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This study tracks how carbohydrate polymers evolve along the coffee process chain from green coffee beans to roasted coffee and spent coffee grounds (SCG), with a focus on how process history shapes the mannan-rich residue that remains after brewing. Complementary analyses by acid methanolysis, total hydrolysis, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and solution-state and solid-state nuclear magnetic resonance (NMR) were used to distinguish losses of labile carbohydrates from structural reorganization within the residual polymer matrix. Roasting and brewing progressively depleted sucrose and other accessible low-molecular-weight or weakly ordered carbohydrate fractions, whereas mannan remained the dominant carbohydrate polymer. Total hydrolysis showed that SCG contained approximately 51% mannan and 17% cellulose. At the same time, XRD, TGA, and solid-state 13C NMR indicated increasing structural order and higher thermal resistance in the spent residue, consistent with selective retention of recalcitrant mannan-rich domains and partial reorganization of cellulose and mannan. These results show that SCGs should not be viewed as a generic cellulose-rich feedstock. Instead, their process-dependent, mannan-dominant polymer structure should guide valorization strategies in food, fiber, and composite applications.
Recent advances in biomaterials have highlighted the immense potential of carbohydrate polymers (CHPs) as biocompatible, multifunctional platforms for cancer therapy. Indeed, the structural diversity, tunable chemistry, and inherent biological affinity of these polymers enable the precise design of systems for immune modulation. Moreover, light- and laser-driven strategies have emerged as powerful tools for achieving spatiotemporal control over therapeutic activation. Therefore, integrating CHPs with photothermal or photodynamic nanocomponents enables these hybrid systems to induce localized tumor ablation, trigger immunogenic cell death, and remodel the tumor immune microenvironment. These synergistic phototherapy-immunotherapy platforms eradicate primary tumors while promoting systemic antitumor immunity and immune memory formation. Therefore, this review aims to summarize recent advances in CHP-based biomaterials for light-mediated immune activation, focusing on mechanisms, design strategies, and therapeutic outcomes. Furthermore, challenges in tumor-specific targeting, deep-tissue light penetration, and clinical translation are critically discussed. Finally, future perspectives are proposed for the development of next-generation, smart, light-responsive carbohydrate nanomedicines to enable precision cancer immunotherapy.
The healing of infected wounds remains a significant clinical challenge, primarily due to persistent bacterial infections and dysregulated inflammation. In this work, we engineered an injectable bilayer hydrogel system (GHL//PCB) from carbohydrate polymers to spatiotemporally modulate macrophage metabolism and polarization via the leucine-mTORC1-HIF-1α axis. The lower layer, comprising methacrylated gelatin and dopamine-modified hyaluronic acid (GelMA/HA-DA), is loaded with leucine. This formulation activates mTORC1, stabilizes HIF-1α, and drives M1-like polarization, thereby conferring potent bactericidal efficacy against both Staphylococcus aureus and Escherichia coli. The upper layer, composed of aldehyde-modified Pluronic® F127 and carboxymethyl chitosan (PF127-CHO/CMCS), delivers the leucyl-tRNA synthetase inhibitor BC-LI-0186 to suppress mTORC1-HIF-1α signaling. This suppression promotes a metabolic shift toward oxidative phosphorylation and facilitates M2-like repolarization. Using a rat model featuring complete-thickness contaminated injuries, the GHL//PCB hydrogel sequentially eliminated bacteria, attenuated inflammation, enhanced collagen deposition, and accelerated re-epithelialization within 14 days. The hydrogel also demonstrated excellent injectability, tissue adhesion, biocompatibility, and hemocompatibility. Collectively, this work presents a carbohydrate-based biomaterial strategy that actively orchestrates the wound immune microenvironment through metabolic reprogramming, offering a promising and clinically translatable platform for the management of infected and chronic wounds.
