Galactomannans (GM) are mannose-galactose (Man-Gal) structure-based polysaccharides with different ratios according to the source, isolation, and purification technique. This work provides an update on GM sources, chemistry, isolation and characterization techniques, bioactivities, and their applications as encapsulation agents and drug delivery systems for natural bioactive compounds. The unique chemical structure of GMs gives them a wide range of physical/chemical properties. Current pre-clinical research indicates that GMs exert a plethora of bioactivities (e.g., prebiotic, anti-inflammatory, antioxidant, anti-obesity, antidiabetic, wound healing, cytotoxic, and immunomodulatory activity). Modifications using physical, chemical, and enzymatic procedures generally lead to a further improvement in GMs' physicochemical properties and superior biological effects. These bioactivities depend on GM chemical structure and other properties (Man/Gal ratio, average Mw, degree and type of substitution, branching pattern, surface charge, solubility, viscosity, etc.). Furthermore, GM based-materials (functional hydrogels and films, microcapsules, and microspheres) are used as encapsulating agents and delivery systems of natural bioactive compounds and for metal nanoparticles' synthesis. Besides being biodegradable and biocompatible, GM-based materials have the capacity to improve bioavailability and are capable of controlling the release and enhancing the therapeutic effect of various natural bioactive agents against various diseases, especially dermal pathologies, inflammation, wounds, and bacterial/fungal infections.
Phytochemical investigation of the leaves of Lansium domesticum (Meliaceae) resulted in the isolation of 10 glycosides, including three previously undescribed glycosides, designated as landomsides A-C (1-3). The structures of these glycosides were elucidated using extensive spectroscopic analyses (HRESIMS, 1D/2D NMR, and ECD data). All isolated glycosides were evaluated for their inhibitory effects on LPS-induced NO production in RAW264.7 macrophages. Glycosides 1-7 and 10 exhibited inhibitory activities, with IC50 values ranging from 19.36 ± 1.60 to 52.18 ± 2.21 μM. Among them, glycosides 1, 2, and 10 showed the strongest activities, with IC50 values of 19.36 ± 1.60, 20.06 ± 1.56, and 22.03 ± 1.81 μM, respectively. These compounds also inhibited TNF-α production, with glycoside 1 displaying the greatest activity (IC50 = 13.96 ± 1.19 μM), followed by glycosides 10 (IC50 = 19.82 ± 1.52 μM) and 2 (IC50 = 26.77 ± 1.64 μM). Integrated network pharmacology and molecular docking analyses suggested that the active glycosides may exert their anti-inflammatory effects through the modulation of multiple inflammation-related targets and signaling pathways, providing a plausible mechanistic basis for their observed anti-inflammatory activity.
Glycosylinositol phosphoceramides (GIPCs) are major sphingolipids in plant plasma membranes. GIPCs possess structurally diverse inositol glycan (IG) head groups. While the chemical structure of hexose-type IGs has been elucidated, the chemical structure of hexosamine (HexN)- and N-acetylhexosamine (HexNAc)-type IGs remain poorly understood. This study reports the synthesis of amino sugar-containing IGs, GlcN-α(1 → 4)-GlcA-α(1 → 2)-Ins 1 and GlcNAc-α(1 → 4)-GlcA-α(1 → 2)-Ins 2, and their application as authentic standards for LC-MS/MS analysis. GlcN- and GlcNAc-type IGs were synthesized via 4,6-O-phenylboronic ester-directed α-selective glucosylation followed by global deprotection and selective N-acetylation. Naturally occurring HexN- and HexNAc-type IGs were obtained by the enzymatic degradation of GIPCs isolated from broad bean pods and radish sprouts. Using amino sugar-containing IGs 1 and 2 as authentic standards, the chemical structures of the HexN- and HexNAc-type IGs were investigated by LC-MS/MS analysis. The retention times and MS/MS fragmentation patterns of the natural IGs were in good agreement with those of the synthetic IGs. These results demonstrate that natural HexN- and HexNAc-type IGs correspond to 1 and 2. This study provides the first direct structural confirmation of amino sugar-containing IGs in plant GIPCs and highlights the utility of authentic synthetic standards for uncovering the hidden IG structural diversity of plant GIPCs.
