{"title":"Effects of Silk Fibroin Hydrogel Degradation on the Proliferation and Chondrogenesis of Encapsulated Stem Cells.","authors":"Tianhao Zhu, Guolong Cai, Weikun Zhao, Xiang Yao, Yaopeng Zhang","doi":"10.1021/acs.biomac.4c01676","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01676","url":null,"abstract":"<p><p>Silk fibroin (SF) hydrogels are widely used in three-dimensional (3D) cell culture and tissue repair. Despite their importance, few studies have focused on regulating their degradation and further revealing the effects of the degradation process on encapsulated cell behaviors. Herein, SF hydrogels with equivalent initial properties and different degradation rates were prepared by adjusting the ratios between the hydrogel-encapsulated normal SF microspheres (MS<sub>N</sub>) and enzyme-loaded SF microspheres (MS<sub>E</sub>). Further, cell experiments revealed that moderately accelerating the hydrogel degradation obviously improved the proliferation of MSCs during 7 days of culture. Slightly accelerating the hydrogel degradation promoted MSC chondrogenesis. However, too rapid of a hydrogel degradation was unfavorable for these cell behaviors. The relevant studies are expected to provide useful strategies for regulating SF hydrogel degradation and also afford new references for the development of excellent SF hydrogels and other protein-based biomaterials for cartilage regeneration.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143021301","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}
BiomacromoleculesPub Date : 2025-01-21DOI: 10.1021/acs.biomac.4c01545
Xuelian Hu, Sai Li, Yuji Pu, Bin He
{"title":"Biodegradable Polymeric Microspheres with Enhanced Hemostatic and Antibacterial Properties for Wound Healing.","authors":"Xuelian Hu, Sai Li, Yuji Pu, Bin He","doi":"10.1021/acs.biomac.4c01545","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01545","url":null,"abstract":"<p><p>Hemostasis is the initial step in wound healing, yet significant challenges, such as massive bleeding and infection, often arise. In this study, we developed amphiphilic biodegradable polyester-based segmented polyurethane (SPU) microspheres modified with epigallocatechin gallate (EGCG)-Ag nanoparticles and calcium-alginate cross-linking shell, combining blood absorption with the pro-coagulation properties of Ca<sup>2+</sup> and the negative charge of EGCG for synergistic hemostatic effects across various stages of the coagulation cascade. The in vitro blood clotting time of the SPU@EAg@CaAlg microsphere (328.7 s) was reduced by half compared to the SPU microsphere (685.0 s). SPU@EAg@CaAlg exhibited a reduced hemostatic time and blood loss in three rat hemostatic models. Additionally, EGCG-Ag nanoparticles imparted strong antibacterial and anti-inflammatory properties both in vitro and in vivo. In vivo infected wound model demonstrated that SPU@EAg@CaAlg effectively eliminated bacteria and reduced the levels of pro-inflammatory factors, thereby promoting wound healing. Thus, the modified SPU microspheres present a promising candidate for effective hemostatic applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996198","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}
BiomacromoleculesPub Date : 2025-01-21DOI: 10.1021/acs.biomac.4c01333
Haeun Kwon, Jieun Choi, Chanoong Lim, Junseong Kim, Asila Osman, Yongseok Jho, Dong Soo Hwang, Dong Woog Lee
{"title":"Strong Hydrophobic Interaction of High Molecular Weight Chitosan in Aqueous Solution.","authors":"Haeun Kwon, Jieun Choi, Chanoong Lim, Junseong Kim, Asila Osman, Yongseok Jho, Dong Soo Hwang, Dong Woog Lee","doi":"10.1021/acs.biomac.4c01333","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01333","url":null,"abstract":"<p><p>Chitosan is a versatile bioactive polysaccharide in various industries, such as pharmaceuticals and environmental applications, owing to its abundance, biodegradability, biocompatibility, and antibacterial properties. To effectively harness its potential for various purposes, it is crucial to understand the mechanisms of its interaction in water. This study investigates the interactions between high molecular weight (HMW, >150 kDa) chitosan and four different functionalized self-assembled monolayers (SAMs) at three different pHs (3.0, 6.5, and 8.5) using a surface forces apparatus (SFA). We report that HMW chitosan exhibits the strongest adhesion to methyl-terminated SAM (CH<sub>3</sub>-SAM) at all pHs, showing potential for strong hydrophobic interactions against other molecules containing hydrophobic moieties. Noting that hydrogen bonding has been considered the dominating interaction mechanism of chitosan, the consequence of this study provides valuable insights into its applications in developing chitosan-based eco-friendly materials.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996224","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}