With the rising interest in eco-safe cosmetic products due to ongoing governmental restrictions and growing public concern regarding the effects of microplastics derived from synthetic products, research for biodegradable alternatives from renewable materials has been accelerated. Carbohydrate-based polymers can be considered suitable materials due to their excellent biodegradability, renewability, abundance, and versatility. In this study, microparticles based on starch, chitosan, and cellulose derivatives were produced using different methods to obtain micrometric particles with specific structural and rheological properties. In parallel, a formulation strategy was developed to establish a sustainable Pickering emulsion platform capable of incorporating and exploiting the functional properties of the produced biodegradable microparticles. Micrometric particles from native and chemically modified tapioca starch were found compatible with the optimized Pickering emulsion formulation. At the same time, the pseudoplastic flow behavior was maintained, and specific effects regarding droplet size distribution were achieved. The results provided evidence that the synthesized microparticles could serve effectively and safely as co-stabilizers and structuring-modifying agents for sustainable cosmetic emulsion formulation, confirming the appropriateness of the proposed biodegradable starch microparticles. In contrast, chitosan-based microparticles did not yield satisfactory texture or stabilization under the tested conditions, pointing toward additional optimization and investigation. This research confirms that chemically modified starch microparticles can be introduced effectively and safely as eco-safe, sustainable ingredients for next-generation, microplastic-free cosmetic formulations.
The development of sustainable polymers from renewable resources has attracted growing attention as an alternative to petroleum-based monomers. In this study, a renewable methacrylate monomer derived from protected d-glucose (MA-IPT-GF) was synthesized and copolymerized with methyl methacrylate (MMA) via UV-induced radical photopolymerization using benzophenone as the photoinitiator. The monomer structure was confirmed by FT-IR and NMR spectroscopy, verifying the successful introduction of the methacrylate functionality into the glucofuranose framework. Photopolymerization of MA-IPT-GF with MMA produced GF-MMA copolymers, which were characterized in terms of their structural, thermal, and morphological properties. Spectroscopic analyses revealed the disappearance of the methacrylate vinyl signals after polymerization, confirming effective copolymer formation. Thermal analysis by TG/DTG and DSC demonstrated that incorporation of the glucofuranose-derived monomer slightly reduced the onset thermal stability compared with PMMA and introduced a multistep degradation profile associated with cleavage of protecting groups and subsequent backbone decomposition. A decrease in glass transition temperature was observed, which was attributed to the presence of bulky carbohydrate side groups that disrupt efficient chain packing and increase free volume within the polymer matrix. SEM analysis revealed heterogeneous surface morphology with dispersed domains within a PMMA-rich matrix, while EDX analysis confirmed the presence of chlorine-containing protecting groups in the copolymer structure. XRD results further indicated that the copolymer maintains a predominantly amorphous structure with increased structural disorder due to the incorporation of the sugar-based monomer. Overall, the results demonstrate that glucose-derived methacrylate monomers can be incorporated into MMA-based copolymers through photopolymerization, providing renewable photocurable polymer systems.
The rational use of carbohydrate polymers as functional matrices for integrating inorganic and organic components remains a key challenge in developing sustainable multifunctional materials. Here, a process-oriented, bio-inspired strategy for fabricating a chitosan-centred multifunctional composite coating is presented. This approach uniquely combines plasma-assisted activation of the silk surface, chitosan immobilisation, and subsequent controlled in situ generation of TiO2 nanoparticles in the presence of curcumin, a naturally derived polyphenolic compound. The resulting chitosan/TiO2/curcumin composite system simultaneously imparts antibacterial, UV-shielding, and photocatalytic self-cleaning functions to the silk. Chitosan provides strong antimicrobial activity, maintaining robust bio-barrier antibacterial protection in the composite system and achieving over 99.5% inhibition of Staphylococcus aureus and Escherichia coli growth. Curcumin acts as a TiO2 photosensitiser and charge-transfer mediator, suppressing electron-hole recombination and enabling efficient visible-light-driven photocatalytic activity, as confirmed by accelerated Rhodamine B dye degradation and effective coffee stain removal. Complementary UV absorption by TiO2 (UV-B) and curcumin (UV-A) delivers broad-spectrum UV protection with a UV protection factor of 32.1. Overall, this work demonstrates a distinct carbohydrate polymer-driven fabrication paradigm for engineering high-performance textiles with integrated multifunctional protective properties.
