Pub Date : 2026-01-12DOI: 10.1021/acs.biomac.5c01763
Soumia Boukind , Amira Najahi , Houssine Khalili , Aleksander Jaworski , Jean-Luc Putaux , Sami Boufi , Houssine Sehaqui
Lignocellulosic nanofibrils (LCNFs) represent a promising resource-efficient alternative to lignin-free cellulose nanofibrils. Yet, developing eco-friendly pretreatments and energy-efficient disintegration of lignocellulosic biomass is essential to enable the facile production of high-quality LCNFs at low cost. This study addresses these challenges by producing multifunctional phosphorylated lignin-cellulose nanofibrils (PLCNFs) from giant reed fibers. PLCNFs containing 22.1 wt % lignin were produced through direct phosphorylation of unbleached fibers in an H3PO4/urea system, followed by alkali-swelling and microfluidization. This simple approach provided a higher yield than conventional lignin-free CNF production. The resulting PLCNFs exhibited a width of 3–5 nm, high aspect ratio, negative zeta potential (-30 mV), and shear-thinning behavior characteristic of a gel-like network. The incorporated phosphate moieties further enhanced flame retardancy. Overall, this work presents an inexpensive, energy-efficient, and sustainable approach to produce multifunctional PLCNFs from unbleached biomass, demonstrating the potential of renewable lignocellulosic resources for developing robust and eco-friendly nanostructured materials.
{"title":"Phosphorylated Lignin–Cellulose Nanofibrils: Elucidating the Preparation Pathway and Structural Features","authors":"Soumia Boukind , Amira Najahi , Houssine Khalili , Aleksander Jaworski , Jean-Luc Putaux , Sami Boufi , Houssine Sehaqui","doi":"10.1021/acs.biomac.5c01763","DOIUrl":"10.1021/acs.biomac.5c01763","url":null,"abstract":"<div><div>Lignocellulosic nanofibrils (LCNFs) represent a promising resource-efficient alternative to lignin-free cellulose nanofibrils. Yet, developing eco-friendly pretreatments and energy-efficient disintegration of lignocellulosic biomass is essential to enable the facile production of high-quality LCNFs at low cost. This study addresses these challenges by producing multifunctional phosphorylated lignin-cellulose nanofibrils (PLCNFs) from giant reed fibers. PLCNFs containing 22.1 wt % lignin were produced through direct phosphorylation of unbleached fibers in an H<sub>3</sub>PO<sub>4</sub>/urea system, followed by alkali-swelling and microfluidization. This simple approach provided a higher yield than conventional lignin-free CNF production. The resulting PLCNFs exhibited a width of 3–5 nm, high aspect ratio, negative zeta potential (-30 mV), and shear-thinning behavior characteristic of a gel-like network. The incorporated phosphate moieties further enhanced flame retardancy. Overall, this work presents an inexpensive, energy-efficient, and sustainable approach to produce multifunctional PLCNFs from unbleached biomass, demonstrating the potential of renewable lignocellulosic resources for developing robust and eco-friendly nanostructured materials.</div></div><div><div><span><figure></figure></span></div></div>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"27 1","pages":"Pages 533-548"},"PeriodicalIF":5.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145852846","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}
Pub Date : 2026-01-12DOI: 10.1021/acs.biomac.5c02110
Anastasiia Murmiliuk , Sergey K. Filippov , Hiroki Iwase , Kuno Schwärzer , Jürgen Allgaier , Aurel Radulescu
The understanding of insulin conformational changes trapped inside a polymeric capsule is obscure, especially at elevated temperatures above 40 °C. We studied the conformational changes of insulin in bulk solution and upon encapsulation into polymeric self-assemblies formed by poly(ethylene oxide)-block-poly(N,N,N-trimethylammonioethyl methacrylate) copolymer that is oppositely charged to the protein. We demonstrated that loading insulin into the nanoparticles does not affect its secondary structure but alters the pH sensitivity of insulin, making it more resistant to pH variation in the presence of the polymer. However, the temperature resistance of insulin is weakened in the environment of polyelectrolyte, which causes a lowering of the unfolding temperature, and the conformational changes begin already at 40 °C in the nanoparticle core. For the first time, we report that insulin fibrillation follows distinct pathways in free and encapsulated forms, a difference driven by insulin oligomeric state (hexamer in bulk and trimer within the polyelectrolyte/insulin complex).
