Julia V Novoselova, Evgenii V Beletskii, Daniil A Lukyanov, Sofia S Filippova, Uliana M Rodionova, Vladimir V Sizov, Elena V Alekseeva, Oleg V Levin
This study investigates the electrochemical degradation mechanisms of nickel-salen (NiSalen) polymers, with a focus on improving the material's stability in supercapacitor applications. We analyzed the effects of steric hindrance near the nickel center by incorporating different bulky substituents into NiSalen complexes, aiming to mitigate water-induced degradation. Electrochemical performance was assessed using cyclic voltammetry, operando conductance, and impedance measurements, while X-ray photoelectron spectroscopy (XPS) provided insights into molecular degradation pathways. The results revealed that increased steric hindrance from methyl groups significantly reduced the degradation rate, particularly in water-containing electrolytes, by hindering water coordination to the Ni center. Among the studied polymers, the highly substituted poly[Ni(Saltmen)] exhibited superior stability with minimal capacity loss. Density functional theory (DFT) calculations further supported that steric protection around the Ni atom effectively lowers the probability of water coordination. These findings suggest that sterically enhanced NiSalen polymers may offer a promising path toward durable supercapacitor electrodes, highlighting the route of molecular engineering to enhance material stability.
{"title":"Sterically Induced Enhancement in the Electrochemical Stability of Salen-Type Cathode Materials.","authors":"Julia V Novoselova, Evgenii V Beletskii, Daniil A Lukyanov, Sofia S Filippova, Uliana M Rodionova, Vladimir V Sizov, Elena V Alekseeva, Oleg V Levin","doi":"10.3390/polym17020178","DOIUrl":"10.3390/polym17020178","url":null,"abstract":"<p><p>This study investigates the electrochemical degradation mechanisms of nickel-salen (NiSalen) polymers, with a focus on improving the material's stability in supercapacitor applications. We analyzed the effects of steric hindrance near the nickel center by incorporating different bulky substituents into NiSalen complexes, aiming to mitigate water-induced degradation. Electrochemical performance was assessed using cyclic voltammetry, operando conductance, and impedance measurements, while X-ray photoelectron spectroscopy (XPS) provided insights into molecular degradation pathways. The results revealed that increased steric hindrance from methyl groups significantly reduced the degradation rate, particularly in water-containing electrolytes, by hindering water coordination to the Ni center. Among the studied polymers, the highly substituted poly[Ni(Saltmen)] exhibited superior stability with minimal capacity loss. Density functional theory (DFT) calculations further supported that steric protection around the Ni atom effectively lowers the probability of water coordination. These findings suggest that sterically enhanced NiSalen polymers may offer a promising path toward durable supercapacitor electrodes, highlighting the route of molecular engineering to enhance material stability.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11769176/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041192","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This article systematically investigated the improvement effect of polypropylene fiber (PPF) on the mechanical and freeze-thaw properties of alkali-activated fly ash slag concrete (AAFSC) with high fly ash content and cured at room temperature. Fly ash and slag were used as precursors, with fly ash accounting for 80% of the total mass. A mixed solution of sodium hydroxide and sodium silicate was used as alkali activator, and short-cut PPF was added to improve the performance of AAFSC. Firstly, the strength characteristics of AAFSC at different curing ages were studied. Then, key indicators such as morphology, residual compressive strength, weight loss, relative dynamic modulus of elasticity (RDME), and pore characteristics of AAFSC after different freeze-thaw cycles were tested and analyzed. The strength performance analysis showed that the optimal dosage of PPF was 0.90%. When the alkali equivalent of the alkali activator was increased from 4% to 6%, the frost resistance of AAFSC could be improved. Furthermore, adding 0.90% PPF could increase the freeze-thaw cycle number of AAFSC by about 50 times (measured by RDME). With the increase in freeze-thaw cycles, the porosity of AAFSC increased, the fractal dimension decreased, and the proportion of harmless and less harmful pores decreased, while the proportion of harmful and multiple harmful pores increased. The relationship model between the porosity and compressive strength of AAFSC after freeze-thaw cycles was established.
