Bacterial infection is a severe challenge faced by artificial bone transplantation, which might cause delayed bone healing or even transplant failure. Photodynamic therapy (PDT) has garnered widespread attention as a treatment for infections due to its noninvasiveness, few side effects, and high spatiotemporal selectivity. Nevertheless, owing to the bacterial membrane obstacle, it is difficult for exogenous reactive oxygen species (ROS) to penetrate into bacteria, which leads to an unsatisfactory antibacterial effect. Herein, a heterojunction of Ti2C3 nanosheets/tin disulfide (MXene/SnS2) is designed, which integrates photothermal and photodynamic properties. Then, MXene/SnS2 was incorporated into a poly-l-lactic acid powder (PLLA) matrix to fabricate an artificial bone scaffold with selective laser sintering (SLS) technology. Under near-infrared laser irradiation, SnS2 can strengthen the near-infrared light absorption of MXene to generate local hyperthermia, thus enhancing bacterial membrane permeability. Meanwhile, MXene/SnS2 enhances charge transfer and inhibits electron–hole pair separation, thereby generating more ROS that can penetrate the bacterial interior. The results indicated that this antibacterial strategy has effective antibacterial activity, and the antibacterial rate reached over 90%. Overall, this research presents an attractive antibacterial strategy for implant-related infection.
{"title":"Photothermal and Photodynamic Synergistic Effect of the MXene/SnS2 Heterojunction Endows the Poly(l-lactic acid) Scaffold with Antibacterial Activity","authors":"Cijun Shuai, Xingming Long, Binxin Sun, Tiantian He, Xiong Shuai, Guoyong Wang, Shuping Peng","doi":"10.1021/acsapm.4c01336","DOIUrl":"https://doi.org/10.1021/acsapm.4c01336","url":null,"abstract":"Bacterial infection is a severe challenge faced by artificial bone transplantation, which might cause delayed bone healing or even transplant failure. Photodynamic therapy (PDT) has garnered widespread attention as a treatment for infections due to its noninvasiveness, few side effects, and high spatiotemporal selectivity. Nevertheless, owing to the bacterial membrane obstacle, it is difficult for exogenous reactive oxygen species (ROS) to penetrate into bacteria, which leads to an unsatisfactory antibacterial effect. Herein, a heterojunction of Ti<sub>2</sub>C<sub>3</sub> nanosheets/tin disulfide (MXene/SnS<sub>2</sub>) is designed, which integrates photothermal and photodynamic properties. Then, MXene/SnS<sub>2</sub> was incorporated into a poly-<span>l</span>-lactic acid powder (PLLA) matrix to fabricate an artificial bone scaffold with selective laser sintering (SLS) technology. Under near-infrared laser irradiation, SnS<sub>2</sub> can strengthen the near-infrared light absorption of MXene to generate local hyperthermia, thus enhancing bacterial membrane permeability. Meanwhile, MXene/SnS<sub>2</sub> enhances charge transfer and inhibits electron–hole pair separation, thereby generating more ROS that can penetrate the bacterial interior. The results indicated that this antibacterial strategy has effective antibacterial activity, and the antibacterial rate reached over 90%. Overall, this research presents an attractive antibacterial strategy for implant-related infection.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141505846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study is the first report on the fabrication of polyacrylonitrile (PAN) nanofiber with rhodamine-based chemosensor (RHE) onto a mass-sensitive quartz crystal substrate using the electrospinning method and its sensing capability toward chlorinated hydrocarbons. Fabricated nanofiber webs via the electrospinning process are characterized by Fourier Transform Infrared (FTIR-ATR), Scanning Electron Microscopy, and Contact Angle measurement techniques, respectively. In order to investigate the vapor sensor properties, a Quartz Crystal Microbalance (QCM) system is employed to collect the real-time experimental data when the nanofiber sensor PAN-RHE is exposed to chlorinated hydrocarbons. Pseudo first-order and Elovich models are applied to elucidate the adsorption behavior. The morphological characterization proved smooth surface morphology without bead formation for all fibers with uniformity in the fiber skeleton. The average diameters of neat PAN and PAN nanofibers with RHE are found to be 449 and 790 nm, respectively. The nanofiber sensor PAN-RHE exhibits excellent sensing characteristics, including a high sensitivity of 0.0276 Hz/ppm, response and recovery times of 2–3 and 5–7 s, respectively, high selectivity for chloroform compared to other vapors tested, a limit of detection (LOD) of about 119.56 ppm, and a limit of quantification (LOQ) of about 362.31 ppm with a good reproducibility. The Pseudo-first-order adsorption rate and the Elovich desorption constants are determined as a function of different concentrations. The results obtained suggest that the QCM-based nanofiber sensor PAN-RHE shows great potential for the design of highly sensitive and selective chloroform sensors.
