Biomacromolecules
· 2026 Jun · PMID 42314045
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Marine biofouling poses a major economic challenge for the maritime industry by increasing frictional drag and fuel consumption. Although nontoxic amphiphilic copolymers have emerged as promising alternatives to purely h...Marine biofouling poses a major economic challenge for the maritime industry by increasing frictional drag and fuel consumption. Although nontoxic amphiphilic copolymers have emerged as promising alternatives to purely hydrophobic or hydrophilic antifouling coatings, to date, the specific role of the steric bulk (hindrance) of hydrophobic moieties in antifouling performance has not been systematically examined. In this study, we investigate the impacts of the steric bulk of hydrophobic comonomers on marine antifouling efficacy. Amphiphilic random copolymers were synthesized via reversible addition-fragmentation chain transfer polymerization using hydrophilic zwitterionic sulfobetaine methacrylate and hydrophobic butyl methacrylate (BMA) isomers (-, -, and -BMA) with varying steric bulk. The resulting polymers were coated onto solid substrates and evaluated through dynamic marine diatom adhesion tests in the presence of silt. Overall, this study highlights that introducing sterically bulky hydrophobic moieties is key to mitigating both silt adsorption and marine biofouling.
Long Y, Liu Y, Sun M
… +3 more, Zhang T, Wu J, Wu W
Biomacromolecules
· 2026 Jun · PMID 42313618
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Alkali-ethanol pretreatment effectively removes lignin while preserving cellulose; however, the structural transformations of lignin during this process and their influence on the inhibition of enzymatic hydrolysis remai...Alkali-ethanol pretreatment effectively removes lignin while preserving cellulose; however, the structural transformations of lignin during this process and their influence on the inhibition of enzymatic hydrolysis remain insufficiently understood. Mitigating the nonproductive adsorption of cellulase enzymes by lignin is of significant industrial importance, as it can reduce enzyme-related costs in large-scale biorefining operations. This study examined lignin fractions derived from alkali-ethanol pretreatment of poplar, specifically black liquor lignin (BL) and pretreatment material milled wood lignin (PMWL), using milled wood lignin (MWL) as a reference. The lignin samples were characterized in terms of molecular weight, functional group composition, surface properties, and cellulase adsorption behavior. BL was found to possess a lower molecular weight, an elevated phenolic hydroxyl content (5.01-5.37 mmol/g), and increased surface polarity. In contrast, PMWL exhibited a higher molecular weight, greater condensation, enhanced hydrophobicity, and a reduced phenolic hydroxyl content (2.56-2.83 mmol/g). Quartz crystal microbalance with dissipation monitoring (QCM-D) analysis demonstrated that BL exhibited the highest levels of nonproductive cellulase adsorption (450-621 ng/cm), which correlated strongly with phenolic hydroxyl density, suggesting that hydrogen bonding is the predominant interaction mechanism. Despite its hydrophobic nature, PMWL showed comparatively lower cellulase adsorption (391-421 ng/cm). These findings indicate distinct inhibitory mechanisms: PMWL restricts enzyme accessibility through aggregation and hydrophobic shielding, whereas BL facilitates nonproductive enzyme binding via abundant polar functional groups. Collectively, this study advances the molecular-level understanding of lignin-enzyme interactions and offers a theoretical framework for optimizing pretreatment methods and lignin modification strategies aimed at minimizing enzyme inhibition in lignocellulosic biorefining processes.
Liao Q, Ren H, Zhou Z
… +5 more, Gao S, Dai O, Du X, Yuan B, Zhang H
Biomacromolecules
· 2026 Jun · PMID 42313482
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The covalent integration of hydrophilic biomacromolecules into hydrophobic synthetic polymer networks remains a key challenge, primarily arising from significant interfacial incompatibility and phase separation. Here, we...The covalent integration of hydrophilic biomacromolecules into hydrophobic synthetic polymer networks remains a key challenge, primarily arising from significant interfacial incompatibility and phase separation. Here, we introduce a complementary dual-dynamic covalent approach that synergistically combines thiourethane chemistry with boronic ester cross-linking to seamlessly incorporate hyaluronic acid (HA) into polyurethane networks. Thiourethane linkages, formed via thiol-isocyanate click chemistry, serve as the network backbone and undergo associative -thiocarbamoylation, while boronic ester bonds between pendant phenylboronic acid groups and the -diols inherent to HA provide dynamic bio-synthetic interlinks. This complementary design creates a hierarchical network with confirmed covalent incorporation, as demonstrated by a 20% reduction in spin-spin relaxation time and a 1.8-fold increase in storage modulus. The resulting network offers strong mechanical performance (25.6 MPa tensile strength, 530% elongation), efficient self-healing (91% recovery), and a broad operating temperature range (-49 to 168 °C). This chemically unified matrix further enables the stable inclusion of liquid metal for strain sensing (gauge factor up to 160). This work establishes a general pathway that leverages complementary dynamic chemistries to address interfacial mismatch in biosynthetic hybrid materials, paving the way for thermally stable and multifunctional biointegrated systems.
