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Polymers, Volume 13, Issue 7 (April-1 2021) – 189 articles

Cover Story (view full-size image): This study introduces a new generation of 3D-bioprinted nanoparticle-functionalized hyperelastic bone scaffold systems, with enhanced bacteriostatic properties, and a complex, porous, and customized structure. This platform was used as a damage-specific implant with significantly diminished risk of infection or rejection to repair non-healing bone fractures. The bioprinted constructs successfully repaired a critical-sized femoral bone defect in the rat model over a 12-week time course. The grafts showed rapid integration with host tissue, ossification, and growth of new bone. These results suggest a great translational potential for 3D-bioprinted bone scaffolds, laden with functional nanoparticles, for hard-tissue engineering applications. View this paper.
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Article
Mechanical Testing and Modeling of the Time–Temperature Superposition Response in Hybrid Fiber Reinforced Composites
Polymers 2021, 13(7), 1178; https://doi.org/10.3390/polym13071178 - 06 Apr 2021
Cited by 2 | Viewed by 539
Abstract
The purpose of this study was to manufacture hybrid composites from fabrics with superior ballistic performance, and to analyze their viscoelastic and mechanical response. Therefore, composites in hybrid lay-up modes were manufactured from Vectran, Kevlar and aluminum fiber-woven fabrics through a vacuum assisted [...] Read more.
The purpose of this study was to manufacture hybrid composites from fabrics with superior ballistic performance, and to analyze their viscoelastic and mechanical response. Therefore, composites in hybrid lay-up modes were manufactured from Vectran, Kevlar and aluminum fiber-woven fabrics through a vacuum assisted resin transfer molding. The specimens were consequently analyzed using static three-point bending, as well as by dynamic mechanical analysis (DMA). Apart from DMA, time–temperature superposition (TTS) analysis was performed by all available models. It was possible to study the intrinsic viscoelastic behavior of hybrid ballistic laminates, with TTS analysis gained from creep testing. A polynomic mathematical function was proposed to provide a high accuracy for TTS curves, when shifting out of the linearity regimes is required. The usual Williams–Landel–Ferry and Arrhenius models proved not useful in order to describe and model the shift factors of the acquired curves. In terms of static results, the highly nonlinear stress–strain curve of both composites was obvious, whereas the differential mechanism of failure in relation to stress absorption, at each stage of deformation, was studied. SEM fractography revealed that hybrid specimens with Kevlar plies are prone to tensile side failure, whereas the hybrid specimens with Vectran plies exhibited high performance on the tensile side of the specimens in three-point bending, leading to compressive failure owing to the high stress retained at higher strains after the maximum bending strength was reached. Full article
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Article
Natural Rubber Biocomposites Filled with Phyto-Ashes Rich in Biogenic Silica Obtained from Wheat Straw and Field Horsetail
Polymers 2021, 13(7), 1177; https://doi.org/10.3390/polym13071177 - 06 Apr 2021
Cited by 1 | Viewed by 533
Abstract
The rich structural hierarchy of plants permits the obtainment of porous structures which can be expected to show improved performances in fields such as pharmaceuticals and cosmetics, catalysis, drug delivery, adsorption, separation or sensors in various chemical reactions. On the other hand, porous [...] Read more.
The rich structural hierarchy of plants permits the obtainment of porous structures which can be expected to show improved performances in fields such as pharmaceuticals and cosmetics, catalysis, drug delivery, adsorption, separation or sensors in various chemical reactions. On the other hand, porous materials can be an active additive to polymer composites. The aim of the study was to obtain natural rubber (NR) biocomposites with the addition of phyto-ashes reach in biogenic silica from plant biomass. For the production of bioadditives, a two-stage method of high-temperature heat treatment was used, preceded by acid hydrolysis of plant tissues in the form of horsetail and wheat straw. Hydrolysis was performed with hydrochloric and citric acid. The efficiency of the processes and their influence on the elemental composition, surface morphology, thermal stability and particle size of the fillers were determined. Modified bioadditives were introduced into the elastomer matrix and their processing properties, as well as the vulcanization characteristics, were examined. Static mechanical properties (tensile strength, elongation at break, stress at 100%, 200% and 300% elongation), dynamic-mechanical analysis and the influence of additives on the cross-link density of the composites were determined. Structural analysis was performed using scanning electron microscopy. It was found that the field horsetail and cereal straw are plants rich in many valuable chemical compounds, especially silica. The specific and appropriate treatment of these plants can lead to bioadditives that significantly affect the properties of rubber materials. Full article
(This article belongs to the Special Issue Natural Additives as Modificators of Polymer Biocomposites)
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Article
Functional Hydrophilic Membrane for Oil–Water Separation Based on Modified Bio-Based Chitosan–Gelatin
Polymers 2021, 13(7), 1176; https://doi.org/10.3390/polym13071176 - 06 Apr 2021
Viewed by 572
Abstract
In this study, we fabricated a modified biomaterial based on chitosan and gelatin, which is an intrinsic hydrophilic membrane for oil–water separation to clean water contamination by oil. Modification of the membrane with a non-toxic natural crosslinker, genipin, significantly enhanced the stability of [...] Read more.
In this study, we fabricated a modified biomaterial based on chitosan and gelatin, which is an intrinsic hydrophilic membrane for oil–water separation to clean water contamination by oil. Modification of the membrane with a non-toxic natural crosslinker, genipin, significantly enhanced the stability of the biopolymer membrane in a water-based medium towards an eco-friendly environment. The effects of various compositions of genipin-crosslinked chitosan–gelatin membrane on the rheological properties, thermal stability, and morphological structure of the membrane were investigated using a dynamic rotational rheometer, thermogravimetry analysis, and chemical composition by attenuated total reflectance spectroscopy (ATR). Modified chitosan–gelatin membrane showed completely miscible blends, as determined by field-emission scanning electron microscopy, differential scanning calorimetry, and ATR. Morphological results showed membrane with establish microstructure to further experiment as filtration product. The membranes were successfully tested for their oil–water separation efficiencies. The membrane proved to be selective and effective in separating water from an oil–water mixture. The optimum results achieved a stable microporous structure of the membrane (microfiltration) and a separation efficiency of above 98%. The membrane showed a high permeation flux, generated as high as 698 and 420 L m−2 h−1 for cooking and crude oils, respectively. Owing to its outstanding recyclability and anti-fouling performance, the membrane can be washed away easily, ensuring the reusability of the prepared membrane. Full article
(This article belongs to the Special Issue Feature Papers of Green and Sustainable Chemistry in Polymer Science)
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Article
Comparison of a Novel Polymeric Hollow Fiber Heat Exchanger and a Commercially Available Metal Automotive Radiator
Polymers 2021, 13(7), 1175; https://doi.org/10.3390/polym13071175 - 06 Apr 2021
Cited by 2 | Viewed by 393
Abstract
A novel heat exchanger for automotive applications developed by the Heat Transfer and Fluid Flow Laboratory at the Brno University of Technology, Czech Republic, is compared with a conventional commercially available metal radiator. The heat transfer surface of this heat exchanger is composed [...] Read more.
