid) (PAAc₄₉) were prepared via a reversible addition−fragmentation chain transfer radical polymerization. Scrips V, S, and A represent VBTAC, NaSS, and PAPTAC blocks, respectively. Water-soluble polyion complex (PIC) vesicles were formed by mixing P(VS)₁₇A₅₀ and PAAc₄₉ in water under basic conditions through electrostatic interactions between the cationic PAPTAC block and PAA_c49 with the deprotonated pendant carboxylate anions. The PIC vesicle collapsed under an acidic medium because the pendant carboxylate anions in PAAc₄₉ were protonated to delete the anionic charges. The PIC vesicle comprises an ionic PAPTAC/PAAc membrane coated with amphoteric random copolymer P(VS)₁₇ shells. The PIC vesicle showed upper critical solution temperature (UCST) behavior in aqueous solutions because of the P(VS)₁₇ shells. The pH- and thermo-responsive behavior of the PIC vesicle were studied using ¹H NMR, static and dynamic light scattering, and percent transmittance measurements. When the ratio of the oppositely charged polymers in PAPTAC/PAAc was equal, the size and light scattering intensity of the PIC vesicle reached maximum values. The hydrophilic guest molecules can be encapsulated into the PIC vesicle at the base medium and released under acidic conditions. It is expected that the PIC vesicles will be applied as a smart drug delivery system. Full article

Intrinsically conducting polymers may undergo significant changes of molecular structure and material properties when exposed to highly oxidizing conditions or very positive electrode potentials, commonly called overoxidation. The type and extent of the changes depend on the experimental conditions and chemical environment. They may proceed already at much lower rates at lower electrode potentials because some of the processes associated with overoxidation are closely related to more or less reversible redox processes employed in electrochemical energy conversion and electrochromism. These changes may be welcome for some applications of these polymers in sensors, extraction, and surface functionalization, but in many cases, the change of properties affects the performance of the material negatively, contributing to material and device degradation. This report presents published examples, experimental observations, and their interpretations in terms of both structural and of material property changes. Options to limit and suppress overoxidation are presented, and useful applications are described extensively. Full article

Polyhemiaminal (PHA) polymers are a new class of thermosetting polymers that have recently gained attention owing to their high mechanical strength and excellent recycling behavior. However, low thermal stability is a common issue in PHA polymers due to the thermally labile crosslinked knots. Herein, crosslinked PHA polymer composites were synthesized by reacting formaldehyde with a precursor solution of 4,4ʹ-oxydianiline (ODA) and cyclodextrins (CDs) (α-, β-, and γ-). The material obtained under optimal conditions (ODA:CD molar ratio of 1:0.5, 37% aqueous solution of formaldehyde (formalin)) exhibited good film formability and high thermal stability with two characteristic decomposition phenomena and a high char yield. The early decomposition of CDs and char formation led to high thermal stability. Time-resolved NMR analysis was conducted to study hemiaminal bond formation via a condensation reaction between ODA and formaldehyde. Furthermore, PHA matrix formation was confirmed by the dissolution of the deposited CD layer in a solution of N-methyl-2-pyrrolidinone containing 8–9 wt.% LiBr at 80 °C and FTIR analysis. Based on the elemental analysis results, PHA network formation was confirmed by considering a single unit of the PHA network with CD composition, including the solvent and water. Full article

Biodegradable and potentially biobased polyesteramide oligomers (PEA-Pro), obtained from melt condensation of sebacic acid and 3-amino-1-propanol, were characterized by nuclear magnetic resonance (NMR), matrix assisted laser desorption/ionization-time of flight/time of flight-mass spectrometry/mass spectrometry (MALDI-TOF/TOF-MS/MS), thermogravimetric analysis (TGA), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). NMR analysis showed the presence of hydroxyl and amino terminal groups as well as carboxylic groups of the sebacate moiety. Hydroxyl and carboxyl termination had the same abundance, while the amine termination was 2.7-times less frequent. Information regarding the fragmentation pathways and ester/amide bond sequences was obtained by MALDI-TOF/TOF-MS/MS analysis performed on sodiated adducts of cyclic species and linear oligomers. Different end groups did not influence the observed fragmentation. Three fragmentation pathways were recognized. The β-hydrogen-transfer rearrangement, which leads to the selective scission of the –O–CH₂– bonds, was the main mechanism. Abundant product ions originating from –CH₂–CH₂– (β–γ) bond cleavage in the sebacate moiety and less abundant ions formed by –O–CO– cleavages were also detected. TGA showed a major weight loss (74%) at 381 °C and a second degradation step (22% weight loss) at 447 °C. Py-GC/MS performed in the temperature range of 350–400 °C displayed partial similarity between the degradation products and the main fragments detected in the MALDI-TOF/TOF-MS/MS experiments. Degradation products derived from amide bonds were related to the formation of CN groups, in agreement with the literature. Full article

