Pub Date : 2025-11-29DOI: 10.1016/j.carres.2025.109771
Wei-Chien Weng , Chi-Kung Ni
Milk free oligosaccharides play critical roles in infant health, supporting beneficial gut microbiota and protecting against pathogens. While most milk free oligosaccharides follow well-characterized biosynthetic pathways initiated by lactose, recent studies have revealed several unusual trisaccharides that deviate from these canonical motifs. To investigate the origin of such atypical milk free trisaccharides, we analyzed the free milk trisaccharide profiles of conventional (microbiota-colonized) and germ-free mice using porous graphitized carbon high-performance liquid chromatography coupled with tandem mass spectrometry. One unique trisaccharide (compound Gal-β1→4-Glc-β1↔1β-Gal) was present exclusively in conventional mice, suggesting microbial contribution to its biosynthesis. In contrast, several other unusual milk free trisaccharides including Gal-β1→4-Glc-β1→4-Glc, Gal-β1→4-[Glc-α1→2]-Glc and Gal-β1→4-[Gal-β1→2]-Glc were detected in both conventional and germ-free mice, indicating an endogenous production. Comparison of the oligosaccharide Gal-β1→4-Glc-β1→4-Glc isolated from milk of mice fed on the normal diet and those maintained on a cellulose-free diet for four weeks revealed no difference in intensity. It suggests that its formation is independent of dietary cellulose and likely arises from endogenous biosynthetic processes.
{"title":"Effects of gut bacteria and diet on unusual trisaccharides in mouse milk","authors":"Wei-Chien Weng , Chi-Kung Ni","doi":"10.1016/j.carres.2025.109771","DOIUrl":"10.1016/j.carres.2025.109771","url":null,"abstract":"<div><div>Milk free oligosaccharides play critical roles in infant health, supporting beneficial gut microbiota and protecting against pathogens. While most milk free oligosaccharides follow well-characterized biosynthetic pathways initiated by lactose, recent studies have revealed several unusual trisaccharides that deviate from these canonical motifs. To investigate the origin of such atypical milk free trisaccharides, we analyzed the free milk trisaccharide profiles of conventional (microbiota-colonized) and germ-free mice using porous graphitized carbon high-performance liquid chromatography coupled with tandem mass spectrometry. One unique trisaccharide (compound Gal-β1→4-Glc-β1↔1β-Gal) was present exclusively in conventional mice, suggesting microbial contribution to its biosynthesis. In contrast, several other unusual milk free trisaccharides including Gal-β1→4-Glc-β1→4-Glc, Gal-β1→4-[Glc-α1→2]-Glc and Gal-β1→4-[Gal-β1→2]-Glc were detected in both conventional and germ-free mice, indicating an endogenous production. Comparison of the oligosaccharide Gal-β1→4-Glc-β1→4-Glc isolated from milk of mice fed on the normal diet and those maintained on a cellulose-free diet for four weeks revealed no difference in intensity. It suggests that its formation is independent of dietary cellulose and likely arises from endogenous biosynthetic processes.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"560 ","pages":"Article 109771"},"PeriodicalIF":2.5,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145660440","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-29DOI: 10.1016/j.carres.2025.109779
Yuvaraj Dinakarkumar , Panneerselvam Theivendren , Natarajan Kiruthiga , J. Jayamuthunagai , B. Bharathiraja
Marine algae remain promising feedstock for renewable biofuel production, yet metabolic bottlenecks such as limited carbon allocation to lipid synthesis, competition from starch pathways, and variable nitrogen assimilation continue to constrain productivity. Small interfering RNA delivered gene silencing offers a targeted route to modulate these pathways, although its application in algae is limited by molecular instability, inconsistent uptake, and poor intracellular retention. This review evaluates marine polysaccharides including alginate, carrageenan, fucoidan, and ulvan as siRNA delivery carriers designed for algal systems, highlighting the structural features that underpin their performance. Alginate contains guluronic rich blocks that support ionic crosslinking with divalent cations to form stable hydrogels that protect and gradually release siRNA. Carrageenan and fucoidan contain dense sulfate groups that promote strong electrostatic binding and stabilisation of siRNA in aquatic culture conditions. Ulvan provides rhamnose and glucuronic acid residues that assist nanoparticle formation and support efficient cellular internalisation. Mechanistic studies in Nannochloropsis and Chlamydomonas show that siRNA mediated knockdown of lipid pathway enzymes such as acetyl CoA carboxylase and diacylglycerol acyltransferase can increase lipid accumulation by around fifteen to thirty five percent. Silencing starch biosynthesis genes further redirects carbon flux towards fatty acid pathways, supported by metabolic flux modelling that predicts enhanced malonyl CoA availability. Critical discussion is included on species dependent uptake variability, ecological considerations, and techno economic constraints linked to polysaccharide extraction and nanoparticle formulation. Emerging advances such as CRISPR RNAi hybrid strategies, AI assisted nanocarrier optimization, and programmable algal gene circuits further strengthen the potential of this platform. Future progress will increasingly rely on integrating polysaccharide based nanocarriers with advances in synthetic biology, dynamic gene circuit design, and AI assisted process modelling. Together, these approaches can enable scalable and precision controlled metabolic engineering in algae, supporting industrial biofuel production and strengthening the technological pathway toward next generation renewable energy systems.
