BiomacromoleculesPub Date : 2025-04-21DOI: 10.1021/acs.biomac.5c0026310.1021/acs.biomac.5c00263
William R. Lowery, Allison C. Portaro, G. Kane Jennings and David E. Cliffel*,
{"title":"Photosystem I Photopolymerizes Pyrrole into Spherical Nanocomposites","authors":"William R. Lowery, Allison C. Portaro, G. Kane Jennings and David E. Cliffel*, ","doi":"10.1021/acs.biomac.5c0026310.1021/acs.biomac.5c00263","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00263https://doi.org/10.1021/acs.biomac.5c00263","url":null,"abstract":"<p >Conductive polymers have been shown to be an effective scaffold for proteins when designing bioelectrochemical systems, particularly for the Photosystem I protein. Utilization of synthetic polymer chemistry has allowed a great deal of tunability within the protein/polymer interface to improve electron transfer from the proteins, ultimately progressing toward direct electron transfer from the active sites. Seeking to address this issue, a new heterogeneous approach is presented to synthesize Photosystem I/polypyrrole (PSI/PPy) composites. The oxidative potential of PSI’s P<sub>700</sub> reaction site was leveraged to polymerize pyrrole into a molecular wire, providing a more efficient means of electron transfer to the protein. Over the course of several hours of photopolymerization of Py in a PSI film, PPy not only wired PSI but began incasing the protein within conductive polymer nanoparticles. These resulting composite nanoparticles were extensively characterized by electron microscopy and electrochemical techniques to showcase their synergistic properties.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"3180–3185 3180–3185"},"PeriodicalIF":5.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.biomac.5c00263","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933883","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}
BiomacromoleculesPub Date : 2025-04-21DOI: 10.1021/acs.biomac.4c0162310.1021/acs.biomac.4c01623
Jeongae Kim, Yanming Zhang, Shweta Burgula, R. Helen Zha* and Yunfeng Shi*,
{"title":"Molecular Dynamics Simulation of Self-Assembly and Tensile Deformation of Silk-Mimetic Polymers","authors":"Jeongae Kim, Yanming Zhang, Shweta Burgula, R. Helen Zha* and Yunfeng Shi*, ","doi":"10.1021/acs.biomac.4c0162310.1021/acs.biomac.4c01623","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01623https://doi.org/10.1021/acs.biomac.4c01623","url":null,"abstract":"<p >Silk is a natural biopolymer with outstanding mechanical properties due to its nanocomposite microstructure of crystalline β-sheets in an amorphous matrix. However, there remains a lack of understanding of the relationship between amino acid sequence, supramolecular structure formation, and mechanical properties. In this work, we developed a reactive coarse-grained molecular dynamics model to simulate the self-assembly, tensile deformation, and fracture of a segmented copolymer based on the repetitive core domain of spider dragline spidroins. We find that the β-sheet nanocrystal content is determined by the length ratio of β-sheet to non-β-sheet segments. We reveal that the chain length affects the chain-to-chain network connectivity between the nanocrystals. High nanocrystal content and high connectivity improve the strength and stiffness at the cost of extensibility. Toughness does not continue to increase past a threshold β-sheet-to-non-sheet segment ratio. Our findings provide important insights to guide the rational molecular design of silk-mimetic materials.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"2852–2867 2852–2867"},"PeriodicalIF":5.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143934040","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 : 2025-04-21DOI: 10.1021/acs.biomac.4c0111010.1021/acs.biomac.4c01110
Sabrina Roussel, Lucia Carrera Fragoso, Philippe Grenier, Quentin Bruxelles, Valérie Chénard, Sébastien Marcoux, Karine Greffard, Sébastien Fortin, Luc Vallières and Nicolas Bertrand*,
{"title":"Glycerol-Based Polymer to Improve the Cellular Uptake of Liposomes","authors":"Sabrina Roussel, Lucia Carrera Fragoso, Philippe Grenier, Quentin Bruxelles, Valérie Chénard, Sébastien Marcoux, Karine Greffard, Sébastien Fortin, Luc Vallières and Nicolas Bertrand*, ","doi":"10.1021/acs.biomac.4c0111010.1021/acs.biomac.4c01110","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01110https://doi.org/10.1021/acs.biomac.4c01110","url":null,"abstract":"<p >Nanomedicines modify the pharmacology of pharmaceutical ingredients, but most require cell internalization to deliver their payloads. Hence, modifying the surface properties of nanomedicines can improve their interactions with cells and modulate