ACS Applied Polymer Materials最新文献

{"title":"Heat-Resistant Shape Memory Fully Biobased Epoxy Resins with High Storage Modulus and Recycle Performance","authors":"Hubiao Yang,&nbsp;Li Yuan,&nbsp;Guozheng Liang* and Aijuan Gu*,&nbsp;","doi":"10.1021/acsapm.4c0328310.1021/acsapm.4c03283","DOIUrl":"https://doi.org/10.1021/acsapm.4c03283https://doi.org/10.1021/acsapm.4c03283","url":null,"abstract":"<p >Combining high heat resistance and green sustainability is a great challenge in developing shape memory epoxy resins. Herein, starting from synthesizing a fully biobased trifunctional epoxy compound (ER), a kind of fully biobased epoxy resin system (EFT<i>x</i>, where <i>x</i> is the molar ratio of carboxyl to epoxy groups) is developed. The effects of <i>x</i> on the structure and properties of EFT<i>x</i> resins were systematically investigated. Results show that cured EFT<i>x</i> resins have excellent heat resistance, high mechanical properties, shape memory performance, and recycle ability. As <i>x</i> of EFT<i>x</i> resin increases, the glass transition temperature (<i>T</i>_g) and initial thermal decomposition temperature (<i>T</i>_di) decrease while both self-healing efficiency and remolding efficiency increase. The <i>T</i>_g and storage modulus of each EFT<i>x</i> resin are much higher than those of reported fully biobased shape memory epoxy resins. Among EFT<i>x</i> resins, EFT_1.0 resin shows the best-integrated performance; specifically, its <i>T</i>_g, <i>T</i>_di, tensile strength, and self-healing efficiency are as high as 156 °C, 293 °C, 40.99 MPa, and 90.5%, respectively, meanwhile it also has outstanding shape memory property reflected by the high shape fixation ratio (<i>R</i>_f = 100%) and shape recovery ratio (<i>R</i>_r = 97.8%) under the bend-recovery experiments as well as high <i>R</i>_f (93.2%) and <i>R</i>_r (66.1%) after four tensile shape memory cycles. The outstanding integrated performance of EFT<i>x</i> resins is attributed to their unique structures that combine rigid stilbene structure, furan ring, and abundant ester bonds.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"6 23","pages":"14905–14915 14905–14915"},"PeriodicalIF":4.4,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849988","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}

{"title":"Extrudable and Highly Creep-Resistant Covalent Adaptable Networks Made from Polyethylene and Ethylene/1-Octene Copolymers by Reactive Processing with Aromatic Disulfide Cross-Links","authors":"Mathew J. Suazo,&nbsp;Logan M. Fenimore,&nbsp;Stephanie M. Barbon,&nbsp;Hayley Brown,&nbsp;Evelyn Auyeung,&nbsp;Gerardo Cespedes,&nbsp;Colin Li Pi Shan and John M. Torkelson*,&nbsp;","doi":"10.1021/acsapm.4c0296910.1021/acsapm.4c02969","DOIUrl":"https://doi.org/10.1021/acsapm.4c02969https://doi.org/10.1021/acsapm.4c02969","url":null,"abstract":"<p >Polyolefins like polyethylene (PE) and ethylene-based copolymers are widely used in consumer and industrial applications due to their versatility, the diversity and tunability of their properties, and their theoretical recyclability at elevated temperatures. However, their recycling rates are markedly low, and, though the cross-linking of PE enhances its properties through the creation of a networked architecture, the resulting thermoset known as PEX is rendered completely unrecyclable. Incorporating associative or dissociative dynamic covalent bonds as cross-links into plastics like PE is a promising route both to make use of spent plastics (via “upcycling” them) and to generate recyclable alternatives to unrecyclable thermosets like PEX. Such materials are known as covalent adaptable networks or CANs (also called vitrimers if the cross-links are exclusively associative). Here, we present a method for imbuing ethylene-based polymers with aromatic disulfide dynamic covalent cross-links, resulting in robust, reprocessable CANs. Radical-based reactive processing of PE and ethylene/1-octene-based copolymers with 1 wt % dicumyl peroxide and 5 wt % bis(4-methacryloyloxyphenyl) disulfide (BiPheS methacrylate or