{"title":"A comprehensive review on marine algal polysaccharide-mediated siRNA delivery systems for biofuel production","authors":"Yuvaraj Dinakarkumar , Panneerselvam Theivendren , Natarajan Kiruthiga , J. Jayamuthunagai , B. Bharathiraja","doi":"10.1016/j.carres.2025.109779","DOIUrl":"10.1016/j.carres.2025.109779","url":null,"abstract":"<div><div>Marine algae remain promising feedstock for renewable biofuel production, yet metabolic bottlenecks such as limited carbon allocation to lipid synthesis, competition from starch pathways, and variable nitrogen assimilation continue to constrain productivity. Small interfering RNA delivered gene silencing offers a targeted route to modulate these pathways, although its application in algae is limited by molecular instability, inconsistent uptake, and poor intracellular retention. This review evaluates marine polysaccharides including alginate, carrageenan, fucoidan, and ulvan as siRNA delivery carriers designed for algal systems, highlighting the structural features that underpin their performance. Alginate contains guluronic rich blocks that support ionic crosslinking with divalent cations to form stable hydrogels that protect and gradually release siRNA. Carrageenan and fucoidan contain dense sulfate groups that promote strong electrostatic binding and stabilisation of siRNA in aquatic culture conditions. Ulvan provides rhamnose and glucuronic acid residues that assist nanoparticle formation and support efficient cellular internalisation. Mechanistic studies in <em>Nannochloropsis</em> and <em>Chlamydomonas</em> show that siRNA mediated knockdown of lipid pathway enzymes such as acetyl CoA carboxylase and diacylglycerol acyltransferase can increase lipid accumulation by around fifteen to thirty five percent. Silencing starch biosynthesis genes further redirects carbon flux towards fatty acid pathways, supported by metabolic flux modelling that predicts enhanced malonyl CoA availability. Critical discussion is included on species dependent uptake variability, ecological considerations, and techno economic constraints linked to polysaccharide extraction and nanoparticle formulation. Emerging advances such as CRISPR RNAi hybrid strategies, AI assisted nanocarrier optimization, and programmable algal gene circuits further strengthen the potential of this platform. Future progress will increasingly rely on integrating polysaccharide based nanocarriers with advances in synthetic biology, dynamic gene circuit design, and AI assisted process modelling. Together, these approaches can enable scalable and precision controlled metabolic engineering in algae, supporting industrial biofuel production and strengthening the technological pathway toward next generation renewable energy systems.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"560 ","pages":"Article 109779"},"PeriodicalIF":2.5,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145647363","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-28DOI: 10.1016/j.carres.2025.109770
Lisa Coddens, Charlotte F. De Schepper, Kristof Brijs, Christophe M. Courtin
Colourimetric assays for quantifying reducing sugars are widely used, including for assessing glycoside hydrolase activities. Consequently, there is a need for reliable high-throughput methodologies. Several protocols have been described in literature, with the most commonly used being the dinitrosalicylic acid (DNS), bicinchoninic acid (BCA) and p-hydroxybenzoic acid hydrazide (PAHBAH) assays. This study presents a comparative evaluation of these assays. Our results show that both the DNS and PAHBAH assays overestimate reducing sugar concentrations mainly due to saccharide degradation under alkaline conditions (pH ≥ 12.9) and high temperatures (100 °C) during the assays. To evaluate the impact of this overestimation, we experimentally measured glycoside hydrolase activity. All three assays overestimated reducing sugar concentrations compared to a reference method, though to varying extents. The BCA assay exhibited the least overestimation, likely due to minimal saccharide degradation under its milder alkaline conditions. It was therefore the most reliable method among those tested.