BiomacromoleculesPub Date : 2025-01-21DOI: 10.1021/acs.biomac.4c01205
Christian Leppin, Agata Pomorska, Maria Morga, Pawel Pomastowski, Piotr Fijałkowski, Aneta Michna, Diethelm Johannsmann
{"title":"Swelling Degree of Polyelectrolyte Layers Determined by an Electrochemical Quartz Crystal Microbalance.","authors":"Christian Leppin, Agata Pomorska, Maria Morga, Pawel Pomastowski, Piotr Fijałkowski, Aneta Michna, Diethelm Johannsmann","doi":"10.1021/acs.biomac.4c01205","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01205","url":null,"abstract":"<p><p>Various polycations and polyanions were sequentially adsorbed onto the gold electrode of a quartz crystal microbalance with dissipation monitoring. The study focused on determining the adsorption kinetics, viscoelastic properties, and electroresponsivity of polyelectrolyte layers. For the first time, it was demonstrated that the structure (compact or expanded) of the layers can be determined by electroresponsivity. Viscoelastic modeling alone did not provide a conclusive answer as to whether the layers were compact or expanded. The study was further enriched by streaming potential and contact angle measurements, where polyelectrolyte multilayers were formed on mica. It was found that successive adsorption of layers led to periodic inversion of the zeta potential. Systematic differences were observed between the different top layers, which were explained by intermixing between layers. The presence or absence of interpenetration, as determined by the measurements of streaming potential and contact angles, correlated well with electroresponsivity.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996236","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":"Engineering of Silkworm Tyrosyl-tRNA Synthetase Variants to Create Halogenated Silk Fiber with Improved Thermal Stability.","authors":"Hidetoshi Teramoto, Yoshimi Amano, Katsura Kojima, Masatoshi Iga, Kensaku Sakamoto","doi":"10.1021/acs.biomac.4c01377","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01377","url":null,"abstract":"<p><p>Silk fiber, produced by the silkworm <i>Bombyx mori</i>, is a protein fiber with an excellent mechanical strength and broad biocompatibility. Multiple approaches, including genetic and chemical methods, must be combined to tailor silk fiber properties for wide applications, such as textiles and biomaterials. Genetic code expansion (GCE) is an alternative method to alter proteins' chemical and physical properties by incorporating synthetic amino acids into their primary structures. Here, we report an efficient system for selecting variants of <i>B. mori</i> tyrosyl-tRNA synthetase (BmTyrRS) used for GCE in silkworms. Four BmTyrRS variants with expanded substrate recognition toward halogenated tyrosine (Tyr) derivatives were selected, and transgenic silkworms expressing these variants were generated. The silkworms incorporated halogenated Tyr derivatives into silk fibroin to produce halogenated silk fiber with improved thermal stability. These results demonstrate the power of GCE to create protein materials with improved physical properties.