A novel heat exchanger for automotive applications developed by the Heat Transfer and Fluid Flow Laboratory at the Brno University of Technology, Czech Republic, is compared with a conventional commercially available metal radiator. The heat transfer surface of this heat exchanger is composed of polymeric hollow fibers made from polyamide 612 by DuPont (Zytel LC6159). The cross-section of the polymeric radiator is identical to the aluminum radiator (louvered fins on flat tubes) in a Skoda Octavia and measures 720 × 480 mm. The goal of the study is to compare the functionality and performance parameters of both radiators based on the results of tests in a calibrated air wind tunnel. During testing, both heat exchangers were tested in conventional conditions used for car radiators with different air flow and coolant (50% ethylene glycol) rates. The polymeric hollow fiber heat exchanger demonstrated about 20% higher thermal performance for the same air flow. The efficiency of the polymeric radiator was in the range 80–93% and the efficiency of the aluminum radiator was in the range 64–84%. The polymeric radiator is 30% lighter than its conventional metal competitor. Both tested radiators had very similar pressure loss on the liquid side, but the polymeric radiator featured higher air pressure loss. Full article
(This article belongs to the Section Polymer Applications)
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Article
Carboxymethyl Cellulose and Carboxymethyl Starch as Surface Modifiers and Greying Inhibitors in Washing of Cotton Fabrics
Polymers 2021, 13(7), 1174; https://doi.org/10.3390/polym13071174 - 06 Apr 2021
Viewed by 462
Abstract
This research is focused on cellulose and starch derivatives, carboxymethyl cellulose (CMC) and carboxymethyl starch (CMS), added to the detergent in washing reference cotton fabric in soft and hard water at 40, 60 and 90 °C. The applied polymers were analyzed through the [...] Read more.
This research is focused on cellulose and starch derivatives, carboxymethyl cellulose (CMC) and carboxymethyl starch (CMS), added to the detergent in washing reference cotton fabric in soft and hard water at 40, 60 and 90 °C. The applied polymers were analyzed through the potential of surface cellulose modification and inhibition of stain transfer from standard stain donors to modified and initial cotton fabrics. The surface modification of the cotton fabrics, characterized by the zeta potential and amounts of deposits, was coupled with the cluster analysis as well as a whiteness assessment. The obtained results of the zeta potential and degree of whiteness of the reference cotton fabrics before and after washing showed differences between CMC and CMS. The appropriateness of the cluster analysis was confirmed in assessing the potential of applied polymers for surface modification of cotton fabrics and greying inhibition. Full article
(This article belongs to the Section Polymer Applications)
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Article
Polytetrafluoroethylene Films in Rigid Polyurethane Foams’ Dielectric Permittivity Measurements with a One-Side Access Capacitive Sensor
Polymers 2021, 13(7), 1173; https://doi.org/10.3390/polym13071173 - 06 Apr 2021
Cited by 1 | Viewed by 629
Abstract
As a non-metallic composite material, widely applied in industry, rigid polyurethane (PUR) foams require knowledge of their dielectric properties. In experimental determination of PUR foams’ dielectric properties protection of one-side capacitive sensor’s active area from adverse effects caused by the PUR foams’ test [...] Read more.
As a non-metallic composite material, widely applied in industry, rigid polyurethane (PUR) foams require knowledge of their dielectric properties. In experimental determination of PUR foams’ dielectric properties protection of one-side capacitive sensor’s active area from adverse effects caused by the PUR foams’ test objects has to be ensured. In the given study, the impact of polytetrafluoroethylene (PTFE) films, thickness 0.20 mm and 0.04 mm, in covering or simulated coating the active area of one-side access capacitive sensor’ electrodes on the experimentally determined true dielectric permittivity spectra of rigid PUR foams is estimated. Penetration depth of the low frequency excitation field into PTFE and PUR foams is determined experimentally. Experiments are made in order to evaluate the difference between measurements on single PUR foams’ samples and on complex samples “PUR foams + PTFE film” with two calibration modes. A modification factor and a small modification criterion are defined and values of modifications are estimated in numerical calculations. Conclusions about possible practical applications of PTFE films in dielectric permittivity measurements of rigid PUR foams with one-side access capacitive sensor are made. Full article
(This article belongs to the Special Issue Polyurethane Foams: Current Advances and Future Perspectives)
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Systematic Review
Alveolar Bone Ridge Augmentation Using Polymeric Membranes: A Systematic Review and Meta-Analysis
Polymers 2021, 13(7), 1172; https://doi.org/10.3390/polym13071172 - 06 Apr 2021
Cited by 1 | Viewed by 660
Abstract
Alveolar bone ridge resorption occurred after natural teeth loss and it can restrict the possibility of dental implants placement. The use of bone regenerative procedures is frequently required. The existing evidence regarding the efficacy of horizontal bone ridge augmentation trough guided bone regeneration [...] Read more.
Alveolar bone ridge resorption occurred after natural teeth loss and it can restrict the possibility of dental implants placement. The use of bone regenerative procedures is frequently required. The existing evidence regarding the efficacy of horizontal bone ridge augmentation trough guided bone regeneration (GBR) using polymeric membranes was stated. A systematic review and meta-analysis were performed. Electronic and manual literature searches were conducted. Screening process was done using the National Library of Medicine (MEDLINE by PubMed), Embase, and the Cochrane Oral Health. Included articles were randomized controlled trials and observational studies. Weighted means were calculated. Heterogeneity was determined using Higgins (I2). If I2 > 50% a random-effects model was applied. It was found that the mean of horizontal bone gain was 3.95 mm, ranging from 3.19 to 4.70 mm (confidence interval 95%). Heterogeneity is I2 = 99% (confidence interval 95%) and significance of the random-effects model was p < 0.001. The complications rate was 8.4% and membrane exposure was the most frequent. Through this study, we were able to conclude that the existing scientific evidence suggests that GBR using polymeric membranes is a predictable technique for achieving horizontal bone augmentation, thus, permitting a proper further implant placement. Full article
(This article belongs to the Special Issue Polymeric Materials as Scaffolds for Tissue Engineering)
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Article
Physicomechanical Properties of Rice Husk/Coco Peat Reinforced Acrylonitrile Butadiene Styrene Blend Composites
Polymers 2021, 13(7), 1171; https://doi.org/10.3390/polym13071171 - 06 Apr 2021
Cited by 3 | Viewed by 565
Abstract
Utilizing agro-waste material such as rice husk (RH) and coco peat (CP) reinforced with thermoplastic resin to produce low-cost green composites is a fascinating discovery. In this study, the effectiveness of these blended biocomposites was evaluated for their physical, mechanical, and thermal properties. [...] Read more.