Huang F, Liu Y, Wang Y
… +5 more, Lv Z, Xu J, Zhang J, Ding F, Sun Y
Biomacromolecules
· 2026 Jun · PMID 42312952
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Alzheimer's disease (AD) is characterized by amyloid plaques and neurofibrillary tangles formed by amyloid-β (Aβ) and tau aggregates, yet the molecular basis of Aβ-tau coaggregation remains unclear. Here, we used multipl...Alzheimer's disease (AD) is characterized by amyloid plaques and neurofibrillary tangles formed by amyloid-β (Aβ) and tau aggregates, yet the molecular basis of Aβ-tau coaggregation remains unclear. Here, we used multiple microsecond-scale discrete molecular dynamics simulations to examine homodimerization of tau microtubule-binding repeats (R1-R4) and their heterodimerization with Aβ. R1, R2, and R4 showed weak homodimerization, whereas heterodimerization with Aβ markedly enhanced interpeptide contacts and β-sheet formation. R3 exhibited strong intrinsic aggregation propensity and was further stabilized into β-sheet-rich conformations upon interacting with Aβ. Residue-level analyses identified Aβ and Aβ as structural templates promoting β-sheet transitions in tau. Thermodynamic analyses further supported an energy-entropy compensation mechanism in which aggregation-prone β-sheet edges of Aβ lowered the potential energy to offset entropic costs, thereby stabilizing low-free-energy coaggregated states. These findings provide atomistic insights into Aβ-facilitated tau coaggregation relevant to early AD pathology.
Oh Y, Kim T, Park K
… +6 more, Moon CW, Jeong Y, Lee Y, Ha SJ, Jung SY, Hong J
Biomacromolecules
· 2026 Jun · PMID 42312473
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Chronic inflammation of the airways plays a crucial role in disease progression and symptom exacerbation in patients with chronic obstructive pulmonary disease (COPD). Nitric oxide (NO) relaxes airway smooth muscle and r...Chronic inflammation of the airways plays a crucial role in disease progression and symptom exacerbation in patients with chronic obstructive pulmonary disease (COPD). Nitric oxide (NO) relaxes airway smooth muscle and regulates the inflammatory response. The multifunctional therapeutic effects of NO are highly attractive for COPD treatment. However, the practical difficulties in long-term and targeted administration remain a limitation. This work presents an inhaled nanotherapeutic, termed AIR (Anti-Inflammatory Relaxer), engineered for targeted NO delivery to proinflammatory M1 macrophages. AIR is constructed from dendritic mesoporous silica nanoparticles (DMSNs) functionalized with hyaluronic acid (HA) and diazeniumdiolates (NONOates). HA enables selective targeting of CD44-overexpressing M1 macrophages, thereby leading to their polarization into anti-inflammatory phenotypes. Moreover, disulfide bonds in AIR are cleaved by intracellular glutathione, which is present at millimolar concentrations, ensuring excellent biocompatibility. Overall, these inhaled nanotherapeutics have great potential in relieving chronic inflammation in COPD while reducing bioaccumulation in the lungs.
