An efficient, triphosphonium salt-catalyzed method for 2-deoxyglycosylation has been developed using glycosyl hemiacetals. This method uses mild protocols, proceeds at room temperature, and is completed within 4 h, yielding 2-deoxyglycosides in 64-96% yields and alpha/beta ratios exceeding 20:1. The method demonstrates broad compatibility with various glycosyl donors and acceptors, underscoring its potential in glycosylation chemistry.
Saccharides are well-established modulators of supramolecular systems and are widely used in designing responsive molecular probes. Their structural diversity and abundant hydroxyl groups enable numerous noncovalent interactions, giving them high molecular specificity essential for biological recognition and modern biosensing. Beyond recognition, saccharides significantly influence micellization by reorganizing the hydrogen-bonding network of water and strengthening hydrophobic interactions that drive micelle formation. Owing to these versatile properties, they are frequently employed as pharmaceutical excipients, particularly in drug delivery. Pluronic (R) block copolymers (BCPs), known for their tunable self-assembly and excellent solubilization capacity, serve as effective carriers. This study examines how various saccharides, including glucose, fructose, galactose, mannose, mannitol, sorbitol, maltose, and trehalose, modulate the micellar properties and drug-solubilizing ability of a 5 %w/v aqueous Pluronic (R) P104 solution, a moderately hydrophobic copolymer with strong micelle-forming behavior. To clarify these interactions, micellar characteristics were probed using cloud point (CP) measurements, dynamic light scattering (DLS), small-angle neutron scattering (SANS), proton nuclear magnetic resonance (H-1-NMR), and UV-visible spectroscopy. The findings reveal a clear enhancement in micellization and solubilization efficiency in the presence of saccharides. Overall, this work deepens the understanding of saccharide-Pluronic (R) interactions and supports the development of advanced drug delivery systems using saccharides as functional, synergistic excipients.
beta-Mannanases are important hemicellulases that cleave beta-1,4-mannosidic bonds in mannan-rich polysaccharides, a common building block of plant cell walls. beta-Mannanases are broadly distributed across bacteria, fungi, and plants and exhibit diverse structural frameworks and catalytic mechanisms that enable their functional diversity. Molecular biology, recombinant expression, and bioprocess optimization have enabled the efficient production of these enzymes, whereas structural and mechanistic studies provide insights for protein engineering. Due to their capacity for mannan modification and degradation, beta-mannanases have been utilized in animal feed, food processing, paper and textile industries, oil recovery, and biorefinery. This review examines existing information on the structure, origin, production strategy, and industrial applications of beta-mannanases, as well as their potential for future use in sustainable biotechnological processes.
Umbelliferose, alpha-D-Galp-(1 -> 2)-alpha-D-Glcp-(1 -> 2)-beta-D-Fruf, is the main trisaccharide present in the plants of Apiaceae family (umbellifers). Umbelliferose can be hydrolyzed to generate a disaccharide-isomelibiose, alpha-D-Galp-(1 -> 2)-D-Glcp, which accumulates sometimes in certain parts of these plants. However, till date no attempt has been made to characterize isomelibiose. Herein we have purified umbelliferose from fennel seeds and subjected it to partial acid hydrolysis to produce isomelibiose. 1D and 2D NMR experiments were performed for isomelibiose, along with the parental trisaccharide, revealing unique spectral characteristics. Hydrophilic interaction liquid chromatography (HILIC)-based chromatographic separation coupled with evaporative light scattering detector (ELSD) resulted in distinct elution pattern of umbelliferose and isomelibiose when compared with respective isomeric oligosaccharides. Thus, for the first time, the structural feature of isomelibiose was determined.
