Hackenstrass K, Solihat NN, Nousiainen P
… +4 more, Österberg M, Florisson S, Wohlert J, Wohlert M
Biomacromolecules
· 2026 Jun · PMID 42012012
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Lignin solubility is critical for extraction, tailoring processing, and downstream applications. Understanding the factors governing its solubility helps understand the behavior of this chemically heterogeneous aromatic...Lignin solubility is critical for extraction, tailoring processing, and downstream applications. Understanding the factors governing its solubility helps understand the behavior of this chemically heterogeneous aromatic biopolymer that has found increasing use in recent years. This study explores the molecular weight dependence of lignin solubility across different solvents. Molecular dynamics simulations are linked to experimental solubility measurements via a ranking of solvents. This integrated approach combines the strength of atomistic insights from simulations with experimental validation. The free energy of solvation and its enthalpic and entropic contributions are determined, and specific interactions such as hydrogen bonds and π-π stacking are quantified. The results show that differences in lignin solubilization efficiency between organic solvents and water are primarily enthalpy-driven with a smaller entropic contribution. In contrast to simplified solubility parameter approaches, molecular dynamics simulations provide a holistic view of lignin solubility and are shown to be a useful tool for understanding its solubilization mechanisms.
Martínez-Orts M, Fuentes E, Gabaldón Y
… +3 more, Berrocal JA, Albertazzi L, Pujals S
Biomacromolecules
· 2026 May · PMID 41995357
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Supramolecular Polymers (SPs) can undergo reversible self-assembly in response to internal or external stimuli. Design strategies based on the benzene-1,3,5-tricarboxamide (BTA) core are gaining increasing attention. In...Supramolecular Polymers (SPs) can undergo reversible self-assembly in response to internal or external stimuli. Design strategies based on the benzene-1,3,5-tricarboxamide (BTA) core are gaining increasing attention. In this study, we describe a BTA amphiphile that self-assembles into supramolecular fibers in water and is able to respond to both light and enzymatic activity. An azobenzene moiety (AZB) and Gly-Phe-Leu-Gly amino acid sequence (GFLG) were incorporated into the BTA monomer skeleton to build three identical wedges that respond to light and Cathepsin B activity. The synergistic application of two orthogonal stimuli enabled modulation of the assembly of BTA-AZB-GFLG fibers through the cooperative response to stimuli. These findings provide new insights into the use of SPs for future drug delivery applications.
Piedmont ER, Distaffen HE, Crompton LC
… +3 more, Krauss TD, Nilsson BL, Partridge BE
Biomacromolecules
· 2026 May · PMID 41988752
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Protein folding is essential for maintaining cellular homeostasis. When proteins misfold, aggregation can occur, contributing to a variety of diseases. Amphiphilic naphthyl-benzyl ether dendrons were recently reported to...Protein folding is essential for maintaining cellular homeostasis. When proteins misfold, aggregation can occur, contributing to a variety of diseases. Amphiphilic naphthyl-benzyl ether dendrons were recently reported to mimic natural chaperone systems by reducing the extent of fibrillation of an amyloid beta (Aβ) peptide fragment. Herein we develop this system using a slower-aggregating mutant Aβ peptide and the essential therapeutic protein, insulin. We show that amphiphilic dendrons strictly mimic the holdase function of chaperones by preventing aggregation, rather than slowing aggregation or disaggregating preformed fibrils. We demonstrate that the activity of these molecules tolerates minor changes to their structure and translates from the model Aβ peptide to insulin without structural optimization. Moreover, second-generation dendron effectively eliminates insulin aggregation for multiple days in the presence of chemical and mechanical stressors. These findings expand both our understanding and the potential therapeutic relevance of amphiphilic dendrons as an emerging approach to tackle protein aggregation.