{"title":"Rhodamine-Based Electrospun Polyacrylonitrile (PAN) Nanofiber Sensor for the Detection of Chlorinated Hydrocarbon Vapors","authors":"Rifat Capan, Inci Capan, Mevlut Bayrakci","doi":"10.1021/acsapm.4c00909","DOIUrl":"https://doi.org/10.1021/acsapm.4c00909","url":null,"abstract":"This study is the first report on the fabrication of polyacrylonitrile (PAN) nanofiber with rhodamine-based chemosensor (RHE) onto a mass-sensitive quartz crystal substrate using the electrospinning method and its sensing capability toward chlorinated hydrocarbons. Fabricated nanofiber webs via the electrospinning process are characterized by Fourier Transform Infrared (FTIR-ATR), Scanning Electron Microscopy, and Contact Angle measurement techniques, respectively. In order to investigate the vapor sensor properties, a Quartz Crystal Microbalance (QCM) system is employed to collect the real-time experimental data when the nanofiber sensor PAN-RHE is exposed to chlorinated hydrocarbons. Pseudo first-order and Elovich models are applied to elucidate the adsorption behavior. The morphological characterization proved smooth surface morphology without bead formation for all fibers with uniformity in the fiber skeleton. The average diameters of neat PAN and PAN nanofibers with RHE are found to be 449 and 790 nm, respectively. The nanofiber sensor PAN-RHE exhibits excellent sensing characteristics, including a high sensitivity of 0.0276 Hz/ppm, response and recovery times of 2–3 and 5–7 s, respectively, high selectivity for chloroform compared to other vapors tested, a limit of detection (LOD) of about 119.56 ppm, and a limit of quantification (LOQ) of about 362.31 ppm with a good reproducibility. The Pseudo-first-order adsorption rate and the Elovich desorption constants are determined as a function of different concentrations. The results obtained suggest that the QCM-based nanofiber sensor PAN-RHE shows great potential for the design of highly sensitive and selective chloroform sensors.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141531445","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Peifang Wang, Yue Su, Min Ma, Yuqing Wang, Shuang Hou, Changqing Wang, Lin Sun, Jianshe Wei, Mingxue Li
An injectable hydrogel loading α-N-heterocyclic thiosemicarbazones with antibacterial activity was designed to attain therapy against wounds with high efficiency. In the present study, the injectable FPZ-H2L hydrogel was synthesized by loading 2,6-diacetylpyridine bis(N4-methylthiosemicarbazone) (H2L) on transition-metal ions (Zn2+)-cross-linked-folic acid (FA)-co-polydopamine (PDA) hydrogel (FPZ hydrogel). The injectable hydrogel (FPZ-H2L) cross-linked by coordination and hydrogen bonds displayed an excellent self-healing performance and completely covered the irregular wound. Compared with the FPZ hydrogel, the FPZ-H2L hydrogel has stronger antibacterial efficacy on typical Gram-positive/negative bacteria and drug-resistant bacteria. The antibacterial mechanisms of the hydrogel were related to biofilm ablation, the disruption of the cell membrane integrity, leakage of nucleic acids and proteins, and the production of oxidative stress response, thus causing bacterial death. Cell Counting Kit-8 (CCK-8) test shows that FPZ-H2L hydrogel has excellent cell compatibility, and gel drug loading technology greatly overcomes the problem of high cytotoxicity of H2L. The wound healing experiments indicated that the hydrogel enhanced the wound healing efficacy of mice. These results prove that the mixed hydrogel has broadened the field of vision for the design of antibacterial wound dressings.