Utilizing agro-waste material such as rice husk (RH) and coco peat (CP) reinforced with thermoplastic resin to produce low-cost green composites is a fascinating discovery. In this study, the effectiveness of these blended biocomposites was evaluated for their physical, mechanical, and thermal properties. Initially, the samples were fabricated by using a combination of melt blend internal mixer and injection molding techniques. Increasing in RH content increased the coupons density. However, it reduced the water vapor kinetics sorption of the biocomposite. Moisture absorption studies disclosed that water uptake was significantly increased with the increase of coco peat (CP) filler. It showed that the mechanical properties, including tensile modulus, flexural modulus, and impact strength of the 15% RH—5% CP reinforced acrylonitrile-butadiene-styrene (ABS), gave the highest value. Results also revealed that all RH/CP filled composites exhibited a brittle fracture manner. Observation on the tensile morphology surfaces by using a scanning electron microscope (SEM) affirmed the above finding to be satisfactory. Therefore, it can be concluded that blend-agriculture waste reinforced ABS biocomposite can be exploited as a biodegradable material for short life engineering application where good mechanical and thermal properties are paramount. Full article
(This article belongs to the Special Issue Bio-Based Materials: Contribution to Advancing Circular Economy)
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Article
Comparison of Corn Stover Pretreatments with Lewis Acid Catalyzed Choline Chloride, Glycerol and Choline Chloride-Glycerol Deep Eutectic Solvent
Polymers 2021, 13(7), 1170; https://doi.org/10.3390/polym13071170 - 06 Apr 2021
Cited by 2 | Viewed by 620
Abstract
Herein, corn stover (CS) was pretreated by less corrosive lewis acid FeCl3 acidified solutions of neat and aqueous deep eutectic solvent (DES), aqueous ChCl and glycerol at 120 °C for 4 h with single FeCl3 pretreatment as control. It was unexpected [...] Read more.
Herein, corn stover (CS) was pretreated by less corrosive lewis acid FeCl3 acidified solutions of neat and aqueous deep eutectic solvent (DES), aqueous ChCl and glycerol at 120 °C for 4 h with single FeCl3 pretreatment as control. It was unexpected that acidified solutions of both ChCl and glycerol were found to be more efficient at removing lignin and xylan, leading to higher enzymatic digestibility of pretreated CS than acidified DES. Comparatively, acidified ChCl solution exhibited better pretreatment performance than acidified glycerol solution. In addition, 20 wt% water in DES dramatically reduced the capability of DES for delignification and xylan removal and subsequent enzymatic cellulose saccharification of pretreated CS. Correlation analysis showed that enzymatic saccharification of pretreated CS was highly correlated to delignification and cellulose crystallinity, but lowly correlated to xylan removal. Recyclability experiments of different acidified pretreatment solutions showed progressive decrease in the pretreatment performance with increasing recycling runs. After four cycles, the smallest decrease in enzymatic cellulose conversion (22.07%) was observed from acidified neat DES pretreatment, while the largest decrease (43.80%) was from acidified ChCl pretreatment. Those findings would provide useful information for biomass processing with ChCl, glycerol and ChCl-glycerol DES. Full article
(This article belongs to the Section Circular and Green Polymer Science)
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Article
Functionalization of Single-Walled Carbon Nanotubes with End-Capped Polystyrene via a Single-Step Diels–Alder Cycloaddition
Polymers 2021, 13(7), 1169; https://doi.org/10.3390/polym13071169 - 06 Apr 2021
Cited by 1 | Viewed by 696
Abstract
A facile, single-step, [4+2] Diels–Alder cycloaddition reaction for the surface functionalization of single-walled carbon nanotubes (SWNTs) with end-capped polystyrene chains is presented. The thermal cycloaddition reaction took place at high temperature (~230 °C) without any catalyst between the sp2 network of carbon [...] Read more.
A facile, single-step, [4+2] Diels–Alder cycloaddition reaction for the surface functionalization of single-walled carbon nanotubes (SWNTs) with end-capped polystyrene chains is presented. The thermal cycloaddition reaction took place at high temperature (~230 °C) without any catalyst between the sp2 network of carbon nanotubes, which acted as dienophile, and the diphenylethylene cyclobutene (DPE-CB) terminal group of the polystyrene chain. Anionic polymerization was employed for the synthesis of the polystyrene macromolecule, and successful and quantitative end-capping reaction with the DPE-CB molecule was confirmed by matrix-assisted laser desorption/ionization time of flight mass spectroscopy. Thermogravimetric analysis revealed the wt % of the grafted macromolecule on the CNT surface as well as the grafting density of the polymer chains on the SWNTs (0.027 chains nm−2). Direct evidence for the surface functionalization and the presence of thin polystyrene film was obtained by transmission electron microscopy (TEM) and by atomic force microscopy (AFM). Full article
(This article belongs to the Special Issue State-of-the-Art Polymer Science and Technology in Greece (2020,2021))
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Article
Latex-Based Polystyrene Nanocomposites with Non-Covalently Modified Carbon Nanotubes
Polymers 2021, 13(7), 1168; https://doi.org/10.3390/polym13071168 - 05 Apr 2021
Viewed by 687
Abstract
We prepared electrically conductive polystyrene (PS) nanocomposites by incorporating non-covalently surface-modified carbon nanotubes (CNTs) with hydrophilic polymers such as polydopamine (PDA) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). Further, ethylene glycol (EG) was introduced as a second dopant to improve the electrical properties of the nanocomposites prepared [...] Read more.
We prepared electrically conductive polystyrene (PS) nanocomposites by incorporating non-covalently surface-modified carbon nanotubes (CNTs) with hydrophilic polymers such as polydopamine (PDA) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). Further, ethylene glycol (EG) was introduced as a second dopant to improve the electrical properties of the nanocomposites prepared with PEDOT:PSS-wrapped CNTs. All conductive PS nanocomposites were prepared through latex-based process, and the morphology and properties of the nanocomposites were investigated. The electrical properties of the nanocomposites with PEDOT:PSS-wrapped CNTs were better than those of the nanocomposites with PDA-coated CNTs owing to the conducting nature of PEDOT:PSS, although the dispersions of both types of modified CNTs in the PS matrix were excellent, as evidenced by morphology and rheology. In the case of PEDOT:PSS modification, the electrical properties of the nanocomposites with EG-doped PEDOT:PSS-wrapped CNTs were superior to those of the nanocomposites without EG treatment. Full article
(This article belongs to the Special Issue Nanofillers in Polymers)
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Article
Bionanocomposite Blown Films: Insights on the Rheological and Mechanical Behavior
Polymers 2021, 13(7), 1167; https://doi.org/10.3390/polym13071167 - 05 Apr 2021
Cited by 3 | Viewed by 571
Abstract
In this work, bionanocomposites based on two different types of biopolymers belonging to the MaterBi® family and containing two kinds of modified nanoclays were compounded in a twin-screw extruder and then subjected to a film blowing process, aiming at obtaining sustainable films [...] Read more.