{"title":"Study on the Improvement Effect of Polypropylene Fiber on the Mechanical Properties and Freeze-Thaw Degradation Performance of High Fly Ash Content Alkali-Activated Fly Ash Slag Concrete.","authors":"Zhu Yuan, Yanmin Jia, Junming Xu","doi":"10.3390/polym17020175","DOIUrl":"10.3390/polym17020175","url":null,"abstract":"<p><p>This article systematically investigated the improvement effect of polypropylene fiber (PPF) on the mechanical and freeze-thaw properties of alkali-activated fly ash slag concrete (AAFSC) with high fly ash content and cured at room temperature. Fly ash and slag were used as precursors, with fly ash accounting for 80% of the total mass. A mixed solution of sodium hydroxide and sodium silicate was used as alkali activator, and short-cut PPF was added to improve the performance of AAFSC. Firstly, the strength characteristics of AAFSC at different curing ages were studied. Then, key indicators such as morphology, residual compressive strength, weight loss, relative dynamic modulus of elasticity (RDME), and pore characteristics of AAFSC after different freeze-thaw cycles were tested and analyzed. The strength performance analysis showed that the optimal dosage of PPF was 0.90%. When the alkali equivalent of the alkali activator was increased from 4% to 6%, the frost resistance of AAFSC could be improved. Furthermore, adding 0.90% PPF could increase the freeze-thaw cycle number of AAFSC by about 50 times (measured by RDME). With the increase in freeze-thaw cycles, the porosity of AAFSC increased, the fractal dimension decreased, and the proportion of harmless and less harmful pores decreased, while the proportion of harmful and multiple harmful pores increased. The relationship model between the porosity and compressive strength of AAFSC after freeze-thaw cycles was established.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11769492/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041213","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nanofibrous dressing materials with an antitumor function can potentially inhibit recurrence of melanoma following the surgical excision of skin tumors. In this study, hydrolyzed polyacrylonitrile (hPAN) nanofibers biofunctionalized with L-carnosine (CAR) and loaded with bio (CAR)-synthesized zinc oxide (ZnO) nanoparticles, ZnO/CAR-hPAN (hereafter called ZCPAN), were employed to develop an antimelanoma wound dressing. Inspired by the formulation of the commercial wound healing Zn-CAR complex, i.e., polaprezinc (PLZ), for the first time, we benefitted from the synergy of zinc and CAR to create an antimelanoma nanofibrous wound dressing. According to scanning electron microscopy (SEM) images, ultrafine ZnO nanoparticles were homogenously distributed throughout the nanofibrous dressing. The ZCPAN nanofiber mat showed a significantly higher toughness (18.7 MJ.m-3 vs. 1.4 MJ.m-3) and an enhanced elongation at break (stretchability) compared to the neat PAN nanofiber mat (12% vs. 9.5%). Additionally, optical coherence elastography (OCE) measurements indicated that the ZCPAN nanofibrous dressing was as stiff as 50.57 ± 8.17 kPa which is notably larger than that of the PAN nanofibrous dressing, i.e., 24.49 ± 6.83 kPa. The optimum mechanical performance of the ZCPAN nanofibers originates from physicochemical interaction of CAR ligands, hPAN nanofibers, and ZnO nanoparticles through hydrogen bonding, electrostatic bonding, and esterification, as verified using ATR-FTIR. An in vitro cell viability assay using human skin melanoma cells implied that the cells are notably killed in the presence of the ZCPAN nanofibers compared to the PAN nanofibers. Thanks to ROS generating ZnO nanoparticles, this behavior originates from the high reactive oxygen species (ROS)-induced oxidative damage of melanoma cells, as verified through a CellROX assay. In this regard, an apoptotic cell response to the ZCPAN nanofibers was recorded through an apoptosis assay. Taken together, the ZCPAN nanofibers induce an antimelanoma effect through oxidative stress and thus are a high potential wound dressing material to suppress melanoma regrowth after surgical excision of skin tumors.