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996207","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":"Multifunctions of Sustainable Chondroitin Sulfates with Predominant Subtypes and Low Molecular Weights on Neurite Outgrowth.","authors":"Shuqin Xu, Meiling Qiu, Liyuan Liang, Yue Chen, Yajia Wang, Jing Wu, Jinghua Chen","doi":"10.1021/acs.biomac.4c01713","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01713","url":null,"abstract":"<p><p>Three chondroitin sulfate (CS) analogues with predominant subtypes (A, C, and E) were prepared from engineered <i>Escherichia coli</i> K4 combined with regioselective sulfation. CS with the designed sulfates as the main components was characterized by nuclear magnetic resonance spectroscopy, elementary analysis, and disaccharide analysis. CS prepared from the native or degraded capsular polysaccharide had molecular weights of 1.55 × 10<sup>4</sup>-1.90 × 10<sup>4</sup> and 5.6 × 10<sup>3</sup>-7.4 × 10<sup>3</sup>, respectively. We found that CS with dual sulfates promoted the outgrowth and survival of hippocampal neurons, whereas CS with monosulfate had an inhibitory effect. CS interacted with the nerve growth factor (NGF) and tyrosine kinase (TrkA), which activated the extracellular signal-regulated kinase (ERK) signaling pathway to modulate the outgrowth of hippocampal neurons. This work clarified the multiple effects of CS on neurite outgrowth based on nonanimal-sourced glycosaminoglycans, which would benefit efforts in discovering their novel functions and therapeutic applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996149","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}
BiomacromoleculesPub Date : 2025-01-19DOI: 10.1021/acs.biomac.4c01729
Xin Cao, Jinghua Li, Weijie Zhai, Bowen Zhou, Hao Lin, Yi Wang
{"title":"Inhibiting Friction-Induced Exogenous Adhesion via Robust Lubricative Core-Shell Nanofibers for High-Quality Tendon Repair.","authors":"Xin Cao, Jinghua Li, Weijie Zhai, Bowen Zhou, Hao Lin, Yi Wang","doi":"10.1021/acs.biomac.4c01729","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01729","url":null,"abstract":"<p><p>Friction is the trigger cause for excessive exogenous adhesion, leading to the poor self-repair of the tendon. To address this problem, we developed electrospun dual-functional nanofibers with surface robust superlubricated performance and bioactive agent delivery to regulate healing balance by reducing exogenous adhesion and promoting endogenous healing. Coaxial electrospinning and our previous developed in situ robust nanocoating growth techniques were employed to create the lubricative/repairable core-shell structured nanofibrous membrane (L/R-NM). The L/R-NM shell featured a robust coating of the zwitterionic PMPC polymer for strong hydration lubrication to resist exogenous healing. The core could achieve sustained platelet-rich plasma release to promote endogenous healing. Friction tests and cell experiments confirmed L/R-NM's prominent lubricating properties and antiadhesive performance in vitro. Rat tendon injury model evaluation indicated that L/R-NM effectively promotes high-quality tendon repair by inhibiting friction-induced exogenous adhesion and promoting endogenous healing. Therefore, we believe that L/R-NM will open a unique novel horizon for tendon repair.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996213","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}
BiomacromoleculesPub Date : 2025-01-16DOI: 10.1021/acs.biomac.4c00999
Xifeng Liu, Areonna C Schreiber, Maria D Astudillo Potes, Babak Dashtdar, Abdelrahman M Hamouda, Asghar Rezaei, Benjamin D Elder, Lichun Lu
{"title":"Bone Enzyme-Responsive Biodegradable Poly(propylene fumarate) and Polycaprolactone Polyphosphoester Dendrimer Cross-Linked via Click Chemistry for Bone Tissue Engineering.","authors":"Xifeng Liu, Areonna C Schreiber, Maria D Astudillo Potes, Babak Dashtdar, Abdelrahman M Hamouda, Asghar Rezaei, Benjamin D Elder, Lichun Lu","doi":"10.1021/acs.biomac.4c00999","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c00999","url":null,"abstract":"<p><p>Traditional polymer systems often rely on toxic initiators or catalysts for cross-linking, posing significant safety risks. For bone tissue engineering, another issue is that the scaffolds often take a longer time to degrade, inconsistent with bone formation pace. Here, we developed an enzyme-responsive biodegradable poly(propylene fumarate) (PPF) and polycaprolactone (PCL) polyphosphoester (PPE) dendrimer cross-linked utilizing click chemistry (EnzDeg-click-PFCLPE scaffold) for enhanced biocompatibility and degradation. The strain-promoted alkyne-azide cycloaddition (SPAAC) offers high efficiency and biocompatibility without harmful agents. The polyphosphoesters render polymer cleavage responsive to alkaline phosphatase (ALP) enzyme in bone formation, ensuring facilitated scaffold biodegradation. The <i>in vitro</i> testing confirmed biocompatibility, enzyme-responsive degradation, and capability to support stem cell differentiation. Further <i>in vivo</i> implantation in rat demonstrated bone regeneration and scaffold integration. In summary, this polymer system combining click chemistry with ALP-responsive biodegradation ensures initial bone support and facilitates scaffold degradation synchronized with the natural bone healing process.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996203","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}
