Biomacromolecules最新文献

Suberin is a protective bark cell-wall polymer whose native organization remains difficult to resolve by extraction-based analysis. Here, a combination of one- and two-dimensional solid-state nuclear magnetic resonance techniques was used to examine native suberin within the intact Salix bark cell-wall material. Major glycerol and fatty-acyl motifs were identified, providing a basis for analyzing local spatial arrangement in native suberin. The characteristic 30 and 33 ppm methylene populations exhibited distinct native environments, with the 30 ppm population showing greater chemical heterogeneity, closer olefinic/aromatic contacts, and higher water accessibility, whereas the 33 ppm population exhibited a largely uniform methylene environment, restricted segmental motion, and reduced effective water accessibility. The two populations coexist within the native suberin matrix but remain partially segregated at the local scale. These data provide a native-state molecular view of aliphatic heterogeneity in bark suberin and refine current models of suberin architecture in plant cell walls.

Lignin is a sustainable photothermal material for solar interfacial evaporation, but its structural heterogeneity and poor dispersion limit efficient utilization. Here, we develop a biomass-derived bilayer LNP@CCH aerogel evaporator comprising a lignin nanoparticle (LNP)/chitosan photothermal layer and a CNF/Chitosan (CCH) water-transport layer. Fractionation reduces lignin heterogeneity and identifies a fraction with favorable photothermal properties, which is subsequently converted into size-controlled LNPs. The resulting LNP@CCH aerogel evaporator combines broadband solar absorption, low thermal conductivity, interconnected capillary channels, and water-state regulation, enabling efficient light harvesting, heat localization, water transport, and reduced apparent evaporation enthalpy. Under 1 sun irradiation, the optimized evaporator achieves an evaporation rate of 2.31 kg m⁻² h⁻¹ and a solar evaporation efficiency of 94.4%. It also exhibits stable saline water evaporation and >99% removal of major ions from real seawater, demonstrating the potential of fractionated lignin for sustainable solar desalination.

Biobased adhesives from renewable feedstocks are promising for better sustainability, but achieving both strong adhesion and degradability remains challenging. Here, we report a fully biobased adhesive based on epoxidized soybean oil, citric acid, and resveratrol. The system can be processed under multiple curing conditions, including rapid heat-gun curing and conventional oven curing, and delivers lap-shear strengths up to 21 MPa on metal substrates, outperforming many previously reported vegetable oil-based adhesives. Incorporation of resveratrol enhances adhesion and network formation due to its planar, conjugated aromaticity, avoiding the severe steric hindrance common to bulkier polyphenol systems while preserving a low-cost, bio-based composition. The adhesive also shows accelerated hydrolytic degradation under basic conditions, losing over 90% of its mass in 12 hours. These results demonstrate a scalable and sustainable adhesive platform that combines high performance and end-of-life degradability.

Cell isolation and banking face challenges, balancing cryoprotective efficacy, functional preservation, and isolation purity, requiring innovative approaches with specificity, scalability, and native functionality. We developed a transformative platform based on DNA nanohydrogels enabling dual preservation-isolation through aptamer-guided trehalose delivery in a single workflow, achieving organic solvent-free cryopreservation and high-efficiency isolation via freeze−thaw lethality disparity, termed cryoisolation. The nanohydrogels encapsulate trehalose in hydrated 3D networks, while aptamer-functionalized frameworks enable receptor-specific targeting, driving rapid cellular internalization and release within 2 h, yielding post-thaw viability comparable to that of DMSO while reducing genomic instability (67% fewer differentially expressed genes). The platform can be extended to cryopreserve mesenchymal stem cells (MSCs), confirming its applicability to sensitive primary cells without compromising functional integrity. Molecular-recognition-guided delivery creates differential freeze−thaw survival, enabling label-free isolation of target cells with >95% purity. By redesigning aptamer sequences, this modular platform demonstrates universal applicability, transforming conventional freeze−thaw cycles into precision cell-selection processes.

Refractile bodies (R-bodies) are protein assemblies that form intracellular rolls and extend into spirals in response to environmental stimuli. Type 51 R-body assembles from four Reb proteins and undergoes rapid, repeatable ∼50-fold extension. Although R-bodies were described more than 70 years ago, the roles of RebC and RebD remained unclear, whereas RebA and RebB are proposed as major components. Here, we characterize the wild-type R-body (Rb_WT) and reb gene knockout mutants using integrated biophysical analyses. RebD was incorporated as a minor component, whereas RebC was not detectably incorporated into the final assembly. Mutants lacking RebA or RebB formed rolls but lost pH-dependent extension and the ordered lamellar architecture characteristic of Rb_WT. In contrast, mutants lacking RebC and/or RebD exhibited reduced roll formation and formed β-sheet-rich aggregation. Thus, pH-responsive actuation is dictated not simply by major architectural components alone, but by a regulated assembly pathway that builds the ordered lamellar architecture.

