Carbohydrate Polymers最新文献

Lignin, a complex natural 3D aromatic polymer compound known for its high thermal stability, stiffness, and ability to effectively withstand chemical and biological attacks. When combined with various other natural biomass components, lignin can offer the promise of fortifying the physical, chemical, and biological stability of matrix materials, which has garnered significant interest. Herein, through the incorporation of alginate with aminated lignin using chemical and ionic double cross-linking and freeze-drying techniques, alginate-lignin composite functional foams (SA-NAL) with improved water affinity, mechanical strength, and overall service performance have been successfully developed. Without further chemical modification, the as-fabricated SA-NAL composite foam demonstrates: i) outstanding mechanical robustness, enduring 2000 times its weight without significant deformation in dry condition, and withstanding tensile stress up to 0.67 MPa in wet condition, ii) superior water affinity and underwater superoleophobicity (θ_oil > 150° for various oils), coupled with effective oil/water separation performance (separation efficiency of 99.5 %, flux of 3.37 L·m⁻²·s⁻¹, and ultimate operating oil pressure of 2.36 kPa), and iii) exceptional resistance to light, heat and oxidation, and excellent flame retardancy. In summary, the synergy between aminated lignin and alginate materials has resulted in complementary functions for high-value applications of polysaccharide-based alginate materials.

The complexity and cost of the biorefinery industry hinder the high-value utilization of lignocellulose. Herein, we propose a green, fast, and economical oxygen-alkali-ethanol (OAE) semi-liquefaction strategy for achieving one-step preparation of hemp stalk material (HSM) biomass into nanocellulose particles (NCPs). Oxygen, alkali, and ethanol have obvious synergistic effects during the semi-liquefaction process, which jointly promote the opening and depolymerization of the crystalline regions of cellulose. The presence of hemicellulose in HSM affects the preparation of NCPs, and the removal of hemicellulose in advance can significantly increase the yield of NCPs. The results showed that the yield of NCPs was as high as 90.14 % with 92.30 % purity after treatment at 120 °C for 2 h. The conversion of rod-shaped nanocellulose to NCPs was successfully captured, and Van der Waals forces were hypothesized to play a dominant role in the formation of NCPs by molecular dynamics simulations. Moreover, the semi-liquefaction can simultaneously fractionate uncondensed lignin with a yield of 46.52 %. With ethanol as a hydrogen donor, the residual lignin was effectively converted to aromatic monomers, predominantly vanillin and syringaldehyde.

The feruloylated sugar chain in sugar beet pectin (SBP) is a natural polyphenol-polysaccharide complex. Its low abundance often leads to be neglected, thereby hindering its bioactivity and mechnism research. In this study, SBP-3 A, a novel feruloylated polysaccharide fragment, was isolated from sugar beet pectin utilizing enzymatic digestion. The presence of ferulic acid on SBP-3 A was confirmed through high-performance liquid chromatography (HPLC), with a mass fraction of 22.5 μg/mg. The average molecular weight was determined to be 33.31 kDa. Methylation analysis, and nuclear magnetic resonance (NMR) spectra revealed that SBP-3 A is a heteroglycan with the main chain structure of →2)-α-Rhap-(1 → 4)-α-GalpA-(1 → 2)-α-Rhap-(1→, and the branched chain structure of ferulic acid (FA) → 3,4)-β-Galp-(1 → 2,4)-α-Rhap-(1→. Subsequently, the antioxidant activity of SBP-3 A was evaluated using the Caenorhabditis elegans (C. elegans). SBP-3 A improved antioxidant enzymes and non-enzymatic defense system, decreased reactive oxygen species levels, and up-regulated the mRNA expression of sod-3, skn-1, and daf-16, while down-regulated the expression of age-1 in C. elegans. Moreover, SBP-3 A modulated the gut flora by favorably affecting the abundances of Lactobacillus, Ligilactobacillus, and Akkermansia, thereby enhancing antioxidant capacity in C. elegans. Consequently, the aforementioned findings support the potential application of SBP-3 A as a functional food for treating oxidative stress-related illnesses.