their pharmacology. Herein, we devised a polymer that increases how nanomedicines are internalized by cells. The alkylated poly(monoglycerol acrylate) (PMGA) polymer was synthesized by reversible addition–fragmentation chain-transfer (RAFT) polymerization with a terminal double 18-carbon moiety that allows its anchoring on the surface of liposomes. PMGA-decorated liposomes are internalized more efficiently in immune cells, compared to formulations without the polymer. Using inhibitors of internalization pathways, we established that PMGA promotes cell entry by the fast endophilin-mediated endocytosis (FEME). In comparison, noncoated control liposomes were mostly internalized by clathrin-mediated endocytosis. This work highlights the potential of PMGA to increase the internalization of nanomedicines by immune cells, and target a novel internalization pathway.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"2811–2824 2811–2824"},"PeriodicalIF":5.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933890","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 : 2025-04-21DOI: 10.1021/acs.biomac.4c0181410.1021/acs.biomac.4c01814
Shenglong Liao, Shuying Zhong, Can Sun, Zhiyong Liu, Daxiang Gui*, Puyou Jia and Ying Lin*,
{"title":"Biomass-Based Functional Composite Resins with Recyclable and Shape Memory Properties","authors":"Shenglong Liao, Shuying Zhong, Can Sun, Zhiyong Liu, Daxiang Gui*, Puyou Jia and Ying Lin*, ","doi":"10.1021/acs.biomac.4c0181410.1021/acs.biomac.4c01814","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01814https://doi.org/10.1021/acs.biomac.4c01814","url":null,"abstract":"<p >A key challenge in developing advanced functional thermosets lies in designing molecular architectures capable of integrating different specific performances into one material to meet diverse application demands. Here, a chitosan-derived trifunctional compound containing maleimide groups was used to directly cross-link tung oil-based polymer for fabricating multifunctional composite bioresins with reversible Diels–Alder bonds. The reversible cross-linking networks within resins were featured with stress relaxation, thermal reprocessability, and recyclability. The retro D–A reaction at relatively high temperatures provided the dynamic characteristics of the resins while ensuring their dimensional stability. Moreover, chitosan enhanced the mechanical properties of the resins while forming supramolecular hydrogen bonds via its abundant amino/hydroxyl groups, realizing shape memory of the resins. Furthermore, the synergistic interaction between chitosan functional groups and hydrogen bonding also imparted proton conductivity to the resins. This work provided a molecular design paradigm that harmonizes multifunctional integration in fully biomass resins, aiming for high-value applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"2922–2933 2922–2933"},"PeriodicalIF":5.5,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143934063","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 : 2025-04-18DOI: 10.1021/acs.biomac.5c0012110.1021/acs.biomac.5c00121
Yuta Komano, Miho Suzuki, Takahiko Matsushita, Tetsuo Koyama, Yoshihiro Ishimaru, Ken Hatano and Koji Matsuoka*,
{"title":"Synthesis of Water-Soluble Glycopolymers Bearing Porphyrin by Means of Glycopolymer Assembly and Physical Properties of Glycopolymers Including Ability for Singlet Oxygen Production","authors":"Yuta Komano, Miho Suzuki, Takahiko Matsushita, Tetsuo Koyama, Yoshihiro Ishimaru, Ken Hatano and Koji Matsuoka*, ","doi":"10.1021/acs.biomac.5c0012110.1021/acs.biomac.5c00121","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00121https://doi.org/10.1021/acs.biomac.5c00121","url":null,"abstract":"<p >Although photodynamic therapy (PDT) is expected to offer advantages in terms of selectivity, increased efficacy, and reduced side effects, the low solubilities of photosensitizers in aqueous media are significant issues. In this study, porphyrin-based monomers were synthesized by acryloylation of known tetraphenylporphyrin [5-(4-aminophenyl)-10,15,20-(triphenyl)porphyrin] (TPP). Simple radical polymerization of the porphyrin monomer and known glycosyl monomers in the presence of acrylamide to avoid steric hindrance yielded the corresponding polymeric photosensitizers, water-soluble glycopolymers with porphyrin moieties. The introduction of a porphyrin core gave polymer fluorescence and reactive oxygen species generation properties, and the addition of <span>d</span>-lactose and <i>N</i>-acetyl-<span>d</span>-glucosamine, respectively, remarkably improved solubility in water. The glycopolymers had high optical absorption, emission, and excitation in the visible light range and a singlet oxygen (SO) generation characteristic of porphyrins in aqueous solution, suggesting incorporation of the TPP into the linear polymer. The glycopolymers are promising not only for PDT but also as anticancer agents.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"3021–3031 3021–3031"},"PeriodicalIF":5.5,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933876","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 : 2025-04-18DOI: 10.1021/acs.biomac.4c0177010.1021/acs.biomac.4c01770
