Polymers, Volume 12, Issue 7 (July 2020) – 191 articles

Light produced by synchrotron radiation (SR) is much brighter than that produced by conventional laboratory X-ray sources. The photon energy of SR X-ray ranges from soft and tender X-rays to hard X-rays. Moreover, X-rays become element sensitive with decreasing photon energy. By using a wide energy range and high-quality light of SR, different scattering and spectroscopic methods were applied to various soft matters. We present five of our recent studies performed using specific light properties of a synchrotron facility, which are as follows: (1) In situ USAXS study to understand the deformation behavior of colloidal crystals during uniaxial stretching; (2) structure characterization of semiconducting polymer thin films along the film thickness direction by grazing-incidence wide-angle X-ray scattering using tender X-rays; (3) X-ray absorption fine structure (XAFS) analysis of the formation mechanism of poly(3-hexylthiophene) (P3HT); (4) soft X-ray absorption and emission spectroscopic analysis of water structure in polyelectrolyte brushes; and (5) X-ray photon correlation spectroscopic analysis of the diffusion behavior of polystyrene-grafted nanoparticles dispersed in a polystyrene matrix. Full article

Solid acid catalysts generally show the disadvantage of low acid amount and low recycling rate. To solve these problems, corn stalk-based solid acid catalysts were synthesized through carbonization and sulfonation processes in this work. The results showed that besides the rod-like structure inherited from raw corn stalk, the catalysts contained some small broken pieces on the surface, and the specific surface area varied from 1120 to 1640 m²/g. The functional groups (-SO₃H) were successfully introduced onto the surface of the obtained solid acid catalysts. The acid amount varied between 1.2 and 2.4 mmol/g, which was higher than most of solid acid catalysts. The catalyst produced at 800 °C for 6 h in carbonation and then at 150 °C for 8 h in sulfonation had larger specific surface area and more sulfonate groups. In the degradation of lignin, the use of catalyst led to the generation of more aromatic compounds (65.6 wt. %) compared to that without using the catalyst (40.5 wt. %). In addition, a stable yield of reaction (85%) was obtained after four reuses. Therefore, corn stalk is suitable for high-value utilization to prepare high-acid amount biochar-based catalyst. Full article

Laminates with unidirectionally arrayed chopped strands (UACS) are one of the advanced short fiber reinforced polymer composites (SFRP) with significant application prospect, which greatly improves mechanical properties compared to the traditional SFRP, meanwhile ensuring excellent flowability. In practice, composite laminate with an open hole is one of the typical connective components, and it is necessary to clarify the allowable load and damage tolerance performance of notched structures. In the present study, UACS laminates were fabricated using the continuous carbon fiber reinforced polymer (CFRP) prepreg, on which regularly arrayed bi-angled slits were introduced by a commercial numerical control cutter. The tensile strength and strain distribution around the open hole of the notched UACS laminate were experimentally investigated, while the damage progression near the open hole of the notched UACS laminate was analyzed by the finite element method (FEM). The tensile strength of the notched UACS laminate was measured at 298 MPa, which is about 60% of the strength of the unnotched UACS laminate. The simulation results match well with the experimental results, although there is a little overestimate on strength, by about 5% and 7%, for unnotched and notched UACS laminates, respectively. The final critical failure mode for the notched UACS laminate is mainly dominated by the delamination instead of the fiber breakage in the unnotched UACS laminate. Full article

Cellulose beads were successfully prepared from waste denim using a dissolution-regeneration approach with ionic liquids as the dissolving solvent. Cellulose beads with different morphologies were achieved by altering the dissolving and coagulating solvents. The morphological differences were quantified by N₂ physisorption. The impact of morphology on the cellulose beads’ potential application was investigated in the context of drug loading and release. The results show that the fibrous morphology showed a better loading capacity than the globular analogue due to its higher surface area and pore volume. Full article