This paper demonstrates the molecular design of stimuli-responsive, methyl cellulose-based, injectable hydrogels consisting of two orthogonal supramolecular networks. Rapidly injectable hydrogels that undergo autonomous gelation without permanent cross-links are crucial for biomedical applications due to minimal invasiveness, adaptability to irregular target sites, and precise spatiotemporal control. However, they often lack sufficient mechanical strength, physicochemical stability, and high biocompatibility. Herein, we develop a molecular design of a non-covalent double-network system by strategically incorporating specific host–guest cross-linking sites into a thermo-responsive network, which is reinforced by interpenetration with a cellulose-based network via their sequential formation. The resulting hydrogel, composed of non-cytotoxic materials, demonstrates high cell viability (>90 %) until its concentration of 25 mg mL⁻¹, rapid self-healing within 1 min, suitable injection pressure (1.1 kPa), and drug release behavior controllable by heat, chemicals, or ultrasound. Therefore, the hydrogel could be loaded with diclofenac (3.5 mg mL⁻¹), a non-steroidal anti-inflammatory drug, and treat osteoarthritis when injected into a rat knee joint, achieving results comparable to those in a control group without osteoarthritis. This system thus holds promise for the delivery of various drugs as a responsive vector, offering synergistic effects via the inclusion of functional polymeric networks or exogenous additives for bio- or environment-related applications.

Streptococci, Lactococci and Enterococci all produce L-rhamnose-containing cell wall polysaccharides which define Lancefield serotypes and represent promising candidates for the design of glycoconjugate vaccines. The L-rhamnose containing Enterococcal Polysaccharide Antigen (EPA), produced by the opportunistic pathogen Enterococcus faecalis, plays a critical role in normal growth, division, biofilm formation, antimicrobial resistance, phage susceptibility, and innate immune evasion. Despite the critical role of this polymer in E. faecalis physiology and host-pathogen interactions, little information is available on its structure and biosynthesis. Here, using an NMR approach, we elucidate the structure of EPA and propose a model for biosynthesis. We report the structure of the EPA-peptidoglycan linkage unit and reveal an unprecedented complexity of the EPA rhamnose backbone and decoration subunits. Finally, we explore the impact of several EPA structural modifications on innate immune evasion and recognition by bacteriophages. This work represents a first step towards the functional characterisation of EPA and the rational design of therapeutic strategies against a group of important pathogens.

Photothermal therapy has gained great attention as an alternative candidate for radiation therapy or chemotherapy for cancers. However, photothermal agents for photothermal therapy are generally in the form of nanoparticles that are too small to remain in the target tissue, and therefore, the agents are rather quickly removed from the targeted site. Furthermore, conventional photothermal agents are generally expensive or complicated to synthesize. As an approach to these issues, here we present new hydrogels with oxidized alginate ionically crosslinked with Ca²⁺, bearing polyaniline:poly(sodium 4-styrenesulfonate) (PANI:PSS) nanoparticles in the polymer network. The presented oxidized alginate PANI:PSS hydrogels exhibited excellent injectability as well as a gradual degradation rate from several days to several months depending on the oxidation degree of alginate chains. The presented oxidized alginate PANI:PSS hydrogels showed an excellent photothermal effect even under a neutral pH environment by showing temperature increased to 53 °C in 5 min upon NIR irradiation, which provide strong potential as a candidate for photothermal agent in photothermal therapy.

Gelation is a critical property of citrus pectin. However, the roles played by neutral sugar side-chains on acid-induced pectin gelation remain poorly understood. Herein, galactan- or/and arabinan-eliminated pectins (P-G, P-A, and P-AG) were used to investigate the effects of side-chains on gelation. The gel hardness values of citrus pectin, P-G, P-A, and P-AG were 42.6, 39.9, 5.3, and 2.1 g, respectively, suggesting that arabinan contributed more to gelation than galactan. We next found that arabinan branches promoted pectin chain entanglement more effectively than arabinan backbones. Destabilizer addition experiments showed that hydrogen bonding, electrostatic interaction, and hydrophobic interaction were the main forces affecting pectin gel networks and strength, which was further validated by molecular dynamic simulations. The total number of hydrogen bonds between the arabinan branches and galactan/HG (65.7) was significantly higher than that between the arabinan backbones and galactan/HG (39.1), indicating that arabinan branches predominated in terms of such interactions. This study thus elucidated the roles played by neutral-sugar side-chains, especially the arabinan branches of acid-induced pectin gels, in term of enhancing high-methoxyl pectin gelation, and offers novel insights into the structure-gelling relationships of citrus pectin.