The increasing attention given to environmental protection, largely through specific regulations on environmental impact and the recycling of materials, has led to a considerable interest of researchers in biocomposites, materials consisting of bio-based or green polymer matrixes reinforced by natural fibers. Among the various reinforcing natural fibers, sisal fibers are particularly promising for their good mechanical properties, low specific weight and wide availability on the current market. As proven in literature by various authors, the hybridization of biocomposites by synthetical fibers or different natural fibers can lead to an interesting improvement of the mechanical properties or, in turn, of the strength against environmental agents. Consequently, this can lead to a significant enlargement of their practical applications, in particular from quite common non-structural applications (dashboards, fillings, soundproofing, etc.) towards semi-structural (panels, etc.) and structural applications (structural elements of civil construction and/or machine components). Hybridizations with natural fibers or with ecofriendly basalt fibers are the most interesting ones, since they permit the improvement of the biocomposite’s performance without an appreciable increment on environmental impact, as occurs instead for synthetic fiber hybridizations that are also widely proposed in the literature. In order to further increase the mechanical performance and, above all, to reduce the aging effects on high-performance sisal-reinforced biocomposites due to environmental agents, the hybridization of such biocomposites with basalt fibers are studied with tensile, compression and delamination tests performed by varying the exposition to environmental agents. In brief, the experimental analysis has shown that hybridization can lead to further enhancements of mechanical performance (strength and stiffness) that increase with basalt volume fraction and can lead to appreciable reductions in the aging effects on mechanical performance by simple hybridization of the surface laminae. Therefore, such a hybridization can be advantageously used in all practical outdoor applications in which high-performance sisal biocomposites can be exposed to significant environmental agents (temperature, humidity, UV). Full article

Stimuli-responsive polymeric nanoparticles (NPs) exhibit reversible changes in the dispersion or aggregation state in response to external stimuli. In this context, we designed and synthesized core-shell NPs with threonine-containing weak polyelectrolyte shells and fluorescent cross-linked cores, which are applicable for the detection of pH changes and amine compounds in aqueous solution. Stable and uniform NP(dTh) and NP(Fl), consisting of fluorescent symmetric diphenyl dithiophene (dTh) and diphenyl fluorene (Fl) cross-linked cores, were prepared by site-selective Suzuki coupling reactions in self-assembled block copolymer. NP(Fl) with the Fl unit in the core showed a high fluorescence intensity in different solvents, which is regarded as an aggregation-induced emission-type NP showing strong emission in aggregated states in the cross-linked core. Unimodal NPs were observed in water at different pH values, and the diameter of NP(Fl) changed from 122 (pH = 2) to 220 nm (pH = 11). Furthermore, pH-dependent changes of the fluorescence peak positions and intensities were detected, which may be due to the core aggregation derived from the deprotonation of the threonine-based shell fragment. Specific interactions between the threonine-based shell of NP(Fl) and amine compounds (triethylamine and p-phenylenediamine) resulted in fluorescence quenching, suggesting the feasibility of fluorescent amine detection. Full article

Three-dimensional printing at the micro-/nanoscale represents a new challenge in research and development to achieve direct printing down to nanometre-sized objects. Here, FluidFM, a combination of microfluidics with atomic force microscopy, offers attractive options to fabricate hierarchical polymer structures at different scales. However, little is known about the effect of the substrate on the printed structures and the integration of (bio)functional groups into the polymer inks. In this study, we printed micro-/nanostructures on surfaces with different wetting properties, and integrated molecules with different functional groups (rhodamine as a fluorescent label and biotin as a binding tag for proteins) into the base polymer ink. The substrate wetting properties strongly affected the printing results, in that the lateral feature sizes increased with increasing substrate hydrophilicity. Overall, ink modification only caused minor changes in the stiffness of the printed structures. This shows the generality of the approach, as significant changes in the mechanical properties on chemical functionalization could be confounders in bioapplications. The retained functionality of the obtained structures after UV curing was demonstrated by selective binding of streptavidin to the printed structures. The ability to incorporate binding tags to achieve specific interactions between relevant proteins and the fabricated micro-/nanostructures, without compromising the mechanical properties, paves a way for numerous bio and sensing applications. Additional flexibility is obtained by tuning the substrate properties for feature size control, and the option to obtain functionalized printed structures without post-processing procedures will contribute to the development of 3D printing for biological applications, using FluidFM and similar dispensing techniques. Full article