Nuri Han, Seung Hyeon Weon, Jiwoo Han, Jeong Eun Cha and Sang Hyun Lee*,
{"title":"Two-Step Carboxymethylation of Cellulose from Halocynthia roretzi Using Ionic Liquid","authors":"Nuri Han, Seung Hyeon Weon, Jiwoo Han, Jeong Eun Cha and Sang Hyun Lee*, ","doi":"10.1021/acs.biomac.4c0177010.1021/acs.biomac.4c01770","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01770https://doi.org/10.1021/acs.biomac.4c01770","url":null,"abstract":"<p >Water-soluble carboxymethylated tunicate cellulose (CMTC) was produced using cellulose from <i>Halocynthia roretzi</i>, known for its uniquely high molecular weight and crystallinity. Among various known methods for cellulose carboxymethylation tested in this study, only the homogeneous method using LiClO<sub>4</sub> yielded water-soluble CMTC. However, industrial application of this method is hindered by LiClO<sub>4</sub>’s toxicity, explosiveness, and high cost. Therefore, we developed a two-step carboxymethylation process utilizing [Emim][Ac], effectively converting crystalline cellulose into an amorphous form and reducing both the degree of polymerization (DP) and polydispersity index (PDI). CMTC prepared by this two-step method exhibited a high degree of substitution (DS = 1.94), excellent water solubility (>100 mg/g), and superior thermal stability. Compared to the LiClO<sub>4</sub>-based CMTC, our product contained only 5% unmodified glucose and demonstrated significantly enhanced thickening properties, with 8-fold greater viscosity in 5% aqueous solutions. Structural properties were confirmed via HPLC, <sup>1</sup>H NMR, XRD, FT-IR, and TGA analyses.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"2909–2921 2909–2921"},"PeriodicalIF":5.5,"publicationDate":"2025-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933975","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 : 2025-04-15DOI: 10.1021/acs.biomac.5c0004110.1021/acs.biomac.5c00041
Yue Zhang*, Liyuan Tian, Jimin Zhang* and Meihui Zhong,
{"title":"pH-Responsive Hyperbranched Polymer Scaffolds for Polymer and Peptide Conjugation through Molecular Recognition: Synthesis and Self-Assembly","authors":"Yue Zhang*, Liyuan Tian, Jimin Zhang* and Meihui Zhong, ","doi":"10.1021/acs.biomac.5c0004110.1021/acs.biomac.5c00041","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00041https://doi.org/10.1021/acs.biomac.5c00041","url":null,"abstract":"<p >Hyperbranched polymers can be suitable polymeric scaffolds for the modification of functional groups and fabrication of applicable nanoparticles considering their good solubility, numerous modification sites, and unique self-assembly behaviors. To facilitate the modification process and obtain various functional hyperbranched polymers, a new inimer 2-((adamantan-1-yl)amino)-1-(4-((2-bromo-2-methylpropanoyl)oxy)phenyl)-2-oxoethyl methacrylate (ABMA) with an adamantyl group was prepared in this research through the Passerini reaction. ABMA was copolymerized with 2-(diisopropylamino)ethyl methacrylate (DPA), affording the pH-responsive hyperbranched polymer hPDPA. Model molecules poly(ethylene glycol) (PEG) and the peptide RRRRRRRRC (PArg) with a cell-penetrating octaarginine fragment were conjugated with β-cyclodextrin (β-CD) to modify the hPDPA through molecular recognition. The inclusion complex hPDPA/PEG self-assembled into micelles in phosphate buffer at pH 7.4, while hPDPA/PEG/PArg self-assembled into vesicles because of the repulsion of the positively charged PArg. It was demonstrated that the DOX-loaded hPDPA/PEG/PArg could be internalized by Hela cells with high efficiency and could induce apoptosis of Hela cells.