{"title":"Encapsulated Control: Shaping Insulin Fibrillation through Polymer Confinement","authors":"Anastasiia Murmiliuk , Sergey K. Filippov , Hiroki Iwase , Kuno Schwärzer , Jürgen Allgaier , Aurel Radulescu","doi":"10.1021/acs.biomac.5c02110","DOIUrl":"10.1021/acs.biomac.5c02110","url":null,"abstract":"<div><div>The understanding of insulin conformational changes trapped inside a polymeric capsule is obscure, especially at elevated temperatures above 40 °C. We studied the conformational changes of insulin in bulk solution and upon encapsulation into polymeric self-assemblies formed by poly(ethylene oxide)-<em>block</em>-poly(<em>N</em>,<em>N</em>,<em>N</em>-trimethylammonioethyl methacrylate) copolymer that is oppositely charged to the protein. We demonstrated that loading insulin into the nanoparticles does not affect its secondary structure but alters the pH sensitivity of insulin, making it more resistant to pH variation in the presence of the polymer. However, the temperature resistance of insulin is weakened in the environment of polyelectrolyte, which causes a lowering of the unfolding temperature, and the conformational changes begin already at 40 °C in the nanoparticle core. For the first time, we report that insulin fibrillation follows distinct pathways in free and encapsulated forms, a difference driven by insulin oligomeric state (hexamer in bulk and trimer within the polyelectrolyte/insulin complex).</div></div><div><div><span><figure></figure></span></div></div>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"27 1","pages":"Pages 845-854"},"PeriodicalIF":5.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145825387","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}
Understanding the long-term stability of cellulose nanofibers is critical for their practical application in advanced functional materials. In this study, we investigated the aging behavior of phosphorylated cellulose nanofibers (PCNFs) sheets under moist-heat accelerated aging conditions (80 °C, 65% relative humidity (RH)) for up to 42 days. PCNFs with different phosphate group densities were prepared by controlling the phosphorylation time, and their chemical and morphological changes were systematically analyzed. Liquid-sta31P NMR revealed a progressive transformation of surface phosphate esters into inorganic phosphate salts during aging. This dephosphorylation was thought to lead to a decrease in the pH within the sheets, which in turn promoted hydrolysis of the cellulose backbone. The resulting degradation manifested as decreases in the degree of polymerization (DP) and fibril length, particularly in PCNFs with higher surface charge. Conversely, the lateral crystallite size of the cellulose increased. These findings provide insights into PCNF aging and highlight the importance of controlling the initial phosphate ester structure and environmental conditions to increase the stability of PCNF-based materials in practical applications.
{"title":"Aging of Phosphorylated Cellulose Nanofibers under Moist-Heat Conditions","authors":"Akane Sakiyama , Tsuguyuki Saito , Audrey Moores , Masato Kato , Shuji Fujisawa","doi":"10.1021/acs.biomac.5c01635","DOIUrl":"10.1021/acs.biomac.5c01635","url":null,"abstract":"<div><div>Understanding the long-term stability of cellulose nanofibers is critical for their practical application in advanced functional materials. In this study, we investigated the aging behavior of phosphorylated cellulose nanofibers (PCNFs) sheets under moist-heat accelerated aging conditions (80 °C, 65% relative humidity (RH)) for up to 42 days. PCNFs with different phosphate group densities were prepared by controlling the phosphorylation time, and their chemical and morphological changes were systematically analyzed. Liquid-sta<sup>31</sup>P NMR revealed a progressive transformation of surface phosphate esters into inorganic phosphate salts during aging. This dephosphorylation was thought to lead to a decrease in the pH within the sheets, which in turn promoted hydrolysis of the cellulose backbone. The resulting degradation manifested as decreases in the degree of polymerization (DP) and fibril length, particularly in PCNFs with higher surface charge. Conversely, the lateral crystallite size of the cellulose increased. These findings provide insights into PCNF aging and highlight the importance of controlling the initial phosphate ester structure and environmental conditions to increase the stability of PCNF-based materials in practical applications.</div></div><div><div><span><figure></figure></span></div></div>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"27 1","pages":"Pages 451-458"},"PeriodicalIF":5.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145646898","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}
Pub Date : 2026-01-12DOI: 10.1021/acs.biomac.5c00967
Yu Sun , Li Cui , Wanqiu Peng , Rong Chen , Xueneng Guan , Jiangyun Liu
Parkinson’s disease (PD) is difficult to treat clinically and lacks an effective treatment. The aim of this study was to synthesize and characterize butyrate-modified hyaluronic acid (HA-But), validate its therapeutic efficacy, and elucidate its mechanisms of action in PD. Behavioral tests, including the open field test, Y-maze, and elevated plus maze test, demonstrated that HA-But significantly alleviated motor dysfunction in PD mice. ELISA results indicated a marked reduction in pro-inflammatory cytokine levels following the HA-But treatment. In addition, immunohistochemistry, immunofluorescence, and Western blot analyses revealed that HA-But improved dopaminergic neuron survival and reduced α-synuclein aggregation. Furthermore, HA-But activated PINK1/Parkin-mediated mitophagy, modulated gut microbiota composition, and increased short-chain fatty acid (SCFA) levels, especially butyric acid. Combining HA-But with gastrodin further improved the PD symptoms in mice. These findings suggested the potential of HA-But as a novel approach for PD treatment.