In this paper, we adopted a simple and efficient strategy to prepare a β-cyclodextrin (β-CD)-modified hyper-crosslinked polymer (CDM-HCP). The structures and physicochemical properties of the as-synthesized polymer were also evaluated. It was applied to the removal of anilines from aqueous solutions. The introduction of β-CD into the hyper-crosslinked polymer significantly enhanced adsorption properties for the removal of various amines. The adsorption kinetics agreed with the pseudo-second-order mode very well. The adsorption isotherm data of p-methylaniline (p-MA) and p-aminobenzoic acid (p-ABC) were in agreement with the Langmuir isotherm, whereas aniline and p-chloroaniline (p-CA) were fitted best with the Freundlich model. The maximum adsorption capacities (q_max) determined by adsorption isotherms were 148.97 mg/g for aniline, 198.45 mg/g for p-MA, 293.71 mg/g for p-CA, and 622.91 mg/g for p-ABC, respectively. It had higher adsorption capacities than those of some commercial polymeric resins, such as XAD-4, PA66, and AB-8. The interaction mechanism was investigated by FTIR, XPS, and the ONIOM2 method. A CDM-HCP can be regenerated efficiently and used repeatedly, indicating its potential technological applications in removing organic pollutants from actual industrial effluents. Full article

A new manufacturing method of thermosetting resins reinforced with dense particles is developed in the present work. A rotary mold is used, avoiding the natural sedimentation of particles through applying centrifuge forces. A deep study of the sedimentation phenomenon is carried out in order to evaluate the main experimental parameters which influence the manufacturing of composite. The used reinforcement is zinc oxide (ZnO) obtained by a new recycling method from spent alkaline batteries. In order to compare the benefits, commercial ZnO nanoparticles are also analyzed. Recycled ZnO particles enhance the interaction of the epoxy matrix due to their inner moisture, allowing the manufacture of composites with relatively high ceramic content. Moreover, an increment in the glass transition temperature of the epoxy matrix and in the mechanical properties, such as its stiffness and hardness, is achieved. Full article

Wastewater remains a global challenge. Various methods have been used in wastewater treatment, including flocculation. The aim of this study was to synthesize iron nanoparticles (FeNPs) using a polymeric bioflocculant and to evaluate its efficacy in the removal of pollutants in wastewater. A comparison between the efficiencies of the bioflocculant and iron nanoparticles was investigated. A scanning electron microscope (SEM) equipped with an energy-dispersive X-ray analyzer (EDX) and Fourier transform-infrared (FT-IR) spectroscopy were used to characterize the material. SEM-EDX analysis revealed the presence of elements such as O and C that were abundant in both samples, while FT-IR studies showed the presence of functional groups such as hydroxyl (–OH) and amine (–NH₂). Fe nanoparticles showed the best flocculation activity (FA) at 0.4 mg/mL dosage as opposed to that of the bioflocculant, which displayed the highest flocculation activity at 0.8 mg/mL, and both samples were found to be cation-dependent. When evaluated for heat stability and pH stability, FeNPs were found thermostable with 86% FA at 100 °C, while an alkaline pH of 11 favored FA with 93%. The bioflocculant flocculated poorly at high temperature and was found effective mostly at a pH of 7 with over 90% FA. FeNPs effectively removed BOD (biochemical oxygen demand) and COD (chemical oxygen demand) in all two wastewater samples from coal mine water and Mzingazi River water. Cytotoxicity results showed both FeNPs and the bioflocculant as nontoxic at concentrations up to 50 µL. Full article

Despite the potential of acrylic bone cement (ABC) loaded with chitosan (CS) for orthopedic applications, there are only a few in vitro studies of this composite with CS loading ≤ 15 wt.% evaluated in bioactivity tests in simulated body fluid (SBF) for duration > 30 days. The purpose of the present work was to address this shortcoming of the literature. In addition to bioactivity, a wide range of cement properties were determined for composites with CS loading ranging from 0 to 20 wt.%. These properties included maximum exotherm temperature (T_max), setting time (t_set), water contact angle, residual monomer content, flexural strength, bending modulus, glass transition temperature, and water uptake. For cement with CS loading ≥ 15 wt.%, there was an increase in bioactivity, increase in biocompatibility, decrease in T_max, increase in t_set, all of which are desirable trends, but increase in residual monomer content and decrease in each of the mechanical properties, with each of these trends, were undesirable. Thus, a composite with CS loading of 15 wt.% should be further characterized to explore its suitability for use in low-weight-bearing applications, such as bone void filler and balloon kyphoplasty. Full article

