BiomacromoleculesPub Date : 2025-07-18DOI: 10.1021/acs.biomac.5c00574
Tomáš Hrivnák, Dušan Račko, M Natália D S Cordeiro, Zuzana Benková
{"title":"Interactions of Protein with Grafted Poly(ethylene oxide) Layer in Two Setups: A Molecular Dynamics Simulation Study.","authors":"Tomáš Hrivnák, Dušan Račko, M Natália D S Cordeiro, Zuzana Benková","doi":"10.1021/acs.biomac.5c00574","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00574","url":null,"abstract":"<p><p>Understanding of interactions between proteins and grafted hydrophilic polymer layers is crucial in the search for antifouling materials. Experimental techniques often use an external force that pushes a protein against the polymer-coated surface, which differs from the situation in living systems. The comparison of both setups using atomistic molecular dynamics simulations is provided in this work. Poly(ethylene oxide) (PEO) chains grafted onto graphene at different grafting densities interact with a fragment of C1q protein. At the lowest grafting density, contradictory outcomes are achieved, attributed to the restricted space of C1q near the grafted PEO layer. The most favorable interactions between C1q and the PEO layer are obtained for the medium grafting density. The secondary structure of C1q undergoes changes during its interactions with the PEO layer, including destabilization of β-sheets and formation of 3<sub>10</sub>-helices. The orientation of C1q anchored to graphene also affects the interactions with the PEO layer.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144666642","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 : 2025-07-18DOI: 10.1021/acs.biomac.5c00184
Saül Llácer Navarro, Elliot Orzan, Ratchawit Janewithayapun, Paavo Penttilä, John Andersson, Anna Ström, Roland Kádár, Tiina Nypelö
{"title":"Tert-Butanol as a Structuring Agent for Cellulose Nanocrystal Fluids and Foams.","authors":"Saül Llácer Navarro, Elliot Orzan, Ratchawit Janewithayapun, Paavo Penttilä, John Andersson, Anna Ström, Roland Kádár, Tiina Nypelö","doi":"10.1021/acs.biomac.5c00184","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00184","url":null,"abstract":"<p><p>Nanocelluloses are uniquely valued for their high surface area and controllable assembly. This study elucidates the assembly of cellulose nanocrystals (CNCs) in tert-butanol (TBA) and water mixtures. We emphasize the influence of TBA on the structure of suspensions and freeze-dried foams. Although the length-scale of CNC organization is large relative to water-TBA structures, adding more than 30 wt % TBA shifted ordered CNC packing into an isotropic network. The change was attributed to the disruption of ionic interactions and adsorption of TBA to hydrophobic CNC interfaces; manifesting as a 5-fold increase in viscosity at 50 wt % TBA content. The freeze-dried foams' morphology was transformed due to TBA-modulated crystal growth during the freezing process. This led to the intriguing capability to control foams' mechanical strength and surface area, achieving up to 3 and 15-fold increases, respectively. The investigations highlight TBA's potential as a structuring agent in solvent-mediated design of nanomaterial systems.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144657852","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":"Lignin Changes during Prehydrolysis of Lignocellulosic Biomass for Cellulose Bioconversion: A Review.","authors":"Nianjie Feng, Xu Yang, Shuang Liang, Xiaotian Zhu, Qian Wu, Ran Bi, Orlando J Rojas","doi":"10.1021/acs.biomac.5c00612","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00612","url":null,"abstract":"<p><p>The bioconversion of a lignocellulosic biomass presents significant challenges due to its complex structure. Various pretreatments have been explored to enhance biomass accessibility for efficient fractionation. Prehydrolysis, known for its environmental friendliness and promising benefits, emerges as an effective strategy. This Review provides a concise account of lignin's chemical structure and its transformations during the prehydrolysis. It explores the mechanisms involved in biomass prehydrolysis, focusing on lignin's degradation, dissolution, and migration. We end with a perspective to deepen the understanding of lignin's role during prehydrolysis in efforts to advance lignocellulose bioconversion.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647972","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 : 2025-07-17DOI: 10.1021/acs.biomac.5c00518