Biomacromolecules
· 2026 May · PMID 41988684
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Fluid gels are soft materials formed by shearing biopolymer solutions during the sol-gel transition. Their ability to yield and flow beyond a critical stress makes them attractive for designing versatile, biocompatible m...Fluid gels are soft materials formed by shearing biopolymer solutions during the sol-gel transition. Their ability to yield and flow beyond a critical stress makes them attractive for designing versatile, biocompatible materials in food, health care and medical applications. Although it is well established that both microstructure and mechanical properties depend on the shear applied during gelation, a unified physical framework linking these features remains lacking. Here, using κ-carrageenan gels as a model system, we use a combination of rheology and confocal microscopy to tackle their shear-induced structuring in fluid gels. We identify a thermo-rheological memory in κ-carrageenan gels formed under flow and show that it arises from a competition between shear and interparticle adhesion, captured by an Adhesion number. The resulting microstructural evolution is reminiscent of the behavior of attractive particulate dispersions under simple shear flow, thereby bridging gels made of macromolecules and particulate gels. This framework provides a route to tune fluid gel properties without altering their composition.
Biomacromolecules
· 2026 May · PMID 41986150
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-Phenyloxycarbonyl-amino acids (NPCs) are promising monomers to synthesize both polypeptides and polypeptoids exhibiting great tolerance for nucleophiles. However, the polymerization mechanism of NPCs remains unclear sin...-Phenyloxycarbonyl-amino acids (NPCs) are promising monomers to synthesize both polypeptides and polypeptoids exhibiting great tolerance for nucleophiles. However, the polymerization mechanism of NPCs remains unclear since it is hard to distinguish intermediates including -carboxyanhydrides (NCA) from byproducts of direct polycondensation. In this contribution, the polycondensation pathway is disproved by the impossible polymerization of alanine dimer NPC. Isocyanate acid (ICA) has been captured as an intermediate of NPC polymerization. In an attempt to monitor the polymerization of N-labeled leucine-NPC by N NMR for the first time, reactive species including ICA are identified and traced. A kinetic model is established based on the N NMR data and validated by Monte Carlo simulation. Two possible polymerization pathways are evidenced by a density functional theory (DFT) calculation. The ICA-meditated NCA ring-closing pathway is preferred over the direct NCA ring-closing pathway for lower Gibbs energy barriers. A direct ring-closing path is feasible only for Sar-NPC, which explains its low polymerization reactivity.
Naka R, Terada K, Willson L
… +4 more, Masunaga H, Tsuchiya K, Cosgrove DJ, Numata K
Biomacromolecules
· 2026 May · PMID 41985885
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This study demonstrated that covalently localized zwitterionic moieties in zwitterionic polypeptides (ZIPs) effectively disrupt hydrogen bonds in cellulosic substrates, including filter paper and plant cell wall material...This study demonstrated that covalently localized zwitterionic moieties in zwitterionic polypeptides (ZIPs) effectively disrupt hydrogen bonds in cellulosic substrates, including filter paper and plant cell wall materials, without significant cytotoxicity. ZIPs with varying densities of zwitterionic side chains were synthesized via the postpolymerization modification of histidine-containing oligopeptides. The newly developed ZIPs predominantly comprised repeating units with zwitterionically converted side chains. Such ZIPs can cleave multiple hydrogen bonds by anchoring the zwitterionic structure at specific sites, thereby partially dissociating the polysaccharide chains in the cell wall. They are especially effective in dissolving amorphous cellulose, even at low concentrations in aqueous solutions. Importantly, this effect was achieved with minimal cellular toxicity, harnessing the advantages of ionic liquid-like properties while mitigating their high-toxicity limitations. This biofriendly approach to cell wall denaturation highlights a novel method for controlling hydrogen bond networks in polysaccharides and cell walls. These findings indicate a new approach for reducing biomass recalcitrance and developing next-generation biobased materials and fuels derived from plant cell walls.