Monolithic electrocatalysts are desired for the electro-Fenton oxidation system. We used a hydrogel consisting of TEMPO-oxidized cellulose nanofibers (TOCN) and cationic guar gum (CGG) to disperse and support Fe-rich sludge and finally obtained a Fe-doped biochar (denoted as C-Sludge@TOCN/CGG) after the freeze-drying and carbonization. This C-Sludge@TOCN/CGG exhibited a porous structure with evenly-distributed Fe due to the inherently three-dimensional porous structure of TOCN/CGG hydrogel and the abundant carbon content. Importantly, Fe and FeO existed in C-Sludge@TOCN/CGG due to the presence of TOCN and CGG during the pyrolysis. The electrochemical properties of C-Sludge@TOCN/CGG demonstrated its good electrocatalytic activity and stability with few side reactions. It had good performance in the electrocatalytic degradation of various azo dyes, attributed to the synergistic integration of TOCN/CGG-derived carbon matrix and carbonized Fe-rich sludge particles. Specifically, two transient radicals (i.e. ·OH and ·O₂⁻) primarily improved the electrocatalytic degradation performance of C-Sludge@TOCN/CGG. This C-Sludge@TOCN/CGG also efficiently degraded a papermill-sourced wastewater containing direct red 23, direct yellow 11, direct black 19 and toner, in which the COD value decreased from 365.12 to 179.13 mg/L within 9 h. This work provides an example of utilizing renewable materials and solid waste to design electrocatalysts to address the wastewater issue.

The present study involved the synthesis of five novel Schiff bases (SB1-SB5) of formyl chromone and their inclusion complexes with β-cyclodextrin through kneading approach to enhance the solubility and stability of SBs. Characterization was conducted using FTIR, NMR, SEM, TEM, p-XRD, and Mass Spectrometry. UV fluorescence and pH stability studies confirmed the formation of the inclusion complex. Structural validation of complexes was conducted via molecular docking (PDB ID: 1BFN) and 50 ns MD simulation study. DFT studies were performed on SBs using B3LYP/6–31 + G(d,p) basis set. All SBs exhibited favorable ADME properties and high binding interactions were observed in molecular docking with ctDNA (PDB Id: 1BNA). Further, in-vitro UV absorption and fluorescence experiments demonstrated strong ctDNA interactions for all Schiff bases, with binding constants in the order of 10⁵ M⁻¹, indicating groove binding mode. Among the SBs, SB4 exhibited the highest affinity for DNA grooves, with a binding constant (K_b) of 1.7 × 10⁶ M⁻¹. However, the SB4/β-Cyd inclusion complex also interacted with DNA but with low binding constants compared to SB4. An in-vitro release study of SB4/β-Cyd, revealed 78.92 % dissolution of the inclusion complex, highlighting its potential for enhanced solubility and stability in biological systems.

The rising prevalence of bone injuries has increased the demand for minimally invasive treatments. Microbead hydrogels, renowned for cell encapsulation, provide a versatile substrate for bone tissue regeneration. They deliver bioactive agents, support cell growth, and promote osteogenesis, aiding bone repair and regeneration. In this study, we synthesized superparamagnetic iron oxide nanoparticles (Sp) coated with a calcium phosphate layer (m-Sp), achieving a distinctive flower-like micro-cluster morphology. Subsequently, sodium alginate (SA) microbead hydrogels containing m-Sp (McSa@m-Sp) were fabricated using a dropping gelation strategy. McSa@m-Sp is magnetically targetable, enhance cross-linking, control degradation rates, and provide strong antibacterial activity. Encapsulation studies with MC3T3-E1 cells revealed enhanced viability and proliferation. These studies also indicated significantly elevated alkaline phosphatase (ALP) activity and mineralization in MC3T3-E1 cells, as confirmed by Alizarin Red S (ARS) and Von Kossa staining, along with increased collagen production within the McSa@m-Sp microbead hydrogels. Immunocytochemistry (ICC) and gene expression studies supported the osteoinductive potential of McSa@m-Sp, showing increased expression of osteogenic markers including RUNX-2, collagen-I, osteopontin, and osteocalcin. Thus, McSa@m-Sp microbead hydrogels offer a promising strategy for multifunctional scaffolds in bone tissue engineering.