Biomacromolecules
· 2026 Jun · PMID 42311088
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Lignin, a natural biomass material, has demonstrated potential for iodine capture. However, in practical implementation, its effectiveness is limited. To address these issues, we screened four electron-rich heteroatom di...Lignin, a natural biomass material, has demonstrated potential for iodine capture. However, in practical implementation, its effectiveness is limited. To address these issues, we screened four electron-rich heteroatom diamine compounds for cross-linking modification of lignin. By precisely controlling reaction parameters, we successfully synthesized four electron-rich heteroatom-cross-linked lignin molecular cages. These molecular cages feature a unique structure: un-cross-linked lignin nanospheres are attached on the inner surface of the cage. EC-L(N) demonstrates exceptional iodine capture performance: its iodine vapor capture capacity reaches 304.95 mg/g, with capture capacities of 595.68 mg/g in -hexane solution and 264.32 mg/g in aqueous solution. Further, EC-L(N) demonstrated exceptional reusability. This study not only provides key technical support for optimizing the adsorption performance of lignin-based iodine capture materials and expanding their practical applications in radioactive wastewater and exhaust gas treatment, but also offers important theoretical insights for the structural design and functional development of electron-rich heteroatom-modified biomass materials.
Zhang X, Zhang H, Sun Z
… +11 more, Yin H, Wu Q, Zheng N, Watabe H, Gao L, Chen Y, F Hamza M, Fouda A, Yue C, Wei Y, Yin X
Biomacromolecules
· 2026 Jun · PMID 42304227
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While lutetium-177 (Lu) holds immense promise as a theranostic radionuclide for image-guided radioembolization of hepatocellular carcinoma, its translation into effective biodegradable microsphere platforms has been crit...While lutetium-177 (Lu) holds immense promise as a theranostic radionuclide for image-guided radioembolization of hepatocellular carcinoma, its translation into effective biodegradable microsphere platforms has been critically hindered by the lack of stable and efficient carriers capable of robustly incorporating the radionuclide while maintaining biodegradability. To bridge this gap, we herein develop biodegradable chitosan microspheres engineered with an aminated surface via sequential grafting of poly(glycidyl methacrylate) (PGMA) and polyethylenimine (PEI) to establish a robust Lu(III) binding capacity as a pivotal carrier for future Lu-based radioembolization. The aminated microspheres exhibit good sphericity, favorable in vitro dispersion, and a gradual biodegradation profile. They exhibit a high Lu(III) adsorption capacity of 70.55 mg·g at 333 K, corresponding to an estimated theoretical specific activity of up to 2.07 MBq per individual CPPs-Lu microsphere. These results demonstrate the potential of PEI-functionalized chitosan microspheres as biodegradable carriers for further investigation into Lu-based transarterial radioembolization.
Kilens F, Fonseca LP, Olazabal A
… +9 more, Unanue L, Olmedo-Martínez JL, Król M, Mantione D, Reis NV, Dove AP, Sardón H, Müller AJ, Jehanno C
Biomacromolecules
· 2026 Jun · PMID 42301265
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The ability of block copolymers (BCPs) to self-assemble into microphases allows the creation of unique materials with enhanced tailored properties. In this study, we combined organocatalyzed polycondensation and ring-ope...The ability of block copolymers (BCPs) to self-assemble into microphases allows the creation of unique materials with enhanced tailored properties. In this study, we combined organocatalyzed polycondensation and ring-opening polymerization (ROP) to create fully biobased ABA triblock copolymers consisting of poly(1,6-hexanediol) (PHDO) and poly(l-lactide) (PLLA). Increasing the segregation strength (χ) from 4 to 11 causes the triblocks to shift from weak to intermediate segregation, with PHDO microphases dispersed within a PLLA-rich matrix. Long-range order appears when χ ≥ 6, resulting in a body-centered cubic (BCC) spherical morphology. Depending on thermal history, distinct hierarchical structures, including BCC spherical morphologies, BCC plus lamellar arrangements, and interdigitated double-lamellar structures, were obtained. Increasing the molar mass of the PLLA terminal blocks ( = 18.5 kDa) enabled the formation of self-supporting films, for which preliminary mechanical and gas permeation properties were evaluated. Overall, this work establishes structure-morphology relationships of fully biobased double-crystalline triblock copolymers.