Perez-Lloret M, Parisi C, Laneri F
… +7 more, Leone GM, Barbagallo C, Mangano K, Nicoletti F, Béni S, Malanga M, Sortino S
Biomacromolecules
· 2026 May · PMID 41982208
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In this contribution, we report the design, synthesis, photochemical characterization, and biological validation of a novel, photoresponsive β-cyclodextrin branched polymer () and its nanoassembly with doxorubicin (). Th...In this contribution, we report the design, synthesis, photochemical characterization, and biological validation of a novel, photoresponsive β-cyclodextrin branched polymer () and its nanoassembly with doxorubicin (). This tailored polymer covalently integrates multiple bichromophoric dyads based on nitroaniline- and coumarin-derived motifs within its macromolecular scaffold. Excitation of the with visible blue light results in the generation of nitric oxide (NO) from the nitroaniline moiety, and the parallel restoration of the typical emission of the coumarin fluorogenic unit, initially suppressed by Förster Resonance Energy Transfer (FRET), which acts as an optical self-reporter for the photoreleased NO. These photochemical properties are enhanced relative to those of the isolated monomer , synthesized as a model compound, and are well preserved after entrapment within the polymeric network. This feature enables real-time optical monitoring of the NO photodelivery in cancer cells using fluorescence microscopy. Preliminary toxicity experiments carried out with -sensitive and -resistant cancer cells demonstrate that is well tolerated in the dark but induces cell death under light irradiation. Besides, the negligible cytotoxic action of , used well below the therapeutic doses, alone or in combination with the polymer in the dark, is enhanced in both cell lines under light irradiation exclusively when the drug is combined with as a result of the combined action of NO.
Biomacromolecules
· 2026 May · PMID 41978546
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Blending lignin in polylactide (PLA) could simultaneously promote lignin valorization and tackle the limitations of PLA. Still, the lack of compatibility between lignin and PLA typically requires chemical modification of...Blending lignin in polylactide (PLA) could simultaneously promote lignin valorization and tackle the limitations of PLA. Still, the lack of compatibility between lignin and PLA typically requires chemical modification of lignin's hydroxyl groups, which could affect the already slow biodegradation rate. Here, the impact of the molecular structure of different lignin types on the properties and degradation processes of PLA/lignin films was investigated. Alkaline lignin and Kraft lignin were blended with PLA as received and after acetylation and/or fractionation. The PLA/lignin materials were aged under hydrolytic and simulated industrial composting conditions. During hydrolytic degradation, PLA/lignin materials with acetylated lignin showed an accelerated degradation rate during the early stages, as a consequence of lignin deacetylation and the release of acetic acid that catalyzed ester hydrolysis. Our results demonstrate that the molecular structure and weight of lignin influence both the physicochemical properties and morphology of the films, as well as the subsequent degradation process.
Yang Y, Pan F, Jiang C
… +10 more, Li X, Fan X, Sun Z, Zhang Y, Wan S, Chen P, Zhong Z, Zhang P, Zhang D, Li Y
Biomacromolecules
· 2026 May · PMID 41972423
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Biodegradable hydrogels represent an effective healing biomaterial for wounds. However, the fabrication of smart hydrogels containing unstable hemiaminal structures remains challenging. Here, we report a biodegradable he...Biodegradable hydrogels represent an effective healing biomaterial for wounds. However, the fabrication of smart hydrogels containing unstable hemiaminal structures remains challenging. Here, we report a biodegradable hemiaminal-type polymeric hydrogel with formaldehyde (FA)-fixed (FP-hydrogel), synthesized via a one-pot aldimine condensation of poly(ethylene glycol) diamines (PEG-DAs) and polyformaldehyde (PFA). This design leverages the stable semiclosed eight-membered cyclic hemiaminal structures within the hydrogel network, which confer remarkable mechanical strength, self-healing capability, and plasticity. The FP-hydrogel degrades in response to diverse biological signals, including acidic pH, reactive oxygen species (ROS), and glutathione (GSH). Active FA is released from FP-hydrogel under weakly acidic conditions (pH 6.5) with a release rate of 74% and displays a significant antibacterial effect, which enables the healing of acute bacterial-infected wounds at safer FA concentrations compared to the commercial urotropine. In addition, the hydrogel effectively scavenges overexpressed ROS in chronic diabetic wounds and modulates the wound microenvironment. Consequently, it accelerates the healing processes of both acute bacteria-infected and chronic diabetic wounds due to the specific responsiveness of hemiaminal structures to multiple physiological signals in the complex wound microenvironment, demonstrating its promising use as versatile and advanced wound dressings.