{"title":"Comparative evaluation of DNS, PAHBAH, and BCA colourimetric assays for quantifying reducing sugars","authors":"Lisa Coddens, Charlotte F. De Schepper, Kristof Brijs, Christophe M. Courtin","doi":"10.1016/j.carres.2025.109770","DOIUrl":"10.1016/j.carres.2025.109770","url":null,"abstract":"<div><div>Colourimetric assays for quantifying reducing sugars are widely used, including for assessing glycoside hydrolase activities. Consequently, there is a need for reliable high-throughput methodologies. Several protocols have been described in literature, with the most commonly used being the dinitrosalicylic acid (DNS), bicinchoninic acid (BCA) and <em>p</em>-hydroxybenzoic acid hydrazide (PAHBAH) assays. This study presents a comparative evaluation of these assays. Our results show that both the DNS and PAHBAH assays overestimate reducing sugar concentrations mainly due to saccharide degradation under alkaline conditions (pH ≥ 12.9) and high temperatures (100 °C) during the assays. To evaluate the impact of this overestimation, we experimentally measured glycoside hydrolase activity. All three assays overestimated reducing sugar concentrations compared to a reference method, though to varying extents. The BCA assay exhibited the least overestimation, likely due to minimal saccharide degradation under its milder alkaline conditions. It was therefore the most reliable method among those tested.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"560 ","pages":"Article 109770"},"PeriodicalIF":2.5,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145660455","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Chitosan, a biopolymer with multifunctionality that occurs naturally from chitin, was found to be an efficacious high-potential platform for building green polymer electrolytes and electrochemical device composite materials. Its inherent properties like dense functional groups, biocompatibility, film-forming nature, and ease of chemical modification, favorably position it as a reliable substitute for conventional synthetic polymers. This review encompasses chitosan-based biopolymer electrolytes and composites, the mechanism of ionic conductance, structural tuning, and their incorporation into high-performance electrochemical devices. The review places particular importance on recent strategies pursued for enhancing ionic conductivity, mechanical stability, and electrochemical performance by chemical functionalization, blending, and nanomaterial inclusion. Particular focus is placed on ion dynamic awareness, proton and cation conducting channels, and polymer–filler interaction for charge transportation optimization. Application domains of fuel cell, battery, supercapacitor, and bioelectronic devices are comprehensively discussed with focus placed on both the achievements and ongoing challenges of chitosan systems. Finally, the review challenges issues of durability, scalability, and sustainability and outlines directions for future material engineering and technology integration. Bridging the gap between fundamental knowledge and real-world applications, this review article serves to illustrate the potential of chitosan-based electrolytes and composites to propel next-generation green and high-performance electrochemical technologies.
