BiomacromoleculesPub Date : 2025-01-13Epub Date: 2024-12-23DOI: 10.1021/acs.biomac.4c01148
Vianna F Jafari, Shirin Nour, Ross A L Wylie, Daniel E Heath, Greg G Qiao
{"title":"Robot-Assisted Synthesis of Structure-Controlled Star-Cluster Hydrogels with Targeted Mechanophysical Properties for Biomedical Applications.","authors":"Vianna F Jafari, Shirin Nour, Ross A L Wylie, Daniel E Heath, Greg G Qiao","doi":"10.1021/acs.biomac.4c01148","DOIUrl":"10.1021/acs.biomac.4c01148","url":null,"abstract":"<p><p>Advancements in polymer chemistry have enabled the design of macromolecular structures with tailored properties for diverse applications. Reversible addition-fragmentation chain-transfer (RAFT) polymerization is a controlled technique for precise polymer design. Automation tools further enhance polymer synthesis by enabling the rapid, reproducible preparation of polymer libraries. This study utilizes an automated platform and a biologically friendly bio-Fenton RAFT synthesis method to create hydrogels with embedded star polymers derived from complex block copolymers with controlled block lengths and sequences. Automation improves the efficiency compared to manual methods, while the choice of prepolymer and polymerization techniques ensures biocompatibility. Hydrogels formed by cross-linking linear block copolymers exhibit tunable physical, chemical, and mechanical properties. By systematically altering the prepolymer block sequences, promising hydrogel candidates for enhanced cell biocompatibility and proliferation are identified. These synthetic hydrogels mimic cellular microenvironments and offer a robust platform for biomedical applications, paving the way for an efficient hydrogel design and synthesis.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"311-322"},"PeriodicalIF":5.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142880642","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 : 2025-01-13Epub Date: 2024-12-29DOI: 10.1021/acs.biomac.4c01116
Mina Ghorbani, Elisabeth Prince
{"title":"Radical Ring-Opening Polymerization: Unlocking the Potential of Vinyl Polymers for Drug Delivery, Tissue Engineering, and More.","authors":"Mina Ghorbani, Elisabeth Prince","doi":"10.1021/acs.biomac.4c01116","DOIUrl":"10.1021/acs.biomac.4c01116","url":null,"abstract":"<p><p>Synthetic vinyl polymers have long been recognized for their potential to be utilized in drug delivery, tissue engineering, and other biomedical applications. The synthetic control that chemists have over their structure and properties is unmatched, allowing vinyl polymer-based materials to be precisely engineered for a range of therapeutic applications. Yet, their lack of biodegradability compromises the biocompatibility of vinyl polymers and has held back their translation into clinically used treatments for disease thus far. In recent years, radical ring-opening polymerization (rROP) has emerged as a promising strategy to render synthetic vinyl polymers biodegradable and bioresorbable. While rROP has long been touted as a strategy for preparing biodegradable vinyl polymers for biomedical applications, the translation of rROP into clinically approved treatments for disease has not yet been realized. This review highlights the opportunities for leveraging rROP to render vinyl polymers biodegradable and unlock their potential for use in biomedical applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"118-139"},"PeriodicalIF":5.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902460","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 : 2025-01-13Epub Date: 2024-12-17DOI: 10.1021/acs.biomac.4c01246
Han Zhang, Shen Zhang, Minting Xie, Fachuang Lu, Fengxia Yue