BPMA) successfully resulted in CANs which fully recovered their cross-link densities and associated thermomechanical properties after multiple reprocessing cycles. These CANs demonstrate remarkable elevated-temperature creep resistance due to the high-temperature thermal stability and high temperatures required for exchanges of the BiPheS-based cross-links. BiPheS-based cross-links in PE and ethylene-based copolymer CANs also enable their (re)processability via extrusion at elevated temperatures, with property recovery demonstrated with extrusion temperatures as high as 260 °C, thereby indicating the feasibility of extending our approach to industrial scales and processes as well as other rigorous applications.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"6 23","pages":"14772–14783 14772–14783"},"PeriodicalIF":4.4,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842151","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}

{"title":"Amoebicidal Potential of β-Caryophyllene-Loaded Polymeric Nanoparticles","authors":"Douglas Santos Porto,&nbsp;Debora Fretes Argenta,&nbsp;Cynthia Camila Ziech,&nbsp;Maira Pereira Balleste,&nbsp;Juliana Priscila Dreyer,&nbsp;Gustavo Amadeu Micke,&nbsp;Ângela Machado Campos,&nbsp;Karin Silva Caumo and Thiago Caon*,&nbsp;","doi":"10.1021/acsapm.4c0249610.1021/acsapm.4c02496","DOIUrl":"https://doi.org/10.1021/acsapm.4c02496https://doi.org/10.1021/acsapm.4c02496","url":null,"abstract":"<p >The investigation of therapeutic agents for <i>Acanthamoeba</i> keratitis (AK) is necessary as nonspecific, toxic, and long-lasting treatments are currently found. In this study, ß-caryophyllene was selected as an anti-<i>Acanthamoeba</i> candidate due to its known anti-inflammatory and analgesic activities, which are pharmacological actions desirable for this application. On the other hand, this sesquiterpene presents a low aqueous solubility, high volatility, and susceptibility to oxidation, which motivated its incorporation into polymeric nanoparticles (NPs). Chitosan (CS) was selected as the biopolymer due to its bioadhesive properties and wide use in ophthalmic preparations, which was cross-linked with tripolyphosphate (TPP) to obtain stable particles. Monodisperse NPs with reduced size (&lt;245 nm) and presenting a positive surface charge (ζ-potential between +15.23 and +18.15 mV) were obtained regardless of the type of chitosan selected. The colloidal suspensions were stable for up to 60 and 90 days after storage at 25 and 4 °C, respectively. The nanoencapsulation of ß-caryophyllene led to a series of benefits: (a) increased its activity against <i>Acanthamoeba castellanii</i> trophozoites; (b) reduced corneal toxicity as no more collagen disruption was found in the stroma; and (c) increased retention and mucoadhesion in corneal tissue. In view of these positive results, <i>in vivo</i> studies are encouraged, as well as formulation studies including potential therapeutic agents in this same nanocarrier.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"6 23","pages":"14447–14457 14447–14457"},"PeriodicalIF":4.4,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842398","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}

{"title":"Synergistic Combination of Cross-Linked Polymer and Concentrated Ionic Liquid for Electrolytes with High Stability in Solid-State Lithium Metal Batteries","authors":"Mingjie Zhang,&nbsp;Faezeh Makhlooghiazad*,&nbsp;Urbi Pal,&nbsp;Mahin Maleki,&nbsp;Shinji Kondou,&nbsp;Giuseppe Antonio Elia,&nbsp;Claudio Gerbaldi* and Maria Forsyth,&nbsp;","doi":"10.1021/acsapm.4c0252010.1021/acsapm.4c02520","DOIUrl":"https://doi.org/10.1021/acsapm.4c02520https://doi.org/10.1021/acsapm.4c02520","url":null,"abstract":"<p >Poly(ethylene oxide)─(PEO-based solid polymer electrolytes (SPEs) are regarded as excellent candidates for solid-state lithium metal batteries (SSLMBs) due to their inherent safety advantages, processability, low cost, and excellent Li+ ion solvation. However, they suffer from limited oxidation stability (up to 4 V vs Li⁺/Li). In this study, a crosslinked