A biopolymer-enriched matrix from hempseed waste (BMH extract) was extracted using hot water and characterized. Biochemical assays pointed out that the BMH extract contained carbohydrates, proteins, and phenols in different percentages, while NMR spectroscopy and monosaccharide analysis revealed starch as the dominant polysaccharide. The BMH extract showed biocompatibility and a stimulatory effect on fibroblast viability. Its antioxidant activity in biochemical and cellular assays was comparable to that of a known potent antioxidant. The BMH extract was added to a hyaluronic acid (HA) solution and exposed to reactive oxygen species (ROS). Rheological measurements on these samples showed that the extract provided protection from ROS-driven polysaccharide degradation, suggesting an application as a scavenger in HA-based viscosupplements. Overall, these results support using of hemp seed waste-derived matrices (either as such or as additives in biomaterials) for biomedical applications characterized by inflammation and oxidative stress to mitigate the negative effects associated with these conditions.

An angle-sensitive polarization device composed of a CNC chiral photonic crystal film and waveplate was fabricated. The modulation of rotation and incident angles on reflected polarization under a three-color laser was characterized. The waveplate endows the composite film with rotation-angle dependence to regulate linear polarization components S₁ and S₂, realizing full-space polarization distribution on the Poincaré sphere. A one-to-one correspondence between the angle combination (α, θ) and polarization states is verified. Algorithm-assisted polarization analysis enables terrain reconstruction, offering new insight for chiral-material-based polarization sensing.

Emerging as innovative multifunctional devices, antenna sensors integrate wireless communication and environmental sensing capabilities into a single architecture. Undoubtedly, it is advantageous for the development of green electronic materials to incorporate natural biomacromolecules into antenna sensors. Herein, a facile vacuum filtration process was reported for fabricating TEMPO-mediated oxidized cellulose paper (TOCP). Subsequently, highly porous Cu-1,3,5-benzenetricarboxylic acid (CuBTC) crystals were in situ introduced onto the surface of oxidized cellulose fibers via a layer-by-layer (LbL) growth technique. The TOCP/2CuBTC composite film with two growth layers exhibited a humidity-induced linear dielectric response. Moreover, simulations were performed for the antenna sensor based on the TOCP/2CuBTC film whose resonant frequency demonstrated a one-to-one correspondence with humidity levels, achieving a sensitivity of 10.6 MHz/% relative humidity (RH). Overall, this work overcomes the inherent limitation of data transmission in conventional humidity sensors and provides a novel and instructive strategy for the advancement of green low-permittivity electronic substrate materials.

Aqueous ring-opening polymerization-induced self-assembly of N-carboxyanhydrides (NCA-ROPISA) provides a powerful route to peptide-based nanomaterials, yet how polymerization outcompetes hydrolysis in water while driving self-assembly remains unclear. Here, time-resolved SAXS/WAXS reveals the mechanism of aqueous NCA-ROPISA during γ-benzyl-l-glutamate N-carboxyanhydride polymerization. Early nucleation of PEG-stabilized micelles creates nanoconfined reaction environments that favor polymerization by concentrating soluble monomers and maintaining reactive amino chain ends despite progressive acidification. Concurrently, β-sheet formation emerges at the onset of self-assembly, stabilizing nascent nuclei and directing anisotropic nanoparticle growth. These findings establish how nanoconfinement and secondary-structure formation cooperatively govern polymerization, self-assembly, and morphology development. Reminiscent of the ribosomal peptidyl transferase center, these self-generated nanoreactors exploit confinement to promote peptide-bond formation in water, identifying nanoconfinement as a general strategy for coupling polymerization, molecular folding, and self-assembly in biomimetic materials.

Fucoidan, a sulfated marine polysaccharide, provides a versatile platform for constructing biocompatible nanostructures through controlled electrostatic assembly. Here, we report ternary nanoparticles formed by sequential complexation of aquated cisplatin with fucoidan, followed by stabilization with biodegradable cationic bis-MPA dendrimers. Fucoidan extracted from Fucus vesiculosus and Undaria pinnatifida, despite their differences in composition and structure, generated nanoparticles with comparable size, surface charge, and drug content. Both systems displayed pH-responsive cisplatin release, consistent with reversible interactions between platinum aqua species and fucoidan sulfate groups. The nanoparticles preserved cisplatin’s cytotoxic activity in T98G and patient-derived glioblastoma cells and showed enhanced early intracellular platinum accumulation relative to free cisplatin. Hemocompatibility assays confirmed minimal hemolysis and no detectable impact on plasma coagulation. The nanoparticles also remained structurally stable after cryopreservation with 5% sucrose. These results identify fucoidan-cisplatin-dendrimer nanoparticles as a robust and biocompatible macromolecular platform for controlled delivery of platinum-based therapeutics.