{"title":"Thiosemicarbazones-Loaded Injectable Hydrogels with Self-Healing and Antibacterial Activity for Wound Healing","authors":"Peifang Wang, Yue Su, Min Ma, Yuqing Wang, Shuang Hou, Changqing Wang, Lin Sun, Jianshe Wei, Mingxue Li","doi":"10.1021/acsapm.4c00994","DOIUrl":"https://doi.org/10.1021/acsapm.4c00994","url":null,"abstract":"An injectable hydrogel loading α-N-heterocyclic thiosemicarbazones with antibacterial activity was designed to attain therapy against wounds with high efficiency. In the present study, the injectable FPZ-H<sub>2</sub>L hydrogel was synthesized by loading 2,6-diacetylpyridine bis(<i>N</i><sup>4</sup>-methylthiosemicarbazone) (H<sub>2</sub>L) on transition-metal ions (Zn<sup>2+</sup>)-cross-linked-folic acid (FA)-<i>co</i>-polydopamine (PDA) hydrogel (FPZ hydrogel). The injectable hydrogel (FPZ-H<sub>2</sub>L) cross-linked by coordination and hydrogen bonds displayed an excellent self-healing performance and completely covered the irregular wound. Compared with the FPZ hydrogel, the FPZ-H<sub>2</sub>L hydrogel has stronger antibacterial efficacy on typical Gram-positive/negative bacteria and drug-resistant bacteria. The antibacterial mechanisms of the hydrogel were related to biofilm ablation, the disruption of the cell membrane integrity, leakage of nucleic acids and proteins, and the production of oxidative stress response, thus causing bacterial death. Cell Counting Kit-8 (CCK-8) test shows that FPZ-H<sub>2</sub>L hydrogel has excellent cell compatibility, and gel drug loading technology greatly overcomes the problem of high cytotoxicity of H<sub>2</sub>L. The wound healing experiments indicated that the hydrogel enhanced the wound healing efficacy of mice. These results prove that the mixed hydrogel has broadened the field of vision for the design of antibacterial wound dressings.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521054","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The aim of this work is to explore the potential application of three-dimensional (3D) needle-punched carbon fiber/poly(ether ether ketone) (CF/PEEK) composites in the field of fractures internal fixation. First, the machinability of 3D needle-punched CF/PEEK composites was explored through mechanical property tests on drilled composite samples; subsequently, the microstrain of composite bone plates at different stages of fracture healing was verified in an in vitro simulation of tibia fracture internal fixation model and compared with titanium alloy bone plates; finally, thinking of the potential debris dropout and exposure of carbon fibers that may occur after implantation of the bone plates in vivo and biocompatibility in vitro tests were conducted. After the above experiments, it can be seen that the composites can still maintain 60% of their ultimate tensile strength and 85% of their ultimate flexural strength after drilling, and the strains in all parts of the composite bone plate are higher than those of the titanium alloy bone plate in all periods of fracture healing, with the maximum being higher than 180%. In addition, debris dropout and exposure of carbon fibers of the composite bone plate will not affect osteoclast activity and will not excessively stimulate immune-inflammation reactions. In this work, we verified 3D needle-punched CF/PEEK composites’ feasibility as bone plates for internal fixation of fractures, providing a direction for the development of composite bone plates.