{"title":"Zinc Oxide Nanoparticle Loaded L-Carnosine Biofunctionalized Polyacrylonitrile Nanofibrous Wound Dressing for Post-Surgical Treatment of Melanoma.","authors":"Shahin Homaeigohar, Danial Kordbacheh, Sourav Banerjee, Jiacheng Gu, Yilong Zhang, Zhihong Huang","doi":"10.3390/polym17020173","DOIUrl":"10.3390/polym17020173","url":null,"abstract":"<p><p>Nanofibrous dressing materials with an antitumor function can potentially inhibit recurrence of melanoma following the surgical excision of skin tumors. In this study, hydrolyzed polyacrylonitrile (hPAN) nanofibers biofunctionalized with L-carnosine (CAR) and loaded with bio (CAR)-synthesized zinc oxide (ZnO) nanoparticles, ZnO/CAR-hPAN (hereafter called ZCPAN), were employed to develop an antimelanoma wound dressing. Inspired by the formulation of the commercial wound healing Zn-CAR complex, i.e., polaprezinc (PLZ), for the first time, we benefitted from the synergy of zinc and CAR to create an antimelanoma nanofibrous wound dressing. According to scanning electron microscopy (SEM) images, ultrafine ZnO nanoparticles were homogenously distributed throughout the nanofibrous dressing. The ZCPAN nanofiber mat showed a significantly higher toughness (18.7 MJ.m<sup>-3</sup> vs. 1.4 MJ.m<sup>-3</sup>) and an enhanced elongation at break (stretchability) compared to the neat PAN nanofiber mat (12% vs. 9.5%). Additionally, optical coherence elastography (OCE) measurements indicated that the ZCPAN nanofibrous dressing was as stiff as 50.57 ± 8.17 kPa which is notably larger than that of the PAN nanofibrous dressing, i.e., 24.49 ± 6.83 kPa. The optimum mechanical performance of the ZCPAN nanofibers originates from physicochemical interaction of CAR ligands, hPAN nanofibers, and ZnO nanoparticles through hydrogen bonding, electrostatic bonding, and esterification, as verified using ATR-FTIR. An in vitro cell viability assay using human skin melanoma cells implied that the cells are notably killed in the presence of the ZCPAN nanofibers compared to the PAN nanofibers. Thanks to ROS generating ZnO nanoparticles, this behavior originates from the high reactive oxygen species (ROS)-induced oxidative damage of melanoma cells, as verified through a CellROX assay. In this regard, an apoptotic cell response to the ZCPAN nanofibers was recorded through an apoptosis assay. Taken together, the ZCPAN nanofibers induce an antimelanoma effect through oxidative stress and thus are a high potential wound dressing material to suppress melanoma regrowth after surgical excision of skin tumors.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768544/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Govindarajan Kannan, Evangelin Ramani Sujatha, Abdullah Almajed, Arif Ali Baig Moghal
Modern innovations increasingly prioritize eco-friendliness, aiming to pave the way for a sustainable future. The field of civil engineering is no exception to this approach, and, in fact, it is associated with almost every sustainable development goal framed by the United Nations. Therefore, the sector has a pivotal role in achieving these goals. One such innovation is exploring the possibilities of using nature-friendly materials in different applications. Biopolymers are substances that are produced either by the chemical synthesis of natural materials or by the biosynthesizing activities of microorganisms. Microbial-derived biopolymers are known for their non-toxic and nature-friendly characteristics. However, their applications are mostly restricted to the field of biotechnology and not fully explored in civil engineering. This article reviews various microbial-derived biopolymers, focusing on the types available on the market, their source and properties, and more importantly, their wide range of applications in the civil engineering field. Additionally, the article explores the prospects for future research and the potential for the practical implementation of these techniques in the pursuit of a sustainable future.