polymer-in-concentrated ionic liquid (PCIL) SPE consisting of PEO, <i>N</i>-propyl-<i>N</i>-methylpyrrolidinium bis(fluorosulfonyl)imide (C₃mpyrFSI) ionic liquid (IL), and lithium bis(fluorosulfonyl)imide (LiFSI) salt is developed. The adopted UV-crosslinking strategy synergistically reduces PEO crystallinity while increasing the amount of encompassed lithium salt and IL and improves PEO oxidative stability, therefore leading to enhanced electrochemical performance. The physical and electrochemical properties of both linear and crosslinked SPEs are explored and compared. The designed cross-linked SPEs exhibited a promisingly high oxidative stability of 4.9 V vs Li⁺/Li and high ambient temperature ionic conductivity of 4 × 10^–4 S cm^–1. Stable and reversible lithium plating/stripping is demonstrated in symmetrical Li||Li cells over hundreds of hours. High-loading solid-state lithium iron phosphate (LFP)||Li cells show favorable cycling with over 90% capacity retention at 0.1C over 100 cycles at 50 °C. High voltage solid-state lithium manganese oxide (LMO)||Li cells exhibit promising cycling with a 93% capacity retention at a 0.2 C rate over 50 cycles at 50 °C. Thus, the combination of concentrated ionic liquid electrolytes in a crosslinked PEO-based matrix enables a pathway for designing high-performing SPEs for high energy density solid-state LMBs.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"6 23","pages":"14469–14476 14469–14476"},"PeriodicalIF":4.4,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsapm.4c02520","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842280","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}

{"title":"Synergistic Combination of Cross-Linked Polymer and Concentrated Ionic Liquid for Electrolytes with High Stability in Solid-State Lithium Metal Batteries.","authors":"Mingjie Zhang, Faezeh Makhlooghiazad, Urbi Pal, Mahin Maleki, Shinji Kondou, Giuseppe Antonio Elia, Claudio Gerbaldi, Maria Forsyth","doi":"10.1021/acsapm.4c02520","DOIUrl":"https://doi.org/10.1021/acsapm.4c02520","url":null,"abstract":"<p><p>Poly(ethylene oxide)-(PEO-based solid polymer electrolytes (SPEs) are regarded as excellent candidates for solid-state lithium metal batteries (SSLMBs) due to their inherent safety advantages, processability, low cost, and excellent Li+ ion solvation. However, they suffer from limited oxidation stability (up to 4 V vs Li⁺/Li). In this study, a crosslinked polymer-in-concentrated ionic liquid (PCIL) SPE consisting of PEO, <i>N</i>-propyl-<i>N</i>-methylpyrrolidinium bis(fluorosulfonyl)imide (C₃mpyrFSI) ionic liquid (IL), and lithium bis(fluorosulfonyl)imide (LiFSI) salt is developed. The adopted UV-crosslinking strategy synergistically reduces PEO crystallinity while increasing the amount of encompassed lithium salt and IL and improves PEO oxidative stability, therefore leading to enhanced electrochemical performance. The physical and electrochemical properties of both linear and crosslinked SPEs are explored and compared. The designed cross-linked SPEs exhibited a promisingly high oxidative stability of 4.9 V vs Li⁺/Li and high ambient temperature ionic conductivity of 4 × 10^-4 S cm^-1. Stable and reversible lithium plating/stripping is demonstrated in symmetrical Li||Li cells over hundreds of hours. High-loading solid-state lithium iron phosphate (LFP)||Li cells show favorable cycling with over 90% capacity retention at 0.1C over 100 cycles at 50 °C. High voltage solid-state lithium manganese oxide (LMO)||Li cells exhibit promising cycling with a 93% capacity retention at a 0.2 C rate over 50 cycles at 50 °C. Thus, the combination of concentrated ionic liquid electrolytes in a crosslinked PEO-based matrix enables a pathway for designing high-performing SPEs for high energy density solid-state LMBs.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"6 23","pages":"14469-14476"},"PeriodicalIF":4.4,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11650632/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851611","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}