Infrared thermography (IRT) is a competitive method for nondestructive testing; yet it is susceptible to errors when testing objects with complex geometries. This work investigates the effects of regulating different thermographic testing parameters to optimize the IRT outcomes when testing complex shaped geometries, particularly cylindrical coupons. These parameters include the scanning routine, feed-rate, and heat intensity. Fine-tuning these parameters will be performed with respect to three different variables consisting of workpiece density, defect size, and defect depth. The experimental work is designed around 3D-printed cylindrical coupons, then the obtained thermal images are stitched via image processing tool to expose defects from different scans. The analysis employs a Signal-to-Noise Ratio (SNR) metric in an orthogonal tabulation following a Taguchi Design of Experiment. Moreover, test sensitivity and the best combination of factor levels are determined using Analysis of Means (ANOM) and Analysis of Variance (ANOVA). The outcomes show that the heating intensity factor is the most dominant in exposing flaws with close to 40% mean shift and up to 47% variance fluctuation. The paper introduces the tools employed in the study, and then explains the methodology followed to test one sample quadrant. The results for running the testing on all the scenarios are presented, interpreted, and their implications are recommended. Full article

Based on mechanical properties of Polyamide 66 (PA66) under complex loading conditions, a Drucker–Prager yield criterion was employed to characterize its yield behavior. Then, a one-dimensional model, which contains a viscoelastic regime and a viscoplastic regime, was introduced and converted into a three-dimensional constitutive model. The three-dimensional model was implemented into a LS-DYNA software, which was used to predict the dynamic response of PA66 under Taylor impact conditions, whose corresponding tests were conducted by gas gun and recorded by high-speed camera. By contrasting the simulation results and these of the corresponding tests, the deformed shapes including the residual length, the maximum diameter and the shape of the mushroom head of the PA66 bars were found to be similar to these obtained from the tests, which verified the accuracy of the three-dimensional constitutive model, and proved that the model was able to be applied to high-rate impact loading conditions. Full article

Several methods to synthesize poly(phenylene) block copolymers through the nickel coupling reaction were attempted to reduce the use of expensive nickel catalysts in polymerization. The model reaction for poly(phenylene) having different types of dichlorobenzene derivative monomers illustrated the potential use of cost-effective catalysts, such as NiBr₂ and NiCl₂, as alternatives to more expensive catalysts (e.g., bis(1,5-cyclooctadiene)nickel(0) (Ni(COD)₂)). By catalyzing the polymerization of multi-block poly(phenylene) with NiBr₂ and NiCl₂, random copolymers with similar molecular weights could be prepared. However, these catalysts did not result in a high-molecular-weight polymer, limiting their wide scale application. Further, the amount of Ni(COD)₂ could be reduced in this study by approximately 50% to synthesize poly(phenylene) multi-block copolymers, representing significant cost savings. Gel permeation chromatography and nuclear magnetic resonance results showed that the degree of polymerization and ion exchange capacity of the copolymers were almost the same as those achieved through conventional polymerization using 2.5 times as much Ni(COD)₂. The flexible quaternized membrane showed higher chloride ion conductivity than commercial Fumatech membranes with comparable water uptake and promising chemical stability. Full article

Commercial inexpensive preparations of poly-γ-glutamic acid were used to obtain films made with a polypeptide constituted by a single repeating unit. The homopolymer was characterized by ¹H-NMR spectroscopy and thermogravimetry, as well as by zeta potential and Z-average measurements. Manipulatable materials were obtained by casting film-forming solutions prepared at pH values between 3.0 and 4.0 and containing extensively dialyzed samples of the commercial product. The analysis of the mechanical properties highlighted a marked extensibility and plasticity of the films obtained without plasticizer, even though the addition of low amounts of glycerol (1–4%) was able to further increase these features. The characterization of poly-γ-glutamic acid molecular species, performed by membrane ultrafiltration and size-exclusion chromatography, coupled with triple-detection analysis of the obtained fractions, suggested that biopolymer chain length is responsible not only for its capacity to form film, but also for conferring to the films different features depending on the homopolymer molecular weight. Full article