{"title":"Butyrate-Modified Hyaluronic Acid Ameliorates MPTP-Induced Parkinson’s Disease via Modulating PINK1/Parkin-Involved Mitophagy and Intestinal Flora","authors":"Yu Sun , Li Cui , Wanqiu Peng , Rong Chen , Xueneng Guan , Jiangyun Liu","doi":"10.1021/acs.biomac.5c00967","DOIUrl":"10.1021/acs.biomac.5c00967","url":null,"abstract":"<div><div>Parkinson’s disease (PD) is difficult to treat clinically and lacks an effective treatment. The aim of this study was to synthesize and characterize butyrate-modified hyaluronic acid (HA-But), validate its therapeutic efficacy, and elucidate its mechanisms of action in PD. Behavioral tests, including the open field test, Y-maze, and elevated plus maze test, demonstrated that HA-But significantly alleviated motor dysfunction in PD mice. ELISA results indicated a marked reduction in pro-inflammatory cytokine levels following the HA-But treatment. In addition, immunohistochemistry, immunofluorescence, and Western blot analyses revealed that HA-But improved dopaminergic neuron survival and reduced α-synuclein aggregation. Furthermore, HA-But activated PINK1/Parkin-mediated mitophagy, modulated gut microbiota composition, and increased short-chain fatty acid (SCFA) levels, especially butyric acid. Combining HA-But with gastrodin further improved the PD symptoms in mice. These findings suggested the potential of HA-But as a novel approach for PD treatment.</div></div><div><div><span><figure></figure></span></div></div>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"27 1","pages":"Pages 134-149"},"PeriodicalIF":5.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145646851","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}
Pub Date : 2026-01-12DOI: 10.1021/acs.biomac.5c01828
Chloé Pascouau , Kamila Wittek , Jessica Erlenbusch , Sebastian Becker , Jochen Fischer-Schuch , Pablo G. Argudo , Pol Besenius
Poly(amino esters) derived from N-acylated-1,4-oxazepan-7-ones (OxPs) emerge as promising candidates in the development of new and degradable amphiphiles for hydrogel preparation and delivery formulations. Here, the synthesis of amphiphilic triblock copolymers by ring-opening copolymerization of OxP monomers with various pendant chains is reported. Copolymerization using organocatalysts and a bifunctional initiator afforded neutral P(OxPMe)-b-P(OxPBn)-b-P(OxPMe) and cationic P(OxPNH2+)-b-P(OxPBn)-b-P(OxPNH2+) amphiphilic triblock copolymers with controlled molar masses ranging from 4,600 to 8,500 g/mol and narrow dispersities (Đ ≤ 1.21). A panel of polymers with various block lengths and compositions was synthesized. Their self-assembly in water revealed the formation of nanostructures, including worm-like or spherical morphologies. Modulation of the copolymer composition and concentration enables control over hydrogelation and its macroscopic properties. Finally, we investigated the formulation of a hydrophobic fungicide and its inhibitory effect on spore proliferation, which shows great promise as dispensable and biodegradable hydrogel formulation for agrochemical applications.