{"title":"Development of Poly(l-lactic acid)-Yellow Propolis Membranes for Antioxidant Applications","authors":"Letícia S Contieri,&nbsp;Catarina Vieira,&nbsp;Bárbara M. C. Vaz,&nbsp;Diana Cláudia Gouveia Alves Pinto,&nbsp;Maurício Rostagno,&nbsp;Sónia P. M. Ventura,&nbsp;Vitor Sencadas and Leonardo Mendes de SouzaMesquita*,&nbsp;","doi":"10.1021/acsapm.4c0189910.1021/acsapm.4c01899","DOIUrl":"https://doi.org/10.1021/acsapm.4c01899https://doi.org/10.1021/acsapm.4c01899","url":null,"abstract":"<p >Propolis-based products, particularly those high in phenolic compounds, are extensively utilized in pharmaceutical applications for their broad therapeutic and health benefits. To improve the delivery and stability of these compounds, researchers are exploring biocompatible materials for encapsulating natural extracts. Polylactic acid (PLA) stands out as a promising biopolymer due to its biocompatibility, nontoxicity, exceptional biodegradability, and favorable mechanical properties, making it well-suited for a range of medical and pharmaceutical applications. This study aimed to develop PLA-based membranes incorporating raw yellow propolis through electrospinning and to identify the maximum feasible concentration of raw propolis that can be incorporated into PLA membranes. The chemical composition of the yellow propolis was analyzed using chromatographic techniques coupled with a photodiode array detector and mass spectrometry (UHPLC-PDA-MS/MS), highlighting its rich array of phenolic compounds, which are known for their significant antioxidant properties. The membranes were thoroughly characterized with Fourier transform infrared spectroscopy and scanning electron microscopy, confirming the successful incorporation of propolis into the PLA membranes, particularly in the sample containing 25% propolis (w/w). Total phenolic content, antioxidant activity, and bioadhesion were also evaluated. Results showed that the membrane with 25% propolis (w/w) exhibits skin-adhesive properties and huge antioxidant activity due to its phenolic content. These findings suggest that the membrane has strong potential for future biomedical applications, where antioxidant activity is essential.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"6 23","pages":"14290–14299 14290–14299"},"PeriodicalIF":4.4,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsapm.4c01899","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142844093","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}

{"title":"Preparation and Performance of Multifunctional Composite Hydrogel Based on Xanthate Lignin/Chitosan/Poly(acrylic acid) with Underwater Adhesion and Sensing Properties","authors":"Xueying Jiao,&nbsp;Amatjan Sawut*,&nbsp;Rena Simayi* and Ayiguzaili Abudiwayiti,&nbsp;","doi":"10.1021/acsapm.4c0293510.1021/acsapm.4c02935","DOIUrl":"https://doi.org/10.1021/acsapm.4c02935https://doi.org/10.1021/acsapm.4c02935","url":null,"abstract":"<p >Multifunctional hydrogel materials with self-healing ability, underwater adhesion, and electrical conductivity have potential application value in many fields. In this study, an LS/CS/PAA composite hydrogel was prepared by one-pot method using lignosulfonate (LS), acrylic acid (AA), and chitosan (CS) as raw materials. The hydrogels are characterized by thermal gravimetric (TG), Fourier transform infrared (FTIR), and scanning electron microscope (SEM). The rich sulfonic acid groups, carboxyl groups, hydroxyl groups, and phenolic hydroxyl groups in the hydrogel give it special properties, including excellent adhesion, electrical conductivity, sensing ability, and humidity response power generation ability. LS/CS/PAA hydrogels strongly adhere to a variety of hydrophobic or hydrophilic surfaces with excellent self-adhesive properties, such as plexiglass, paper, and plastic, and obtained adhesion strengths of up to 324.59, 196.13, and 255.76 kPa, respectively, in tests. In particular, the hydrogel showed significantly improved underwater adhesion strength in different solutions, increasing by up to 33.17% in 10 min and maintaining a stable bonding effect. In addition, LS/CS/PAA hydrogels are attractive in humidity sensing power generation with a maximum output voltage of 40.7 mV. Its good adhesion and antibacterial properties make the material more suitable for the skin and effectively inhibit bacterial growth. Its excellent ion conductivity shows high sensitivity when detecting curved body movements. In summary, this multifunctional LS/CS/PAA composite hydrogel will play an important role in many fields such as biomedicine, sensor, environmental monitoring, and energy conversion.