{"title":"Microbial-Derived Biopolymers: A Pathway to Sustainable Civil Engineering.","authors":"Govindarajan Kannan, Evangelin Ramani Sujatha, Abdullah Almajed, Arif Ali Baig Moghal","doi":"10.3390/polym17020172","DOIUrl":"10.3390/polym17020172","url":null,"abstract":"<p><p>Modern innovations increasingly prioritize eco-friendliness, aiming to pave the way for a sustainable future. The field of civil engineering is no exception to this approach, and, in fact, it is associated with almost every sustainable development goal framed by the United Nations. Therefore, the sector has a pivotal role in achieving these goals. One such innovation is exploring the possibilities of using nature-friendly materials in different applications. Biopolymers are substances that are produced either by the chemical synthesis of natural materials or by the biosynthesizing activities of microorganisms. Microbial-derived biopolymers are known for their non-toxic and nature-friendly characteristics. However, their applications are mostly restricted to the field of biotechnology and not fully explored in civil engineering. This article reviews various microbial-derived biopolymers, focusing on the types available on the market, their source and properties, and more importantly, their wide range of applications in the civil engineering field. Additionally, the article explores the prospects for future research and the potential for the practical implementation of these techniques in the pursuit of a sustainable future.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768209/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041447","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tegginamath Akshat, Michal Petru, Rajesh Kumar Mishra
This article is a numerical and experimental study of the mechanical properties of different glass, flax and hybrid composites. By utilizing hybrid composites consisting of natural fibers, the aim is to eventually reduce the percentage usage of synthetic or man-made fibers in composites and obtain similar levels of mechanical properties that are offered by composites using synthetic fibers. This in turn would lead to greener composites being utilized. The advantage of which would be the presence of similar mechanical properties as those of composites made from synthetic fibers along with a reduction in the overall weight of components, leading to much more eco-friendly vehicles. Finite element simulations (FEM) of mechanical properties were performed using ANSYS. The FEM simulations and analysis were performed using standards as required. Subsequently, actual beams/frames with a defined geometry were fabricated for applications in automotive body construction. The tensile performance of such frames was also simulated using ANSYS-based models and was experimentally verified. A correlation with the results of the FEM simulations of mechanical properties was established. The maximum tensile strength of 415 MPa was found for sample 1: G-E (glass-epoxy composite) and the minimum strength of 146 MPa was found for sample 2: F-G-E (G-4) (flax-glass-epoxy composite). The trends were similar, as obtained by simulation using ANSYS. A comparison of the results showed the accuracy of the numerical simulation and experimental specimens with a maximum error of about 8.05%. The experimental study of the tensile properties of polymer matrix composites was supplemented with interlaminar shear strength, and a high accuracy was found. Further, the maximum interlaminar shear strength (ILSS) of 18.5 MPa was observed for sample 1: G-E and the minimum ILSS of 17.0 MPa was observed for sample 2: F-G-E (G-4). The internal fractures were analyzed using a computer tomography analyzer (CTAn). Sample 2: F-G-E (G-4) showed significant interlaminar cracking, while sample 1: G-E showed fiber failure through the cross section rather than interlaminar failure. The results indicate a practical solution of a polymer composite frame as a replacement for existing heavier components in a car, thus helping towards weight reduction and fuel efficiency.