Terada K, Takemura S, Naka R
… +4 more, Tsuji Y, Masunaga H, Tsuchiya K, Numata K
Biomacromolecules
· 2026 May · PMID 41964967
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Resilin, an elastic protein found in insect cuticles, is exceptionally resilient because of its amino acid sequence and dityrosine cross-linking. In this study, the chemoenzymatic synthesis of resilin-mimetic polypeptide...Resilin, an elastic protein found in insect cuticles, is exceptionally resilient because of its amino acid sequence and dityrosine cross-linking. In this study, the chemoenzymatic synthesis of resilin-mimetic polypeptides based on minimal peptide motifs incorporating glycine, proline, serine, and tyrosine residues is reported. Using papain-catalyzed copolymerization of tripeptide motifs (GPG: glycine-proline-glycine and SYS: serine-tyrosine-serine) and subsequent dityrosine cross-linking with horseradish peroxidase, we synthesized polypeptides mimicking key structural features of resilin. SYS-rich and GPG-rich copolypeptides were selectively separated from the polymerization mixture based on solubility. Structural analyses revealed that the SYS-rich copolypeptides adopted β-sheet-rich conformations and exhibited low solubility, whereas the GPG-rich copolypeptides were disordered and highly soluble. Despite their lower molecular weight, the GPG-rich copolypeptides formed stable dityrosine cross-linked networks under aqueous conditions, as confirmed by spectroscopic and rheological measurements. These findings demonstrate that short, bioinspired peptide motifs can construct simplified yet structurally relevant resilin-mimetic materials.
Biomacromolecules
· 2026 May · PMID 41960769
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Efficient gene delivery coupled with tumor-specific cell death remains a key challenge in cancer gene therapy. Herein, we report a multifunctional cationic polymer (PFFc) that integrates gene delivery and ferroptosis ind...Efficient gene delivery coupled with tumor-specific cell death remains a key challenge in cancer gene therapy. Herein, we report a multifunctional cationic polymer (PFFc) that integrates gene delivery and ferroptosis induction. Low-molecular-weight PEI (600 Da) was used as a backbone and cross-linked with fluorinated and ferrocene-functionalized epoxides via ring-opening polymerization to yield fluorinated linker polymer (PF), ferrocene linker polymer (PFc), and their copolymer (PFFc). Fluorinated chains imparted hydrophobicity, self-assembly, and biocompatibility, while ROS-responsive thioacetal-ferrocene units served as an intracellular labile iron source, promoting Fenton reactions to induce ferroptosis. Structure-activity relationship studies showed that PFFc could achieve an optimal balance between the transfection efficiency and cytotoxicity. In proliferation assays, PFFc/p53 polyplexes exhibited strong gene-specific cytotoxicity, surpassing nontherapeutic controls (pGL-3) and even PF/p53 group, highlighting the critical role of p53. Mechanistically, PFFc/p53 simultaneously increased intracellular ROS via ferrocene-mediated Fenton reactions and suppressed the SLC7A11-GSH antioxidant axis, weakening antioxidant defenses and causing lipid peroxide accumulation, leading to efficient ferroptosis. Rescue experiments with ferroptosis inhibitors confirmed this mechanism. Overall, PFFc enables synergistic gene delivery and ferroptosis induction, achieving high transfection efficiency while precisely regulating programmed cell death, providing a promising platform for multifunctional antitumor nanomedicine.