{"title":"Biopolymer electrolytes and composites based on chitosan for electrochemical processes: developing technologies, device integration, and ion transport mechanisms","authors":"Mesut Yılmazoğlu , Tarek Kouka , İlkay Güzel , Ozan Coban , Hikmet Okkay , Noureddine El Messaoudi , Mouslim Messali","doi":"10.1016/j.carres.2025.109778","DOIUrl":"10.1016/j.carres.2025.109778","url":null,"abstract":"<div><div>Chitosan, a biopolymer with multifunctionality that occurs naturally from chitin, was found to be an efficacious high-potential platform for building green polymer electrolytes and electrochemical device composite materials. Its inherent properties like dense functional groups, biocompatibility, film-forming nature, and ease of chemical modification, favorably position it as a reliable substitute for conventional synthetic polymers. This review encompasses chitosan-based biopolymer electrolytes and composites, the mechanism of ionic conductance, structural tuning, and their incorporation into high-performance electrochemical devices. The review places particular importance on recent strategies pursued for enhancing ionic conductivity, mechanical stability, and electrochemical performance by chemical functionalization, blending, and nanomaterial inclusion. Particular focus is placed on ion dynamic awareness, proton and cation conducting channels, and polymer–filler interaction for charge transportation optimization. Application domains of fuel cell, battery, supercapacitor, and bioelectronic devices are comprehensively discussed with focus placed on both the achievements and ongoing challenges of chitosan systems. Finally, the review challenges issues of durability, scalability, and sustainability and outlines directions for future material engineering and technology integration. Bridging the gap between fundamental knowledge and real-world applications, this review article serves to illustrate the potential of chitosan-based electrolytes and composites to propel next-generation green and high-performance electrochemical technologies.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"560 ","pages":"Article 109778"},"PeriodicalIF":2.5,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145616999","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-27DOI: 10.1016/j.carres.2025.109768
Arely Bautista Rodríguez , Apolonio Vargas-Torres , Sylvia Rosales Chimal , Ricardo O. Navarro Cortez , Beatriz del Carmen Coutiño Laguna , Heidi M. Palma-Rodríguez
Taro starch was modified by ultrasound, enzymes, and a combination of both to evaluate structural changes and its performance as a wall material for encapsulation of Hibiscus sabdariffa extract. The double-modified starch (DMS) exhibited the lowest amylose content (6.7 %) and particle size (2.5 μm), in comparison with the native taro starch, which had 9.3 % and 3.3 μm, respectively. Pasting properties showed a 42 % decrease in peak viscosity of DMS relative to native starch, improving the efficiency of spray-drying. Stability studies showed that dual modification encapsulation (DME) retained 82 % of total phenolic compounds and 79 % of anthocyanins after seven days of storage under aging conditions. However, the retention decreased to 55 % and 48 %, respectively, after 35 days of storage. In the in vitro digestion model, ultrasound modification encapsulation (UME) showed the highest anthocyanin release (63 % gastric phase, 41 % intestinal phase), indicating gradual and controlled delivery. These findings indicate the potential of modified taro starch treatments to enhance the protection of bioactive drugs and provide greater control over the rate of compound release during the digestive process. These benefits are achieved while maintaining the stability and efficacy of the encapsulated compound.
{"title":"Evaluation of double-modified taro starch for the encapsulation and protection of bioactive compounds in Hibiscus Sabdariffa extract","authors":"Arely Bautista Rodríguez , Apolonio Vargas-Torres , Sylvia Rosales Chimal , Ricardo O. Navarro Cortez , Beatriz del Carmen Coutiño Laguna , Heidi M. Palma-Rodríguez","doi":"10.1016/j.carres.2025.109768","DOIUrl":"10.1016/j.carres.2025.109768","url":null,"abstract":"<div><div>Taro starch was modified by ultrasound, enzymes, and a combination of both to evaluate structural changes and its performance as a wall material for encapsulation of <em>Hibiscus sabdariffa</em> extract. The double-modified starch (DMS) exhibited the lowest amylose content (6.7 %) and particle size (2.5 μm), in comparison with the native taro starch, which had 9.3 % and 3.3 μm, respectively. Pasting properties showed a 42 % decrease in peak viscosity of DMS relative to native starch, improving the efficiency of spray-drying. Stability studies showed that dual modification encapsulation (DME) retained 82 % of total phenolic compounds and 79 % of anthocyanins after seven days of storage under aging conditions. However, the retention decreased to 55 % and 48 %, respectively, after 35 days of storage. In the <em>in vitro</em> digestion model, ultrasound modification encapsulation (UME) showed the highest anthocyanin release (63 % gastric phase, 41 % intestinal phase), indicating gradual and controlled delivery. These findings indicate the potential of modified taro starch treatments to enhance the protection of bioactive drugs and provide greater control over the rate of compound release during the digestive process. These benefits are achieved while maintaining the stability and efficacy of the encapsulated compound.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"560 ","pages":"Article 109768"},"PeriodicalIF":2.5,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145647415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-25DOI: 10.1016/j.carres.2025.109769
Shuhan Li , Huwei Bian , Yuting Tan , Yan Li , Dan Shou , Tao Jiang , Yong Kong
Breast cancer is one of the most life-threatening malignancies worldwide, and the chemotherapy of breast cancer is often hindered by drug resistance and systemic toxicity. Developing safer and more efficient multi-therapy strategies is therefore urgently needed. Doxorubicin (DOX) is first combined with Cu2+ through coordination bonds, and the resulting DOX-Cu2+ prodrug is then co-encapsulated with glucose oxidase (GOx) in the oxidized hyaluronic acid (OHA)/carboxymethyl chitosan (CMCS) hydrogels cross-linked through the Schiff base reaction. The weakly acidic environment of tumor cells can cause the degradation of the hydrogels and the dissociation of the DOX-Cu2+ complex, resulting in the release of DOX for chemotherapy. The released Cu2+ can be reduced to Cu + by glutathione (GSH), and the Cu+ can participate in the Fenton-like reaction with the overexpressed H2O2 in tumor cells to produce hydroxyl radicals (·OH) for chemodynamic therapy (CDT). During the degradation of the hydrogels, the GOx is also released, which can deplete the glucose in tumor cells for starvation therapy; meanwhile, the H2O2 generated during the GOx-catalyzed oxidation of glucose can in turn participate in the Fenton-like reaction with Cu+ to enhance CDT. The results of cytotoxicity assay indicate that the OHA/CMCS hydrogels have good biocompatibility, while the DOX-Cu2+ and GOx co-encapsulated hydrogels (OHA/CMCS/DOX-Cu2+/GOx) display significant cytotoxicity due to the multi-therapy synergies of chemotherapy, enhanced CDT and starvation therapy.