{"title":"Numerical Modelling of Hybrid Polymer Composite Frame for Selected Construction Parts and Experimental Validation of Mechanical Properties.","authors":"Tegginamath Akshat, Michal Petru, Rajesh Kumar Mishra","doi":"10.3390/polym17020168","DOIUrl":"10.3390/polym17020168","url":null,"abstract":"<p><p>This article is a numerical and experimental study of the mechanical properties of different glass, flax and hybrid composites. By utilizing hybrid composites consisting of natural fibers, the aim is to eventually reduce the percentage usage of synthetic or man-made fibers in composites and obtain similar levels of mechanical properties that are offered by composites using synthetic fibers. This in turn would lead to greener composites being utilized. The advantage of which would be the presence of similar mechanical properties as those of composites made from synthetic fibers along with a reduction in the overall weight of components, leading to much more eco-friendly vehicles. Finite element simulations (FEM) of mechanical properties were performed using ANSYS. The FEM simulations and analysis were performed using standards as required. Subsequently, actual beams/frames with a defined geometry were fabricated for applications in automotive body construction. The tensile performance of such frames was also simulated using ANSYS-based models and was experimentally verified. A correlation with the results of the FEM simulations of mechanical properties was established. The maximum tensile strength of 415 MPa was found for sample 1: G-E (glass-epoxy composite) and the minimum strength of 146 MPa was found for sample 2: F-G-E (G-4) (flax-glass-epoxy composite). The trends were similar, as obtained by simulation using ANSYS. A comparison of the results showed the accuracy of the numerical simulation and experimental specimens with a maximum error of about 8.05%. The experimental study of the tensile properties of polymer matrix composites was supplemented with interlaminar shear strength, and a high accuracy was found. Further, the maximum interlaminar shear strength (ILSS) of 18.5 MPa was observed for sample 1: G-E and the minimum ILSS of 17.0 MPa was observed for sample 2: F-G-E (G-4). The internal fractures were analyzed using a computer tomography analyzer (CTAn). Sample 2: F-G-E (G-4) showed significant interlaminar cracking, while sample 1: G-E showed fiber failure through the cross section rather than interlaminar failure. The results indicate a practical solution of a polymer composite frame as a replacement for existing heavier components in a car, thus helping towards weight reduction and fuel efficiency.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11769343/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143040939","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Transitions seen in the electric properties of water-absorbable poly(2,5-benzimidazole) (ABPBI) films were confirmed by electric conductivity, dielectric constant, and time-domain nuclear magnetic resonance (NMR) measurements. The electric resistance of the films was measured at room temperature using a high-resistance meter, and the dielectric constant at room temperature was measured using an LCR meter in the frequency range of 90 Hz to 8 MHz. The water absorption ratio at equilibrium absorption for the films was 37%, which corresponded to a volume fraction of water of 0.33. The electric conductivity of the films without water absorption was ~1014 S·cm-1, and it increased to ~1010 S·cm-1 with increasing volume fraction, showing a percolation threshold at a volume fraction of 0.025, and remarkable transitions at volume fractions of 0.075 and 0.135. The dielectric constant of the films without water absorption was 3.4, and it increased to 8.1 with increasing volume fraction, showing a transition only at a volume fraction of 0.135. Above a volume fraction of 0.075, where a transition in conductivity was observed, there were two relaxation times at 18-31 μs and 20-93 μs, as determined from the time-domain NMR, and these relaxation times increased with increasing volume fraction. The longer relaxation time increased significantly at a volume fraction of 0.072, which was close to the volume fraction of the transition seen in conductivity. The relationship between the chain mobility of ABPBI and the deterioration in electric insulating properties is discussed.
{"title":"Electric Conductivity Transitions of Water-Absorbable Polybenzimidazole Films.","authors":"Kaito Watanabe, Junko Ikeda, Xianzhu Zhong, Jiabei Zhou, Tatsuo Kaneko, Mika Kawai, Tetsu Mitsumata","doi":"10.3390/polym17020167","DOIUrl":"10.3390/polym17020167","url":null,"abstract":"<p><p>Transitions seen in the electric properties of water-absorbable poly(2,5-benzimidazole) (ABPBI) films were confirmed by electric conductivity, dielectric constant, and time-domain nuclear magnetic resonance (NMR) measurements. The electric resistance of the films was measured at room temperature using a high-resistance meter, and the dielectric constant at room temperature was measured using an LCR meter in the frequency range of 90 Hz to 8 MHz. The water absorption ratio at equilibrium absorption for the films was 37%, which corresponded to a volume fraction of water of 0.33. The electric conductivity of the films without water absorption was ~10<sup>14</sup> S·cm<sup>-1</sup>, and it increased to ~10<sup>10</sup> S·cm<sup>-1</sup> with increasing volume fraction, showing a percolation threshold at a volume fraction of 0.025, and remarkable transitions at volume fractions of 0.075 and 0.135. The dielectric constant of the films without water absorption was 3.4, and it increased to 8.1 with increasing volume fraction, showing a transition only at a volume fraction of 0.135. Above a volume fraction of 0.075, where a transition in conductivity was observed, there were two relaxation times at 18-31 μs and 20-93 μs, as determined from the time-domain NMR, and these relaxation times increased with increasing volume fraction. The longer relaxation time increased significantly at a volume fraction of 0.072, which was close to the volume fraction of the transition seen in conductivity. The relationship between the chain mobility of ABPBI and the deterioration in electric insulating properties is discussed.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768338/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maryam Najam, Sana Javaid, Shazia Iram, Kingkham Pasertsakoun, Marianna Oláh, András Székács, László Aleksza