{"title":"Microstrain Ability and Biocompatibility of 3D Needle-Punched Carbon Fiber/Poly(ether ether ketone) Composite Bone Plates","authors":"Xingyu Zhou, Dahui Sun, Shanshan Zhao, Junhui Jiang, Junbo Dang, Ruifu Lv, Guibin Wang, Mei Zhang","doi":"10.1021/acsapm.4c01189","DOIUrl":"https://doi.org/10.1021/acsapm.4c01189","url":null,"abstract":"The aim of this work is to explore the potential application of three-dimensional (3D) needle-punched carbon fiber/poly(ether ether ketone) (CF/PEEK) composites in the field of fractures internal fixation. First, the machinability of 3D needle-punched CF/PEEK composites was explored through mechanical property tests on drilled composite samples; subsequently, the microstrain of composite bone plates at different stages of fracture healing was verified in an in vitro simulation of tibia fracture internal fixation model and compared with titanium alloy bone plates; finally, thinking of the potential debris dropout and exposure of carbon fibers that may occur after implantation of the bone plates in vivo and biocompatibility in vitro tests were conducted. After the above experiments, it can be seen that the composites can still maintain 60% of their ultimate tensile strength and 85% of their ultimate flexural strength after drilling, and the strains in all parts of the composite bone plate are higher than those of the titanium alloy bone plate in all periods of fracture healing, with the maximum being higher than 180%. In addition, debris dropout and exposure of carbon fibers of the composite bone plate will not affect osteoclast activity and will not excessively stimulate immune-inflammation reactions. In this work, we verified 3D needle-punched CF/PEEK composites’ feasibility as bone plates for internal fixation of fractures, providing a direction for the development of composite bone plates.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141529252","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Distinguished from traditional power sources such as batteries and capacitors, triboelectric nanogenerators have higher freedom of material selection and application flexibility and thus can fulfill the needs of flexible self-supplied electronic devices for advanced e-skin, human–computer interaction, and sensing. Here, a flexible (1100% of elongation at break, 0.2 MPa of breaking strength), highly conductive and adhesive (120 kPa), and environmentally stable ionogel was fabricated by introducing ionic liquids into a physical cross-linking polymer framework. The ionic liquid built a nonaqueous solvent system that made the ionogel environmentally stable. The introduction of amphiphilic ions both improved the mechanical properties of the polymer network and acted as ion channels to enhance the mobility of the ionic liquid and thus the electrical conductivity. Meanwhile, dynamic hydrogen bonding and dipole–dipole interaction made the ionogel have good adhesion properties. The ionogel can be applied as a flexible sensor for strain and pressure monitoring, and more importantly, the assembly of the ionogel with silicone rubber elastomer films into a sandwich-structured triboelectric nanogenerator enabled its application in scenarios such as self-supplied messaging and all-weather traffic monitoring, and it can also provide wired and wireless signal outputs with fast response (∼0.04 s). This work provides a direction for the application of gel-based electronic devices in the fields of intelligent human–computer interaction, information transfer, health monitoring, and traffic detection.