Plant-based foods are essential for sustainable diets but often lack the texture, stability, and nutritional quality of animal-derived products. This review examines the critical role of protein-polysaccharide interactions in overcoming these challenges and enabling the development of next-generation plant-based foods with improved sensory and functionality. Key molecular mechanisms, including electrostatic, hydrophobic, and covalent interactions, govern the formation of complex networks, gels, and emulsions. Advanced technologies like 3D printing and enzymatic crosslinking can create food matrices that mimic animal textures. Food innovation should include unique and regionally appropriate ingredients like duckweed, moringa, sweet potato byproducts, and upcycled agro-industrial waste to match with circular economy concepts and regional agricultural capabilities, according to the evaluation. Life cycle analysis consistently reveals that protein-polysaccharide systems minimize carbon footprint, water usage, and land occupation compared to animal-based diets. Using fiber-protein synergy, these systems improve protein bioavailability, minimize anti-nutritional factors, and boost metabolic health. Technical, legislative, and cultural issues and AI-driven formulation and policy innovation prospects are also covered. Protein-polysaccharide synergy in food design is crucial to sustainable, nutritious, and broadly accepted plant-based food systems that improve planetary and human health.
Five N-benzyl chitosan (NBCh) derivatives were synthesized through a two-step process. In the first step, chitosan (Ch) underwent a Schiff base reaction with various aromatic aldehydes to produce corresponding imines. Subsequently, these Schiff bases were subjected to reductive amination using sodium borohydride, yielding the desired amine products as NBChs. Sodium tripolyphosphate was then ionotropically gelled with Ch and NBChs to form Ch nanoparticles (ChNPs) and N-benzyl chitosan nanoparticles (NBChNPs), respectively. The NBCh derivatives were characterized using H-1-NMR and FT-IR spectroscopy, while ChNPs and NBChNPs were analyzed by scanning electron microscopy (SEM), particle size analysis, determination of polydispersity index (PDI) and zeta potential, and FT-IR spectroscopy. The products were tested in vitro for antimicrobial activity against Escherichia coli, Staphylococcus aureus, Aspergillus flavus, and Candida albicans. The results exhibited that the nanoparticles were the most active products compared to unmodified Ch and NBChs. This research has led to the development of novel Ch derivatives demonstrating enhanced antimicrobial activity compared to unmodified Ch molecule. These novel nanomaterials show strong potential for applications in biomedical anti-infective coatings, wound healing, food preservation, and agriculture, offering a sustainable strategy to combat microbial pathogens.
The mannose-binding protein (MBP) of the mushroom Agaricus bisporus (Abmb) structurally belongs to the Ricin B-like type lectin (RTL) family. Abmb affinity to mannose is uncommon because MBP is usually of Collectin type lectin (CTL); RTL is mostly glucose- and/or galactose-binding proteins. Abmb is absorbable in the intestine and withstands the harsh conditions of gastrointestinal tract; therefore, it could be developed as a drug carrier for oral drug administration. In this instance, a drug molecule or nanoparticle decorated with mannosyl group could be loaded onto Abmb for enhancing its absorption in the body. Here is reported, for the first time, the potential delivery of mannose to the liver by Abmb as suggested by an in vitro observation of the mannose receptor level on the surface of liver cells.
This study reports the chemical synthesis of a series of structurally defined oligosaccharide derivatives related to the galactomannan polysaccharide of Antrodia cinnamomea, employing a stepwise glycosylation strategy. Structure-immunostimulatory activity relationship studies demonstrated that, within this series of precisely designed and synthesized compounds, those incorporating a continuous trimannose epitope—such as tetrasaccharides 2a, 2b, 2e and trimannoside 3c—exhibited significant proliferative activity against both the murine monocytic macrophage leukemia RAW264.7 cell and the human monocytic leukemia THP-1 cell. These findings elucidate the structural basis of the active core fragment of A. cinnamomea galactomannan polysaccharide and provide a molecular foundation for the rational design and development of novel immunomodulatory agents.
Glycosides have gained increasing significance due to their roles in energy provision, structural function, and intercellular communication in living organisms. This recognition laid the foundation for advancements in glycobiology and pharmacology. This review traces the evolution of sugar modification methodologies to aglycones throughout the 20th century, culminating in the development of a groundbreaking coupling approach utilizing triazoles as molecular linkers. The “Click Chemistry,” an innovation in [2 + 3] cycloaddition, has allowed for the formation of glyco-compounds through energetically favorable reactions, and usually requires prior preparation of the terminal alkyne precursor and organic azide. This strategy has the significant benefit as a “synthetic structural access tool” – providing a way to achieve structures with regioselectivity that would not be accessible via other methods. This coupling method has emerged as a powerful tool in modern glyco-chemistry, enabling the synthesis of novel compounds with significant therapeutic potential. The triazole linkage can improve the stability (dependent on the individual molecules) and bioactivity of glycosides but also opens new venues for the development of drug candidates with enhanced efficacy and broader applications in medicinal chemistry. This review highlights the importance of glycotriazoles in advancing the field of medicinal chemistry and their potentials in future therapeutic development.