Biomacromolecules
· 2026 May · PMID 41954390
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Rapamycin (Rapa) is a potent inhibitor of the mammalian target of rapamycin complex 1 (mTORC1) with possible applications in multiple diseases; however, it and its analogues exhibit low solubility, variable bioavailabili...Rapamycin (Rapa) is a potent inhibitor of the mammalian target of rapamycin complex 1 (mTORC1) with possible applications in multiple diseases; however, it and its analogues exhibit low solubility, variable bioavailability, and dose-limiting side effects. To engineer a long-release carrier, we employ Rapa's cognate receptor (FKBP12) to modulate its solubility, rate of release, and cellular uptake. To target its internalization into cancer cells under stress with an unfolded protein response (UPR), we use an L-peptide that binds cell-surface glucose-regulated protein 78 (GRP78). Herein, the L-peptide was fused to five FKBP domains linked by an elastin-like polypeptide (ELP) selected to form a biomolecular condensate depot at body temperature. This novel GRP78-targeted carrier (L-5FV) was characterized by UV-vis spectrophotometry, dynamic light scattering (DLS), surface plasmon resonance (SPR), and dialysis under sink conditions to assess its thermosensitivity, particle assembly, binding kinetics to both Rapa and GRP78, and drug release, respectively. Functional delivery of cellular internalization and mTORC1 inhibition were confirmed using fluorescence microscopy and Western blot in dose- and time-dependent manners in a breast cancer cell line, BT-474. Both targeted and untargeted formulations are phase-separated at physiological temperatures and exhibit nanomolar affinity for FKBP12 and Rapa. Notably, L-5FV demonstrated a more significant cellular association and inhibition of p-rpS6, a mechanistic target of mTORC1 activity. This report provides insight into how to construct long-release, molecularly targeted drug carriers with applications in UPR-active cancers.
Sha L, Wu F, Pan S
… +22 more, Hu C, Ding G, Sun X, Wang N, Zhou X, Zhang X, Zhou S, Yang H, Li K, Xu J, Guo G, Li Y, Zhou Y, Cao Z, Yin K, Yuan T, Zhong L, Mu B, Li J, Zhang W, Li Y, Pan S
Biomacromolecules
· 2026 May · PMID 41950466
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Hepatocellular carcinoma (HCC) is the third leading cause of cancer-related death worldwide, with limited therapeutic options. Cucurbitacin B () demonstrates potent anti-HCC activity but suffers from systemic toxicity an...Hepatocellular carcinoma (HCC) is the third leading cause of cancer-related death worldwide, with limited therapeutic options. Cucurbitacin B () demonstrates potent anti-HCC activity but suffers from systemic toxicity and poor pharmacokinetics. To address these challenges, we developed a series of asialoglycoprotein receptor (ASGPR)-targeted small molecule-drug conjugates (SMDCs) for the precision delivery of . The trivalent conjugate SMDC exhibited efficient ASGPR-mediated cellular uptake and controlled drug release. It induced both autophagy and immunogenic cell death, triggered ROS-mediated DNA damage, activated the DNA damage response, and arrested the cell cycle, consequently enhancing the radiosensitivity of HCC cells. In HepG2-derived models, SMDC achieved superior tumor accumulation, suppressed tumor growth by 76% at 30 mg/kg, and synergized with low-dose radiotherapy (2 Gy) to achieve 98% tumor inhibition, all with no observable systemic toxicity. This ASGPR-targeted platform, particularly in combination with radiotherapy, represents a promising precision chemoradiotherapy strategy for HCC.