{"title":"UV Resistance Properties of Lignin Influenced by Its Oxygen-Containing Groups Linked to Aromatic Rings.","authors":"Han Zhang, Shen Zhang, Minting Xie, Fachuang Lu, Fengxia Yue","doi":"10.1021/acs.biomac.4c01246","DOIUrl":"10.1021/acs.biomac.4c01246","url":null,"abstract":"<p><p>The influence of lignin's primary oxygen-containing functional groups, phenolic OH (Ph-OH) and methoxyl (OMe) groups, especially the Ph-OH/OMe ratio, on its UV absorptivity and long-lasting UV blocking remains unclear. In this study, organosolv lignins (OLs) with varying Ph-OH and OMe contents were prepared to evaluate their UV absorptivity and photostability by EPR (electron paramagnetic resonance). As the Ph-OH contents increased from 0.32 to 6.09 mmol/g, lignin with a higher Ph-OH content displayed better absorptivity with a strong correlation (Pearson's <i>r</i> = 0.95). However, an excessive Ph-OH content (>5.5 mmol/g) reduced the spin content of lignin, negatively affecting its photostability. Taking Ph-OH and OMe groups as the cofactor, OLs with Ph-OH/OMe ratios between 0.44 and 0.64 showed more favorable UV-blocking performance both in the initial state and after UV irradiation. Moreover, lignin-based sunscreens exhibited increasing SPF value even after 8 h of UV exposure, confirming lignin's long-lasting UV-blocking property.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"428-436"},"PeriodicalIF":5.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845303","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 : 2025-01-13Epub Date: 2024-12-03DOI: 10.1021/acs.biomac.4c01004
Yu Hu, Zhi Luo, Yinyin Bao
{"title":"Trends in Photopolymerization 3D Printing for Advanced Drug Delivery Applications.","authors":"Yu Hu, Zhi Luo, Yinyin Bao","doi":"10.1021/acs.biomac.4c01004","DOIUrl":"10.1021/acs.biomac.4c01004","url":null,"abstract":"<p><p>Since its invention in the 1980s, photopolymerization-based 3D printing has attracted significant attention for its capability to fabricate complex microstructures with high precision, by leveraging light patterning to initiate polymerization and cross-linking in liquid resin materials. Such precision makes it particularly suitable for biomedical applications, in particular, advanced and customized drug delivery systems. This review summarizes the latest advancements in photopolymerization 3D printing technology and the development of biocompatible and/or biodegradable materials that have been used or shown potential in the field of drug delivery. The drug loading methods and release characteristics of the 3D printing drug delivery systems are summarized. Importantly, recent trends in the drug delivery applications based on photopolymerization 3D printing, including oral formulations, microneedles, implantable devices, microrobots and recently emerging systems, are analyzed. In the end, the challenges and opportunities in photopolymerization 3D printing for customized drug delivery are discussed.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"85-117"},"PeriodicalIF":5.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11733939/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142764619","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 : 2025-01-13Epub Date: 2024-12-26DOI: 10.1021/acs.biomac.4c01219
Gestél C Kuyler, Elaine Barnard, Pooja Sridhar, Rebecca J Murray, Naomi L Pollock, Mark Wheatley, Timothy R Dafforn, Bert Klumperman
{"title":"Tunable Terpolymer Series for the Systematic Investigation of Membrane Proteins.","authors":"Gestél C Kuyler, Elaine Barnard, Pooja Sridhar, Rebecca J Murray, Naomi L Pollock, Mark Wheatley, Timothy R Dafforn, Bert Klumperman","doi":"10.1021/acs.biomac.4c01219","DOIUrl":"10.1021/acs.biomac.4c01219","url":null,"abstract":"<p><p>Membrane proteins (MPs) are critical to cellular processes and serve as essential therapeutic targets. However, their isolation and characterization are often impeded by traditional detergent-based methods, which can compromise their native states, and retention of their native lipid environment. Amphiphilic polymers have emerged as effective alternatives, enabling the formation of nanoscale discs that preserve MPs' structural and functional integrity. We introduce a novel series of poly(styrene-<i>co</i>-maleic acid-<i>co</i>-(<i>N</i>-benzyl)maleimide) (BzAM) terpolymers with tunable amphiphilicity, synthesized through controlled polymerization. Designed to mimic and improve upon industry-standard poly(styrene-<i>co</i>-maleic acid), these well-defined terpolymers offer enhanced control over molecular weight and distribution, allowing for systematic evaluation of polymer properties and their effect on membrane solubilization. The BzAM series effectively solubilized membranes and demonstrated a direct correlation between polymer hydrophobicity and solubilization efficiency of bacterial ABC transporter, Sav1866. This research highlights the importance of rational polymer design in MP research and provides a foundation for future developments.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"415-427"},"PeriodicalIF":5.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11733950/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142890646","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 : 2025-01-13Epub Date: 2025-01-02DOI: 10.1021/acs.biomac.4c01305