{"title":"Synthesis, Supramolecular Assembly, and Hydrogelation of Poly(amino ester) ABA Triblock Copolymers","authors":"Chloé Pascouau , Kamila Wittek , Jessica Erlenbusch , Sebastian Becker , Jochen Fischer-Schuch , Pablo G. Argudo , Pol Besenius","doi":"10.1021/acs.biomac.5c01828","DOIUrl":"10.1021/acs.biomac.5c01828","url":null,"abstract":"<div><div>Poly(amino esters) derived from <em>N</em>-acylated-1,4-oxazepan-7-ones (OxPs) emerge as promising candidates in the development of new and degradable amphiphiles for hydrogel preparation and delivery formulations. Here, the synthesis of amphiphilic triblock copolymers by ring-opening copolymerization of OxP monomers with various pendant chains is reported. Copolymerization using organocatalysts and a bifunctional initiator afforded neutral P(OxP<sub>Me</sub>)-<em>b</em>-P(OxP<sub>Bn</sub>)-<em>b</em>-P(OxP<sub>Me</sub>) and cationic P(OxP<sub>NH2</sub> <sup>+</sup>)-<em>b</em>-P(OxP<sub>Bn</sub>)-<em>b</em>-P(OxP<sub>NH2</sub> <sup>+</sup>) amphiphilic triblock copolymers with controlled molar masses ranging from 4,600 to 8,500 g/mol and narrow dispersities (Đ ≤ 1.21). A panel of polymers with various block lengths and compositions was synthesized. Their self-assembly in water revealed the formation of nanostructures, including worm-like or spherical morphologies. Modulation of the copolymer composition and concentration enables control over hydrogelation and its macroscopic properties. Finally, we investigated the formulation of a hydrophobic fungicide and its inhibitory effect on spore proliferation, which shows great promise as dispensable and biodegradable hydrogel formulation for agrochemical applications.</div></div><div><div><span><figure></figure></span></div></div>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"27 1","pages":"Pages 567-579"},"PeriodicalIF":5.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145761722","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}
Pub Date : 2026-01-12DOI: 10.1021/acs.biomac.5c01157
Weijing Chu , Gayathri R. Ediriweera , Amber Prior , Pie Huda , Benedict Lum , Christopher B. Howard , Nicholas L. Fletcher , Paul V. Bernhardt , Kristofer J. Thurecht
This study developed a nanoscaled system combining chemotherapeutic (Temozolomide, TMZ) and radionuclide (177Lu) for targeted glioblastoma (GBM) treatment. Bioorthogonal click chemistry was utilized to produce a selective delivery platform, and the impacts of nanomedicine structure on the efficiency of bioorthogonal reactions were explored in vivo. This was achieved by developing two parallel polymers with trans-cyclooctene (tCO) in positions differing in terms of the accessibility to the tetrazine-containing moiety. Both in vitro assessment of reaction kinetics and the in vivo distribution behavior demonstrated that tCO conjugated at the chain end of the polymer (PTtCOext) instead of those within chains (PTtCOint) exhibited better accessibility to the tetrazine-modified material ([177Lu]Lu-DPT). This then led to a more efficient click reaction in vivo and higher 177Lu accumulation in the tumor. This study provides key information on design considerations for optimal positioning of bioorthogonal reactive species in nanomedicine and a potential treatment approach for GBM.