Osei FB, Dangat Y, Yasay R
… +6 more, Esposto J, Twum K, Huber RJ, Martic S, Torabifard H, Beyeh NK
Biomacromolecules
· 2026 Jun · PMID 42287286
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Cataract is a leading cause of blindness worldwide, with no clear pharmacological agent for treatment. An octa-sulfonated polyanionic resorcinarene was synthesized and investigated for its ability to inhibit the aggrega...Cataract is a leading cause of blindness worldwide, with no clear pharmacological agent for treatment. An octa-sulfonated polyanionic resorcinarene was synthesized and investigated for its ability to inhibit the aggregation of αA66-80-Crystallin peptide, a key peptide of the αA-Crystallin protein involved in cataract formation. Nuclear magnetic resonance (NMR) and isothermal titration calorimetry (ITC) experiments revealed strong interactions between and the nine amino acids that make up the αA66-80-Crystallin peptide as well as the peptide. ITC revealed dissociation constants ranging between 1 nm and 1000 μM. Fluorescence aggregation assays, dynamic light scattering (DLS) experiments, and transmission electron microscopy (TEM) graphs illustrated a concentration-dependent deaggregation ability of toward αA66-80-Crystallin peptide in physiological solutions. At 1:1 equivalence of αA66-80-Crystallin and , the average particle size of αA66-80 peptide aggregate dropped almost 9-fold (from 13293 ± 1072 d.nm to 1483 ± 15 d.nm), which was less than that determined for previously reported macrocycles with the same batch of peptide at a similar concentration. Evident from TEM imaging, varying ratios of and αA66-80-Crystallin peptide produced fibrillar aggregates of the peptide when compared to pure αA66-80 Crystallin peptide. A concentration of 44 ± 1 μM of was needed to break down 50% of αA66-80 peptide aggregates, which was significantly lower than reported IC values for two reported functionalized resorcinarenes and doubles that of a third macrocycle. Molecular dynamics (MD) simulations further showed that aggregation of the αA66-80 peptide was driven by core hydrophobic residues, which were effectively shielded by , thereby inhibiting the formation of peptide aggregates. Among the four polyionic resorcinarenes tested, displayed the strongest deaggregation effects, highlighting its potential as a molecular scaffold for the development of anticataract therapeutics.
Mayer M, Helberg J, Stirnweiß K
… +5 more, Kumar NS, Van Opdenbosch D, Schieder D, Zollfrank C, Sieber V
Biomacromolecules
· 2026 Jun · PMID 42286455
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Poly(3-hydroxybutyrate) (PHB) is a biocompatible and biodegradable polyhydroxyalkanoate, but its highly regular stereomicrostructure causes high crystallinity and poor processability. Here, we demonstrate that stereoirre...Poly(3-hydroxybutyrate) (PHB) is a biocompatible and biodegradable polyhydroxyalkanoate, but its highly regular stereomicrostructure causes high crystallinity and poor processability. Here, we demonstrate that stereoirregular PHB can be produced microbially, challenging the view that strict PHA synthase stereospecificity makes such structures inaccessible. In a proof-of-concept study, we produced stereoirregular PHB containing 6.84% ± 0.04% ()-3-hydroxybutyrate, with an -dyad fraction of 11.8% ± 0.7%. Compared with conventional PHB, the stereoirregular material exhibited a reduced melting temperature, from 179.3 °C ± 0.7 to 154.3 °C ± 1.1 °C, and decreased molar-mass decomposition during processing. These results demonstrate that microbial synthesis can access stereochemically diverse PHB. Importantly, they show that biologically produced polymers can exhibit the improved processability and recyclability previously associated with chemically synthesized analogues. These findings overturn a long-standing assumption in PHB biosynthesis and provide a basis for biologically tuning polymer microstructure and performance through microbial engineering.
Sultan MT, Valkonen M, Awais M
… +4 more, Nousiainen P, Lillqvist K, Wang S, Rautkari L
Biomacromolecules
· 2026 Jun · PMID 42275250
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Acetylation is one of the most widely applied chemical modification methods for enhancing the dimensional stability and durability of wood. In this work, we investigate a diffusion-driven solvent-exchange method for acet...Acetylation is one of the most widely applied chemical modification methods for enhancing the dimensional stability and durability of wood. In this work, we investigate a diffusion-driven solvent-exchange method for acetylating never-dried Scots pine wood, eliminating the energy-intensive drying typically required before wood acetylation. Results from two-dimensional confocal Raman microspectroscopic imaging, coupled with multivariate data analysis and high-performance liquid chromatography, suggest a uniform distribution of acetyl groups within the cell walls and increased lignin acetylation using the solvent-exchange method. The uniform distribution of acetyl groups and increased lignin modification in the cell corners and the middle lamella resulted in less shrinkage and much-improved antiswelling efficiency at the macroscale. Overall, this diffusion-driven solvent-exchange pretreatment provides a uniform, direct acetylation of never-dried wood, bypassing the conventional oven- or kiln-drying step, with targeted lignin modification playing a crucial role in controlling wood-water interactions.