Donn Adam D Gito, Alireza Akbarinejad, Alexander Dixon, Thomas Loho, Michel Nieuwoudt, Qun Chen, Laura J Domigan, Jenny Malmström
{"title":"Self-Assembled Piezoelectric Films from Aligned Lysozyme Protein Fibrils.","authors":"Donn Adam D Gito, Alireza Akbarinejad, Alexander Dixon, Thomas Loho, Michel Nieuwoudt, Qun Chen, Laura J Domigan, Jenny Malmström","doi":"10.1021/acs.biomac.4c01305","DOIUrl":"10.1021/acs.biomac.4c01305","url":null,"abstract":"<p><p>Piezoelectric organic polymers are promising alternatives to their inorganic counterparts due to their mechanical flexibility, making them suitable for flexible and wearable piezoelectric devices. Biological polymers such as proteins have been reported to possess piezoelectricity, while offering additional benefits, such as biocompatibility and biodegradability. However, questions remain regarding protein piezoelectricity, such as the impact of the protein secondary structure. This study examines the piezoelectric properties of lysozyme amyloid fibril films, plasticized by polyethylene glycol (PEG). The films demonstrated a measurable d<sub>33</sub> coefficient of 1.4 ± 0.1 pCN<sup>-1</sup>, for the optimized PEG concentration, confirming piezoelectricity. The PEG was found to hydrogen-bond with the fibrils, likely impacting the piezoelectric response of the film. Polarization imaging revealed long-range alignment of the amyloid fibrils in a circumferential arrangement. These results demonstrate the potential of using amyloid fibrils, which can be formed from various proteins, to create bulk self-assembled piezoelectric materials.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"514-527"},"PeriodicalIF":5.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11733944/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142918651","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 : 2025-01-13DOI: 10.1021/acs.biomac.4c01168
Carlo Kupfernagel, Mohammed Rahman, Rosalie Cresswell, Morwenna J Spear, Andrew Pitman, Steven P Brown, Graham A Ormondroyd
{"title":"Investigating Cell Wall Diffusion in Wood Modified with Phenol Urea Formaldehyde Resin in Different Length Scales.","authors":"Carlo Kupfernagel, Mohammed Rahman, Rosalie Cresswell, Morwenna J Spear, Andrew Pitman, Steven P Brown, Graham A Ormondroyd","doi":"10.1021/acs.biomac.4c01168","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01168","url":null,"abstract":"<p><p>Wood modification using low molecular weight thermosetting resins improves the biological durability and dimensional stability of wood while avoiding increasingly regulated biocides. During the modification process, resin monomers diffuse from the cell lumen to the cell wall, occupying micropore spaces before <i>in situ</i> curing at 150 °C. This study investigated the mechanism of cell wall diffusion at multiple scales, comparing two test groups where diffusion was either facilitated or restricted. Antiswelling efficiency tests demonstrated improved dimensional stability when diffusion was facilitated. Differential scanning calorimetry showed that bound water was excluded more effectively from the cell wall if cell wall diffusion was enabled. Solid-state NMR spectroscopy (<sup>1</sup>H MAS and <sup>13</sup>C MAS) with relaxation time analysis indicated that resin migrated to distinct locations within the cell wall, influenced by diffusion and drying conditions. These findings highlight how optimizing cell wall diffusion can significantly improve the performance of wood modification processes using thermosetting resins.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142976836","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 : 2025-01-13Epub Date: 2024-12-12DOI: 10.1021/acs.biomac.4c01407
Feng Huang, Jiajie Chen, Xuan Tang, Yujian Li, Haixin Bao, Xuan Mao, Shunqing Tang