{"title":"Pretargeted Polymeric Systems for Conducting Chemo-Radiotherapy on Glioblastoma: An Evaluation of the Impact of Nanomedicine Structure on Bioorthogonal Chemistry In Vivo","authors":"Weijing Chu , Gayathri R. Ediriweera , Amber Prior , Pie Huda , Benedict Lum , Christopher B. Howard , Nicholas L. Fletcher , Paul V. Bernhardt , Kristofer J. Thurecht","doi":"10.1021/acs.biomac.5c01157","DOIUrl":"10.1021/acs.biomac.5c01157","url":null,"abstract":"<div><div>This study developed a nanoscaled system combining chemotherapeutic (Temozolomide, TMZ) and radionuclide (<sup>177</sup>Lu) for targeted glioblastoma (GBM) treatment. Bioorthogonal click chemistry was utilized to produce a selective delivery platform, and the impacts of nanomedicine structure on the efficiency of bioorthogonal reactions were explored <em>in vivo</em>. This was achieved by developing two parallel polymers with <em>trans</em>-cyclooctene (<em>t</em>CO) in positions differing in terms of the accessibility to the tetrazine-containing moiety. Both <em>in vitro</em> assessment of reaction kinetics and the <em>in vivo</em> distribution behavior demonstrated that <em>t</em>CO conjugated at the chain end of the polymer (PT<em>t</em>CO<sub>ext</sub>) instead of those within chains (PT<em>t</em>CO<sub>int</sub>) exhibited better accessibility to the tetrazine-modified material ([<sup>177</sup>Lu]Lu-DPT). This then led to a more efficient click reaction <em>in vivo</em> and higher <sup>177</sup>Lu accumulation in the tumor. This study provides key information on design considerations for optimal positioning of bioorthogonal reactive species in nanomedicine and a potential treatment approach for GBM.</div></div><div><div><span><figure></figure></span></div></div>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"27 1","pages":"Pages 205-216"},"PeriodicalIF":5.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145720014","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}
Pub Date : 2026-01-12DOI: 10.1021/acs.biomac.5c02106
Lixia Liao , Jiaqi Ding , Xiao Xiong , Fengjiao Quan , Xingxing Liu , Min Zhu , Zehui Chen , Sheng Li , Lian Zhu , Benmei Wei , Juntao Zhang , Haibo Wang
Conductive hydrogels are promising for flexible electronics, yet integrating high conductivity, mechanical robustness, biocompatibility, and environmental stability for flexible supercapacitors (FSCs) and wearable epidermal sensors remains challenging. Herein, a self-healing hydrogel with multiple energy dissipation pathways was constructed using synergistic dynamic borate ester bonds, Schiff base bonds, and hydrogen bonds. Incorporating polydopamine-coated MXene (MP) enhanced the mechanical strength, conductivity, and antibacterial/antioxidant properties. FSCs with the hydrogel electrolyte exhibited excellent electrochemical performance with a specific capacitance of 373.41 mF/cm2, an energy density of 74.67 μWh/cm2, a capacitance retention of 82.43% after 5000 cycles, and high deformation tolerance. As a strain sensor, it effectively detected both large and subtle human motions, including physiological microexpressions and pulse beats due to its high sensitivity (gauge factor = 1.73) and repeatability. Importantly, its notable degradability owing to the inherent degradability of the chitosan framework and the reversible dissociation of dynamic bonds addresses environmental concerns from traditional electronics.
{"title":"Triple-Dynamic-Bond-Engineered Self-Healing Conductive Hydrogels for Deformation-Immune Flexible Supercapacitors and Wearable Epidermal Sensors","authors":"Lixia Liao , Jiaqi Ding , Xiao Xiong , Fengjiao Quan , Xingxing Liu , Min Zhu , Zehui Chen , Sheng Li , Lian Zhu , Benmei Wei , Juntao Zhang , Haibo Wang","doi":"10.1021/acs.biomac.5c02106","DOIUrl":"10.1021/acs.biomac.5c02106","url":null,"abstract":"<div><div>Conductive hydrogels are promising for flexible electronics, yet integrating high conductivity, mechanical robustness, biocompatibility, and environmental stability for flexible supercapacitors (FSCs) and wearable epidermal sensors remains challenging. Herein, a self-healing hydrogel with multiple energy dissipation pathways was constructed using synergistic dynamic borate ester bonds, Schiff base bonds, and hydrogen bonds. Incorporating polydopamine-coated MXene (MP) enhanced the mechanical strength, conductivity, and antibacterial/antioxidant properties. FSCs with the hydrogel electrolyte exhibited excellent electrochemical performance with a specific capacitance of 373.41 mF/cm<sup>2</sup>, an energy density of 74.67 μWh/cm<sup>2</sup>, a capacitance retention of 82.43% after 5000 cycles, and high deformation tolerance. As a strain sensor, it effectively detected both large and subtle human motions, including physiological microexpressions and pulse beats due to its high sensitivity (gauge factor = 1.73) and repeatability. Importantly, its notable degradability owing to the inherent degradability of the chitosan framework and the reversible dissociation of dynamic bonds addresses environmental concerns from traditional electronics.</div></div><div><div><span><figure></figure></span></div></div>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"27 1","pages":"Pages 805-821"},"PeriodicalIF":5.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145699301","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}
Pub Date : 2026-01-12DOI: 10.1021/acs.biomac.5c02128
Marianna Spyridakou , Iren G. Stavrakaki , Evangelia Tsagkaraki , Christina Varfi , Robert Graf , Hermis Iatrou , George Floudas
A series of poly(γ-benzyl-l-glutamate) (PBLG) peptides are synthesized, with a broad range of molar masses and different end-groups. By combining static (wide-angle X-ray scattering and 13C solid-state nuclear magnetic resonance (NMR)) with dynamic probes (13C solid-state NMR, dielectric spectroscopy (DS) as a function of temperature and pressure, and rheology), we could identify distinct local and global dynamics associated with α-helices and β-sheets. The local dynamics reflect segmental relaxations of amorphous segments interrupting the α-helices/β-sheets and at their chain-ends. Two glass temperatures (Tgs) were identified in oligopeptides exhibiting both secondary structures. This is the first report for β-sheet-associated Tg in completely nonhydrated polypeptides. At longer timescales, the relaxation of the α-helical and β-sheet macrodipoles was also evident in DS. Peptides with different secondary structures have distinct viscoelastic signatures. Overall, polypeptide chain length and end-group chemistry can be employed to engineer α-helices and/or β-sheets, enabling deliberate control over the structural, dynamical, and viscoelastic properties.