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"6 23","pages":"14726–14739 14726–14739"},"PeriodicalIF":4.4,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142844097","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}

{"title":"Combining Electrospinning and Photoinduced Reactions to Fabricate Cytocompatible and Antibacterial Ag Nanoparticle-Decorated Polymeric Membranes","authors":"Parnian Kianfar,&nbsp;Sara Dalle Vacche,&nbsp;Roberta Bongiovanni,&nbsp;Chiara Mollea,&nbsp;Francesca Bosco,&nbsp;Ziba Najmi,&nbsp;Alessandro C. Scalia,&nbsp;Andrea Cochis and Alessandra Vitale*,&nbsp;","doi":"10.1021/acsapm.4c0295310.1021/acsapm.4c02953","DOIUrl":"https://doi.org/10.1021/acsapm.4c02953https://doi.org/10.1021/acsapm.4c02953","url":null,"abstract":"<p >Composite nanofibrous membranes hold significant potential for the development of innovative biomedical materials and applications as their properties can be tuned by combining the synergistic effects of the nanofiller and the polymer matrix. Moreover, the nanofibrous structure can further enhance this feature thanks to the extremely high functional surface area. In the present work, a simple and fast method for the preparation of electrospun composite membranes based on cross-linked poly(ethylene oxide) (PEO) nanofibers and silver nanoparticles (Ag NPs) is proposed. For this purpose, a precursor of the Ag NPs (i.e., AgNO₃) is introduced into the aqueous solution of PEO in the presence of a suitable photoinitiator and a photo-cross-linker. Electrospinning of the solution is carried out, and the subsequent irradiation of the electrospun mat allows the simultaneous photoinduced cross-linking of PEO and the photoinduced synthesis of Ag NPs. The <i>in situ</i> generation of Ag NPs is confirmed through different characterization techniques (i.e., UV–vis spectroscopy, dynamic light scattering, and scanning electron microscopy). The structural, morphological, and mechanical properties of the resulting electrospun composite nanofibers are analyzed, and the effect of the content of the Ag NP precursor is evaluated. It is demonstrated that PEO fibers are chemically resistant and mechanically robust thanks to cross-linking, while Ag NPs induce significant antibacterial activity to the electrospun materials, which are also shown to be noncytotoxic by using both human fibroblasts and 3D-reconstructed skin equivalents. The proposed PEO-based nanofibrous mats decorated with Ag NPs thus exhibit promising potential as biomedical materials, especially for wound healing applications.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"6 23","pages":"14749–14759 14749–14759"},"PeriodicalIF":4.4,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142844096","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}

{"title":"Copper-Loaded Microporous Chitosan Generated within a 3D-Printed Polylactic Acid-Pearl Scaffold: Structure and Performance","authors":"Wang Guo*,&nbsp;Yufeng Mao,&nbsp;Xinru Tang,&nbsp;Enyu Wang,&nbsp;Ziying Peng,&nbsp;Yunlei Wu,&nbsp;Mingzhi Zhang,&nbsp;Feng Guo,&nbsp;Huaming Mai,&nbsp;Yong Zhang,&nbsp;Wenjie Zhang,&nbsp;Hui You* and Yu Long*,&nbsp;","doi":"10.1021/acsapm.4c0254110.1021/acsapm.4c02541","DOIUrl":"https://doi.org/10.1021/acsapm.4c02541https://doi.org/10.1021/acsapm.4c02541","url":null,"abstract":"<p >This study employed a combination of fused deposition modeling (FDM) 3D printing and freeze-drying techniques to fabricate a polylactic acid-pearl-chitosan-copper (PLA-P-CS/Cu) scaffold with a dual-scale porous structure