This study attempted to isolate and identify pedospheric microbes originating in dumpsites and utilized them for the degradation of selected synthetic polymers for the first time in a cost-effective, ecologically favorable and sustainable manner. Specifically, low-density polyethylene (LDPE) and polyurethane (PUR) were converted by the isolated fungi, i.e., Aspergillus flavus, A terreus, A. clavatus, A. nigers and bacterial coccus and filamentous microbes and assessed in a biotransformative assay under simulated conditions. Commendable biodegradative potentials were exhibited by the isolated microbes against polymers that were analyzed over a span of 30 days. Among the selected fungal microbes, the highest activity was achieved by A. niger, expressing 55% and 40% conversion of LDPE and PUR, respectively. In the case of bacterial strains, 50% and 40% conversion of LDPE and PUR degradation was achieved by coccus. Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA) were utilized to analyze the degradative patterns in terms of vibrational and thermal characteristics, and stereomicroscopic analysis was performed for the visual assessment of morphological variations. Profound structural transformations were detected in FT-IR spectra and TGA thermograms for the selected microbes. Stereomicroscopic analysis was also indicative of the remarkable transformation of the surface morphology of these polymers after degradation by microbes in comparison to the reference samples not treated with any pedospheric microbes. The results are supportive of the utilization of the selected pedospheric microbes as environmental remediators for the cleanup of persistent polymeric toxins. This current work can be further extended for the successful optimization of further augmented percentages by using other pedospheric microbes for the successful adoption of these biotechnological tools at a practical level.
{"title":"Microbial Biodegradation of Synthetic Polyethylene and Polyurethane Polymers by Pedospheric Microbes: Towards Sustainable Environmental Management.","authors":"Maryam Najam, Sana Javaid, Shazia Iram, Kingkham Pasertsakoun, Marianna Oláh, András Székács, László Aleksza","doi":"10.3390/polym17020169","DOIUrl":"10.3390/polym17020169","url":null,"abstract":"<p><p>This study attempted to isolate and identify pedospheric microbes originating in dumpsites and utilized them for the degradation of selected synthetic polymers for the first time in a cost-effective, ecologically favorable and sustainable manner. Specifically, low-density polyethylene (LDPE) and polyurethane (PUR) were converted by the isolated fungi, i.e., <i>Aspergillus flavus</i>, <i>A terreus</i>, <i>A. clavatus</i>, <i>A. nigers</i> and bacterial coccus and filamentous microbes and assessed in a biotransformative assay under simulated conditions. Commendable biodegradative potentials were exhibited by the isolated microbes against polymers that were analyzed over a span of 30 days. Among the selected fungal microbes, the highest activity was achieved by <i>A. niger</i>, expressing 55% and 40% conversion of LDPE and PUR, respectively. In the case of bacterial strains, 50% and 40% conversion of LDPE and PUR degradation was achieved by coccus. Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA) were utilized to analyze the degradative patterns in terms of vibrational and thermal characteristics, and stereomicroscopic analysis was performed for the visual assessment of morphological variations. Profound structural transformations were detected in FT-IR spectra and TGA thermograms for the selected microbes. Stereomicroscopic analysis was also indicative of the remarkable transformation of the surface morphology of these polymers after degradation by microbes in comparison to the reference samples not treated with any pedospheric microbes. The results are supportive of the utilization of the selected pedospheric microbes as environmental remediators for the cleanup of persistent polymeric toxins. This current work can be further extended for the successful optimization of further augmented percentages by using other pedospheric microbes for the successful adoption of these biotechnological tools at a practical level.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11769026/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ana C Pinho, Paula V Morais, Manuel F Pereira, Ana P Piedade
The idea supporting the investigation of the current manuscript was to develop customized filters for air conditioners with different pore percentages and geometry with the additional advantage of presenting antibacterial performance. This property was expected due to the reinforcement of Cu nanoparticles in the polymeric matrix of poly(lactic acid) (PLA) and polyurethane (TPU). The filaments were characterized by their chemical composition, thermal and mechanical properties, and antibacterial behavior before and after processing by fused filament fabrication. An X-ray photoelectron spectroscopy showed that the nanocomposite filaments presented Cu particles at their surface in different valence states, including Cu0, Cu+, and Cu2+. After processing, the metallic particles are almost absent from the surface, a result confirmed by micro-computer tomography (μ-CT) characterization. Antibacterial tests were made using solid-state diffusion tests to mimic the dry environment in air conditioner filters. The tests with the nanocomposite filaments showed that bacteria proliferation was hindered. However, no antibacterial performance could be observed after processing due to the absence of the metallic element on the surface. Nevertheless, antimicrobial performance was observed when evaluated in liquid tests. Therefore, the obtained results provide valuable indications for developing new nanocomposites that must maintain their antimicrobial activity after being processed and tested in the dry conditions of solid-state diffusion.