In this work, bionanocomposites based on two different types of biopolymers belonging to the MaterBi® family and containing two kinds of modified nanoclays were compounded in a twin-screw extruder and then subjected to a film blowing process, aiming at obtaining sustainable films potentially suitable for packaging applications. The preliminary characterization of the extruded bionanocomposites allowed establishing some correlations between the obtained morphology and the material rheological and mechanical behavior. More specifically, the morphological analysis showed that, regardless of the type of biopolymeric matrix, a homogeneous nanofiller dispersion was achieved; furthermore, the established biopolymer/nanofiller interactions caused a restrain of the dynamics of the biopolymer chains, thus inducing a significant modification of the material rheological response, which involves the appearance of an apparent yield stress and the amplification of the elastic feature of the viscoelastic behavior. Besides, the rheological characterization under non-isothermal elongational flow revealed a marginal effect of the embedded nanofillers on the biopolymers behavior, thus indicating their suitability for film blowing processing. Additionally, the processing behavior of the bionanocomposites was evaluated and compared to that of similar systems based on a low-density polyethylene matrix: this way, it was possible to identify the most suitable materials for film blowing operations. Finally, the assessment of the mechanical properties of the produced blown films documented the potential exploitation of the selected materials for packaging applications, also at an industrial level. Full article
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Article
A Sustainable Recycling Alternative: Electrospun PET-Membranes for Air Nanofiltration
Polymers 2021, 13(7), 1166; https://doi.org/10.3390/polym13071166 - 05 Apr 2021
Cited by 4 | Viewed by 1262
Abstract
Currently, the inappropriate disposal of plastic materials, such as polyethylene terephthalate (PET) wastes, is a major environmental problem since it can cause serious damage to the environment and contribute to the proliferation of pathogenic microorganisms. To reduce this accumulation, PET-type bottles have been [...] Read more.
Currently, the inappropriate disposal of plastic materials, such as polyethylene terephthalate (PET) wastes, is a major environmental problem since it can cause serious damage to the environment and contribute to the proliferation of pathogenic microorganisms. To reduce this accumulation, PET-type bottles have been recycled, and also explored in other applications such as the development of membranes. Thus, this research aims to develop electrospun microfiber membranes from PET wastes and evaluate their use as an air filter media. The solution concentrations varied from 20 to 12% wt% of PET wastes, which caused a reduction of the average fiber diameter by 60% (from 3.25 µm to 1.27 µm). The electrospun filter membranes showed high mechanical resistance (4 MPa), adequate permeability (4.4 × 10−8 m2), high porosity (96%), and provided a high collection efficiency (about 100%) and low-pressure drop (212 Pa, whose face velocity was 4.8 cm/s) for the removal of viable aerosol nanoparticles. It can include bacteria, fungi, and also viruses, mainly SARS-CoV-2 (about 100 nm). Therefore, the developed electrospun membranes can be applied as indoor air filters, where extremely clean air is needed (e.g., hospitals, clean zones of pharmaceutical and food industry, aircraft, among others). Full article
(This article belongs to the Special Issue Polymer Nanocomposite Membranes for Environmental Applications)
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Article
Influence of Elongation of Paclitaxel-Eluting Electrospun-Produced Stent Coating on Paclitaxel Release and Transport through the Arterial Wall after Stenting
Polymers 2021, 13(7), 1165; https://doi.org/10.3390/polym13071165 - 05 Apr 2021
Viewed by 564
Abstract
It was previously shown that polycaprolactone (PCL)-based electrospun-produced paclitaxel (PTX)-enriched matrices exhibit long-term drug release kinetics and can be used as coatings for drug-eluting stents (DES). The installation of vascular stents involves a twofold increase in stent diameter and, therefore, an elongation of [...] Read more.
It was previously shown that polycaprolactone (PCL)-based electrospun-produced paclitaxel (PTX)-enriched matrices exhibit long-term drug release kinetics and can be used as coatings for drug-eluting stents (DES). The installation of vascular stents involves a twofold increase in stent diameter and, therefore, an elongation of the matrices covering the stents, as well as the arterial wall in a stented area. We studied the influence of matrix elongation on its structure and PTX release using three different electrospun-produced matrices. The data obtained demonstrate that matrix elongation during stent installation does not lead to fiber breaks and does not interfere with the kinetics of PTX release. To study PTX diffusion through the expanded artery wall, stents coated with 5%PCL/10%HSA/3%DMSO/PTX and containing tritium-labeled PTX were installed into the freshly obtained iliac artery of a rabbit. The PTX passing through the artery wall was quantified using a scintillator β-counter. The artery retained the PTX and decreased its release from the coating. The retention of PTX by the arterial wall was more efficient when incubated in blood plasma in comparison with PBS. The retention/accumulation of PTX by the arterial wall provides a prolonged drug release and allows for the reduction in the dose of the drugs in electrospun-produced stent coatings. Full article
(This article belongs to the Special Issue Advanced Polymeric Materials for Pharmaceutical Applications)
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Article
Nano-Assemblies from Amphiphilic PnBA-b-POEGA Copolymers as Drug Nanocarriers
Polymers 2021, 13(7), 1164; https://doi.org/10.3390/polym13071164 - 05 Apr 2021
Cited by 1 | Viewed by 597
Abstract
The focus of this study is the development of highly stable losartan potassium (LSR) polymeric nanocarriers. Two novel amphiphilic poly(n-butyl acrylate)-block-poly(oligo(ethylene glycol) methyl ether acrylate) (PnBA-b-POEGA) copolymers with different molecular weight (Mw) of PnBA are synthesized via reversible addition fragmentation chain [...] Read more.
The focus of this study is the development of highly stable losartan potassium (LSR) polymeric nanocarriers. Two novel amphiphilic poly(n-butyl acrylate)-block-poly(oligo(ethylene glycol) methyl ether acrylate) (PnBA-b-POEGA) copolymers with different molecular weight (Mw) of PnBA are synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization, followed by the encapsulation of LSR into both PnBA-b-POEGA micelles. Based on dynamic light scattering (DLS), the PnBA30-b-POEGA70 and PnBA27-b-POEGA73 (where the subscripts denote wt.% composition of the components) copolymers formed micelles of 10 nm and 24 nm in water. The LSR-loaded PnBA-b-POEGA nanocarriers presented increased size and greater mass nanostructures compared to empty micelles, implying the successful loading of LSR into the inner hydrophobic domains. A thorough NMR (nuclear magnetic resonance) characterization of the LSR-loaded PnBA-b-POEGA nanocarriers was conducted. Strong intermolecular interactions between the biphenyl ring and the butyl chain of LSR with the methylene signals of PnBA were evidenced by 2D-NOESY experiments. The highest hydrophobicity of the PnBA27-b-POEGA73 micelles contributed to an efficient encapsulation of LSR into the micelles exhibiting a greater value of %EE compared to PnBA30-b-POEGA70 + 50% LSR nanocarriers. Ultrasound release profiles of LSR signified that a great amount of the encapsulated LSR is strongly attached to both PnBA30-b-POEGA70 and PnBA27-b-POEGA73 micelles. Full article
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Article
Chelating Fabrics Prepared by an Organic Solvent-Free Process for Boron Removal from Water
Polymers 2021, 13(7), 1163; https://doi.org/10.3390/polym13071163 - 05 Apr 2021
Cited by 3 | Viewed by 591
Abstract
A chelating fabric was prepared by graft polymerization of glycidyl methacrylate (GMA) onto a nonwoven fabric, followed by attachment reaction of N-methyl-D-glucamine (NMDG) using an organic solvent-free process. The graft polymerization was performed by immersing the gamma-ray pre-irradiated fabric into the GMA emulsion, [...] Read more.