BiomacromoleculesPub Date : 2025-01-15DOI: 10.1021/acs.biomac.4c01571
Suzhen Wang, Zhezhe Li, Lili Zhao, Yuerong Lin, Hailong Che
{"title":"Polycarbonate-Based Polymersome Photosensitizers with Cell-Penetrating Properties for Improved Killing of Cancer Cells.","authors":"Suzhen Wang, Zhezhe Li, Lili Zhao, Yuerong Lin, Hailong Che","doi":"10.1021/acs.biomac.4c01571","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01571","url":null,"abstract":"<p><p>Polymer-based photosensitizers have found various applications in photodynamic therapy (PDT). However, the absence of targeting ability commonly results in a substantial reduction in photosensitizer accumulation at the tumor site, significantly limiting the therapeutic efficacy of the system. In addition, the development of biodegradable polymeric photosensitizers is of critical importance for biological applications. In this work, we present the development of guanidine-functionalized biodegradable photosensitizers based on poly(trimethylene carbonate) (PTMC) block copolymers, which can self-assemble into polymersomes. The presence of guanidine groups on the surface of polymersomes can significantly enhance the cellular uptake efficiency of photosensitizers, thereby improving the intracellular production of reactive oxygen species (ROS). The in vitro study demonstrates that the guanidinylated polymersome photosensitizers can promote the killing of cancer cells compared to unfunctionalized polymersomes in the presence of light irradiation. The guanidine-functionalized PTMC-based polymersome photosensitizers, with the integration of cell-targeting ability and biodegradability, are anticipated to provide a novel strategy for developing advanced biomedical polymer systems for PDT.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142982322","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}
BiomacromoleculesPub Date : 2025-01-15DOI: 10.1021/acs.biomac.4c01281
Larissa Paza, Wendhy C Vicente, Marília Miotto, Marcel Afonso Provenzi, Daniane Aparecida Netzel, Larissa N Carli, Patrícia B Brondani
{"title":"Surface Treatment of Polyamide 6 through Enzymatic Hydrolysis and Covalent Incorporation of Chitosan Nanoparticles.","authors":"Larissa Paza, Wendhy C Vicente, Marília Miotto, Marcel Afonso Provenzi, Daniane Aparecida Netzel, Larissa N Carli, Patrícia B Brondani","doi":"10.1021/acs.biomac.4c01281","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01281","url":null,"abstract":"<p><p>Polyamide (PA) has notable physical and chemical properties and is one of the most versatile synthetic materials in the industrial sector. However, its hydrophobicity creates significant challenges in its beneficiation and modification. Modifications of PA with chitosan nanoparticles (CNPs) can improve its undesired properties but are rarely found in the literature due to the weak interaction between the chemical groups of both structures. Surface hydrolysis mediated by enzymes can mildly improve the PA properties and create reactive sites. These sites can react with CNPs to confer enhanced properties to the fabrics, such as antimicrobial activity and flame retardancy. This study investigated the action of 14 hydrolases in the surface hydrolysis of 100% polyamide 6 (PA 6) fabric. Such an extensive study applying several enzymes for this process is uncommon. Under the optimum conditions, the hydrolyzed fabric was covalently bonded to the CNPs, generating material with reduced bacterial proliferation and flame retardancy properties. The uncommon covalent bond attachment achieved high material durability, even after five washing cycles.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996230","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}