{"title":"Changes in the Antibacterial Performance of Polymer-Based Nanocomposites Induced by Additive Manufacturing Processing.","authors":"Ana C Pinho, Paula V Morais, Manuel F Pereira, Ana P Piedade","doi":"10.3390/polym17020171","DOIUrl":"10.3390/polym17020171","url":null,"abstract":"<p><p>The idea supporting the investigation of the current manuscript was to develop customized filters for air conditioners with different pore percentages and geometry with the additional advantage of presenting antibacterial performance. This property was expected due to the reinforcement of Cu nanoparticles in the polymeric matrix of poly(lactic acid) (PLA) and polyurethane (TPU). The filaments were characterized by their chemical composition, thermal and mechanical properties, and antibacterial behavior before and after processing by fused filament fabrication. An X-ray photoelectron spectroscopy showed that the nanocomposite filaments presented Cu particles at their surface in different valence states, including Cu<sup>0</sup>, Cu<sup>+</sup>, and Cu<sup>2+</sup>. After processing, the metallic particles are almost absent from the surface, a result confirmed by micro-computer tomography (μ-CT) characterization. Antibacterial tests were made using solid-state diffusion tests to mimic the dry environment in air conditioner filters. The tests with the nanocomposite filaments showed that bacteria proliferation was hindered. However, no antibacterial performance could be observed after processing due to the absence of the metallic element on the surface. Nevertheless, antimicrobial performance was observed when evaluated in liquid tests. Therefore, the obtained results provide valuable indications for developing new nanocomposites that must maintain their antimicrobial activity after being processed and tested in the dry conditions of solid-state diffusion.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768115/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohit Agarwal, Alexander Zika, Müge Yücel, Ralf Schweins, Joachim Kohlbrecher, Franziska Gröhn
pH-responsive polyamidoamine (PAMAM) dendrimers are used as well-defined building blocks to design light-switchable nano-assemblies in solution. The complex interplay between the photoresponsive di-anionic azo dye Acid Yellow 38 (AY38) and the cationic PAMAM dendrimers of different generations is presented in this study. Electrostatic self-assembly involving secondary dipole-dipole interactions provides well-defined assemblies within a broad size range (10 nm-1 μm) with various shapes. The size and shape of these assemblies were determined using dynamic and static light scattering (DLS/SLS) and small-angle neutron scattering (SANS); ζ-potential measurements were performed to elucidate the charge characteristics, revealing the effective surface charge density of the nano-objects as an important parameter in the size and shape control. UV-vis spectroscopy and isothermal titration calorimetry (ITC) were employed to investigate the interaction on a molecular level and from a thermodynamic point of view. The results show that the amount of isomerized cis dye depends on the dendrimer generation because of a photoprotective effect through electrostatics for lower generations and through dipole-dipole interactions for higher generations; as the cis dye and trans dye bind with different strength, the amount of cis dye then again encodes the charge density and thereby the particle size and shape.