{"title":"Distinct Local and Global Dynamics of α‑Helices and β‑Sheets in Poly(γ-benzyl‑l‑glutamate) Peptides","authors":"Marianna Spyridakou , Iren G. Stavrakaki , Evangelia Tsagkaraki , Christina Varfi , Robert Graf , Hermis Iatrou , George Floudas","doi":"10.1021/acs.biomac.5c02128","DOIUrl":"10.1021/acs.biomac.5c02128","url":null,"abstract":"<div><div>A series of poly(γ-benzyl-<span>l</span>-glutamate) (PBLG) peptides are synthesized, with a broad range of molar masses and different end-groups. By combining static (wide-angle X-ray scattering and <sup>13</sup>C solid-state nuclear magnetic resonance (NMR)) with dynamic probes (<sup>13</sup>C solid-state NMR, dielectric spectroscopy (DS) as a function of temperature and pressure, and rheology), we could identify distinct local and global dynamics associated with α-helices and β-sheets. The local dynamics reflect segmental relaxations of amorphous segments interrupting the α-helices/β-sheets and at their chain-ends. Two glass temperatures (<em>T</em> <sub>g</sub>s) were identified in oligopeptides exhibiting both secondary structures. This is the first report for β-sheet-associated <em>T</em> <sub>g</sub> in completely nonhydrated polypeptides. At longer timescales, the relaxation of the α-helical and β-sheet macrodipoles was also evident in DS. Peptides with different secondary structures have distinct viscoelastic signatures. Overall, polypeptide chain length and end-group chemistry can be employed to engineer α-helices and/or β-sheets, enabling deliberate control over the structural, dynamical, and viscoelastic properties.</div></div><div><div><span><figure></figure></span></div></div>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"27 1","pages":"Pages 855-872"},"PeriodicalIF":5.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145792793","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}
Pub Date : 2026-01-12DOI: 10.1021/acs.biomac.5c01202
Angel Buendía , Natalia Sanz Del Olmo , Irene Rodríguez-Clemente , Jacob Wohlert , Krzysztof Sztandera , Jorge San Jacinto García , Faridah Namata , Michael Malkoch , Valentín Ceña
We report the biological evaluation of bis-MPA dendrimers terminated with either cysteamine (CYS) or 2-(dimethylamino)ethanethiol (DA) groups for siRNA transfection. The results show that aggregation phenomena are critical to the biological performance of these constructs. Confocal and 2D microscopy demonstrated that only the G3-CYS dendrimer transported siRNA into cells. Accordingly, G3-CYS-mediated siRNA transfection reduced intracellular levels of the target proteinsp42-MAPK, Rheb, and MGMTto 15–25% of control levels in a human glioblastoma cell line and mouse astrocytes. G3-CYS transfection efficiency was similar to that of commercial transfectants. However, its self-degradable bis-MPA backbone and tunable peripheral groups render it markedly superior, making it a promising transfection agent and emphasize the critical balance between structural design, biological efficacy, and safety. Despite its efficacy, G3-CYS displayed a narrow therapeutic window with pronounced cytotoxicity above 1 μM. In vivo studies further confirmed dose-dependent systemic toxicity, likely associated with enhanced blood coagulation.