Sara Lipari, Andrea Marfoglia, Giovanni Sorrentino, Sophie Cazalbou, Ludovic Pilloux, Pasquale Sacco, Ivan Donati
{"title":"Thermally Cured Gelatin-Methacryloyl Hydrogels Form Mechanically Modulating Platforms for Cell Studies.","authors":"Sara Lipari, Andrea Marfoglia, Giovanni Sorrentino, Sophie Cazalbou, Ludovic Pilloux, Pasquale Sacco, Ivan Donati","doi":"10.1021/acs.biomac.5c00518","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00518","url":null,"abstract":"<p><p>Gelatin methacryloyl (GelMA) is a polypeptide derived from the methacryloylation of gelatin and retains the thermoresponsive behavior of gelatin. When cooled, GelMA undergoes a sol-gel transition. By photo-cross-linking GelMA in a heated (\"Hot\") or cooled (\"Cold\") state, it results in a set of hydrogels with distinct properties. To date, the mechanical properties of these resulting hydrogels have not been fully elucidated. Here, we show that \"Cold\" hydrogels are viscoelastic, while \"Hot\" hydrogels are almost completely elastic. These features have remarkable implications for cell-substrate interactions <i>in vitro</i>: here, we show that fibroblasts, when cultured on these different substrates, adhere preferentially to Cold hydrogels. These results suggest that efficient cell adhesion requires specific mechanical properties of the substrate. This novel platform enables the precise control of different mechanical properties of GelMA by simply adjusting the cross-linking temperature, providing a flexible approach for the design of biologically inspired microenvironments <i>in vitro</i>.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647975","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 : 2025-07-17DOI: 10.1021/acs.biomac.5c00766
Ilaria Porello, Federico Stucchi, Rosachiara Guarini, Giulia Sbaruffati, Francesco Cellesi
{"title":"TCEP-Enabled Click Modification of Glycidyl-Bearing Polymers with Biorelevant Sulfhydryl Molecules: Toward Chemoselective Bioconjugation Strategies.","authors":"Ilaria Porello, Federico Stucchi, Rosachiara Guarini, Giulia Sbaruffati, Francesco Cellesi","doi":"10.1021/acs.biomac.5c00766","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00766","url":null,"abstract":"<p><p>Thiol-epoxy ring opening is a highly efficient and versatile click reaction for postpolymerization modification, ideal for the conjugation of sulfhydryl-containing biomolecules. This study investigated the reactivity of thiols, disulfides, and amines toward glycidyl-bearing polymers, aiming to optimize thiol conjugation using tris(2-carboxyethyl)phosphine (TCEP) as a disulfide-reducing agent. Epoxide groups were introduced via glycidyl methacrylate (GMA) polymerized by ATRP to yield PGMA homopolymers and poly(ε-caprolactone) (PCL)-based block copolymers. <sup>1</sup>H NMR confirmed quantitative thiol functionalization, while amines showed poor reactivity. l-cysteine conjugation further demonstrated the reaction's chemoselectivity. Thioglycerol conjugation yielded poly(2-hydroxy-3-(thioglycerol)propyl methacrylate) (PTGMA), a highly hydroxylated PEG alternative. Functionalization was extended to PCL-<i>b</i>-PGMA and PEGMA-based copolymers, forming amphiphilic nanoparticles via nanoprecipitation. Sequential modification with thioglycerol and the cRGD peptide yielded bioactive, size-controlled nanocarriers. Overall, a robust strategy has emerged for synthesizing multifunctional polymeric nanomaterials. Its compatibility with equimolar reactants under ambient conditions makes it particularly suited for the efficient incorporation of sensitive, high-value biomolecules into targeted drug delivery systems.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647974","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 : 2025-07-16DOI: 10.1021/acs.biomac.5c01107
Penelope E Jankoski, Abdul-Razak Masoud, Jenna Dennis, Sophia Trinh, Loria R DiMartino, Jessica Shrestha, Luis Marrero, Jeffery Hobden, Jeffrey Carter, Jonathan Schoen, Herbert Phelan, Alison A Smith, Tristan D Clemons