{"title":"Highly Stretchable, Conductive, Adhesive, and Self-Powered Ionogel Sensor for Human Motion Detection, Signal Transmission, and Traffic Monitoring","authors":"Tengyu Long, Weizhong Yuan, Bing Wang","doi":"10.1021/acsapm.4c01552","DOIUrl":"https://doi.org/10.1021/acsapm.4c01552","url":null,"abstract":"Distinguished from traditional power sources such as batteries and capacitors, triboelectric nanogenerators have higher freedom of material selection and application flexibility and thus can fulfill the needs of flexible self-supplied electronic devices for advanced e-skin, human–computer interaction, and sensing. Here, a flexible (1100% of elongation at break, 0.2 MPa of breaking strength), highly conductive and adhesive (120 kPa), and environmentally stable ionogel was fabricated by introducing ionic liquids into a physical cross-linking polymer framework. The ionic liquid built a nonaqueous solvent system that made the ionogel environmentally stable. The introduction of amphiphilic ions both improved the mechanical properties of the polymer network and acted as ion channels to enhance the mobility of the ionic liquid and thus the electrical conductivity. Meanwhile, dynamic hydrogen bonding and dipole–dipole interaction made the ionogel have good adhesion properties. The ionogel can be applied as a flexible sensor for strain and pressure monitoring, and more importantly, the assembly of the ionogel with silicone rubber elastomer films into a sandwich-structured triboelectric nanogenerator enabled its application in scenarios such as self-supplied messaging and all-weather traffic monitoring, and it can also provide wired and wireless signal outputs with fast response (∼0.04 s). This work provides a direction for the application of gel-based electronic devices in the fields of intelligent human–computer interaction, information transfer, health monitoring, and traffic detection.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521056","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hua-Xin Huang, Xin-Yi Ouyang, Jia-Le Zhang, Chen-Chen Lu, Peng Li, Wei Wu, Robert K Y Li, Xiao-Ming Ren, Hui Zhao
Ultraviolet (UV) shielding materials have garnered widespread applications in biological protection, aerospace, intelligent coating, and other fields. However, they are vulnerable to external friction scratches due to prolonged exposure, which leads to a decline in their UV shielding ability, further limiting their long-term applications. In this work, a series of waterborne polyurethane–polydopamine nanocomposites with excellent self-healing and UV shielding properties were prepared, among which using waterborne polyurethane with Diels–Alder thermally reversible cross-linked networks as the substrate and polydopamine (PDA) nanoparticles as the UV shielding agent. The developed nanocomposites can achieve a good self-healing effect at 120 °C in 30 min, and the self-healing efficiency can reach more than 68%. Adding PDA nanoparticles can enhance the mechanical and UV shielding properties of the nanocomposite. The nanocomposite with 0.5 wt % PDA contents has both the highest tensile strength and elongation at break, with values of 9.9 MPa and 667.27%, respectively. UV–vis tests exhibit that the residual amount of methylene blue solution under the protection of the nanocomposite film containing 2 wt % PDA content could reach 63.81%, concluding that the as-prepared nanomaterials have excellent UV shielding properties. This study offers an idea for the production of excellent and durable UV shielding materials with self-healing properties.
{"title":"Thermal-Driven Self-Healing Polyurethane Based on Polydopamine Nanoparticles with Enhanced Mechanical and UV Shielding Properties","authors":"Hua-Xin Huang, Xin-Yi Ouyang, Jia-Le Zhang, Chen-Chen Lu, Peng Li, Wei Wu, Robert K Y Li, Xiao-Ming Ren, Hui Zhao","doi":"10.1021/acsapm.4c00997","DOIUrl":"https://doi.org/10.1021/acsapm.4c00997","url":null,"abstract":"Ultraviolet (UV) shielding materials have garnered widespread applications in biological protection, aerospace, intelligent coating, and other fields. However, they are vulnerable to external friction scratches due to prolonged exposure, which leads to a decline in their UV shielding ability, further limiting their long-term applications. In this work, a series of waterborne polyurethane–polydopamine nanocomposites with excellent