{"title":"Synthesis and in vitro studies of doxorubicin-Cu2+ prodrug and glucose oxidase co-encapsulated oxidized hyaluronic acid/carboxymethyl chitosan hydrogels on breast cancer cell line 4T1","authors":"Shuhan Li , Huwei Bian , Yuting Tan , Yan Li , Dan Shou , Tao Jiang , Yong Kong","doi":"10.1016/j.carres.2025.109769","DOIUrl":"10.1016/j.carres.2025.109769","url":null,"abstract":"<div><div>Breast cancer is one of the most life-threatening malignancies worldwide, and the chemotherapy of breast cancer is often hindered by drug resistance and systemic toxicity. Developing safer and more efficient multi-therapy strategies is therefore urgently needed. Doxorubicin (DOX) is first combined with Cu<sup>2+</sup> through coordination bonds, and the resulting DOX-Cu<sup>2+</sup> prodrug is then co-encapsulated with glucose oxidase (GOx) in the oxidized hyaluronic acid (OHA)/carboxymethyl chitosan (CMCS) hydrogels cross-linked through the Schiff base reaction. The weakly acidic environment of tumor cells can cause the degradation of the hydrogels and the dissociation of the DOX-Cu<sup>2+</sup> complex, resulting in the release of DOX for chemotherapy. The released Cu<sup>2+</sup> can be reduced to Cu <sup>+</sup> by glutathione (GSH), and the Cu<sup>+</sup> can participate in the Fenton-like reaction with the overexpressed H<sub>2</sub>O<sub>2</sub> in tumor cells to produce hydroxyl radicals (·OH) for chemodynamic therapy (CDT). During the degradation of the hydrogels, the GOx is also released, which can deplete the glucose in tumor cells for starvation therapy; meanwhile, the H<sub>2</sub>O<sub>2</sub> generated during the GOx-catalyzed oxidation of glucose can in turn participate in the Fenton-like reaction with Cu<sup>+</sup> to enhance CDT. The results of cytotoxicity assay indicate that the OHA/CMCS hydrogels have good biocompatibility, while the DOX-Cu<sup>2+</sup> and GOx co-encapsulated hydrogels (OHA/CMCS/DOX-Cu<sup>2+</sup>/GOx) display significant cytotoxicity due to the multi-therapy synergies of chemotherapy, enhanced CDT and starvation therapy.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109769"},"PeriodicalIF":2.5,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-24DOI: 10.1016/j.carres.2025.109766
Tianyu Zhang , Zefei Fan , Yongyan Fu , Yafei Hou , Guanghui Ni
A novel method for the preparation of thioglycoside donors from d-glucose and 2-indolone was developed. This method is straightforward to operate and enables highly efficient catalysis under mild conditions. In addition, a method for O-glycosylation of thioglycosides with various alcohols using trifluoromethyl thianthrenium triflate (TT-CF3+TfO−) as an initiator and a visible light-induced photoredox catalysis method was also developed. The method is green, mild, easy to perform and does not require a neutralization step.