A chelating fabric was prepared by graft polymerization of glycidyl methacrylate (GMA) onto a nonwoven fabric, followed by attachment reaction of N-methyl-D-glucamine (NMDG) using an organic solvent-free process. The graft polymerization was performed by immersing the gamma-ray pre-irradiated fabric into the GMA emulsion, while the attachment reaction was carried out by immersing the grafted fabric in the NMDG aqueous solution. The chelating capacity of the chelating fabric prepared by reaction in the NMDG aqueous solution without any additives reached 1.74 mmol/g, which further increased to above 2.0 mmol/g when surfactant and acid catalyst were added in the solution. The boron chelation of the chelating fabric was evaluated in a batch mode. Fourier transform infrared spectrophotometer (FTIR) was used to characterize the fabrics. The chelating fabric can quickly chelate boron from water to form a boron ester, and a high boron chelating ability close to 18.3 mg/g was achieved in the concentrated boron solution. The chelated boron can be eluted completely by HCl solution. The regeneration and stability of the chelating fabric were tested by 10 cycles of the chelation-elution operations. Considering the organic solvent-free preparation process and the high boron chelating performance, the chelating fabric is promising for the boron removal from water. Full article
(This article belongs to the Collection Polymer Materials for Adsorption Applications)
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Review
Recent Research Progress on Lignin-Derived Resins for Natural Fiber Composite Applications
Polymers 2021, 13(7), 1162; https://doi.org/10.3390/polym13071162 - 05 Apr 2021
Cited by 3 | Viewed by 839
Abstract
By increasing the environmental concerns and depletion of petroleum resources, bio-based resins have gained interest. Recently, lignin, vanillin (4-hydroxy-3-methoxybenzaldehyde), and divanillin (6,6′-dihydroxy-5,5′-dimethoxybiphenyl-3,3′-dicarbaldehyde)-based resins have attracted attention due to the low cost, environmental benefits, good thermal stability, excellent mechanical properties, and suitability for high-performance [...] Read more.
By increasing the environmental concerns and depletion of petroleum resources, bio-based resins have gained interest. Recently, lignin, vanillin (4-hydroxy-3-methoxybenzaldehyde), and divanillin (6,6′-dihydroxy-5,5′-dimethoxybiphenyl-3,3′-dicarbaldehyde)-based resins have attracted attention due to the low cost, environmental benefits, good thermal stability, excellent mechanical properties, and suitability for high-performance natural fiber composite applications. This review highlights the recent use of lignin, vanillin, and divanillin-based resins with natural fiber composites and their synthesized processes. Finally, discussions are made on the curing kinetics, mechanical properties, flame retardancy, and bio-based resins’ adhesion property. Full article
(This article belongs to the Special Issue Advanced Epoxy-Based Materials)
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Article
Barium/[email protected] Glycol Nanocomposites for Dye Removal from Aqueous Solutions
Polymers 2021, 13(7), 1161; https://doi.org/10.3390/polym13071161 - 05 Apr 2021
Cited by 1 | Viewed by 525
Abstract
Dyes are known as one of the most dangerous industrial pollutants which can cause skin diseases, allergy, and provoke cancer and mutation in humans. Therefore, one of the important environmental issues is the effective removal of dyes from industrial wastewater. In the current [...] Read more.
Dyes are known as one of the most dangerous industrial pollutants which can cause skin diseases, allergy, and provoke cancer and mutation in humans. Therefore, one of the important environmental issues is the effective removal of dyes from industrial wastewater. In the current work, BaFe12O19/CoFe2O4@polyethylene glycol (abbreviated as BFO/[email protected]) nanocomposite was synthesized and evaluated regarding its capacity for adsorptive removal of a model dye Acid Blue 92 (denoted as AB92) from aqueous solutions. The characteristics of the prepared nanocomposite was determined by tests such as X-ray diffraction (XRD), scanning electron microscope (SEM), vibration sample magnetization (VSM), and Fourier transform infrared spectroscopy (FTIR). The effects of conditional parameters including pH (2–12), initial concentration of dye (20–100 mg/L), adsorbent dosage (0.02–0.1 g/L) and contact time (0-180 min) on the adsorption of dye were investigated and then optimized. The results indicated that with the increase of the adsorbent dosage from 0.02 to 0.1 g/L, the removal efficiency increased from 74.1% to 78.6%, and the adsorbed amount decreased from 148.25 to 31.44 mg/g. The maximum removal efficiency (77.54%) and adsorption capacity (31.02 mg/g) were observed at pH 2. Therefore, the general optimization conditions revealed that the maximum adsorption efficiency of dye was obtained in condition of initial concentration of 20 mg/L, contact time of 1 h and pH of solution equal 2. The adsorption isotherm and kinetic data were evaluated using a series of models. The pseudo-second order kinetic model and Freundlich isotherm model show the best fitting with experimental data with R2∼0.999. Full article
(This article belongs to the Collection Polymer Materials for Adsorption Applications)
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Article
Synthesis, Characterization of Chitosan-Aluminum Oxide Nanocomposite for Green Synthesis of Annulated Imidazopyrazol Thione Derivatives
Polymers 2021, 13(7), 1160; https://doi.org/10.3390/polym13071160 - 05 Apr 2021
Viewed by 584
Abstract
Chitosan-aluminum oxide nanocomposite was synthesized, characterized, and used as a green heterogeneous catalyst to synthesize novel imidazopyrazolylthione derivatives. Nanocomposite polymeric material was characterized by EDS-SEM and XRD. The powerful catalytic activity, and its base character of the nanocomposite, was used to synthesize imidazopyrazolylthione [...] Read more.
Chitosan-aluminum oxide nanocomposite was synthesized, characterized, and used as a green heterogeneous catalyst to synthesize novel imidazopyrazolylthione derivatives. Nanocomposite polymeric material was characterized by EDS-SEM and XRD. The powerful catalytic activity, and its base character of the nanocomposite, was used to synthesize imidazopyrazolylthione (1) in a good yield compared to traditional cyclocondensation synthesis. Using the nanocomposite catalyst, substitution of the thiol group (1) afforded the corresponding thiourea (2) and the corresponding ester (3). The efficiency of the nanocomposite over the traditional base organic catalyst, Et3N and NaOH, makes it an effective, economic, and reproducible nontoxic catalyst. Moreover, the heterogeneous nanocomposite polymeric film was easily isolated from the reaction medium, and recycled up to four times, without a significant loss of its catalytic activity. The newly synthesized derivatives were screened as antibacterial agents and showed high potency. Molecular docking was also performed for a more in-depth investigation. The results of the docking studies have demonstrated that the docked compounds have strong interaction energies with both Gram-positive and Gram-negative bacteria. Full article
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Article
Recyclability Analysis of Starch Thermoplastic/Almond Shell Biocomposite
Polymers 2021, 13(7), 1159; https://doi.org/10.3390/polym13071159 - 05 Apr 2021
Viewed by 532
Abstract
This article is focused on studying the effect of the reprocessing cycles on the mechanical, thermal, and aesthetic properties of a biocomposite. This process is based on starch thermoplastic polymer (TPS) filled with 20 wt% almond shell powder (ASP) and epoxidized linseed oil [...] Read more.