self-healing and UV shielding properties were prepared, among which using waterborne polyurethane with Diels–Alder thermally reversible cross-linked networks as the substrate and polydopamine (PDA) nanoparticles as the UV shielding agent. The developed nanocomposites can achieve a good self-healing effect at 120 °C in 30 min, and the self-healing efficiency can reach more than 68%. Adding PDA nanoparticles can enhance the mechanical and UV shielding properties of the nanocomposite. The nanocomposite with 0.5 wt % PDA contents has both the highest tensile strength and elongation at break, with values of 9.9 MPa and 667.27%, respectively. UV–vis tests exhibit that the residual amount of methylene blue solution under the protection of the nanocomposite film containing 2 wt % PDA content could reach 63.81%, concluding that the as-prepared nanomaterials have excellent UV shielding properties. This study offers an idea for the production of excellent and durable UV shielding materials with self-healing properties.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521055","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Toby R. Edwards, Rahul Shankar, Paul G. H. Smith, Jacob A. Cross, Zoe A. B. Lequeux, Lisa K. Kemp, Zhe Qiang, Scott T. Iacono and Sarah E. Morgan*,
{"title":"Correction to “β-Phase Crystallinity, Printability, and Piezoelectric Characteristics of Polyvinylidene Fluoride (PVDF)/Poly(methyl methacrylate) (PMMA)/Cyclopentyl-polyhedral Oligomeric Silsesquioxane (Cp-POSS) Melt-Compounded Blends”","authors":"Toby R. Edwards, Rahul Shankar, Paul G. H. Smith, Jacob A. Cross, Zoe A. B. Lequeux, Lisa K. Kemp, Zhe Qiang, Scott T. Iacono and Sarah E. Morgan*, ","doi":"10.1021/acsapm.4c01719","DOIUrl":"https://doi.org/10.1021/acsapm.4c01719","url":null,"abstract":"","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":4.4,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsapm.4c01719","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141478423","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nilanjan Mukherjee, Olivia Basu, Subhabrata Mukhopadhyay, Tushar Jana
In recent times, surface-modified metal organic frameworks (MOFs), obtained using different postsynthetic modifications (PSMs) on MOFs, are being explored frequently to develop hybrid materials for numerous applications. In continuation of our recent work on the grafting of polymer chains on the MOF surface to make hybrid materials (polymer-MOF conjugates) with enhanced physical properties, in this work, we grafted a proton conducting polymer, namely, poly(vinyl phosphonic acid) [PVPA] chains of various length and grafting density, on UiO-66 MOF, using surface-initiated reversible addition–fragmentation chain transfer (SI-RAFT) polymerization in order to develop an advanced class of proton conducting MOF-based hybrid materials with superior performance. Grafting of PVPA chains was confirmed by TGA, GPC, FT-IR, NMR, FESEM, TEM, EDX, and mapping studies. The stability of the freshly synthesized hybrid material under various harsh environments was further analyzed. Pendent phosphonic acid groups of the PVPA chains grafted on the MOF surface create strong H-bonding, acid–base, ionic, and noncovalent interactions with the neighboring PGMs and water molecules, which are responsible for displaying high stability, water sorption ability, and high proton conductivity of 1.26 × 10–2 S cm–1 at 80 °C for the PGM-L3 sample under 98% relative humidity and 9.8 × 10–3 S cm–1 at 60 °C for the PGM-H1 sample under 75% relative humidity, which are among the highest values reported so far for MOF-based systems.
近来，人们频繁探索通过对金属有机框架（MOFs）进行不同的后合成修饰（PSMs）而获得的表面修饰金属有机框架（MOFs），以开发具有多种应用的混合材料。为了延续我们最近关于在 MOF 表面接枝聚合物链以制造物理性能更强的杂化材料（聚合物-MOF 共轭物）的研究成果，在这项研究中，我们利用表面引发的可逆加成-断裂链转移（SI-RAFT）聚合反应，在 UiO-66 MOF 上接枝了不同长度和接枝密度的质子传导聚合物，即聚（乙烯基膦酸）[PVPA] 链，从而开发出一类性能优越的基于 MOF 的高级质子传导杂化材料。TGA、GPC、FT-IR、NMR、FESEM、TEM、EDX 和制图研究证实了 PVPA 链的接枝。研究还进一步分析了新合成的杂化材料在各种恶劣环境下的稳定性。接枝在 MOF 表面的 PVPA 链上的悬垂膦酸基团与相邻的 PGMs 和水分子之间产生了强烈的 H 键、酸碱、离子和非共价相互作用，这是该材料具有高稳定性、吸水性和高质子电导率（1.在相对湿度为 98% 的条件下，PGM-L3 样品在 80 °C 时的质子电导率为 26 × 10-2 S cm-1；在相对湿度为 75% 的条件下，PGM-H1 样品在 60 °C 时的质子电导率为 9.8 × 10-3 S cm-1。