Biomacromolecules
· 2026 May · PMID 41944692
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The interface of biomolecular condensates plays a crucial role in droplet stability, growth, and biochemical function, yet their properties remain poorly understood. Here, we develop an inhomogeneous mean-field theory to...The interface of biomolecular condensates plays a crucial role in droplet stability, growth, and biochemical function, yet their properties remain poorly understood. Here, we develop an inhomogeneous mean-field theory to investigate the interfacial structure of condensates formed by polypeptides containing positively charged, polar, and aromatic residues in aqueous solutions. Our study focuses on the synergistic interplay between electrostatic interactions among charged residues and specific nonelectrostatic interactions among aromatics. We systematically explore how charge fraction α, aromatic fraction β, specific interaction strength ε, and salt concentration ρ regulate interfacial organization in aqueous solutions. At finite α, the condensate interface typically exhibits an electric double-layer structure with a positively charged periphery surrounded by a diffuse counterion cloud. In the absence of added salt, the polypeptide concentration profile develops a depletion layer on the supernatant side and an overshoot on the coacervate side of the interface. Increasing ρ narrows the interfacial width and weakens the local charge separation in condensates stabilized by specific attractions. The electrostatic potential displays an asymmetric diffuse profile across the interface. Overall, our predictions are qualitatively consistent with experimental observations, and the insights provided here may aid the rational design of biomolecular condensates with tailored interfacial properties.
Biomacromolecules
· 2026 May · PMID 41944539
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Cholera is a diarrheal disease caused by , which secretes cholera enterotoxin (CTX) in the small intestinal epithelium. The pentameric B subunit (CTB) of CTX binds to glycans on the cellular surface through a primary bin...Cholera is a diarrheal disease caused by , which secretes cholera enterotoxin (CTX) in the small intestinal epithelium. The pentameric B subunit (CTB) of CTX binds to glycans on the cellular surface through a primary binding site for GM glycosphingolipid or galactose. However, GM is undetectable in the human SI, and fucose is a key alternative ligand. Previously, we developed linear norbornenyl glycopolymers that block CTB binding by forming CTB-glycopolymer aggregates. Here, we evaluate CTB-glycopolymer binding kinetics under flow conditions using surface plasmon resonance. A copolymer randomly displaying galactose and fucose formed stable complexes with nanomolar avidity, driven primarily by slow dissociation, even from low CTB density surfaces. In contrast, an equimolar mixture of homopolymers exhibited similar binding avidity and comparable inhibitory efficacy but did not display slow dissociation. These findings underscore the importance of codisplaying galactose and fucose on a single polymer backbone for stable complex formation and for developing clinically useful therapies.
Biomacromolecules
· 2026 May · PMID 41940681
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The extracellular matrix (ECM) is a critical three-dimensional scaffold that maintains the structural integrity and physiological function of tissues and organs. While native ECM structural proteins like collagen and ela...The extracellular matrix (ECM) is a critical three-dimensional scaffold that maintains the structural integrity and physiological function of tissues and organs. While native ECM structural proteins like collagen and elastin have been widely studied for their ECM-mimetic properties, their clinical translation faces challenges such as pathogen transmission, immunogenicity, and batch variability. Self-assembling peptides, particularly collagen-mimetic peptides (CMPs) and elastin-like peptides (ELPs), offer a promising alternative due to their reproducibility, low immunogenicity, and tunable properties. Recent advances in peptide design have enabled precise mimicry of the ECM's composition, hierarchical structure, nanoscale morphology, and biological function. These peptides can controllably self-assemble into nanofibers, hydrogels, and 3D scaffolds that recapitulate key aspects of the native ECM microenvironment, broadening their utility in biomedical applications. This review summarizes progress in the design and application of ECM-mimetic peptides, focusing on their roles in tissue engineering, regenerative medicine, and drug delivery. We also discuss emerging challenges and future directions to advance the field toward clinical implementation.