McLauchlan J, Bolinsson H, Nilsson L
… +4 more, Sirijovski N, Tyler AII, Orfila C, Sarkar A
Biomacromolecules
· 2026 Jun · PMID 42274104
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Despite extensive research linking oat β-glucan (OBG) to improvements in cardiometabolic health, little is known about how OBG influences the structure and surface behavior of oat protein. To this end, enzymatic hydrolys...Despite extensive research linking oat β-glucan (OBG) to improvements in cardiometabolic health, little is known about how OBG influences the structure and surface behavior of oat protein. To this end, enzymatic hydrolysis of an oat protein-β-glucan coextract (OPBG) from defatted oat flour was performed. The effect of OBG cleavage was characterized using asymmetric flow field-flow fractionation with ultraviolet-visible (UV-vis) and in situ fluorescence detection, allowing for deconvolution of protein and OBG signals. Partial OBG cleavage increased oat protein dispersibility and accelerated adsorption to the air-water interface, albeit partly driven by thermal treatment during enzymatic hydrolysis. Although full cleavage resulted in protein aggregation, all OPBG samples offered decreased air-water surface tension and faster solid surface-water adsorption kinetics compared to oat protein isolate (OPI). Novel findings highlight that oat protein surface behavior can be adjusted by omitting isoelectric precipitation, while retaining inherent OBG in the system to ultimately reduce protein-protein hydrophobic aggregation.
Wakabayashi R, Fujiwara Y, Matsuba G
… +2 more, Kamiya N, Goto M
Biomacromolecules
· 2026 Jun · PMID 42273797
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Self-assembling fibrous materials exhibit tunable properties and adaptive responsiveness derived from dynamic self-assembly behavior, making them attractive platforms for biofunctional supramolecular materials. Despite t...Self-assembling fibrous materials exhibit tunable properties and adaptive responsiveness derived from dynamic self-assembly behavior, making them attractive platforms for biofunctional supramolecular materials. Despite the recognized importance of dynamic behavior in self-assembling systems, the relationship between dynamics and cellular interactions remains poorly understood. Herein, we investigated this relationship using peptide amphiphiles (PAs) as model fiber-forming self-assembling molecules. By modifying hydrogen-bond-forming units at the peptide N-terminus or within the alkyl domain, we tuned the dynamics and intermolecular interactions of PA assemblies without altering their fibrous morphology. Replacement of the N-terminal amide group with a urea group decreased the dynamics of the assemblies through enhanced intermolecular hydrogen bonding and π-π stacking interactions, whereas introduction of an additional amide group in the alkyl chain increased dynamics. These changes in dynamics influence interactions with cell membranes and subsequent cellular uptake. PAs containing urea groups exhibited strong membrane affinity and efficient cellular uptake, while more dynamic assemblies showed reduced uptake. These findings highlight the dynamics of self-assembling materials as an important design parameter for controlling cellular interactions and cellular internalization, offering a new strategy for the rational design of self-assembling materials for drug delivery applications.
Biomacromolecules
· 2026 Jun · PMID 42272275
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A surfactant-like peptide (SLP) bearing six non-native 3-(4-pyridyl)-l-alanine (Pal) residues and a C-terminal arginine residue, PalR, is shown to exhibit pH-dependent self-assembly which arises from the acid-base proper...A surfactant-like peptide (SLP) bearing six non-native 3-(4-pyridyl)-l-alanine (Pal) residues and a C-terminal arginine residue, PalR, is shown to exhibit pH-dependent self-assembly which arises from the acid-base properties of the Pal residue (p ∼ 5). At a native pH of 2.4, "polyelectrolyte" correlation hole scattering is observed due to the electrostatic repulsion of highly charged molecules. The scaling of the domain size with concentration agrees with theoretical predictions for weakly charged flexible polyelectrolytes in a semidilute solution. In contrast, twisted nanotapes are observed at pH 7. The nanotapes are shown to comprise β-sheet structures packed in interdigitated bilayers. Atomistic molecular dynamics (MD) simulations confirmed the bilayer structure of the nanotapes, with extensive hydrogen bonding, and a twisting tendency. The novel SLP can stabilize water-in-oil emulsions at pH 7, forming β-sheet bilayer structures at the water droplet interface. PalR represents a model polyelectrolyte system with additional self-assembly and emulsion stabilization properties at neutral pH.