Overcoming the performance trade-offs among mechanical strength, bioactivity, and processability remains a pivotal challenge for Guided Bone Regeneration (GBR) membranes. Herein, we present a multi-level design strategy that systematically integrates material engineering across molecular, microstructural, and macroscopic scales to address this challenge. Specifically, at the macroscopic level, a sisal fiber-reinforced chitosan base layer provides robust structural support, achieving exceptional mechanical strength (39.48 MPa). At the molecular level, a hybrid hydroxyapatite co-functionalized with carboxymethyl cellulose, zoledronic acid, and phytic acid confers enhanced osteogenic activity and antioxidant capacity (87-95% DPPH scavenging). At the microstructural level, sophisticated surface micropatterning is constructed via a scalable process combining dynamic crosslinking and temperature-modulated phase separation, which actively guide cell behavior. This integrated design synergistically enhances osteogenic differentiation and mineralization, as evidenced by in vitro studies demonstrating the cooperative effects of its unique topology and sustained bioactive signals from the hybrid HAp. In a rat calvarial defect model, the membrane achieved exceptional bone regeneration (97.17 ± 1.7% BV/TV) at 8 weeks, markedly outperforming the control (64.04 ± 3.55%). This work presents a versatile platform highlighting the pivotal role of engineered carbohydrate polymers (chitosan and CMC) and plant-derived fibers in advanced bone biomaterials, offering a new design paradigm.
Mangrove ecosystems contain abundant lignocellulosic biomass and mangrove microorganisms that are capable of degrading plant polymers. In this study, a shotgun metagenomic approach was employed to explore the bacterial communities from Tanjung Piai National Park, Malaysia and their genes involved in lignocellulosic biomass degradation. A total of 148 of carbohydrate active enzymes (CAZy) genes spanning GH, CE, and AA families were identified with lignocellulolytic abilities. These enzymes included 20 cellulases, 46 hemicellulases, and 82 lignin-modifying enzymes. Approximately 89.19% of these genes were found from underexplored bacterial lineages. A set of lignocellulolytic genes derived from diverse bacterial taxa highlighted the synergistic action of mangrove bacteria in lignocellulose degradation. To validate the functionality of these genetic resources, one of the genes (BGL3_GH1) encoding a β-glucosidase was selected for expression and characterisation. The recombinant enzyme showed optimal activity at 60 ℃ and pH 7, retained up to 75% activity at 10% (w/v) NaCl. The enzyme exhibited a 1.6 to 2.1-fold in enzyme activity with glucose concentration up to 2 M. In a two-step saccharification assay using sugarcane bagasse, supplementation with recombinant BGL3_GH1 enhanced the saccharification yield (0.0674 g g- 1 biomass) compared with treatments using commercial cellulase or recombinant BGL3_GH1 alone. These findings reveal the functional diversity of lignocellulose-degrading genes in mangrove bacteria and identify recombinant BGL3_GH1 as a potential enzyme candidate for biomass conversion application. The online version contains supplementary material available at 10.1007/s13205-026-04788-x.