The self-assembly of hydrophobically modified polymers has become a research hotspot due to its wide application in the biomedical field. Recombinant human epidermal growth factors (rhEGFs) are molecules that are able to enhance wound healing; however, they have a short half-life and require sustained action to enhance their mitogenic effect on epithelial cells. Here, we proposed a new delivery system to avoid the inhibition of rhEGF by various enzymes, thus improving its bioavailability and sustained release. The amphiphilic polymer was composed of conjugated linoleic acid (CLA) and carboxymethyl chitosan (CMCS), which were further characterized by fourier transformed infrared spectroscopy (FTIR) and ¹H nuclear magnetic resonance (¹H NMR). Then, the self-assembly behavior of CLA–CMCS (CC) polymer in water was observed in which the particle size of CC decreased from 196 to 155 nm with the degree of CLA substitution increasing. The nanoparticles were loaded with rhEGF and the maximum rhEGF loading efficiency (LE) of CC3 nanoparticles was 82.43 ± 3.14%. Furthermore, CC nanoparticles (NPs) exhibited no cytotoxicity for L929 cells, and cell proliferation activity was well preserved after rhEGF loading to CC-NPs and was comparable to that of free rhEGF. Topically applied rhEGF:CC-NPs significantly accelerated the wound-closure rate in full thickness, which was most probably due to its sustained release and enhanced skin permeation. In conclusion, carboxymethyl chitosan-based nanoparticles were constructed and showed good cytocompatibility. Moreover, these findings also demonstrated the therapeutic potential of rhEGF:CC-NPs as a topical wound-healing drug carrier. Full article

In this study, we investigated the barrier properties of a montmorillonite-reinforced biomass material, starch. Organically modified montmorillonite materials were prepared from natural montmorillonite by reacting it with dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride or octadecyl trimethyl ammonium chloride under ultrasonic conditions. The composite starch films incorporated with these organically modified montmorillonite samples were characterized by scanning electron microscopy, transmission electron microscopy, infrared spectroscopy and X-ray diffraction. The results showed that the introduction of montmorillonite decreases the transmittance of the composite film by 10% in the visible region and significantly inhibits UV-light transmittance. The decomposition temperature of the composite film ranges from 200 to 500 °C, with a weight loss rate of 80%. The distance between the montmorillonite layers increases from 0.14 nm in the non-magnetized state to 1.49 nm after magnetization. The oxygen permeability of the starch film modified by organic montmorillonite (0.067 cm³/m²·d) is lower than that of the montmorillonite starch film without magnetization (0.097cm³/m²·d). The oxygen barrier capacity is close to zero. Particularly in the ordered magnetic montmorillonite starch composite film, the oxygen barrier ability is the best. Therefore, modified montmorillonite could serve as an excellent reinforcing agent for cassava starch films and effectively improve the oxygen barrier performance of the films. Full article

Herein, poly(amic acid) (PAA) was synthesized using 4,4’-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) as a dianhydride and 2,2-bis(3-aminophenyl)hexafluoropropane (6FAm) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAm-OH) as diamines. Poly(vinyl alcohol) (PVA) at various contents (0–5.0 wt%) was blended with PAA to prepare a composite material. Then, colorless and transparent polyimide (CPI) composite films were prepared by applying various stages of heat treatment using the PAA/PVA blend film as a precursor. These film-type composites were immersed in water to completely dissolve PVA, a water-soluble polymer, and their pore sizes were investigated to determine their potential as a porous membrane. According to the results of scanning electronic microscopy (SEM), as the concentration of PVA increased from 0 to 5.0 wt% in the CPI/PVA composite films, the size of the pores resulting from the dissolution of water-soluble PVA increased. Further, the micrometer-sized pores were uniformly dispersed in the CPI films. The thermal properties, morphology, and optical transparency of the two types of CPI membranes synthesized using 6FAm and 6FAm-OH monomers were examined and compared. Full article

The self-assembled multinuclear Pd^II complexes {(Li-OPO^OMe2)PdMe(4-5-nonyl-pyridine)}₄Li₂Cl₂ (C, Li-OPO^OMe2 = PPh(2-SO₃Li-4,5-(OMe)₂-Ph)(2-SO₃⁻-4,5-(OMe)₂-Me-Ph)), {(Zn-OP-P-SO)PdMe(L)}₄ (D, L = pyridine or 4-^tBu-pyridine, [OP-P-SO]³⁻ = P(4-^tBu-Ph)(2-PO₃²⁻-5-Me-Ph)(2-SO₃⁻-5-Me-Ph)), and {(Zn-OP-P-SO)PdMe(pyridine)}₃ (E) copolymerize ethylene and vinyl fluoride (VF) to linear copolymers. VF is incorporated at levels of 0.1–2.5 mol% primarily as in-chain -CH₂CHFCH₂- units. The molecular weight distributions of the copolymers produced by D and E are generally narrower than for catalyst C, which suggests that the Zn-phosphonate cores of D and E are more stable than the Li-sulfonate-chloride core of C under copolymerization conditions. The ethylene/VF copolymerization activities of C–E are over 100 times lower and the copolymer molecular weights (MWs) are reduced compared to the results for ethylene homopolymerization by these catalysts. Full article