{"title":"The Role of Light Irradiation and Dendrimer Generation in Directing Electrostatic Self-Assembly.","authors":"Mohit Agarwal, Alexander Zika, Müge Yücel, Ralf Schweins, Joachim Kohlbrecher, Franziska Gröhn","doi":"10.3390/polym17020170","DOIUrl":"10.3390/polym17020170","url":null,"abstract":"<p><p>pH-responsive polyamidoamine (PAMAM) dendrimers are used as well-defined building blocks to design light-switchable nano-assemblies in solution. The complex interplay between the photoresponsive di-anionic azo dye Acid Yellow 38 (AY38) and the cationic PAMAM dendrimers of different generations is presented in this study. Electrostatic self-assembly involving secondary dipole-dipole interactions provides well-defined assemblies within a broad size range (10 nm-1 μm) with various shapes. The size and shape of these assemblies were determined using dynamic and static light scattering (DLS/SLS) and small-angle neutron scattering (SANS); ζ-potential measurements were performed to elucidate the charge characteristics, revealing the effective surface charge density of the nano-objects as an important parameter in the size and shape control. UV-vis spectroscopy and isothermal titration calorimetry (ITC) were employed to investigate the interaction on a molecular level and from a thermodynamic point of view. The results show that the amount of isomerized <i>cis</i> dye depends on the dendrimer generation because of a photoprotective effect through electrostatics for lower generations and through dipole-dipole interactions for higher generations; as the <i>cis</i> dye and <i>trans</i> dye bind with different strength, the amount of <i>cis</i> dye then again encodes the charge density and thereby the particle size and shape.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11769078/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143041296","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
As a veterinary drug, sulfamethazine is frequently used to control animal diseases. In this study, a novel molecularly imprinted photonic crystal sensor for the fast visual detection of sulfamethazine in milk and chicken has been developed. Under optimum preparation conditions, a molecularly imprinted, photonic crystal with an anti-opal structure and a clear bright color was prepared and characterized. The adsorption conditions, including adsorption solvent, solvent pH, and detection time, were studied in detailed. Based on its excellent selectivity and fast response, a photonic crystal sensor detection method for the quantitative analysis of sulfamethazine was established, which achieved good linearity, ranging from 10-4 mg/L to 10 mg/L, a limit detection of 1.16 μg/L, and spiked recoveries of 80.56% to 103.59%, with a relative standard deviation (RSD) <6.41%. More importantly, the detection process could be completed within 3 min. This method provides an alternative for the rapid screening of sulfamethazine in food samples.
{"title":"Development of Molecularly Imprinted Photonic Crystals Sensor for High-Sensitivity, Rapid Detection of Sulfamethazine in Food Samples.","authors":"Jinxing He, Mengke Wu, Xin Wang, Ruoxuan Xu, Shuting Zhang, Xiaolei Zhao","doi":"10.3390/polym17020160","DOIUrl":"10.3390/polym17020160","url":null,"abstract":"<p><p>As a veterinary drug, sulfamethazine is frequently used to control animal diseases. In this study, a novel molecularly imprinted photonic crystal sensor for the fast visual detection of sulfamethazine in milk and chicken has been developed. Under optimum preparation conditions, a molecularly imprinted, photonic crystal with an anti-opal structure and a clear bright color was prepared and characterized. The adsorption conditions, including adsorption solvent, solvent pH, and detection time, were studied in detailed. Based on its excellent selectivity and fast response, a photonic crystal sensor detection method for the quantitative analysis of sulfamethazine was established, which achieved good linearity, ranging from 10<sup>-4</sup> mg/L to 10 mg/L, a limit detection of 1.16 μg/L, and spiked recoveries of 80.56% to 103.59%, with a relative standard deviation (RSD) <6.41%. More importantly, the detection process could be completed within 3 min. This method provides an alternative for the rapid screening of sulfamethazine in food samples.</p>","PeriodicalId":20416,"journal":{"name":"Polymers","volume":"17 2","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11768265/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143040723","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}