Corn fiber is a major carbohydrate-rich by-product of the corn-processing industry, but its efficient utilization is hindered by the structural recalcitrance of hemicellulose. To analyze its resistance structure to enzymes, hemicellulose enzymatic oligosaccharides (HEOs) were generated by hydrolyzing corn fiber holocellulose with crude enzyme from Penicillium oxalicum MCAX. Integrated analyses of monosaccharide composition, glycosidic linkages, NMR, and MALDI-TOF-MS showed that HEOs retained glucuronic acid and acetyl substituents and contained key recalcitrant features, including T-α-Xyl-(1 → 3)-Ara, T-β-Xyl-(1 → 2)-Ara, T-β-Gal-(1 → 2)-Ara side chains, Ara-Ara linkages, and a previously unreported T-α-Gal-(1 → 3)-Ara motif in corn fiber hemicellulose. Based on these findings, structural models of HEOs were proposed, providing a framework for targeted enzyme selection strategies. Among seven GH31 α-xylosidases screened from diverse sources, only rAnXyl31A from Aspergillus niger showed activity toward HEOs and synergized with MCAX to increase the release of hemicellulose-derived monosaccharides. 2D NMR analysis of hydrolysates supported cleavage of the resistant T-α-Xyl-(1 → 3)-Ara motif by rAnXyl31A and its cooperative debranching effect with MCAX, resulting in a more extensive removal of terminal α-xylosyl and α-galactosyl substitutions. These results provide structural insights into corn fiber hemicellulose recalcitrance and offer practical guidance for the rational design of enzyme systems to achieve more efficient biomass conversion and utilization.
Sepsis triggered by lipopolysaccharide (LPS) is a life-threatening condition. Inspired by the specific capture mechanism of innate proteins like LBP and CD14, we develop oxidized chitosan microspheres functionalized with hyperbranched polylysine (OCS-HBPL) as a sepsis detoxification agent. Isothermal titration calorimetry (ITC) reveals that HBPL-LPS binding is an enthalpy-driven process, distinct from the entropy-driven interaction of linear polylysine (LPL)-LPS. Validated by surface plasmon resonance (SPR), HBPL demonstrates superior affinity with a dissociation constant (KD) of 2.44 × 10-6 M, being 3.8-fold lower than that of LPL. Although both polymers show similar saturation adsorption capacities by quartz crystal microbalance with dissipation (QCM-D), HBPL exhibits significantly superior erythrocyte compatibility compared to LPL. The OCS-HBPL microspheres achieved a remarkable 73.6% LPS clearance ratio in simulated whole-blood hemoperfusion. Simultaneously, their bovine serum albumin (BSA) adsorption was restricted to 34 μg/g, only 10% of the OCS-LPL control. Crucially, the OCS-HBPL microspheres exhibit a negligible hemolysis ratio, standing in sharp contrast to the unsafe levels (>2%) observed in OCS-LPL. These results demonstrate that HBPL endows chitosan microspheres with both high LPS clearance capacity and excellent hemocompatibility. Thus, OCS-HBPL microspheres show great potential applications in sepsis treatment and open new routes in the development of biocompatible polysaccharide materials.
As the most abundant natural carbohydrate in nature, polysaccharides have emerged as core carriers and key raw materials for developing fluorescent materials (FMs) with green attributes and excellent fluorescence performance, owing to their biocompatibility, modifiability, structural diversity, and environmental friendliness. They play a decisive role in advancing the green and functional development of FMs. This review clearly defines polysaccharide-based FMs as fluorescent systems constructed with natural polysaccharides as core raw materials, and systematically analyzes the pivotal role of polysaccharides in fluorescence generation. These materials can either generate intrinsic fluorescence through cluster-triggered emission (CTE) mechanisms or serve as carriers, enhancers, and soft templates to introduce fluorescent components and regulate fluorescence properties via physical, chemical, in situ synthesis, or hybrid methods. Subsequently, the preparation methods of polysaccharide-based FMs with different morphological dimensions are summarized, and their application potential in fields such as environmental monitoring, biomedicine, information anti-counterfeiting, and intelligent textiles is discussed. Finally, the current challenges and future development trends of polysaccharide-based FMs are analyzed, aiming to highlight the core value of polysaccharides in the field of FMs and provide theoretical references and practical guidance for promoting the sustainable progress of green FMs.