The locust bean gum (LBG) is a galactomannan polymeric compound extracted from the seeds of Ceratonia siliqua, which has recently gained substantial interest due to its distinctive structure and physical properties. The mannose-galactose chains present in the LBG molecules provides favourable sites for modifications and interactions with proteins, polysaccharides and nanoparticles. In addition, chemical modifications such as carboxymethylation, etherification, and esterification can be used effectively to increase solubility, reactivity, mechanical strength and stimuli response capabilities. Synergistic interplay of LBG with hydrocolloids, biopolymers and nanomaterials results in targeted viscoelasticity, swelling behaviour and network formation. Such composites exhibit superior functionality in a wide range of industries from food packaging to pharmaceutical drug carriers, antibacterial hydrogels, tissue engineering scaffolds and pollution control devices. Further addition of inorganic/bioactive nanoparticles offers additional benefits in regulating mechanical durability, thermal resilience and sustained release features. In summary, the LBG-based hybrid materials provide a green and versatile matrix that bridges classical hydrocolloid research with state-of-the-art functional materials. This review aims to provide comprehensive insights into the chemistry, modification methods, interaction modes and potential applications of locust bean gum-composite materials. The present paper ends with a discussion of ongoing obstacles and future trends, where smart nano enhanced LBG systems are viewed as the emerging materials of the future for biomedical, technological, and environmental applications.
Esterified starch exhibits emulsifying properties and holds significant potential for application in the food and pharmaceutical industries. However, research on the influence of acid anhydride chain length on the physicochemical properties of starch and its capacity to encapsulate curcumin remains insufficient. In this study, two types of esterified starches, each with distinct hydrophobic chains, were synthesized: dodecenyl succinic anhydride starch (DDSAS) and octenyl succinic anhydride starch (OSAS). It was found that, in comparison to octenyl succinic anhydride (OSA), dodecenyl succinic anhydride (DDSA) led to a lower degree of substitution (DS) in the starch but imparted enhanced surface hydrophobicity to the starch (with a contact angle > 120°). With respect to emulsion morphology and storage stability, starches modified by OSA consistently produced more stable Pickering emulsions. Significantly, the emulsion stabilized with 5% octenyl succinic anhydride-modified starch (OSAS-5) exhibited outstanding performance, achieving an emulsification index of 64.8% and maintaining a curcumin retention rate of 67.7% after 7 d of storage. This study provides novel insights into the efficient encapsulation and controlled release of bioactive components in functional foods.
A method for synthesizing glycosyl haloacetimidates in a two-chamber reaction vessel is used to access new glycosyl haloacetimidates. Simple haloacetamides are transformed into the corresponding gaseous halonitriles in one chamber and these react with the hemiacetal in the other chamber. In this paper the properties of the new glycosyl haloacetimidates are studied with a focus on glycosylation properties. Especially the solvolysis reactions in neat simple alcohols are studied and compared with seminal work by Schmidt and coworkers. For the α-anomeric acetimidates inversion is seen with less bulky acceptors while increasing steric bulk increases the amount of α-product. For the β-anomeric acetimidates inversion is seen in all cases. Glycosylation screening of five model glycosyl acceptors reveals that the glycosyl haloacetimidates are glycosylating agents comparable with the Schmidt donor.