This article is focused on studying the effect of the reprocessing cycles on the mechanical, thermal, and aesthetic properties of a biocomposite. This process is based on starch thermoplastic polymer (TPS) filled with 20 wt% almond shell powder (ASP) and epoxidized linseed oil (ELO) as a compatibilizing additive. To do so, the biocomposite was prepared in a twin-screw extruder, molded by injection, and characterized in terms of its mechanical, thermal, and visual properties (according to CieLab) and the melt flow index (MFI). The analyses carried out were tensile, flexural, Charpy impact tests, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The effects of the reprocessing were also studied for the biodegradable unfilled TPS polymer. The results showed that TPS and TPS/ASP biocomposite suffer changes progressively on the properties studied after each reprocessing cycle. Furthermore, it was observed that the addition of ASP intensified these effects regarding TPS. However, in spite of the progressive degradation in both cases, it is technically feasible to reprocess the material at least three times without needing to incorporate virgin material. Full article
(This article belongs to the Special Issue Advances in Biocompatible and Biodegradable Polymers)
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Article
Synthesis, Optical, Chemical and Thermal Characterizations of PMMA-PS/CeO2 Nanoparticles Thin Film
Polymers 2021, 13(7), 1158; https://doi.org/10.3390/polym13071158 - 04 Apr 2021
Viewed by 599
Abstract
We report the synthesis of hybrid thin films based on polymethyl methacrylate) (PMMA) and polystyrene (PS) doped with 1%, 3%, 5%, and 7% of cerium dioxide nanoparticles (CeO2 NPs). The As-prepared thin films of (PMMA-PS) incorporated with CeO2 NPs are deposited [...] Read more.
We report the synthesis of hybrid thin films based on polymethyl methacrylate) (PMMA) and polystyrene (PS) doped with 1%, 3%, 5%, and 7% of cerium dioxide nanoparticles (CeO2 NPs). The As-prepared thin films of (PMMA-PS) incorporated with CeO2 NPs are deposited on a glass substrate. The transmittance T% (λ) and reflectance R% (λ) of PMMA-PS/CeO2 NPs thin films are measured at room temperature in the spectral range (250–700) nm. High transmittance of 87% is observed in the low-energy regions. However, transmittance decreases sharply to a vanishing value in the high-energy region. In addition, as the CeO2 NPs concentration is increased, a red shift of the absorption edge is clearly observed suggesting a considerable decrease in the band gap energy of PMMA-PS/CeO2 NPs thin film. The optical constants (n and k) and related key optical and optoelectronic parameters of PMMA-PS/Ce NPs thin films are reported and interpreted. Furthermore, Tauc and Urbach models are employed to elucidate optical behavior and calculate the band gaps of the as-synthesized nanocomposite thin films. The optical band gap energy of PMMA-PS thin film is found to be 4.03 eV. Optical band gap engineering is found to be possible upon introducing CeO2 NPs into PMMA-PS polymeric thin films as demonstrated clearly by the continuous decrease of optical band gap upon increasing CeO2 content. Fourier-transform infrared spectroscopy (FTIR) analysis is conducted to identify the major vibrational modes of the nanocomposite. The peak at 541.42 cm−1 is assigned to Ce–O and indicates the incorporation of CeO2 NPs into the copolymers matrices. There were drastic changes to the width and intensity of the vibrational bands of PMMA-PS upon addition of CeO2 NPs. To examine the chemical and thermal stability, thermogravimetric (TGA) thermograms are measured. We found that (PMMA-PVA)/CeO2 NPs nanocomposite thin films are thermally stable below 110 °C. Therefore, they could be key candidate materials for a wide range of scaled multifunctional smart optical and optoelectronic devices. Full article
(This article belongs to the Special Issue Polymer-Inorganic Composites for Special Applications)
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Article
Modelling Sorption Thermodynamics and Mass Transport of n-Hexane in a Propylene-Ethylene Elastomer
Polymers 2021, 13(7), 1157; https://doi.org/10.3390/polym13071157 - 04 Apr 2021
Cited by 1 | Viewed by 677
Abstract
Optimization of post polymerization processes of polyolefin elastomers (POE) involving solvents is of considerable industrial interest. To this aim, experimental determination and theoretical interpretation of the thermodynamics and mass transport properties of POE-solvent mixtures is relevant. Sorption behavior of n-hexane vapor in a [...] Read more.
Optimization of post polymerization processes of polyolefin elastomers (POE) involving solvents is of considerable industrial interest. To this aim, experimental determination and theoretical interpretation of the thermodynamics and mass transport properties of POE-solvent mixtures is relevant. Sorption behavior of n-hexane vapor in a commercial propylene-ethylene elastomer (V8880 VistamaxxTM from ExxonMobil, Machelen, Belgium) is addressed here, determining experimentally the sorption isotherms at temperatures ranging from 115 to 140 °C and pressure values of n-hexane vapor up to 1 atm. Sorption isotherms have been interpreted using a Non Random Lattice Fluid (NRLF) Equation of State model retrieving, from data fitting, the value of the binary interaction parameter for the n-hexane/V8880 system. Both the cases of temperature-independent and of temperature-dependent binary interaction parameter have been considered. Sorption kinetics was also investigated at different pressures and has been interpreted using a Fick’s model determining values of the mutual diffusivity as a function of temperature and of n-hexane/V8880 mixture composition. From these values, n-hexane intra-diffusion coefficient has been calculated interpreting its dependence on mixture concentration and temperature by a semi-empiric model based on free volume arguments. Full article
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Article
Non-Isothermal Crystallization Kinetics of Poly(Ethylene Glycol)–Poly(l-Lactide) Diblock Copolymer and Poly(Ethylene Glycol) Homopolymer via Fast-Scan Chip-Calorimeter
Polymers 2021, 13(7), 1156; https://doi.org/10.3390/polym13071156 - 04 Apr 2021
Cited by 1 | Viewed by 439
Abstract
The non-isothermal crystallization kinetics of double-crystallizable poly(ethylene glycol)–poly(l-lactide) diblock copolymer (PEG-PLLA) and poly(ethylene glycol) homopolymer (PEG) were studied using the fast cooling rate provided by a Fast-Scan Chip-Calorimeter (FSC). The experimental data were analyzed by the Ozawa method and the Kissinger [...] Read more.
The non-isothermal crystallization kinetics of double-crystallizable poly(ethylene glycol)–poly(l-lactide) diblock copolymer (PEG-PLLA) and poly(ethylene glycol) homopolymer (PEG) were studied using the fast cooling rate provided by a Fast-Scan Chip-Calorimeter (FSC). The experimental data were analyzed by the Ozawa method and the Kissinger equation. Additionally, the total crystallization rate was represented by crystallization half time t1/2. The Ozawa method is a perfect success because secondary crystallization is inhibited by using fast cooling rate. The first crystallized PLLA block provides nucleation sites for the crystallization of PEG block and thus promotes the crystallization of the PEG block, which can be regarded as heterogeneous nucleation to a certain extent, while the method of the PEG block and PLLA block crystallized together corresponds to a one-dimensional growth, which reflects that there is a certain separation between the crystallization regions of the PLLA block and PEG block. Although crystallization of the PLLA block provides heterogeneous nucleation conditions for PEG block to a certain extent, it does not shorten the time of the whole crystallization process because of the complexity of the whole crystallization process including nucleation and growth. Full article
(This article belongs to the Section Polymer Physics and Theory)
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Article
Blends of Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate) with Fruit Pulp Biowaste Derived Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate-co-3-Hydroxyhexanoate) for Organic Recycling Food Packaging
Polymers 2021, 13(7), 1155; https://doi.org/10.3390/polym13071155 - 04 Apr 2021
Viewed by 892
Abstract
In the present study, a new poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) [P(3HB-co-3HV-co-3HHx)] terpolyester with approximately 68 mol% of 3-hydroxybutyrate (3HB), 17 mol% of 3-hydroxyvalerate (3HV), and 15 mol% of 3-hydroxyhexanoate (3HHx) was obtained via the mixed microbial culture (MMC) [...] Read more.