Cellulose is a polysaccharide composed of numerous glucose subunits connected by β-linkages. They are the richest sources of dietary fiber on Earth. Above all, elevated water solubility renders it an exceptional medium for amalgamating water-insoluble pharmaceuticals, such as enzymes and antibiotics. The presence of hydroxyl groups in each glucose unit affects the reactivity and applicability of cellulose to various pharmaceutical formulations. Diverse techniques, such as oxidation, amination, esterification and radical copolymerization, are usually adopted to modify these hydroxyl groups for improving the properties of cellulose. Chemically modified cellulose derivatives have been extensively used in the formulation of enteric-coated solid dosage forms, osmotic drug delivery systems, mucoadhesive and bio-adhesive drug delivery systems, and extended-release formulations. In addition, cellulose-based polymers also play various roles in pharmaceutical formulations, such as binding, filling, disintegrating, coating, gelling, thickening, stabilizing, and flavor-masking agents. The pharmaceutical industry has adopted cellulose-based polymers as significant components in the formulation, development, and production of new derivatives. The prevalence of cellulose-based polymers in pharmaceuticals has increased owing to continuous research that reveals new applications for chemically modified cellulose, as well as the development of new cellulose-based derivatives with optimized properties.
A photo-assisted oligosaccharide assembly strategy is reported for the facile synthesis of a branched heptasaccharide with potential anti-panceratic cancer activity in a four-component [2 + 1 + 1 + 3] one-pot coupling manner. A key feature of this strategy is the incorporation of photocleavable o-nitrobenzyl group-protected saccharide building blocks. Upon exposure to ultraviolet radiation, these blocks can generate in situ the corresponding acceptors for subsequent glycosylations without the purification step, thereby facilitating the one-pot coupling process and enabling the rapid assembly of the heptasaccharide.
8-Iodo-1-naphthoate is a key intermediate for the versatile preparation of 1,8-difunctionalized naphthalene derivatives, particularly the glycosyl 8-alkynyl-1-naphthoate donors. Herein, we report an efficient and scalable approach for the synthesis of a variety of 8-iodo-1-naphthoates via a modified photoinduced Su & aacute;rez halodecarboxylation reaction. Derivatization of the 8-iodo-naphthoates enables access to a wide range of 1,8-difunctionalized naphthalene derivatives. In particular, Sonogashira coupling reactions using diverse alkynes clearly demonstrate the superior reactivity and functional group tolerance of 8-iodo-1-naphthoate compared to its bromide counterpart. This practical and cost-effective synthetic approach is expected to greatly facilitate the broader application of glycosyl 8-alkynyl-1-naphthoates in glycosylation chemistry.
This work aims to design a stimuli-responsive photosensitizer chlorin e6 (Ce6)-coated stromal-cell-derived factor-1 alpha (SDF-1 alpha)-enclosed chitosan nanoparticles (Ce6-CNs-SDF-1 alpha) by the ionotropic gelation method and investigate its photocontrol sustained-release properties by using near-infrared (NIR) light. The studies highlight these Ce6-CNs-SDF-1 alpha fine particles with a size of 90-135 nm, charge of -32 +/- 0.7 mV, and a spherical shape and smooth surface morphology. The positively charged chitosan and negatively charged tripolyphosphate (TPP) interaction along with SDF-1 alpha and Ce6 was based on electrostatic interface between protonated amino and deprotonated phosphate groups. The photoinduced singlet oxygen generation (SOG), in which the ground state triplet oxygen (3O2) was excited into higher energy state singlet oxygen (1O2) as a result of energy transfer, was determined by the p-nitrosodimethylaniline (RNO) method with 660 nm irradiation. This indicated that the therapeutic activities were not changed after Ce6 being enclosed with CNs. The investigation comprised the Ce6 and SDF-1 alpha releases from Ce6-CNs-SDF-1 alpha as a function of time at pH 7.2. These compounds were found to have greater biocompatibility and no cytotoxicity as evaluated with the fibroblast cell lines from human skin by Alamar Blue assay and observed by confocal images. These smart NIR-responsive CNs can have potential uses in light-driven SDF-1 alpha delivery for various diseases.