{"title":"Visible-light-promoted O-glycosylation with indolylthio glycosides","authors":"Tianyu Zhang , Zefei Fan , Yongyan Fu , Yafei Hou , Guanghui Ni","doi":"10.1016/j.carres.2025.109766","DOIUrl":"10.1016/j.carres.2025.109766","url":null,"abstract":"<div><div>A novel method for the preparation of thioglycoside donors from <span>d</span>-glucose and 2-indolone was developed. This method is straightforward to operate and enables highly efficient catalysis under mild conditions. In addition, a method for O-glycosylation of thioglycosides with various alcohols using trifluoromethyl thianthrenium triflate (TT-CF<sub>3</sub><sup>+</sup>TfO<sup>−</sup>) as an initiator and a visible light-induced photoredox catalysis method was also developed. The method is green, mild, easy to perform and does not require a neutralization step.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"560 ","pages":"Article 109766"},"PeriodicalIF":2.5,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145617007","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-24DOI: 10.1016/j.carres.2025.109767
Aliakbar Ebrahimi
The possible leaching of chitosan (CS), which could result in a loss of bioactivity and structural instability, is a significant drawback of CS/polycaprolactone (PCL) blend nanofibers. This work offers a way to produce inherently cationic and long-lasting nanofibers by synthesizing a CS-graft-PCL (CS-g-PCL) copolymer. PCL and CS are Food and Drug Administration (FDA) approved polymers that are widely used in biomedical applications. PCL is a biodegradable and biocompatible polymer and has good electrospinnable character, but suffers from a lack of functional groups. Instead, CS is biocompatible, biodegradable, non-toxic, non-allergenic, bio-adhesive, and has attractive biological activities, but has poor electrospinability. Synthesized copolymers and PCL were characterized with Fourier Transform Infrared (FTIR), Hydrogen Nuclear Magnetic Resonance (1HNMR), Gel Permeation Chromatography (GPC), Thermogravimetric analysis (TGA), and X-ray diffraction (XRD). Results of characterization showed that the synthesis procedures were done successfully. Then, different blends of PCL with Graft copolymers were used to prepare nanofibers with electrospinning. Surface morphology of nanofibers investigated by scanning electron microscopy (SEM). Surface chemistry, hydrophilic and hydrophobic character, and mechanical strength of nanofiber matrices were characterized with X-ray Photoelectron Spectroscopy (XPS), water contact angle, and mechanical tests, respectively. Importantly, CS was covalently bonded inside the fiber matrix, inhibiting its diffusion and producing no inhibitory zone, as demonstrated by XPS and antibacterial disk diffusion studies. This suggests a long-lasting, non-leaching architecture in which the fiber structure retains its cationic and antibacterial qualities for prolonged bioactivity after breakdown. This study effectively creates a cationic nanofiber platform that is structurally stable and perfectly suitable for uses that need a long-lasting positive charge, such as scaffolds for tissue engineering and long-term antimicrobial filtration systems.
{"title":"Non-leaching cationic nanofibers from chitosan-g-PCL copolymer: A structurally durable platform for biomedical applications","authors":"Aliakbar Ebrahimi","doi":"10.1016/j.carres.2025.109767","DOIUrl":"10.1016/j.carres.2025.109767","url":null,"abstract":"<div><div>The possible leaching of chitosan (CS), which could result in a loss of bioactivity and structural instability, is a significant drawback of CS/polycaprolactone (PCL) blend nanofibers. This work offers a way to produce inherently cationic and long-lasting nanofibers by synthesizing a CS-graft-PCL (CS-g-PCL) copolymer. PCL and CS are Food and Drug Administration (FDA) approved polymers that are widely used in biomedical applications. PCL is a biodegradable and biocompatible polymer and has good electrospinnable character, but suffers from a lack of functional groups. Instead, CS is biocompatible, biodegradable, non-toxic, non-allergenic, bio-adhesive, and has attractive biological activities, but has poor electrospinability. Synthesized copolymers and PCL were characterized with Fourier Transform Infrared (FTIR), Hydrogen Nuclear Magnetic Resonance (<sup>1</sup>HNMR), Gel Permeation Chromatography (GPC), Thermogravimetric analysis (TGA), and X-ray diffraction (XRD). Results of characterization showed that the synthesis procedures were done successfully. Then, different blends of PCL with Graft copolymers were used to prepare nanofibers with electrospinning. Surface morphology of nanofibers investigated by scanning electron microscopy (SEM). Surface chemistry, hydrophilic and hydrophobic character, and mechanical strength of