Ratnatilaka Na Bhuket P, Eastwood JRB, Qin Z
… +7 more, Kessler JL, Li Y, Katz D, Whitby FG, Hill CP, Kirshenbaum K, Yu SM
Biomacromolecules
· 2026 May · PMID 41931485
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The collagen triple helix, composed of three protein strands with a repeating GlyXaaYaa sequence, achieves maximum stability with proline (Pro) and hydroxyproline (Hyp) at the Xaa and Yaa positions. Previously, we demons...The collagen triple helix, composed of three protein strands with a repeating GlyXaaYaa sequence, achieves maximum stability with proline (Pro) and hydroxyproline (Hyp) at the Xaa and Yaa positions. Previously, we demonstrated that peptoid residues (N-substituted glycines, N-Glys) at the Xaa position significantly enhance the triple helix stability. Here, we show that N-Glys at the Yaa position also stabilize the triple helix, with stability influenced by the N-Gly's position and side chain structure. Over 22 N-Glys with various natural and unnatural side chains were investigated using CD spectroscopy, X-ray crystallography, and computational simulations. The results show that N-Glys at the Yaa position support triple helical folding and are more stabilizing than their corresponding amino acids but less so than Hyp due to suboptimal ϕ-ψ angles. Metadynamics simulations revealed that N-Glys at the Yaa position have a broader conformational space due to minimal steric hindrance from neighboring glycine residues. N-Glys' side chain bulkiness influenced stability only at the Xaa position and not the Yaa position. Additionally, only -isomers of chiral N-C-branched N-Glys were compatible with triple helical folding, presenting different backbone conformations and accessible rotamers based on their position. At the Yaa position, ()-N-(1-phenylethyl)-Gly (Nspe) stabilized the triple helix better than all other residues except Hyp through newly discovered intrachain CH···π interactions. This research deepens our understanding of triple helical folding and introduces new strategies for designing stable collagen mimetic peptides with diverse side chains, expanding potential applications in biomedicine and biomaterials.
Biomacromolecules
· 2026 May · PMID 41928675
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Liquid crystalline elastomers (LCEs) are being increasingly explored as biomaterials; however, many LCE properties were not designed with biomedical use in mind. Here, we examine LCE hydrolytic degradation, including inv...Liquid crystalline elastomers (LCEs) are being increasingly explored as biomaterials; however, many LCE properties were not designed with biomedical use in mind. Here, we examine LCE hydrolytic degradation, including investigating approaches to accelerate degradation and whether thermal and mechanical properties change with degradation. Among 3D-printable LCE chemistries, we find that networks formed via thiol-Michael addition followed by thiol-ene photo-cross-linking degrade most rapidly. The integration of hydrophilic chain extenders (e.g., PEG) accelerates LCE degradation and demonstrates their potential tunability for various applications. We monitor representative LCEs throughout degradation and show that as samples undergo heterogeneous surface erosion, nematic-to-isotropic transition temperatures increase, while actuation potential, alignment, and mechanical anisotropy remain stable until failure. H NMR, SAXS, and DSC studies reveal that thermal changes arise from retained degradation products enriched in liquid crystal mesogens, which increase mesogenic interactions per unit volume and require greater thermal energy to disrupt the nematic state.
Addressing the imperative of sustainable development, this study demonstrates an eco-friendly luminescent platform integrating high-efficiency room-temperature phosphorescence (RTP) with programmable humidity responsivit...Addressing the imperative of sustainable development, this study demonstrates an eco-friendly luminescent platform integrating high-efficiency room-temperature phosphorescence (RTP) with programmable humidity responsivity. Leveraging carboxymethyl cellulose (CMC) as a matrix, a covalent cross-linked network was constructed through reaction with epichlorohydrin. 4,4',4″-Nitrilotribenzoic acid (NTA) was introduced and confined within the cross-linked network, successfully yielding a multifunctional RTP material. This hierarchical architecture establishes a synergistic rigidification mechanism via covalent-hydrogen-bonding cooperativity, effectively suppressing nonradiative decay pathways while stabilizing triplet excitons. The resultant material achieved outstanding phosphorescent properties with a maximum quantum yield of 44.44% and a maximum phosphorescence lifetime of 231.20 ms. The prepared CMC-based films demonstrate excellent solvent resistance, maintaining stable phosphorescence performance even after immersion in organic solvents. Simultaneously, the material possesses unique humidity-responsive characteristics, enabling reversible information writing and encryption using water as an "ink". Moreover, this material system can be continuously drawn into fibers with distinct RTP properties via wet spinning, achieving morphological expansion from 2D films to one-dimensional fibers. This work provides a promising strategy for developing sustainable, solvent-resistant, and stimulus-responsive RTP materials with excellent processability.