Endo-beta-N-acetylglucosaminidases (ENGases) cleave the N-glycan core from glycoproteins and are important tools for structural analysis of glycans. Currently, only a few ENGases can specifically cleave the complex-type N-glycans, highlighting the need for discovering novel ENGases for glycoengineering applications. Nevertheless, conventional techniques for ENGase analysis are limited by low throughput and a lack of real-time detection. Herein, we describe the development of a fluorescence quenching assay to measure the hydrolytic activity of ENGases against fucosylated and afucosylated biantennary complex-type N-glycans. Two chemically synthesized probes, MG2FD (1) and MG2D (2)-a decasaccharide and a nonasaccharide, respectively-were labeled with an N-methylanthraniloyl group (fluorophore) and a 2,4-dinitrophenyl group (quencher). These probes were used to evaluate commercially available ENGases: Endo-M, Endo-CC, Endo-F3, Endo-H, and Endo-S. Endo-M and Endo-CC selectively cleaved probe 2 but not probe 1; Endo-F3 cleaved only probe 1; however, Endo-H and Endo-S showed no detectable activity. These findings align with known substrate specificities, validating the assay as a rapid and reliable method for assessing ENGase activity, profiling substrate specificity, and identifying novel ENGases targeting complex-type glycans.
A water-soluble polysaccharide (AFP) was extracted from Athyrium Multidentatum (Doll.) Ching by water extraction and alcohol precipitation method and purified by column chromatography. AFP was characterized by Fourier transform infrared (FT-IR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy, circular dichroism (CD) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), Congo red (CR) binding assay, monosaccharide composition and molecular weight analyses. 1D and 2D nuclear magnetic resonance (NMR) studies revealed two structural components in AFP, which are -> 4-beta-D-Manp-(1 -> 4)-beta-D-Xylp-(1 -> 4)-beta-D-Xylp-(1 -> 2)-beta-D-Galp-(1 -> and beta-D-Glcp-(1 -> 4)-beta-D-Glcp-(1 -> 4)-beta-D-Glcp-(1 -> 2)-beta-D-Galp-(1 ->. AFP exhibited significant immunological activities in both normal and immunosuppressed mice. Dectin-2/SYK/MAPK/non-classical NF-kappa B signaling pathways might play a crucial role in the immunomodulatory actions of AFP. Current results provided an important basis for the development of AFP as a natural immunoregulator.
In this work, the anticancer activities of an exopolysaccharide (EPS) from Trichoderma pseudokoningii, as well as its influence on WEHI-3 mouse myeloid leukemia cells, were investigated. This EPS not only inhibited the proliferation of WEHI-3 cells in a time- and concentration-dependent manner but also altered the morphology of WEHI-3 cells in a manner similar to that of apoptotic cells, as demonstrated by fluorescence staining experiments. Moreover, flow cytometry analysis also revealed that the EPS induced apoptosis in WEHI-3 cells. Additionally, the results indicated that the endoplasmic reticulum (ER) stress may be involved in this apoptotic process. Apoptotic factors related to the ER pathway were assessed subsequently. The results revealed that after treatment with the EPS for 48 h, the concentration of intracellular calcium in WEHI-3 cells increased. Exposure of WEHI-3 cells to different concentrations of the EPS (0.25, 0.50, and 1.0 mg/mL) resulted in decreased GRP78 mRNA transcription and increased CHOP mRNA expression in relation to the ER pathway. In addition, the Western blot results revealed that EPS significantly increased the p-PERK/PERK ratio, decreased the protein levels of GRP78 and Bcl-2, and increased the protein levels of CHOP and Bax. Caspase activity analysis also revealed that EPS treatment of WEHI-3 cells resulted in a dose-dependent increase in the activities of caspase-4 and caspase-3. Taking all together, these results provide evidence that the endoplasmic reticulum pathway is one of the potential pathways for the EPS-induced apoptosis in WEHI-3 cells.