β-1,3-Glucan is a bioactive polysaccharide highly relevant to functional food applications, yet large-scale production remains constrained by high costs, poor structural control, and environmental concerns. Here, we identify TaβGP from Thermosipho africanus as the first thermostable glycoside hydrolase family 161 β-1,3-glucan phosphorylase, exhibiting a half-life of 137 h (95% CI: 125.1-150.2 h) at 80 °C and strong activity with glucose as a primer, eliminating the need for costly laminaribiose. TaβGP displayed remarkable tolerance to metal ions and lignocellulose-derived inhibitors. A three-enzyme biosystem comprising TaβGP, cellobiose phosphorylase, and polyphosphate glucokinase achieved 94% conversion of 150 mM cellobiose into soluble β-1,3-glucan within 1 h, yielding monodisperse polymers (Đ = 1.05-1.08) with tunable chain lengths (average degree of polymerization 11-14). This study establishes a green and efficient enzymatic route for producing structurally uniform β-1,3-glucan from renewable cellobiose, offering a sustainable approach for the development of β-1,3-glucan with potential immunomodulatory and functional food applications.
Cellulose, as an abundant and sustainable carbohydrate polymer, has emerged as a promising platform for radiative cooling due to the intrinsic infrared activity of its C-O-C and CC vibrational bonds. However, conventional cellulose material face critical challenges in cooling efficiency, environmental durability, and scalable fabrication for outdoor portable applications. Herein, inspired by the "flexible and tough" structure of pangolin scales, a biomimetic, scalable, and high-performance ultra-lightweight radiative cooling ZnO@ZIF-8 carboxymethylated fiber paper (ZZCFP) fabricated via in-situ growth of porous core-shell ZnO@ZIF-8 (ZZ) within a carboxymethylated cellulose paper (CFP) was developed. The tight binding and uniform dispersion of ZnO@ZIF-8 with CFP endow it with a hierarchical pore structure, simultaneously enhancing light scattering and thermal emission effects, leading to outstanding solar reflectance (98.2%) and high thermal emittance (96.5%). In addition, ZZCFP exhibits remarkable mechanical robustness (16.8 MPa tensile strength) along with superhydrophobicity, UV resistance, and biodegradability. Outdoor testing demonstrates a sub-ambient cooling effect of 15.4 °C under direct sunlight. Practical applications in automotive engine and temporary strawberry storage achieved cooling of 10.6 °C and 11.7 °C, respectively. This work provides a scalable and sustainable pathway to high-performance, durable radiative cooling materials, establishing a design paradigm for multifunctional cellulose-based composites in sustainable thermal management.
Enzymatic polymerisation of sucrose creates nature-identical polysaccharides, such as poly α-1,3-glucan, offering a scalable approach to introduce biopolymers into industrial applications. In this study, we explored the solubility, diffusivity, and permeability of various fluids (CO2, O2, liquid and vapour water) in films of α-1,3-glucan and its long-chain acid esters, specifically two glucan palmitates (GP) and one glucan laurate acetate (GLA) with varying degrees of substitution (DoS), highlighting the potential of glucan derivatives in packaging and membrane separation applications. Additionally, we evaluated films' wettability through contact angle measurements and examined dimethyl carbonate as an alternative to chloroform for film production. GP2, the ester with the highest degree of substitution studied here, reached water uptake of ~2 g mm/m2 day at 100% RH, which is 400 times lower compared to the unmodified glucan. CO2 and O2 permeability exhibited patterns seen in cellulose esters, with GPs showing CO2 permeability levels higher than 100 Barrer (3.34 × 10-14 mol m/(m2 s Pa)), promising for CO2 separation in membrane processes. A quantitative correlation between water uptake in glucan- and cellulose-based materials and their structure is provided as a first tool to assess applicability of these materials in processes where water transport is a key factor.