Polymer composites with enhanced thermal and dielectric properties can be widely used in electric and energy related applications. In this work, epoxy composites have been prepared with Ti₃C₂T_x, one of the most studied MXene materials that can be massively produced by direct etching using hydrofluoric acid. The addition of conductive two dimensional Ti₃C₂T_x platelet fillers leads to improved but anisotropic thermal conductivity of the composites. The through-plane thermal conductivity reaches 0.583 Wm⁻¹K⁻¹ and the in-plane thermal conductivity reaches 1.29 Wm⁻¹K⁻¹ when filler content is 40 wt% (21.3 vol%), achieving enhancements of 2.92 times and 10.65 times respectively, as compared with epoxy matrix. The dielectric permittivity of epoxy composite is enhanced by a factor of ~2.25 with 40 wt% fillers, and the dielectric losses are within a small value of 0.02. The results prove the effectiveness of Ti₃C₂T_x in simultaneously improving thermal and dielectric performance of epoxy composites, and it is deduced that further improvements may be obtained by using Ti₃C₂T_x nanoflake fillers. Full article

We measured the changes in the higher-order structure of DNA molecules (λ phage DNA, 48 kbp) at different concentrations of 1- and 2-propanol through single-molecular observation. It is known that 2-propanol is usually adapted for the procedure to isolate genomic DNA from living cells/organs in contrast to 1-propanol. In the present study, it was found that with an increasing concentration of 1-propanol, DNA exhibits reentrant conformational transitions from an elongated coil to a folded globule, and then to an unfolded state. On the other hand, with 2-propanol, DNA exhibits monotonous shrinkage into a compact state. Stretching experiments under direct current (DC) electrical potential revealed that single DNA molecules intermediately shrunk by 1- and 2-propanol exhibit intrachain phase segregation, i.e., coexistence of elongated and compact parts. The characteristic effect of 1-propanol causing the reentrant transition is argued in terms of the generation of water-rich nanoclusters. Full article

To improve the functional properties of starch-based films, chitin (CH) was prepared from shrimp shell powder and incorporated into corn starch (CS) matrix. Before blending, maleic anhydride (MA) was introduced as a cross-linker. Composite CS/MA-CH films were obtained by casting-evaporation approach. Mechanical property estimation showed that addition of 0–7 wt % MA-CH improved the tensile strength of starch films from 3.89 MPa to 9.32 MPa. Elongation at break of the films decreased with the addition of MA-CH, but the decrease was obviously reduced than previous studies. Morphology analysis revealed that MA-CH homogeneously dispersed in starch matrix and no cracks were found in the CS/MA-CH films. Incorporation of MA-CH decreased the water vapor permeability of starch films. The water uptake of the films was reduced when the dosage of MA-CH was below 5 wt %. Water contact angles of the starch films increased from 22° to 86° with 9 wt % MA-CH incorporation. Besides, the composite films showed better inhibition effect against Escherichia coli and Staphylococcus aureus than pure starch films. Full article

Film blowing of Poly(ethylene terephthalate) (PET) is challenging due its inherently low melt viscosity and poor melt strength. In this study, it is shown how the rheological properties of a commercial PET can be altered by reactive extrusion using either pyromellitic dianhydride (PMDA) or a multifunctional epoxy (Joncryl^® ADR 4368) as chain extender, in order to improve the processing behavior during film blowing. The modified materials were characterized by shear and elongation rheometry and relevant processing characteristics, like melt pressure, bubble stability, and film thickness uniformity, were used to assess the influence of the type of modifier on processing and product performance. It is shown that PMDA is useful to increase the melt strength which leads to an improved bubble stability, while epoxy modified PET shows a reduced drawability that can cause problems at high take-up ratios. On the other hand, the epoxy modifier indicates a pronounced strain hardening during elongational deformation, and therefore leads to a better film thickness uniformity compared to the neat PET and the PET modified with PMDA. The differences with respect to processing performance are discussed and ascribed to the molecular structure of the materials. Full article