Cai H, Zhu Z, Zhang Z
… +5 more, Yu X, Gao YQ, Yang L, Qi M, Lu H
Biomacromolecules
· 2026 Jun · PMID 42269115
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Natural polyphenols extensively interact with proteins, with proline-rich proteins (PRPs) identified as their primary binding partners. While the structural rigidity of proline is widely considered as the main driver of...Natural polyphenols extensively interact with proteins, with proline-rich proteins (PRPs) identified as their primary binding partners. While the structural rigidity of proline is widely considered as the main driver of these interactions, its exact molecular role remains poorly understood. In this study, we utilize poly(-proline) (PLP) and polysarcosine (PSar) as structurally related but conformationally distinct minimalist models to delineate these interactions. Surprisingly, both the rigid PLP and the highly flexible PSar exhibit strong, micromolar-level binding affinities with polyphenols. Isothermal titration calorimetry (ITC) and molecular dynamics (MD) simulations reveal that their binding modes have different thermodynamic profiles dictated by backbone flexibility. For the rigid PLP, binding is synergistically driven by enthalpy and entropy; hydrogen bonds provide enthalpic stabilization, while solvent displacement yields entropic gains. In contrast, the flexible PSar backbone introduces a conformational entropy penalty upon binding. Leveraging this unexpected high-affinity interaction, a hydrogel with the noncovalent/covalent network using EGCG and star-shaped PSar polymers was fabricated, exhibiting unique macroscopic assembly and sustained release capabilities. In conclusion, our study provides a unified thermodynamic framework for understanding the interactions between natural polyphenols and polypept(o)ides.
Biomacromolecules
· 2026 Jun · PMID 42268731
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Machine learning (ML) is transforming materials research, yet potential for biopolymer discovery remains constrained by fragmented data and nonstandardized reporting. Biopolymers differ significantly from synthetic polym...Machine learning (ML) is transforming materials research, yet potential for biopolymer discovery remains constrained by fragmented data and nonstandardized reporting. Biopolymers differ significantly from synthetic polymers, requiring specialized approaches to represent their biosynthetic origins, hierarchical structures, and application-specific metrics. In this Perspective, we identify three core challenges limiting biopolymer representation: information encoding, data quality, and data sharing. We describe the most pressing issues and propose commensurate approaches to address each key challenge. Recommendations include the design and adoption of biopolymer-specific fingerprinting and representation frameworks, development of hybrid human-large language model (LLM) data extraction strategies, and expanding Findable, Accessible, Interoperable, Reusable (FAIR)-compliant repositories. We propose a robust foundation to define interoperable, high-quality data sets that capture the full context of biopolymer materials. Standardized metadata, shared ontologies, and community-driven infrastructure would enable scalable, reproducible workflows and accelerate the ML-driven development of biopolymers.
Biomacromolecules
· 2026 Jun · PMID 42261619
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Chitin is a ubiquitous marine biopolymer, yet its role as a functional biointerface in higher plants remains poorly understood. This study elucidates the molecular mechanisms driving the robust underwater adhesion of the...Chitin is a ubiquitous marine biopolymer, yet its role as a functional biointerface in higher plants remains poorly understood. This study elucidates the molecular mechanisms driving the robust underwater adhesion of the surfgrass in high-energy rocky intertidal zones. Unlike sediment-rooting species, secretes a hierarchical adhesive matrix comprising fibrous extracellular matrices (ECMs) and granular mucilage matrix (GMM) microparticles. Histochemical and proteomic analyses identify the GMM as a specialized filler characterized by peripheral enrichment of -acetyl-d-glucosamine (GlcNAc). This architecture is integrated through high-affinity molecular docking with cognate chitin-binding proteins (CBPs) identified within the root cell wall. These findings reveal a previously unrecognized CBP-based underwater adhesion strategy. This mechanism provides a promising biomimetic template for chitin-based underwater adhesives and marine reforestation technologies to enhance blue carbon sequestration.