and enhanced antibacterial, biological, and mechanical performance. The process began with FDM 3D printing to create a PLA-P scaffold featuring an interconnected macroporous structure with a pore size of hundreds of micrometers. Subsequently, freeze-drying was used to generate CS/Cu microporous foam with a pore size of tens of micrometers within the macroporous structure of the PLA-P scaffold. The formation of the dual-scale interconnected porous structure was confirmed through digital microscopy and scanning electron microscopy. Additionally, infrared spectroscopy and X-ray diffraction demonstrated the formation of coordination bonds between the amino and hydroxyl groups of chitosan and Cu²⁺ through chelation. Biomineralization test in simulated body fluid indicated that the PLA-P-CS/Cu dual-scale porous scaffold enhanced the nucleation, growth, and deposition of apatite by providing a larger specific surface area and sustained release of Cu²⁺. The dual-scale porous structure and Cu²⁺ release also promoted cell proliferation and osteogenic differentiation of bone marrow mesenchymal stem cells. Antibacterial assay using the plate count method revealed that the Cu-loaded scaffold exhibited a 66.72–82.84% antibacterial rate against <i>Escherichia coli</i>, depending on the Cu loading amount. Finally, a mechanical test indicated that the compressive strength and modulus of the dual-scale porous scaffold were as high as 17.23 and 295.10 MPa, respectively. This study provides a strategy for developing gradient porous bone scaffolds with enhanced antibacterial, biological, and mechanical properties through comprehensive optimization of the material design, porous structure, and manufacturing processes.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"6 23","pages":"14505–14517 14505–14517"},"PeriodicalIF":4.4,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850771","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}

{"title":"Fluorescent Polyamides with Piperazine and Valerolactam Structures Prepared by the Modified Ugi Reaction and Its Specific Detection to NO2– Ions","authors":"Yunfei Liu,&nbsp;Yayu Feng,&nbsp;Yue Sun,&nbsp;Meijing Zhang,&nbsp;Pengfei Zhang,&nbsp;Ronghui Zhao and Kuilin Deng*,&nbsp;","doi":"10.1021/acsapm.4c0250410.1021/acsapm.4c02504","DOIUrl":"https://doi.org/10.1021/acsapm.4c02504https://doi.org/10.1021/acsapm.4c02504","url":null,"abstract":"<p >In this investigation, a nonconjugated fluorescent polyamide with piperazine and valerolactam moieties (PAM–PV) has been synthesized by the modified Ugi polymerization using 1,4-bis(3-aminopropyl)piperazine, levulinic acid, and 1,4-bis(3-isocyanopropyl)piperazine as monomers. In the polymerization, the special construction of levulinic acid leads to the formation of valerolactam on PAM–PV chains via the Mumm rearrangement. PAM–PV shows a strong fluorescence emission at 428 nm due to the intramolecular aggregation of piperazine and valerolactam moieties along the backbone. Impressively, PAM–PV can specifically detect NO₂^– ions via static quenching with a linear range of 10^–6–10^–5 M and a detection limit of 0.6 μM (0.0276 mg/L), which was far less than the minimum allowable concentration of 3 mg/L for NO₂^– in drinking water specified by WHO. Furthermore, the several common anions and cations have no interference effects on the specific detection of PAM–PV to NO₂^– ions. The quenching mechanism of NO₂^– and PAM–PV by FTIR, UV, and ¹H NMR measurements indicates that the strong electrostatic interaction between NO₂^– and PAM–PV makes the macromolecular chains more relaxed and outstretched, leading to a formation of a nonfluorescent complex. Moreover, the practical detection of NO₂^– in the three water bodies, sauerkraut, and ham sausage and the fabrication of a portable detecting paper to NO₂^– ions were conducted in this experiment.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"6 23","pages":"14458–14468 14458–14468"},"PeriodicalIF":4.4,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843849","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}