To cope with the demand for cleaner alternative energy, polymer electrolyte membrane fuel cells (PEMFCs) have received significant research attention owing to their high-power density, high fuel efficiency, and low polluting by-product. However, the water requirement of these cells has necessitated research on systems that do not require water and/or use other mediums with higher boiling points. In this work, a highly porous meta-polybenzimidazole (m-PBI) membrane was fabricated through the non-solvent induced phase inversion technique and thermal cross-linking for high-temperature PEMFC (HT-PEMFC) applications. Standard non-thermally treated porous membranes are susceptible to phosphoric acid (PA) even at low concentrations and are unsuitable as polymer electrolyte membranes (PEMs). With the porous structure of m-PBI membranes, higher PA uptake and minimal swelling, which is controlled via cross-linking, was achieved. In addition, the membranes exhibited partial asymmetrical morphology and are directly applicable to fuel cell systems without any further modifications. Membranes with insufficient cross-linking resulted in an unstable performance in HT-PEMFC environments. By optimizing thermal treatment, a high-performance membrane with limited swelling and improved proton conductivity was achieved. Finally, the m-PBI membrane exhibited enhanced acid retention, proton conductivity, and fuel cell performance. Full article

DNA folding is a core phenomenon in genome packaging within a nucleus. Such a phenomenon is induced by polyelectrolyte complexation between anionic DNA and cationic proteins of histones. In this regard, complexes formed between DNA and cationic polyelectrolytes have been investigated as models to gain insight into genome packaging. Upon complexation, DNA undergoes folding to reduce its occupied volume, which often results in multi-complex associated aggregates. However, when cationic copolymers comprising a polycation block and a neutral hydrophilic polymer block are used instead, DNA undergoes folding as a single molecule within a spontaneously formed polyplex micelle (PM), thereby allowing the observation of the higher-order structures that DNA forms. The DNA complex forms polymorphic structures, including globular, rod-shaped, and ring-shaped (toroidal) structures. This review focuses on the polymorphism of DNA, particularly, to elucidate when, how, and why DNA organizes into these structures with cationic copolymers. The interactions between DNA and the copolymers, and the specific nature of DNA in rigidity; i.e., rigid but foldable, play significant roles in the observed polymorphism. Moreover, PMs serve as potential gene vectors for systemic application. The significance of the controlled DNA folding for such an application is addressed briefly in the last part. Full article

Starches were extracted from chickpea (C.P.), corn (C.S.), Turkish bean (T.B.), sweet potato (S.P.S.), and wheat starches (W.S.). These starches exhibited different amylose contents. The extracted starches were annealed in excess water and in germinated sorghum extract (GSE) (1.0 g starch/9 mL water). The α-amylase concentration in the GSE was 5.0 mg/10 mL. Annealing was done at 40, 50, and 60 °C for 30 or 60 min. The pasting properties of annealed starches were studied using Rapid Visco-Analyzer (RVA), in addition to the swelling power. These starches exhibited diverse pasting properties as evidenced by increased peak viscosity with annealing, where native starches exhibited peak viscosity as: 2828, 2438, 1943, 2250, and 4601 cP for the C.P., C.S., T.B., W.S., and S.P.S., respectively, which increased to 3580, 2482, 2504, 2514, and 4787 cP, respectively. High amylose content did not play a major role on the pasting properties of the tested starches because sweet potato starch (S.P.S.) (22.4% amylose) exhibited the highest viscosity, whereas wheat starch (W.S.) (25% amylose) had the least. Therefore, the dual effects of granule structure and packing density, especially in the amorphous region, are determinant factors of the enzymatic digestion rate and product. Swelling power was found to be a valuable predictive tool of amylose content and pasting characteristics of the tested starches. The studied starches varied in their digestibility and displayed structural differences in the course of α-amylase digestion. Based on these findings, W.S. was designated the most susceptible among the starches and S.P.S. was the least. The most starch gel setback was observed for the legume starches, chickpeas, and Turkish beans (C.P. 2553 cP and T.B. 1172 cP). These results were discussed with regard to the underlying principles of swelling tests and pasting behavior of the tested starches. Therefore, GSE is an effortless economic technique that can be used for starch digestion (modification) at industrial scale. Full article