{"title":"Hydrolytically Stable Cationic Bis-MPA Dendrimers as Efficient Transfectants for Glioblastoma Cells and Primary Astrocytes","authors":"Angel Buendía , Natalia Sanz Del Olmo , Irene Rodríguez-Clemente , Jacob Wohlert , Krzysztof Sztandera , Jorge San Jacinto García , Faridah Namata , Michael Malkoch , Valentín Ceña","doi":"10.1021/acs.biomac.5c01202","DOIUrl":"10.1021/acs.biomac.5c01202","url":null,"abstract":"<div><div>We report the biological evaluation of bis-MPA dendrimers terminated with either cysteamine (CYS) or 2-(dimethylamino)ethanethiol (DA) groups for siRNA transfection. The results show that aggregation phenomena are critical to the biological performance of these constructs. Confocal and 2D microscopy demonstrated that only the G3-CYS dendrimer transported siRNA into cells. Accordingly, G3-CYS-mediated siRNA transfection reduced intracellular levels of the target proteinsp42-MAPK, Rheb, and MGMTto 15–25% of control levels in a human glioblastoma cell line and mouse astrocytes. G3-CYS transfection efficiency was similar to that of commercial transfectants. However, its self-degradable bis-MPA backbone and tunable peripheral groups render it markedly superior, making it a promising transfection agent and emphasize the critical balance between structural design, biological efficacy, and safety. Despite its efficacy, G3-CYS displayed a narrow therapeutic window with pronounced cytotoxicity above 1 μM. In vivo studies further confirmed dose-dependent systemic toxicity, likely associated with enhanced blood coagulation.</div></div><div><div><span><figure></figure></span></div></div>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"27 1","pages":"Pages 234-248"},"PeriodicalIF":5.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145666388","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}
Pub Date : 2026-01-12DOI: 10.1021/acs.biomac.5c02248
Shicheng Xia , Jing Yang , Zhaoyang Wang , Shun Lu , Shanshan Wen , Kaiyu Guo , Lei Yang
Silk sericin (SS) is often regarded as a significant byproduct and discarded during degumming processes. Concerns over resource waste and environmental pollution have drawn widespread attention to the substantial amounts of waste SS generated during production. Effectively utilizing SS and applying it in the field of biomaterials presents both a major challenge and profound significance. With its biocompatibility and unique physical properties, SS can be transformed into multifunctional biomaterials through optimized extraction and purification processes. SS-based hydrogels, scaffolds, and bioinks exhibit excellent biocompatibility, controllable degradability, and cell-proliferation-promoting capabilities. These materials find applications in biomedical engineering, including wound repair dressings, drug delivery systems, antimicrobial agents, and tissue engineering scaffolds. Transforming SS into valuable resources not only reduces waste emissions from the silk processing industry but also pioneers a new pathway for developing low-cost, recyclable biomaterials. This approach holds broad application prospects in the biomedical field.
{"title":"Waste-to-Health Revolution: Upcycling Silk Sericin Byproducts into Circular Biomaterials for Biomedical Engineering","authors":"Shicheng Xia , Jing Yang , Zhaoyang Wang , Shun Lu , Shanshan Wen , Kaiyu Guo , Lei Yang","doi":"10.1021/acs.biomac.5c02248","DOIUrl":"10.1021/acs.biomac.5c02248","url":null,"abstract":"<div><div>Silk sericin (SS) is often regarded as a significant byproduct and discarded during degumming processes. Concerns over resource waste and environmental pollution have drawn widespread attention to the substantial amounts of waste SS generated during production. Effectively utilizing SS and applying it in the field of biomaterials presents both a major challenge and profound significance. With its biocompatibility and unique physical properties, SS can be transformed into multifunctional biomaterials through optimized extraction and purification processes. SS-based hydrogels, scaffolds, and bioinks exhibit excellent biocompatibility, controllable degradability, and cell-proliferation-promoting capabilities. These materials find applications in biomedical engineering, including wound repair dressings, drug delivery systems, antimicrobial agents, and tissue engineering scaffolds. Transforming SS into valuable resources not only reduces waste emissions from the silk processing industry but also pioneers a new pathway for developing low-cost, recyclable biomaterials. This approach holds broad application prospects in the biomedical field.</div></div><div><div><span><figure></figure></span></div></div>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"27 1","pages":"Pages 59-86"},"PeriodicalIF":5.4,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145761638","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}