{"title":"Grafting of Poly(vinyl phosphonic acid) to MOF Surfaces to Achieve Proton Conducting Hybrid Materials","authors":"Nilanjan Mukherjee, Olivia Basu, Subhabrata Mukhopadhyay, Tushar Jana","doi":"10.1021/acsapm.4c00821","DOIUrl":"https://doi.org/10.1021/acsapm.4c00821","url":null,"abstract":"In recent times, surface-modified metal organic frameworks (MOFs), obtained using different postsynthetic modifications (PSMs) on MOFs, are being explored frequently to develop hybrid materials for numerous applications. In continuation of our recent work on the grafting of polymer chains on the MOF surface to make hybrid materials (polymer-MOF conjugates) with enhanced physical properties, in this work, we grafted a proton conducting polymer, namely, poly(vinyl phosphonic acid) [PVPA] chains of various length and grafting density, on UiO-66 MOF, using surface-initiated reversible addition–fragmentation chain transfer (SI-RAFT) polymerization in order to develop an advanced class of proton conducting MOF-based hybrid materials with superior performance. Grafting of PVPA chains was confirmed by TGA, GPC, FT-IR, NMR, FESEM, TEM, EDX, and mapping studies. The stability of the freshly synthesized hybrid material under various harsh environments was further analyzed. Pendent phosphonic acid groups of the PVPA chains grafted on the MOF surface create strong H-bonding, acid–base, ionic, and noncovalent interactions with the neighboring PGMs and water molecules, which are responsible for displaying high stability, water sorption ability, and high proton conductivity of 1.26 × 10<sup>–2</sup> S cm<sup>–1</sup> at 80 °C for the PGM-L3 sample under 98% relative humidity and 9.8 × 10<sup>–3</sup> S cm<sup>–1</sup> at 60 °C for the PGM-H1 sample under 75% relative humidity, which are among the highest values reported so far for MOF-based systems.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521058","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xin Ren, Hongjun Xu, Li Jin, Changbiao Chen, Xueting Lu, Shuaibo Han, Hui Wang, Yan Zhang, Fangli Sun
Bamboo, attributed to its short growth cycle and excellent mechanical properties, has become a popular alternative to wood and other building materials such as cement and steel. However, its susceptibility to cracking and molds hinders its broad application in architecture and furniture. In this study, the bioresin polyfurfuryl alcohol (PFA)-modified epoxy resin (EP)/polyetheramine (PEA) system was constructed and in situ cured inside bamboo. Results showed that the epoxy/PFA bioresin could fill in the vascular bundles and parenchyma cells of bamboo, in situ cured and combined with it via hydrogen bond to form a composite with good overall performance. Especially, the epoxy/PFA bioresin possessed good shape memory performance, which was able to counteract the dry shrinkage stress of bamboo. The three cycles of extreme heating–cooling tests and 6 h continuous drying test at 103 °C were conducted to verify the modification effect on crack resistance of bamboo. The PFA/EP/PEA-modified bamboo culms remained crack-free, while 75% of untreated ones cracked in heating–cooling tests. Besides, when all of the untreated bamboo culms cracked, only 33.3% of the PFA/EP/PEA-modified bamboo had cracks in the continuous drying test. Furthermore, the epoxy/PFA bioresin system in bamboo also improved the mold resistance. The bioresin composites comprising bamboo, epoxy, and PFA exhibit considerable potential for advancing the incorporation of bamboo into ecologically sustainable practices within the realms of construction and furniture applications. This advancement extends the lifespan of bamboo products as well as expands their application scope particularly in regions experiencing substantial fluctuations in outdoor humidity.