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 5","pages":"2960–2970 2960–2970"},"PeriodicalIF":5.5,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143933713","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":"Efficient and Size-Controllable Method and Mechanism for Preparing Cellulose Nanospheres.","authors":"Weixiong Zhao, Yuhang Zhou, Guichao Zhang, Yue Li, Zixuan Liao, Gaorong Lai, Yongze Jiang, Shanshan Jia, Zhiping Su, Jinqiu Qi, Shaobo Zhang","doi":"10.1021/acs.biomac.5c00103","DOIUrl":"10.1021/acs.biomac.5c00103","url":null,"abstract":"<p><p>Cellulose nanosphere (CNS), reported as a novel cellulose material, has encountered significant challenges in achieving efficient and size-controllable preparation, which has considerably constrained its development. In this study, we have developed an innovative and size-controllable method that synthesizes CNS within only 7 min. A detailed investigation into the morphology, chemical structure, and crystalline structure of CNS was conducted, leading to the proposal of a formation mechanism for CNS. The mechanism is described as follows: cellulose dissolution, hydrophobic triethoxymethylsilane hydrolysis, condensation nucleation in supersaturation, growth through hydrogen-bonding interactions and condensation, and CNS forms in the critical supersaturation. The supersaturation level was controlled by adjusting the stirring speed, thus realizing the size-controllable preparation of CNS and verifying the proposed mechanism. The results demonstrate that the particle size of CNS increases from 63.4 ± 14.0 nm to 108.6 ± 27.1 nm as the stirring speed decreases from 1000 r/min to 300 r/min.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"2665-2674"},"PeriodicalIF":5.5,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555308","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 : 2025-04-14Epub Date: 2025-03-04DOI: 10.1021/acs.biomac.4c01338
Jiahui Yang, Zhiyuan Wang, Zepeng Li, Haoyang Xu, Bin Xue, Yi Cao, Zhaojie Li, Yiran Li
{"title":"Halogen-Atom-Substituted DOPA with Enhanced Wet Adhesion and Antioxidization Ability.","authors":"Jiahui Yang, Zhiyuan Wang, Zepeng Li, Haoyang Xu, Bin Xue, Yi Cao, Zhaojie Li, Yiran Li","doi":"10.1021/acs.biomac.4c01338","DOIUrl":"10.1021/acs.biomac.4c01338","url":null,"abstract":"<p><p>3,4-Dihydroxyphenylalanine (DOPA) has inspired the development of artificial adhesives, but efforts to enhance its adhesion strength and durability continue to evolve. However, it is tough work to improve DOPA wet adhesion by chemically decorating DOPA itself, despite the potential benefit of a concise and high-quality adhesion unit. Here, we synthesized a series of DOPA substituents by introducing different electron-withdrawing groups at the ortho position of the phenyl ring. This modification allowed us to effectively control the adhesion and antioxidation properties of DOPA. Combining atomic force microscopy (AFM)-based single-molecule force spectroscopy (SFMS) and cyclic voltammetry, we comprehensively investigated DOPA's antioxidation and adhesion capabilities. We found that adding a chlorine or bromine atom to the catechol ring significantly increases the DOPA wet adhesion strength. Additionally, halogen-substituted DOPA exhibited greater stability than dopamine in liquid solutions. Notably, chlorine-substituted DOPA maintained a strong adhesion ability even in salt water, offering potential benefits for bioadhesive applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"2146-2156"},"PeriodicalIF":5.5,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555309","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":"Regulating the Characteristic Networks of Biodegradable Poly(l-malic acid-ε-caprolactone) Shape-Memory Materials: From Plastics to Elastomers.","authors":"Jing Song, Jiali Jiao, Chenguang Jiang, Yaxin Qiu, Defeng Wu","doi":"10.1021/acs.biomac.5c00163","DOIUrl":"10.1021/acs.biomac.5c00163","url":null,"abstract":"<p><p>Developing new biodegradable polyesters with well-defined structures is of interest. We reported an attractive two-component aliphatic polyester-based thermoset, which was prepared via the esterification of biomass-derived l-malic acid oligomers and three-arm poly(ε-caprolactone) (3a-PCL) triols. The chemical network formed via the ester bonding and physical network caused by the crystallization of a 3a-PCL arm chain coexist in the thermoset, and the competition of the two characteristic networks leads to a negative correlation between the degree of covalent cross-linking and the degree of crystallization; thereby, the mechanical state of the thermosets can be easily tuned: from the plastic to elastomer state. Moreover, the crystallization temperature and melting point of the thermosets range in 30 °C ∼ 50 °C and -7 °C ∼ 18 °C, respectively, which are favorable for shape morphing as the thermosets are used as shape-memory materials. This work also provides valuable information about tailoring the mechanical and thermal properties of star-shaped polyester-based thermosets.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"2720-2732"},"PeriodicalIF":5.5,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143622854","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}