Chemotherapy remains a cornerstone of cancer treatment, but its toxicity toward immune cells can compromise host defense. In this study, we investigated the structural features and cellular processes associated with the effects of low-dose lipopolysaccharide (LPS) on chemotherapy-injured macrophages. Treatment with 100 ng/mL LPS markedly restored the chemotherapy-reduced normalized CCK-8 metabolic signal in Adriamycin (ADR)- and vincristine (VCR)-treated RAW264.7 macrophages, and this response was reproduced in NR8383 rat alveolar macrophages and primary mouse peritoneal macrophages. In an indirect RAW264.7-4T1 co-culture system, LPS did not measurably alter the ADR-associated CCK-8 response or cell-cycle distribution of 4T1 tumor cells. LPS preparations from different bacterial sources produced comparable responses, while Kdo2-lipid A partially reproduced the LPS-associated effect, supporting a contribution of lipid A-associated bioactivity. FITC-LPS imaging and flow cytometry demonstrated cellular association and an intracellular fluorescence component, and pharmacological inhibition implicated actin-dependent and other endocytosis-related processes in LPS handling by macrophages. Colchicine sensitivity further implicated microtubule-related processes, while chloroquine attenuated the LPS-associated response and qRT-PCR and western blotting revealed increased expression of multiple lysosome-related genes and proteins. Together, these findings support a model in which lipid A-associated bioactivity, endocytosis-related cellular processing, microtubule-related trafficking, and lysosome-related processes contribute to the macrophage response to low-dose LPS during chemotherapeutic injury. This study provides a theoretical basis for further exploration of the underlying molecular mechanisms of LPS and supports its potential application in immune-cell preservation during chemotherapy.
Chitosan, a pH-sensitive cationic biopolymer possessing reactive amino groups (pKa 6.3), good biocompatibility, and functionalizability, makes an excellent adsorbent for biomedical application. Its combination with water hyacinth activated carbon through cross-linking provides synergistic adsorption that could be used in the treatment of drug overdose in oral medication. A systematic literature of Web of science, Scopus, PubMed and Google Scholar between January 2000 to April 2025, consisting of 59 original research papers and 41 non research papers. In this review, synthesis methods maintaining chitosan functional groups, adsorption mechanisms including electrostatic interactions, hydrogen bonding, hydrophobic effects, pore diffusion mechanism, relationship between structure and properties of nanocomposites, and their comparative environmental and biomedical performances will be discussed with the emphasis on challenges and translational strategies including in vitro physiological studies. The proposed review for the first time comprehensively discusses the field related to detoxification therapy and is distinct from other environment-oriented reviews.
Alginate-based hydrogels have emerged as versatile biomaterials because of their biocompatibility, high water content, mild aqueous processing, and tunable network architecture. However, their performance is strongly dependent on molecular characteristics, including molecular weight, mannuronic-to-guluronic acid (M/G) ratio, block distribution, degree of functionalization, and crosslinking density. This review critically examines how these parameters govern the physicochemical, mechanical, biological, and translational performance of alginate-based nanostructured hydrogels. Particular emphasis is placed on ionotropic gelation, covalent functionalization, oxidation, sulfation, grafting, and hybrid covalent-ionic crosslinking, together with nanocomposite reinforcement and advanced biofabrication strategies. Recent studies demonstrate that controlling network architecture and nanoscale organization can substantially improve mechanical stability, degradation behavior, drug-loading and release characteristics, cellular interactions, and tissue-regeneration performance. For example, re-cent alginate systems have achieved optimized pore dimensions in the ∼100-200 μm range for cell-supporting scaffolds, drug encapsulation efficiencies approaching or exceeding 90% in selected nanostructured systems, and high cell viability (>95%) in representative double-network hydrogel platforms. The review further identifies persistent challenges involving source-to-source variability, batch reproducibility, ion exchange, insufficient intrinsic bioactivity, controlled degradation, sterilization, and clinical translation. Finally, future opportunities are discussed in stimulus-responsive networks, hierarchical biofabrication, multifunctional nanocomposites, sustainable alginate extraction, and data-driven structure-property optimization. The review establishes a structure-processing-property-biological performance framework for the rational design of next-generation alginate-based nanostructured hydrogels.