A novel class of graphene-based materials incorporated into natural lignocellulosic fiber (NLF) polymer composites is surging since 2011. The present overview is the first attempt to compile achievements regarding this novel class of composites both in terms of technical and scientific researches as well as development of innovative products. A brief description of the graphene nature and its recent isolation from graphite is initially presented together with the processing of its main derivatives. In particular, graphene-based materials, such as nanographene (NG), exfoliated graphene/graphite nanoplatelet (GNP), graphene oxide (GO) and reduced graphene oxide (rGO), as well as other carbon-based nanomaterials, such as carbon nanotube (CNT), are effectively being incorporated into NLF composites. Their disclosed superior mechanical, thermal, electrical, and ballistic properties are discussed in specific publications. Interfacial shear strength of 575 MPa and tensile strength of 379 MPa were attained in 1 wt % GO-jute fiber and 0.75 wt % jute fiber, respectively, epoxy composites. Moreover, a Young’s modulus of 44.4 GPa was reported for 0.75 wt % GO-jute fiber composite. An important point of interest concerning this incorporation is the fact that the amphiphilic character of graphene allows a better way to enhance the interfacial adhesion between hydrophilic NLF and hydrophobic polymer matrix. As indicated in this overview, two basic incorporation strategies have so far been adopted. In the first, NG, GNP, GO, rGO and CNT are used as hybrid filler together with NLF to reinforce polymer composites. The second one starts with GO or rGO as a coating to functionalize molecular bonding with NLF, which is then added into a polymeric matrix. Both strategies are contributing to develop innovative products for energy storage, drug release, biosensor, functional electronic clothes, medical implants, and armor for ballistic protection. As such, this first overview intends to provide a critical assessment of a surging class of composite materials and unveil successful development associated with graphene incorporated NLF polymer composites. Full article

This study evaluated the shape memory and tensile property of 3D-printed sinusoidal sample/nylon composite for various thickness and cycles. Sinusoidal pattern of five thicknesses: 0.2 mm, 0.4 mm, 0.6 mm, 0.8 mm, and 1.0 mm were 3D-printed on nylon fabric by the fused deposition modeling (FDM) 3D printer using shape memory thermoplastic polyurethane (SMTPU). Afterward, shape memory and tensile property was investigated up to 50 shape memory cycles. The study found that 3D-printed sinusoidal sample/nylon composite had a 100% shape recovery ratio for various thicknesses up to 50 cycles. The average shape recovery rate gradually decreased from 3.0°/s to 0.7°/s whereas the response time gradually increased with the increase of a 3D-printed pattern thickness. The stress and initial modulus gradually increased with the increase of the cycle’s number. Thus, the shape memory property had a similar tendency for various cycles whereas the tensile property gradually increased with the increase of the cycle number. Moreover, this study demonstrated that this 3D-printed sinusoidal sample/nylon composite can go through more than 50 cycles without losing its tensile or shape memory property. This 3D-printed sinusoidal sample/nylon composite has vast potential as smart, reinforced, and protective clothing that requires complex three-dimensional shapes. Full article

A novel choline-based deep eutectic solvent (DES) with low halogen content—namely choline lactate-lactic acid (CLL)—was synthesized by replacing the chloride anion with lactate anion in choline chloride-lactic acid (CCL). CLL and CCL treatments were conducted at 140 °C for 12 h with hydrogen bond acceptor/hydrogen bond donor =1/10, thereafter composition analysis and characterizations of the lignin extracted by DES treatment (DES lignin) and the solid residue were carried out. The proposed low halogen content DES presented an improved lignin extraction efficiency. The CLL treatment extracted 90.13% of initial lignin from poplar, while CCL extracted 86.02%. In addition, the CLL treatment also provided DES lignin with an improved purity (91.17%), lower molecular weight (Mw/Mn=1805/971 g/mol) and more concentrated distribution (polydispersity index=1.86). The efficient lignin extraction was mainly ascribed to the cleavage of β-O-4 bonds in lignin macromolecule, especially in the guaiacyl units, thereby breaking them into smaller molecules, facilitating the lignin extraction. The replacement of chloride anion allowed CLL acting as a more efficient DES to interact with lignin macromolecules, thus providing lignin with higher uniformity and suitable molecular weight. The low halogen content DES system proposed in present work could benefit the fractionation of biomass, improve the valorization of lignin compounds and facilitate industrial process in the downstream. Full article