In the present study, a new poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) [P(3HB-co-3HV-co-3HHx)] terpolyester with approximately 68 mol% of 3-hydroxybutyrate (3HB), 17 mol% of 3-hydroxyvalerate (3HV), and 15 mol% of 3-hydroxyhexanoate (3HHx) was obtained via the mixed microbial culture (MMC) technology using fruit pulps as feedstock, a processing by-product of the juice industry. After extraction and purification performed in a single step, the P(3HB-co-3HV-co-3HHx) powder was melt-mixed, for the first time, in contents of 10, 25, and 50 wt% with commercial poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). Thereafter, the resultant doughs were thermo-compressed to obtain highly miscible films with good optical properties, which can be of interest in rigid and semirigid organic recyclable food packaging applications. The results showed that the developed blends exhibited a progressively lower melting enthalpy with increasing the incorporation of P(3HB-co-3HV-co-3HHx), but retained the PHB crystalline morphology, albeit with an inferred lower crystalline density. Moreover, all the melt-mixed blends were thermally stable up to nearly 240 °C. As the content of terpolymer increased in the blends, the mechanical response of their films showed a brittle-to-ductile transition. On the other hand, the permeabilities to water vapor, oxygen, and, more notably, limonene were seen to increase. On the overall, this study demonstrates the value of using industrial biowaste derived P(3HB-co-3HV-co-3HHx) terpolyesters as potentially cost-effective and sustainable plasticizing additives to balance the physical properties of organic recyclable polyhydroxyalkanoate (PHA)-based food packaging materials. Full article
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Article
Assessment of a PCL-3D Printing-Dental Pulp Stem Cells Triplet for Bone Engineering: An In Vitro Study
Polymers 2021, 13(7), 1154; https://doi.org/10.3390/polym13071154 - 04 Apr 2021
Viewed by 768
Abstract
The search of suitable combinations of stem cells, biomaterials and scaffolds manufacturing methods have become a major focus of research for bone engineering. The aim of this study was to test the potential of dental pulp stem cells to attach, proliferate, mineralize and [...] Read more.
The search of suitable combinations of stem cells, biomaterials and scaffolds manufacturing methods have become a major focus of research for bone engineering. The aim of this study was to test the potential of dental pulp stem cells to attach, proliferate, mineralize and differentiate on 3D printed polycaprolactone (PCL) scaffolds. A 100% pure Mw: 84,500 ± 1000 PCL was selected. 5 × 10 × 5 mm3 parallelepiped scaffolds were designed as a wood-pilled structure composed of 20 layers of 250 μm in height, in a non-alternate order ([0,0,0,90,90,90°]). 3D printing was made at 170 °C. Swine dental pulp stem cells (DPSCs) were extracted from lower lateral incisors of swine and cultivated until the cells reached 80% confluence. The third passage was used for seeding on the scaffolds. Phenotype of cells was determined by flow Cytometry. Live and dead, Alamar blue™, von Kossa and alizarin red staining assays were performed. Scaffolds with 290 + 30 μm strand diameter, 938 ± 80 μm pores in the axial direction and 689 ± 13 μm pores in the lateral direction were manufactured. Together, cell viability tests, von Kossa and Alizarin red staining indicate the ability of the printed scaffolds to support DPSCs attachment, proliferation and enable differentiation followed by mineralization. The selected material-processing technique-cell line (PCL-3D printing-DPSCs) triplet can be though to be used for further modelling and preclinical experiments in bone engineering studies. Full article
(This article belongs to the Special Issue Polymeric Materials as Scaffolds for Tissue Engineering)
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Article
The Double-Faced Electrostatic Behavior of PNIPAm Microgels
Polymers 2021, 13(7), 1153; https://doi.org/10.3390/polym13071153 - 04 Apr 2021
Cited by 1 | Viewed by 685
Abstract
PNIPAm microgels synthesized via free radical polymerization (FRP) are often considered as neutral colloids in aqueous media, although it is well known, since the pioneering works of Pelton and coworkers, that the vanishing electrophoretic mobility characterizing swollen microgels largely increases above the lower [...] Read more.
PNIPAm microgels synthesized via free radical polymerization (FRP) are often considered as neutral colloids in aqueous media, although it is well known, since the pioneering works of Pelton and coworkers, that the vanishing electrophoretic mobility characterizing swollen microgels largely increases above the lower critical solution temperature (LCST) of PNIPAm, at which microgels partially collapse. The presence of an electric charge has been attributed to the ionic initiators that are employed when FRP is performed in water and that stay anchored to microgel particles. Combining dynamic light scattering (DLS), electrophoresis, transmission electron microscopy (TEM) and atomic force microscopy (AFM) experiments, we show that collapsed ionic PNIPAm microgels undergo large mobility reversal and reentrant condensation when they are co-suspended with oppositely charged polyelectrolytes (PE) or nanoparticles (NP), while their stability remains unaffected by PE or NP addition at lower temperatures, where microgels are swollen and their charge density is low. Our results highlight a somehow double-faced electrostatic behavior of PNIPAm microgels due to their tunable charge density: they behave as quasi-neutral colloids at temperature below LCST, while they strongly interact with oppositely charged species when they are in their collapsed state. The very similar phenomenology encountered when microgels are surrounded by polylysine chains and silica nanoparticles points to the general character of this twofold behavior of PNIPAm-based colloids in water. Full article
(This article belongs to the Special Issue Polymer Microgels: Synthesis and Application)
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Article
Influence of Salt on the Self-Organization in Solutions of Star-Shaped Poly-2-alkyl-2-oxazoline and Poly-2-alkyl-2-oxazine on Heating
Polymers 2021, 13(7), 1152; https://doi.org/10.3390/polym13071152 - 04 Apr 2021
Cited by 3 | Viewed by 528
Abstract
The water–salt solutions of star-shaped six-arm poly-2-alkyl-2-oxazines and poly-2-alkyl-2-oxazolines were studied by light scattering and turbidimetry. The core was hexaaza[26]orthoparacyclophane and the arms were poly-2-ethyl-2-oxazine, poly-2-isopropyl-2-oxazine, poly-2-ethyl-2-oxazoline, and poly-2-isopropyl-2-oxazoline. NaCl and N-methylpyridinium p-toluenesulfonate were used as salts. Their concentration [...] Read more.