Chen Y, Shan F, Yuan J
… +3 more, Pan Y, Duan Y, Chen G
Biomacromolecules
· 2026 Jun · PMID 42252588
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Synthetic glycopolymers are potent immunomodulators, yet the role of programmable interfacial cues in engaging Toll-like receptors (TLRs) remains poorly defined. Here, we investigate the self-assembly behavior of degrada...Synthetic glycopolymers are potent immunomodulators, yet the role of programmable interfacial cues in engaging Toll-like receptors (TLRs) remains poorly defined. Here, we investigate the self-assembly behavior of degradable amphiphilic glycopolymers synthesized via radical ring-opening copolymerization. We demonstrate that dendritic cell (DC) maturation exhibits a pronounced nonlinear dependence on backbone hydrophobicity, with an MDO molar fraction between 30 and 40% identified as the "sweet spot" for maximizing DC maturation markers (CD80/CD86, MHC II, and CCR7). By integrating ANS fluorescence assays, multiscale DPD simulations, and molecular docking, we confirm that this dependence is primarily dictated by the formation of surface "hydrophobic patches." Specifically, a surface hydrophobic patch content of ∼29% (exemplified by the PGM-4 formulation) provides the ideal interface for TLR4-associated signaling by optimizing the balance between hydrophobic anchoring and multivalent glycan recognition, as evidenced by inhibition studies with the TLR4-selective antagonist TAK-242. Furthermore, these nanoparticles maintain sufficient structural stability in the short term while exhibiting enzyme-responsive backbone degradation over a longer duration. This study establishes a quantitative framework for designing "patchy" glyco-nanoparticles, where the synergy between hydrophobic domains and glycan clusters dictates potent adjuvant activity.
Biomacromolecules
· 2026 Jun · PMID 42252577
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Herein, novel biobased polymers with adhesion properties to glass were obtained from glycerol-derived vinyl ethers with cyclic acetal substituents, possessing short alkyl chains at the acetal position. The radical copoly...Herein, novel biobased polymers with adhesion properties to glass were obtained from glycerol-derived vinyl ethers with cyclic acetal substituents, possessing short alkyl chains at the acetal position. The radical copolymerization of this cyclic vinyl ether and vinyl acetate was conducted, followed by saponification to form the poly(vinyl butyral)-like polymer. The obtained copolymers showed similar thermal properties to poly(vinyl butyral) and, more importantly, exhibited high adhesion properties to glass, suggesting that a biobased polymer analogous to poly(vinyl butyral) could be obtained through radical copolymerization and one polymer reaction.
Axioti E, Berfi NA, Jacob PL
… +14 more, Saller KM, Maitland GL, Patel A, Paruchuri SN, Topham PD, Derry MJ, Chatterjee S, Couturaud B, Galantini L, Francolini I, Cuzzucoli Crucitti V, Chauhan VM, Cavanagh RJ, Taresco V
Biomacromolecules
· 2026 Jun · PMID 42249537
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Recent studies have highlighted the limitations of conventional high degrees of PEGylation in drug delivery systems, including immune recognition and reduced efficacy. Approaches such as poly(ethylene glycol) (PEG) isome...Recent studies have highlighted the limitations of conventional high degrees of PEGylation in drug delivery systems, including immune recognition and reduced efficacy. Approaches such as poly(ethylene glycol) (PEG) isomerization and shortening of PEG chains have emerged as strategies to mitigate anti-PEG immune responses while preserving key physicochemical properties required for drug delivery. Inspired by these advancements, this study aims to enzymatically synthesize new hybrid polymers incorporating a limited fraction of PEG and biosourced polyols, such as glycerol and diglycerol, as the hydrophilic counterpart, minimizing the amount of PEG by 50% (compared to our previous work). These novel adipate-based tetrapolymers, generated using four different starting materials, outperformed previous systems, offering a tunable and sustainable design for nanomedicine. By strategically limiting the PEG fraction, we preserved the functional benefits of PEGylation, including stealth and amphiphilicity, while advancing toward greener chemistry. The resulting biodegradable PEGylated polyesters were formulated from film rehydration of solid dispersions and increased the water solubility of the model drug curcumin via direct encapsulation of the compound in polymeric nanoparticles. The best performing polymer variant consisted of diglycerol, 1,6-hexanediol, and PEG combined with divinyl adipate (PEGDGA-Hex 50%). Its drug interactions, colloidal stability, biodegradability, and biocompatibility, in both in vitro (Caco2, human intestinal epithelial cells MCF-7, human breast cancer cells, and MDA-MB-231 late-stage triple-negative breast cancer cells) and invertebrate in vivo models that align with 3R principles ( and ), support its potential use in systemic drug delivery.