Fluorescent cellulose nanofibers (FCNFs), with a high yield, were prepared via one-pot hydrolysis and the grafting reaction of cellulose with thiazolipyridine carboxylic acid (TPCA). The hydrolysis and Fischer esterification of cellulose were conducted under microwave-hydrothermal conditions; meanwhile, TPCA formation was induced by the dehydration reaction between L-cysteine and citric acid. The effects of the reaction temperature and reaction time on the yield and performance of FCNF were investigated. The morphology and size, surface chemical property, crystal structure, thermostability, and fluorescent performance of FCNF were characterized. The results revealed that the yield of FCNF reached 73.2% under a microwave power of 500 W, reaction temperature of 110 °C, and reaction time of 5 h. The FCNF obtained presents a short rod-like morphology. The crystallinity of the FCNFs is 80%, and their thermal stability did not decline significantly. Additionally, the fluorescent performance of the FCNFs is excellent, which results in them having good sensitivity to chloride ions. The good fluorescent performance and significant responsiveness to chloride ions of FCNFs lead to them having broad prospects in bio-labeling, biosensing, information storage, chloride ion detection, among others. Full article

Plastics have become an essential part of the modern world thanks to their appealing physical and chemical properties as well as their low production cost. The most common type of polymers used for plastic account for 90% of the total production and are made from petroleum-based nonrenewable resources. Concerns over the sustainability of the current production model and the environmental implications of traditional plastics have fueled the demand for greener formulations and alternatives. In the last decade, new plastics manufactured from renewable sources and biological processes have emerged from research and have been established as a commercially viable solution with less adverse effects. Nevertheless, economic and legislative challenges for biobased plastics hinder their widespread implementation. This review summarizes the history of plastics over the last century, including the most relevant bioplastics and production methods, the environmental impact and mitigation of the adverse effects of conventional and emerging plastics, and the regulatory landscape that renewable and recyclable bioplastics face to reach a sustainable future. Full article

MK-2048 is a second-generation integrase inhibitor active against HIV, which has been applied vaginally using ring formulations. In this work, a nanoparticle-in-film technology was developed as a discrete pre-exposure prophylactic product option against HIV for an extended duration of use. A film platform loaded with poly (lactic-co-glycolic acid) nanoparticles (PNP) encapsulating MK-2048 was engineered. MK-2048 PNPs were loaded into films that were manufactured via the solvent casting method. Physicochemical and mechanical properties, in vitro efficacy, Lactobacillus compatibility, in vitro and ex vivo permeability, and in vivo pharmacokinetics in macaques were evaluated. PNPs with a mean diameter of 382.2 nm and −15.2 mV zeta potential were obtained with 95.2% drug encapsulation efficiency. PNP films showed comparable in vitro efficacy to free MK-2048 (IC₅₀ 0.46 vs. 0.54 nM) and were found to have no impact on Lactobacillus. MK-2048 encapsulated in PNPs showed an increase in permeability (>4-fold) compared to the free MK-2048 in MDCKII cell lines. Furthermore, PNPs had higher ectocervical tissue permeability (1.7-fold) compared to free MK-2048. PNP films showed sustained drug levels for at least 3 weeks in the macaque vaginal fluid. This work demonstrates the synergy of integrating nanomedicine and polymeric film technology to achieve sustained vaginal drug delivery. Full article

The impact of plastics on the environment can be mitigated by employing biobased and/or biodegradable materials (i.e., bioplastics) instead of the traditional “commodities”. In this context, poly (butylene succinate) (PBS) emerges as one of the most promising alternatives due to its good mechanical, thermal, and barrier properties, making it suitable for use in a wide range of applications. Still, the PBS has some drawbacks, such as its high crystallinity, which must be overcome to position it as a real and viable alternative to “commodities”. This contribution covers the actual state-of-the-art of the PBS through different sections. The first section reviews the different synthesis routes, providing a complete picture regarding the obtained molecular weights and the greener alternatives. Afterward, we examine how different strategies such as random copolymerization and the incorporation of fillers can effectively modulate PBS properties to satisfy the needs for different applications. The impact of these strategies is evaluated in the crystallization behavior, crystallinity, mechanical and barrier properties, and biodegradation. The biodegradation is carefully analyzed, highlighting the wide variety of methodologies existing in the literature to measure PBS degradation through different routes (hydrolytic, enzymatic, and soil). Full article