The water–salt solutions of star-shaped six-arm poly-2-alkyl-2-oxazines and poly-2-alkyl-2-oxazolines were studied by light scattering and turbidimetry. The core was hexaaza[26]orthoparacyclophane and the arms were poly-2-ethyl-2-oxazine, poly-2-isopropyl-2-oxazine, poly-2-ethyl-2-oxazoline, and poly-2-isopropyl-2-oxazoline. NaCl and N-methylpyridinium p-toluenesulfonate were used as salts. Their concentration varied from 0–0.154 M. On heating, a phase transition was observed in all studied solutions. It was found that the effect of salt on the thermosensitivity of the investigated stars depends on the structure of the salt and polymer and on the salt content in the solution. The phase separation temperature decreased with an increase in the hydrophobicity of the polymers, which is caused by both a growth of the side radical size and an elongation of the monomer unit. For NaCl solutions, the phase separation temperature monotonically decreased with growth of salt concentration. In solutions with methylpyridinium p-toluenesulfonate, the dependence of the phase separation temperature on the salt concentration was non-monotonic with minimum at salt concentration corresponding to one salt molecule per one arm of a polymer star. Poly-2-alkyl-2-oxazine and poly-2-alkyl-2-oxazoline stars with a hexaaza[26]orthoparacyclophane core are more sensitive to the presence of salt in solution than the similar stars with a calix[n]arene branching center. Full article
(This article belongs to the Special Issue Polymer Dynamics: Bulk and Nanoconfined Polymers)
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Article
Photophysical, Thermal and Structural Properties of Thiophene and Benzodithiophene-Based Copolymers Synthesized by Direct Arylation Polycondensation Method
Polymers 2021, 13(7), 1151; https://doi.org/10.3390/polym13071151 - 04 Apr 2021
Cited by 1 | Viewed by 495
Abstract
Three low-band-gap copolymers based on isoindigo acceptor units were designed and successfully synthesized by direct arylation polycondensation method. Two of them were benzodithiophene (BDT)-isoindigo copolymers (PBDTI-OD and PBDTI-DT) with 2-octlydodecyl (OD) and 2-decyltetradecyl (DT) substituted isoindigo units, respectively. Thiophene donor and [...] Read more.
Three low-band-gap copolymers based on isoindigo acceptor units were designed and successfully synthesized by direct arylation polycondensation method. Two of them were benzodithiophene (BDT)-isoindigo copolymers (PBDTI-OD and PBDTI-DT) with 2-octlydodecyl (OD) and 2-decyltetradecyl (DT) substituted isoindigo units, respectively. Thiophene donor and DT-substituted isoindigo acceptor units were copolymerized to synthesize PTI-DT. The copolymers have a broad absorption range that extends to over 760 nm with a band gap ≈1.5 eV. The photophysical property studies showed that the BDT-based copolymers have non-polar ground states. Their emission exhibited the population of the intramolecular charge transfer (ICT) state in polar solvents and tightly bound excitonic state in non-polar solvents due to self-aggregation. On the contrary, the emission from the thiophene-based copolymers was only from the tightly bound excitonic state. The thermal decomposition temperature of the copolymers was above 380 °C. The X-ray diffraction pattern of the three copolymers showed a halo due to ππ stacking. A second, sharper peak was observed in the BDT-based copolymer with a longer side chain on the isoindigo unit (PBDTI-DT), and the thiophene-based copolymers with PTI-DT, exhibiting a better structural order. Full article
(This article belongs to the Special Issue Polymers Synthesis and Characterization)
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Article
Li-Nafion Membrane Plasticised with Ethylene Carbonate/Sulfolane: Influence of Mixing Temperature on the Physicochemical Properties
Polymers 2021, 13(7), 1150; https://doi.org/10.3390/polym13071150 - 03 Apr 2021
Cited by 1 | Viewed by 735
Abstract
The use of dipolar aprotic solvents to swell lithiated Nafion ionomer membranes simultaneously serving as electrolyte and separator is of great interest for lithium battery applications. This work attempts to gain an insight into the physicochemical nature of a Li-Nafion ionomer material whose [...] Read more.
The use of dipolar aprotic solvents to swell lithiated Nafion ionomer membranes simultaneously serving as electrolyte and separator is of great interest for lithium battery applications. This work attempts to gain an insight into the physicochemical nature of a Li-Nafion ionomer material whose phase-separated nanostructure has been enhanced with a binary plasticiser comprising non-volatile high-boiling ethylene carbonate (EC) and sulfolane (SL). Gravimetric studies evaluating the influence both of mixing temperature (25 to 80 °C) and plasticiser composition (EC/SL ratio) on the solvent uptake of Li-Nafion revealed a hysteresis between heating and cooling modes. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) revealed that the saturation of a Nafion membrane with such a plasticiser led to a re-organisation of its amorphous structure, with crystalline regions remaining practically unchanged. Regardless of mixing temperature, the preservation of crystallites upon swelling is critical due to ionomer crosslinking provided by crystalline regions, which ensures membrane integrity even at very high solvent uptake (≈200% at a mixing temperature of 80 °C). The physicochemical properties of a swollen membrane have much in common with those of a chemically crosslinked polymer gel. The conductivity of ≈10−4 S cm−1 demonstrated by Li-Nafion membranes saturated with EC/SL at room temperature is promising for various practical applications. Full article
(This article belongs to the Special Issue Conducting Polymer-Based Hybrid Nanomaterials)
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Article
Characteristics of Metakaolin-Based Geopolymer with Cathode Ray Tube Glass
Polymers 2021, 13(7), 1149; https://doi.org/10.3390/polym13071149 - 03 Apr 2021
Cited by 4 | Viewed by 536
Abstract
Geopolymers can be treated as an environmentally friendly alternative for concrete and enables utilization of various wastes. This paper focuses on the possibility of application of discarded cathode ray tube (CRT) glass inside a metakaolin-based geopolymer in the form of an aggregate, providing [...] Read more.
Geopolymers can be treated as an environmentally friendly alternative for concrete and enables utilization of various wastes. This paper focuses on the possibility of application of discarded cathode ray tube (CRT) glass inside a metakaolin-based geopolymer in the form of an aggregate, providing an ecological method of recycling of this hazardous material. The main goal of this paper was to develop an optimal composition of a new geopolymer and to describe its behavior under varying curing conditions. A geopolymer made of different mixtures was subjected to flexural and compressive strength tests. The density, mass loss, temperature changes, and metals leaching were determined as well. The results demonstrated that neither the content of CRT glass nor the curing regime has a significant influence on the mechanical behavior. However, the strength of the geopolymer containing 50% CRT glass by mass increased with time in contrast to a geopolymer with a higher CRT glass content. The development of temperature inside the mixture was dependent on the amount of metakaolin. The concentration of toxic metals in an aqueous extract decreased considerably after the encapsulation of CRT glass inside the geopolymer. The presented results indicate that discarded CRT glass can be considered an aggregate for a metakaolin-based geopolymer. The new material shows high strength and makes the CRT glass safe for the environment. Full article
(This article belongs to the Special Issue Geopolymers - Design, Preparation, Applications)
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