Starch-based materials have gained increasing attention as renewable biopolymers amenable to functionalization for advanced applications. Among starch derivatives, carboxymethyl starch (CMS) and its nanoparticles (CMS NPs) offer significant advantages over native starch, particularly improved solubility, colloidal stability, and thermal performance, owing to the introduction of tunable anionic carboxymethyl groups. Precise control over degree of substitution (DS), amylose content, and nanoscale morphology enables CMS-based systems with enhanced absorption capacity, stimuli-responsiveness, and film-forming behavior. Despite extensive research efforts, the existing literature remains fragmented and lacks a unified framework linking synthesis parameters and nanostructure to functional performance. This review integrates current knowledge on CMS and CMS NP production, covering carboxymethylation chemistry, reaction efficiency (RE), and nanosizing strategies such as enzymatic hydrolysis, nanoprecipitation, and ultrasonication. The analysis highlights how variations in DS, particle size, amylose content, crystallinity, and molecular architecture govern the physicochemical properties and technological suitability of CMS-based materials. Practical applications, including drug delivery and controlled release, emulsification, bioplastics, absorption, biocatalyst, and adhesives, are critically evaluated, alongside existing limitations and future research needs. By mapping key structure-property-performance relationships and identifying unresolved challenges, this review provides a strategic roadmap for the rational design of next-generation CMS-based materials, bridging molecular engineering with green and sustainable nanotechnology.
Efficient conversion of agricultural waste into fermentable sugars is central to sustainable second-generation biofuel technologies. This study reports the covalent immobilization of amyloglucosidase onto a magnetic silver nanoparticle (Ag-MNP) hybrid support for the saccharification of cassava peel. The Ag-MNP hybrid support was employed to combine magnetic recovery with a favourable immobilization microenvironment for enhanced catalytic performance during cassava peel saccharification. X-ray diffraction identified a multi-phase iron oxide system comprising maghemite, hematite, and goethite, with a mesoporous architecture of 18-20 nm pore diameter. Covalent enzyme attachment via glutaraldehyde-mediated imine bond formation was confirmed by infrared spectroscopy. The immobilized biocatalyst achieved 92.32% total reducing sugar recovery within 50 min, surpassing the free enzyme performance of 86.87% under identical conditions. Kinetic analysis revealed an elevated maximum reaction rate of 6.4 μmol min-1, compared with 5.0 μmol min-1 for the free enzyme, attributed to favourable active-site orientation and the physicochemical properties of the Ag-MNP hybrid support. Chromatographic analysis confirmed glucose as the dominant hydrolysate product at 90.26%. The biocatalyst retained 54% of its initial activity after seven operational cycles at pH 5.0 and 65 °C. No inhibitory byproducts were detected under the conditions tested, supporting its potential as a reusable biocatalyst for generating fermentable sugars for bioethanol production.
Five new glycolipids, leucosposins A-E (1-5), were isolated from fungus Leuconeurospora sp. CPCC 401603, collected from seawater in the Fildes region of Antarctica. Their structures and absolute configurations were elucidated by spectroscopic analyses including HRESIMS, IR, and NMR data, as well as ECD spectra. This study represents the first report on the chemical constituents of genus Leuconeurospora. Compounds 1-5 exhibited significant antifungal activities against Candida albicans ATCC 10231 with MIC values in the range of 1-8 μg/mL. Compounds 1 and 3 displayed moderate antibacterial activities against Staphylococcus aureus ATCC 29213 and Enterococcus faecalis ATCC 29212. These findings not only expand the chemical diversity of genus Leuconeurospora, but also provide new lead compounds for antifungal therapeutic strategies.