{"title":"Enhancing Crack and Mold Resistance of Bamboo by In Situ Construction of Shape Memory Epoxy/Poly(furfuryl alcohol) Bioresin","authors":"Xin Ren, Hongjun Xu, Li Jin, Changbiao Chen, Xueting Lu, Shuaibo Han, Hui Wang, Yan Zhang, Fangli Sun","doi":"10.1021/acsapm.4c00584","DOIUrl":"https://doi.org/10.1021/acsapm.4c00584","url":null,"abstract":"Bamboo, attributed to its short growth cycle and excellent mechanical properties, has become a popular alternative to wood and other building materials such as cement and steel. However, its susceptibility to cracking and molds hinders its broad application in architecture and furniture. In this study, the bioresin polyfurfuryl alcohol (PFA)-modified epoxy resin (EP)/polyetheramine (PEA) system was constructed and <i>in situ</i> cured inside bamboo. Results showed that the epoxy/PFA bioresin could fill in the vascular bundles and parenchyma cells of bamboo, <i>in situ</i> cured and combined with it via hydrogen bond to form a composite with good overall performance. Especially, the epoxy/PFA bioresin possessed good shape memory performance, which was able to counteract the dry shrinkage stress of bamboo. The three cycles of extreme heating–cooling tests and 6 h continuous drying test at 103 °C were conducted to verify the modification effect on crack resistance of bamboo. The PFA/EP/PEA-modified bamboo culms remained crack-free, while 75% of untreated ones cracked in heating–cooling tests. Besides, when all of the untreated bamboo culms cracked, only 33.3% of the PFA/EP/PEA-modified bamboo had cracks in the continuous drying test. Furthermore, the epoxy/PFA bioresin system in bamboo also improved the mold resistance. The bioresin composites comprising bamboo, epoxy, and PFA exhibit considerable potential for advancing the incorporation of bamboo into ecologically sustainable practices within the realms of construction and furniture applications. This advancement extends the lifespan of bamboo products as well as expands their application scope particularly in regions experiencing substantial fluctuations in outdoor humidity.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521057","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ye Sun, Wanying Yang, Yunfei Wang, Fan Yang, Xiunan Li, Yanhua Yang, Dong Jiang
Nanofiltration is seen as a potential technique for desalination and purification of drinking water. Improving water permeability without compromising on the high rejection rate in nanofiltration membranes is a major challenge. This article describes interfacial polymerization (IP) mediated by tannic acid (TA)–MXene interlayer to prepare an ultrathin film composite membrane (TFCi) possessing negative surface charge and optimized water transport channel. Nanofiltration process and the formation of the polyamide surface layer are both dependent on the TA–MXene intermediate layer. It is capable of storing amine monomer, decelerating interfacial polymerization, and producing a 30-nm-thick polyamide selective layer devoid of defects. With a rejection rate of 96.0% for divalent ions and a permeation flux of 22.3 L m–2 h–1 bar–1, the nanofiltration membrane that was acquired exhibits exceptional performance and stability in the operation of long-term nanofiltration. In contrast to traditional TFC membranes, the TFCi membrane successfully overcomes the long-standing contradiction between permeability and selectivity. This study offers a straightforward method for fabricating TFC membranes that exhibit outstanding performance.
{"title":"MXene Film as an Interlayer for Thin-Film Composite Membranes with High-Performance Nanofiltration","authors":"Ye Sun, Wanying Yang, Yunfei Wang, Fan Yang, Xiunan Li, Yanhua Yang, Dong Jiang","doi":"10.1021/acsapm.4c01307","DOIUrl":"https://doi.org/10.1021/acsapm.4c01307","url":null,"abstract":"Nanofiltration is seen as a potential technique for desalination and purification of drinking water. Improving water permeability without compromising on the high rejection rate in nanofiltration membranes is a major challenge. This article describes interfacial polymerization (IP) mediated by tannic acid (TA)–MXene interlayer to prepare an ultrathin film composite membrane (TFC<sub>i</sub>) possessing negative surface charge and optimized water transport channel. Nanofiltration process and the formation of the polyamide surface layer are both dependent on the TA–MXene intermediate layer. It is capable of storing amine monomer, decelerating interfacial polymerization, and producing a 30-nm-thick polyamide selective layer devoid of defects. With a rejection rate of 96.0% for divalent ions and a permeation flux of 22.3 L m<sup>–2</sup> h<sup>–1</sup> bar<sup>–1</sup>, the nanofiltration membrane that was acquired exhibits exceptional performance and stability in the operation of long-term nanofiltration. In contrast to traditional TFC membranes, the TFC<sub>i</sub> membrane successfully overcomes the long-standing contradiction between permeability and selectivity. This study offers a straightforward method for fabricating TFC membranes that exhibit outstanding performance.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":5.0,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141521059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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