{"title":"Bioactive Supramolecular Polymers for Skin Regeneration Following Burn Injury.","authors":"Penelope E Jankoski, Abdul-Razak Masoud, Jenna Dennis, Sophia Trinh, Loria R DiMartino, Jessica Shrestha, Luis Marrero, Jeffery Hobden, Jeffrey Carter, Jonathan Schoen, Herbert Phelan, Alison A Smith, Tristan D Clemons","doi":"10.1021/acs.biomac.5c01107","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c01107","url":null,"abstract":"<p><p>Severe deep dermal burns present a significant challenge for the clinician, often resulting in complications including infection, scarring, and potentially multisystem organ failure. The current standard of care, which involves debridement and skin coverage, has improved survival rates but remains insufficient for optimal tissue regeneration and functional recovery. Additionally, there can be limited donor skin availability with severe burns, leading to the use of skin substitutes to be applied with varying degrees of success reported. Biomaterial scaffolds, designed to reduce the reliance on skin grafting, could promote improved healing and patient outcomes. Recent research has focused on promoting the proliferative phase of wound healing through the use of extracellular matrix (ECM) mimetic scaffolds; however, these constructs continue to exhibit critical limitations, including mechanical fragility, heightened infection susceptibility, limited morphological conformity to host tissue architecture, and the necessity for secondary surgical intervention for scaffold retrieval. This study presents a bioactive supramolecular polymer capable of rapid self-assembly into nanofibers, which act as a scaffold to promote tissue regeneration following burn injury. The scaffold is biocompatible, biodegradable, and capable of presenting a bioactive peptide designed to reduce acute inflammation and promote keratinocyte migration in the scaffold. The supramolecular polymers significantly accelerated early wound healing in a clinically relevant deep dermal murine burn injury model. This work provides a promising approach to the development of biomaterials that combine both therapeutic strategies, with scaffolding to promote skin regeneration following severe burn injury.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647971","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 : 2025-07-16DOI: 10.1021/acs.biomac.5c00767
Kamonthira Wichai, Xinxin Deng, Helen Gorges, Stanislav N Gorb, Florian Müller-Plathe
{"title":"Structural and Adhesive Properties of Cellulosic Mucilage: A Molecular-Level Investigation.","authors":"Kamonthira Wichai, Xinxin Deng, Helen Gorges, Stanislav N Gorb, Florian Müller-Plathe","doi":"10.1021/acs.biomac.5c00767","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00767","url":null,"abstract":"<p><p>Several plant seeds release a mucilaginous envelope upon hydration, rich in pectin and stabilized by cellulose fibers, generating adhesion. However, the mechanisms governing mucilage adhesion remain unclear. Using a multibody dissipative particle dynamics (MDPD) model, we investigated the roles of cellulose, pectin, and water in seed adhesion. The softer pectin polymers exhibit stronger adhesion than stiffer cellulose chains. Adhesion decreases with increasing polymer stiffness but plateaus beyond a threshold. The presence of water enhances cellulose adhesion. As water content decreases, the adhesive force initially increases due to more cellulose contact with the substrate. As the polymer aggregates, however, adhesion primarily depends on water since reduced cellulose mobility limits its contribution. As a result, the adhesion goes through a maximum and then decreases with lower water content. For pectin, adhesion consistently increases as water content decreases, driven by enhanced pectin-substrate contact.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144641235","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 : 2025-07-16DOI: 10.1021/acs.biomac.5c00374
Jeon Il Kang, Kyung Min Park