This review characterizes the mechanisms of action of animal polysaccharides (chitin, chitosan, hyaluronan, chondroitin sulfate, dermatan sulfate, keratan sulfate, heparin/heparan sulfate) based on their structural and conformational features. A systematic search was conducted in PubMed, Scopus, Web of Science, and the Russian Citation Index (2015-2026). The review organizes polysaccharides according to three structure-dependent targeting paradigms: (1) charge-mediated targeting (chitosan, dermatan sulfate), where cationic or anionic density determines electrostatic interactions; (2) molecular weight-dependent receptor selection (hyaluronan, chitosan), where chain length dictates receptor engagement and signaling outcomes; and (3) sulfation pattern-directed protein recognition (heparin/heparan sulfate, chondroitin sulfate, keratan sulfate), where specific O- and N-sulfation codes enable selective protein binding. Key findings reveal that biological activity depends largely on molecular weight, sulfation pattern, and charge density, with concentration-dependent reversal of immunomodulatory effects - low doses elicit anti-inflammatory while high doses induce pro-inflammatory activation - representing a critical consideration for therapeutic design. Recent methodological advances (UPLC-MS/MS, chemical synthesis, chemoenzymatic synthesis) now enable detailed structure-activity studies, particularly for keratan sulfate, though knowledge gaps remain. The convergence of mechanisms across polysaccharide classes - particularly NF-κB pathway modulation - suggests common principles underlying bioactivity. The review also addresses major obstacles to clinical translation, including polydispersity, batch variability, and characterization challenges, and proposes future research directions to overcome these limitations.
An acidic tetrasaccharide repeating unit corresponding to the cell wall O-antigen of Proteus vulgaris O8 strain has been synthesized in very good yield applying [2 + 2] block glycosylation strategy. Stereoselective α-glycosylated products were obtained using ether-based solvents in glycosylation reactions. The incorporation of the d-glucuronic acid moiety in the tetrasaccharide was achieved by glycosylation with d-glucose intermediate and TEMPO-Bis(acetoxy)iodobenzene (BAIB) mediated oxidation at the late stage. Non-participating groups (e.g. N3 and benzyl) were placed at C-2 position of the glycosyl donor for the preparation of the 1,2-cis-glycosylated products. The yields of the reactions were very good.
This work presents a novel carbohydrate-based molecule, 1,10-N,N'-bis-(β-d-ureidolactosyl)-4,7,13,16-tetraoxa-1,10-diazacyclooctadecane (TL), which was synthesised via a multistep synthetic route, with the final deprotection of the carbohydrate moieties achieved through Zemplén deacetylation. In TL, lactose units are linked to a diazacrown ether through urea bridges. The incorporation of lactose moieties is responsible for the favorable physicochemical properties of TL, including its solubility, cytotoxicity profile, and complexation ability. The host-guest complexation properties were investigated using the recently synthesised compound butane-1,4-diyl bis(2,2,2-trifluoroethane-1-sulfonate) (BFS), which has demonstrated cytotoxic activity against leukemia cell lines. The formation of TL and its complex was confirmed by advanced multidimensional NMR techniques, FT-IR spectroscopy, and conductometric analysis. Biological assays indicated that TL is non-toxic toward healthy human keratinocytes (HaCaT), while complex formation with BFS reduces its cytotoxicity. The water solubility of TL was determined to be 25.74 g/100 mL H2O at 298.15 K. Theoretical calculations further revealed that TL adopts a conformation stabilised by intramolecular hydrogen bonding in aqueous solution, with up to ten hydrogen bonds identified in the most stable conformer, significantly influencing its structural geometry. Moreover, TL forms a stable complex with BFS, with a calculated complexation energy of -79.94 kJ/mol.