Methacrylated hyaluronic acid (MeHA) and chondroitin sulfate (CS)-biofunctionalized MeHA (CS-MeHA), were crosslinked in the presence of a matrix metalloproteinase 7 (MMP7)-sensitive peptide. The synthesized hydrogels were embedded with either human mesenchymal stem cells (hMSCs) or chondrocytes, at low concentrations, and subsequently cultured in a stem cell medium (SCM) or chondrogenic induction medium (CiM). The pivotal role of the synthesized hydrogels in promoting the expression of cartilage-related genes and the formation of neocartilage tissue despite the low concentration of encapsulated cells was assessed. It was found that hMSC-laden MeHA hydrogels cultured in an expansion medium exhibited a significant increase in the expression of chondrogenic markers compared to hMSCs cultured on a tissue culture polystyrene plate (TCPS). This favorable outcome was further enhanced for hMSC-laden CS-MeHA hydrogels, indicating the positive effect of the glycosaminoglycan binding peptide on the differentiation of hMSCs towards a chondrogenic phenotype. However, it was shown that an induction medium is necessary to achieve full span chondrogenesis. Finally, the histological analysis of chondrocyte-laden MeHA hydrogels cultured on an ex vivo osteochondral platform revealed the deposition of glycosaminoglycans (GAGs) and the arrangement of chondrocyte clusters in isogenous groups, which is characteristic of hyaline cartilage morphology. Full article

Native collagen scaffolds were prepared in this work, in which both materials and environmental approaches were considered with the aim of providing a global strategy towards more sustainable biomaterials. From the environmental perspective, it is worth mentioning that acid and enzymatic treatments have been avoided to extract collagen, allowing the reduction in the use of resources, in terms of chemicals, energy, and time, and leading to a low environmental load of this step in all the impact categories under analysis. With the incorporation of chitosan into the scaffold-forming formulations, physical interactions occurred between collagen and chitosan, but the native collagen structure was preserved, as observed by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) analyses. The incorporation of chitosan also led to more homogenous porous microstructures, with higher elastic moduli and compression resistance for both dry and hydrated scaffolds. Furthermore, hydrated scaffolds preserved their size and shape after some compression cycles. Full article

From the global spread of COVID-19 we learned that SARS-CoV-2 virus can be transmitted via respiratory liquid droplets. In this study, we performed first-principles calculations suggesting that water molecules once in contact with the graphene oxide (GO) layer interact with its functional groups, therefore, developing an electric field induced by the heterostructure formation. Experiments on GO polymer composite film supports the theoretical findings, showing that the interaction with water aerosol generates a voltage output signal of up to −2 V. We then developed an electrostatic composite fiber by the coagulation method mixing GO with poly(methyl methacrylate) (PMMA). These findings could be used to design protective fabrics with antiviral activity against negatively charged spike proteins of airborne viruses. Full article

Poly(amidoamine) (PAMAM)-based electrolytes are prepared by dissolving the PAMAM half-generations G1.5 or G2.5 in propylene carbonate (PC), either with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) or sodium bis(trifluoromethylsulfonyl)imide (NaTFSI) salts. The solutions, designed for ion battery applications, are studied in terms of ions transport properties. Raman Spectroscopy reveals information about the interactions between cations and PAMAM dendrimers as well as full dissociation of the salts in all solutions. Pulsed-field gradient Nuclear Magnetic Resonance (PFG NMR), measured as a function of both temperature and PAMAM concentration, are obtained for the cation, anion, solvent, and dendrimer molecules using lithium (⁷Li), sodium (²³Na), fluorine (¹⁹F), and hydrogen (¹H) NMR, respectively. It was found that lithium diffusion is slow compared to the larger TFSI anion and decreases with PAMAM concentration due to interactions between cation and dendrimer. Comparison of conductivities calculated from diffusion coefficients using the Nernst–Einstein equation, with conductivity measurements obtained from Impedance Spectroscopy (IS), shows slightly higher IS conductivities, caused among others by PAMAM conductivity. Full article