{"title":"Oxygen-Supplying Containers to Fabricate Immunomodulatory Hydrogels for Expediting Wound Healing via Acute Oxidative Stress.","authors":"Jeon Il Kang, Kyung Min Park","doi":"10.1021/acs.biomac.5c00374","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00374","url":null,"abstract":"<p><p>Chronic wounds impose severe health and economic burdens due to persistent inflammation and complications. Immunomodulatory hydrogels have emerged as promising therapies that modulate inflammatory responses for wound healing. Oxygen plays a crucial role in immune modulation and tissue regeneration; however, current oxygen-delivering biomaterials are limited by the mandatory incorporation of oxygen-generating agents and cytotoxic byproducts. Herein, we develop an oxygen-supplying container (Oxygener) via dopamine-mediated catalase immobilization to create oxygen-delivering and immunomodulatory hydrogels. Oxygener supplies oxygen in various solutions by hydrogen peroxide decomposition, producing cytocompatible, oxygen-enriched media for fabricating implantable oxygen-delivering hydrogels. These oxygenated systems facilitate the transition from pro-inflammatory to anti-inflammatory states by reducing macrophage recruitment while improving cellular proliferation and tissue remodeling at the gene and tissue levels <i>in vivo</i>. Our findings establish the minimum oxygen tension and supply duration required for effective wound healing. In summary, Oxygener holds great potential for developing various oxygen-delivering formulations for advanced wound care.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647973","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":"Structurally Colored Thermochromic Gels Derived from Plasmonic Gold Nanoparticles and Cholesteric Hydroxypropyl Cellulose.","authors":"Shunfeng Yu, Ziyi He, Han Tao, Wenwen Fang, Jiaqi Guo, Guang Chu","doi":"10.1021/acs.biomac.5c00693","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00693","url":null,"abstract":"<p><p>The integration of functional components into thermochromic photonic crystals has attracted considerable interest due to their potential for developing stimuli-responsive materials with distinctive optical characteristics. In this study, we demonstrate a series of optically tunable thermochromic gels, formed through the coassembly of gold nanoparticles with hydroxypropyl cellulose (HPC) at high concentrations (60-68 wt %), producing vibrant structural colors with enhanced light absorption. These composites not only preserve the chiral self-assembly of HPC in the presence of nanoparticles but also introduce tunable photonic-plasmonic coupling that responds to both temperature and concentration variations. Moreover, by exploiting the chiral light-matter interactions between the gold nanoparticles and the HPC, we observed a pronounced temperature-sensitive plasmonic optical activity, characterized by a strong negative peak on CD spectra, resulting from the chiral photonic modulation of the HPC. This approach for fabricating optically tunable thermochromic materials with engineered photonic-plasmonic coupling opens new avenues for advanced optical applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144635725","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":"Inversion of Enzymatic Enantiocatalysis Mediated by Biomolecular Condensates.","authors":"Shikha Shikha, Priyanka Priyanka, Subhabrata Maiti","doi":"10.1021/acs.biomac.5c00520","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00520","url":null,"abstract":"<p><p>Herein, we report the enantioselective phosphodiesterase behavior of an enzyme, alkaline phosphatase (ALP) (using both R- and S-forms of the RNA-model substrate, 2-hydroxypropyl-<i>p</i>-nitrophenyl phosphate (HPNPP)), in protein (bovine serum albumin (BSA)) and DNA-based biocondensates. The native preference toward ALP enzyme is toward S-HPNPP in aqueous buffer with an enantiomeric excess ratio (E) value of around 33%. This preference for S-HPNPP remains intact when ALP is encapsulated in BSA condensate (E-value range: 10 to 34%). A complete reversal of the E value (-20 to -47%) is observed in the DNA-based complex coacervate, as ALP here reacts faster with R-HPNPP. We finally demonstrate that the reversal of enzyme enantioselectivity in the condensed phase is linked to the enzyme's conformational dynamics inside the coacervate. This work will be important in synthetic protocells studies, as it provides novel insights into enzyme promiscuity and chiral selectivity in the diversified internal environment of biocondensates.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144641233","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}