The endophyte of Chamaecytisus albus named Rhizobium sp. CAS 24 is a soil bacterium belonging to Rhizobium giardinii bv. giardinii species, as was established by multilocus sequence analysis. Chemical analysis, mass spectrometry and NMR spectroscopy, revealed that the CAS 24 lipid A consist species bearing tri-, tetra- and penta-acyl residues. All share the same glucosaminyl-(1 → 6)-glucosamine backbone which is mono- or di-phosphorylated. The penta-acylated lipid A contain 14:0(3-OH) ester-linked acids with free 3-hydroxyls at the C-3 and C-3' positions of the backbone. Two amide-linked residues (18:0(3-OH) and 18:1(3-OH)) occupy positions C-2 and C-2', respectively. The 18:1(3-OH) is esterified on its hydroxyl by a 29-hydroxytriacontanoic acid. The tetra-acylated lipid A lack the 14:0(3-OH) on proximal GlcpN while the tri-acylated lipid A species lack both 14:0(3-OH). Other variants of lipid A CAS 24 were created by substituting the acyl residues indicated above on the sugar backbone with their chain homologues. Genome sequence analyses of the CAS 24 strain revealed that the genes encoding the lipid A biosynthetic pathway showed significant sequence similarity (close to 100%) and gene organization to the corresponding genes of Sinorhizobium melilotii and S. fredii. The presented structure of the CAS 24 lipid A is similar but not identical to that previously described for Sinorhizobium fredii HH103.
OBJECTIVE:To optimize the extraction-purification process of Dendrobium officinale polysaccharides (DOPs) and characterize the fine structures of two homogeneous fractions (DOP-1, DOP-2), as well as to evaluate their anti-photoaging activity on HFF cells. METHODS:An integrated process including petroleum ether defatting, cellulase hydrolysis, water extraction-ethanol precipitation, trypsin-Sevag deproteinization, activated carbon decolorization, and dialysis was used. DOP-1 and DOP-2 were separated by DEAE-52 and Sephadex G-100 chromatography. Their structures were analyzed by FT-IR, methylation-GC/MS, NMR, and SEM. Anti-photoaging effects were assessed via CCK-8, SA-β-Gal staining, and qPCR of TGF-β/Smad pathway genes. RESULTS:The optimized process increased crude polysaccharide yield from 30.34% to 35.03% and polysaccharide content from 31.23% to 49.34%. DOP-1 (Mn 989 Da, PDI 1.15) was a linear oligosaccharide composed of →4)-β-D-Manp (72.32%) and →4)-β-D-Glcp (23.78%) in an alternating pattern. DOP-2 (Mn 2970 Da, PDI 1.67) was a branched polysaccharide with a backbone of →6)-α-D-Glcp (58.06%) and branches at →2,6)-Manp and →4,6)-Glcp. Both DOP-1 and DOP-2 (62.5 μg/mL) protected HFF cells from UVA-induced photoaging, upregulated TGF-β1, Smad3, Smad4, and Collagen I, and downregulated Smad7 and MMP-1, with DOP-2 showing dose-dependent effects. CONCLUSION:The optimized process enables efficient preparation of DOPs. DOP-1 and DOP-2 possess distinct structural features and exert anti-photoaging effects via regulation of the TGF-β/Smad signaling pathway.
Herpes is a viral disease with high worldwide prevalence. The lack of herpes vaccines and the growing viral resistance to acyclovir and its analogues create an urgent need for new treatment strategies. Anionic polysaccharides, especially sulfated derivatives, can inhibit herpes simplex virus (HSV) infection by interfering with viral attachment to heparan sulfate on host cells. Building on our previous work, we designed and prepared a heparan sulfate-mimetic derivative of botryosphaeran, a fungal β-glucan, by sequential oxidation and sulfonation. Firstly, oxidation converted approximately one-half of the C-6 primary hydroxyl groups into carboxyl groups, yielding BOTOX. Subsequent sulfonation yielded the heparan sulfate mimetic (BOTOX/SULF) with a degree of sulfonation of 0.3 and sulfate groups mainly at C-6 of the remaining glucose units. In vitro assays showed that BOTOX/SULF had high anti-HSV-1 activity, while BOTOX was inactive. The antiviral effect of BOTOX/SULF was comparable to that of previously reported botryosphaeran sulfonated derivatives with a higher degree of sulfonation, suggesting that the combined presence of carboxylate and sulfate groups contributes to activity. These results support heparan sulfate mimicry as a promising strategy for designing entry inhibitors against enveloped viruses.