We report a convenient and highly efficient protocol for the acetonation of free sugars, enabling cis-O-isopropylidene saccharide derivatives under ultrasonic irradiation at ambient temperature. Triflic acid (TfOH) in acetone is identified as a mild and effective reagent for the chemoselective O-isopropylidenation of polyhydroxy compounds comprising aldo/keto-hexoses or aldo-pentoses. The synthetic utility of this approach was demonstrated through the preparation of various O-isopropylidene-protected sugar derivatives, which serve as key chiral intermediates for assembling important carbohydrate scaffolds and glycoconjugates. The use of ultrasonic irradiation as an environmentally benign energy source highlights the potential for this method to make a significant contribution to synthetic organic chemistry.
Understanding intermolecular interactions between cellulose and metal salts, and in particularly with anions, is crucial in development of cellulose composites and processing methods. Intermolecular interactions between cellulose model compound D-cellobiose and 14 sodium salts were evaluated using Fourier-Transform Infrared (FT-IR) spectroscopy, thermogravimetric (TG), and computational analysis tools. In FT-IR, shifts in 10 distinct bands in the D-cellobiose spectra were monitored to evaluate interactions between D-cellobiose and sodium salts. Na2B4O3 and Na3PO4 caused the highest total shifts of 61.85 and 34.08 cm-1, respectively. Mixing with salt caused lowering the initial decomposition temperatures in 10 out of the 14 salts. In density functional theory (DFT) study, Na2B4O7 and D-cellobiose mixture showed negative binding energies of -11.18, -25.3, -30.9, and -12.2 kJ/mol in approaching alpha- and beta-D-cellobiose from up and down faces. In addition, FT-IR data showed the strong interaction between borate anion and carbohydrate, where mixing Na2B4O7 with D-cellobiose resulted in the largest total shift of 61.85 cm-1 in the ten IR bands monitored. The strong interactions between Na2B4O7 and D-cellobiose were explained as a result of Lewis acidity of boron, as well as multiple B and O atoms present in the anion and strong hydrogen bonding and dipolar interactions between B and O atoms.
Exopolysaccharides (EPSs) are sugar-based biopolymers produced by bacteria in response to environmental stress. Bacterial EPSs (BEPSs) have attracted attention across multiple industries due to their biodegradable and nontoxic nature. Their large-scale production and ease of purification make BEPSs more favorable than other intracellular and cell wall polysaccharides. Two key approaches are used to enhance BEPS yields: metabolic engineering and the utilization of low-cost materials for eco-friendly production. Despite ongoing efforts to isolate and classify new marine BEPSs, only a few have been industrially utilized. The discovery of BEPSs with novel sugar compositions or structural modifications could unlock new applications. Currently, marine BEPSs are used as thickeners, stabilizers, and gelling agents in the food industry and show potential in cosmetics, biotechnology, wastewater treatment, petroleum recovery, and textiles. While their use is still in the early stage, BEPSs hold significant promise as versatile biomaterials. This review highlights bacterial sources of marine EPSs and explores their industrial potential.
For patients with hepatocellular carcinoma (HCC), recurrence and metastasis lead to approximately 90% deaths, even after various standard therapies, indicating the need for novel therapies and antimetastatic drugs. Recently, mitochondrial dysfunction has been shown to be closely associated with HCC recurrence and metastasis. Herein, a novel glycosylated naphthalimide conjugate 4a was explored to target HCC and HCC metastasis by inducing ROS-mediated mitochondrial metabolic programs in HCC, remarkably improving the efficacy of amonafide and prolonging the survival of mice. Mechanistically, 4a, as a potential fluorescent chemical probe, could target mitochondria, which is completely different from amonafide. Preliminary investigation into the mechanism of 4a indicates that it localizes in the mitochondria and selectively causes reactive oxygen species (ROS) overproduction in HCC instead of the matched normal liver cells, leading to HCC cell apoptosis and migration inhibition via multiple ROS-mediated signaling pathways. In addition to exposing a previously undefined mitochondrial metabolic program in HCC, our study further illuminates an unrecognized naphthalimide-based tumor therapeutic strategy to prolong the life of terminal HCC in a completely new field.