{"title":"Preparation and Wound Repair of Injectable and Self-Healing Benzaldehyde-Modified Konjac Glucomannan Oligosaccharide/Polyglutamic Acid/ε-Polylysine Hydrogel.","authors":"Feng Huang, Jiajie Chen, Xuan Tang, Yujian Li, Haixin Bao, Xuan Mao, Shunqing Tang","doi":"10.1021/acs.biomac.4c01407","DOIUrl":"10.1021/acs.biomac.4c01407","url":null,"abstract":"<p><p>Oligosaccharides always have better water solubility, higher possibilities for modification, and unique biofunctions compared with polysaccharides, but they are rarely used as the matrix of a hydrogel. Here, we prepared a composite BKOS/HPGA/PL hydrogel (BKPP hydrogel) constructed by hydrazone/imine bonds between the aldehyde groups of benzaldehyde-modified konjac glucomannan oligosaccharide (BKOS) and the primary amino groups of both hydrazide-modified polyglutamic acid (HPGA) and ε-polylysine (ε-PL). The hydrogels had both injectable and self-healing properties. The gelation time reached 23 s when 2% of BKOS (DS = 21.7%), 10% HPGA (DS = 11.5%), and 10% ε-PL solutions were mixed in a volume ratio of 5:4.5:0.5. Besides high water-retention capability and good cytocompatibility, the hydrogel also maintained both the immunoactivities of BKOS and the antibacterial performances of ε-PL and HPGA, and thus exhibited good wound healing performance in the whole cortex wound repair process of rats, which might have potential for its biomedical application.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"609-622"},"PeriodicalIF":5.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816698","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 : 2025-01-13Epub Date: 2024-12-27DOI: 10.1021/acs.biomac.4c01303
Anastasia K Varanko, Sonal Deshpande, Xinghai Li, Ashutosh Chilkoti
{"title":"Binding Strength, Not Valency, Dictates Accumulation and Penetration of Affinity Targeted Macromolecules into Solid Tumors.","authors":"Anastasia K Varanko, Sonal Deshpande, Xinghai Li, Ashutosh Chilkoti","doi":"10.1021/acs.biomac.4c01303","DOIUrl":"10.1021/acs.biomac.4c01303","url":null,"abstract":"<p><p>The efficacy of tumor-targeted therapeutics, engineered to engage specific cellular receptors to promote accumulation and penetration, is strongly influenced by the carrier's affinity for its target and the valency of binding molecules incorporated into the carrier. Previous research has primarily focused on improving targeting by augmenting the number of binding proteins on the carrier, inadvertently raising avidity without isolating the individual effects of binding strength and valency. Herein, we precisely evaluate the impact of multivalency on tumor targeting with a recombinant approach to independently control valency, avidity, and size. Our findings reveal that constructs with equivalent binding strength exhibit comparable receptor engagement and tumor extravasation, regardless of valency. Moreover, excessive avidity adversely affected tumor accumulation and penetration, with the highest-avidity construct showing diminished exposure. These results indicate that overall binding strength, not valency, is the primary determinant of tumor targeting, providing valuable insights for designing effective macromolecular drug carriers.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"503-513"},"PeriodicalIF":5.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142890639","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 : 2025-01-13Epub Date: 2024-11-27DOI: 10.1021/acs.biomac.4c01556
Mohammad Shafee Alkanawati, Richard da Costa Marques, Volker Mailänder, Katharina Landfester, Héloïse Thérien-Aubin
{"title":"Correction to \"Polysaccharide-Based pH-Responsive Nanocapsules Prepared with Bio-orthogonal Chemistry and Their Use as Responsive Delivery Systems\".","authors":"Mohammad Shafee Alkanawati, Richard da Costa Marques, Volker Mailänder, Katharina Landfester, Héloïse Thérien-Aubin","doi":"10.1021/acs.biomac.4c01556","DOIUrl":"10.1021/acs.biomac.4c01556","url":null,"abstract":"","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":"751"},"PeriodicalIF":5.5,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11733928/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142737692","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}