nanofiber matrices were characterized with X-ray Photoelectron Spectroscopy (XPS), water contact angle, and mechanical tests, respectively. Importantly, CS was covalently bonded inside the fiber matrix, inhibiting its diffusion and producing no inhibitory zone, as demonstrated by XPS and antibacterial disk diffusion studies. This suggests a long-lasting, non-leaching architecture in which the fiber structure retains its cationic and antibacterial qualities for prolonged bioactivity after breakdown. This study effectively creates a cationic nanofiber platform that is structurally stable and perfectly suitable for uses that need a long-lasting positive charge, such as scaffolds for tissue engineering and long-term antimicrobial filtration systems.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109767"},"PeriodicalIF":2.5,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621025","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-24DOI: 10.1016/j.carres.2025.109764
Saad Salman , Fahad Hassan Shah
Carrageenan (CG), a sulfated galactan derived from red seaweed, has emerged as a versatile biopolymer for developing sustainable, smart, and multifunctional biomaterials. This review critically surveys recent advances in CG bio(nano)composites, emphasizing their structural design, crosslinking mechanisms, and performance across biomedical and environmental interfaces. Ionic (K+, Ca2+), covalent, and polyelectrolyte complexation strategies are compared in terms of mechanical reinforcement, swelling behavior, and controlled drug release, highlighting CG's tunable viscoelasticity and physicochemical adaptability. Integration with metallic, polymeric, and biodegradable nanofillers has expanded its functionality to include antimicrobial, antioxidant, and regenerative applications. Despite these advances, systematic evaluation of parameters such as modulus, mesh size, ion leaching, and cytotoxicity remains inconsistent across studies. This review underscores the need for standardized characterization and predictive modeling frameworks. Finally, emerging artificial intelligence and machine learning approaches are discussed for data-driven optimization of kappa carrageenan (κ-CG) formulation, structure–property correlation, and performance prediction. Together, these insights position κ-CG bio(nano)composites as next-generation, sustainable platforms bridging carbohydrate chemistry with intelligent material design.
{"title":"Toward sustainable, smart, and multifunctional Carrageenan bio(nano)composites: Mechanistic insights, physicochemical properties, biomedical interfaces, and AI-driven design perspectives","authors":"Saad Salman , Fahad Hassan Shah","doi":"10.1016/j.carres.2025.109764","DOIUrl":"10.1016/j.carres.2025.109764","url":null,"abstract":"<div><div>Carrageenan (CG), a sulfated galactan derived from red seaweed, has emerged as a versatile biopolymer for developing sustainable, smart, and multifunctional biomaterials. This review critically surveys recent advances in CG bio(nano)composites, emphasizing their structural design, crosslinking mechanisms, and performance across biomedical and environmental interfaces. Ionic (K<sup>+</sup>, Ca<sup>2+</sup>), covalent, and polyelectrolyte complexation strategies are compared in terms of mechanical reinforcement, swelling behavior, and controlled drug release, highlighting CG's tunable viscoelasticity and physicochemical adaptability. Integration with metallic, polymeric, and biodegradable nanofillers has expanded its functionality to include antimicrobial, antioxidant, and regenerative applications. Despite these advances, systematic evaluation of parameters such as modulus, mesh size, ion leaching, and cytotoxicity remains inconsistent across studies. This review underscores the need for standardized characterization and predictive modeling frameworks. Finally, emerging artificial intelligence and machine learning approaches are discussed for data-driven optimization of kappa carrageenan (κ-CG) formulation, structure–property correlation, and performance prediction. Together, these insights position κ-CG bio(nano)composites as next-generation, sustainable platforms bridging carbohydrate chemistry with intelligent material design.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"560 ","pages":"Article 109764"},"PeriodicalIF":2.5,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145617006","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-19DOI: 10.1016/j.carres.2025.109763
Tian-Yuan Wu , Yong-Xin Huang , Xu Liu , Yu Shen , Jun Liang , Hai-Xue Kuang , Yong-Gang Xia
A novel glucuronoarabinogalactooligosaccharide-complex pectin, designated as AEFP-B1 (molecular weight: 7.352 × 104 g/mol), was isolated from the fruits of Aralia elata using multiple chromatographic techniques. Its chemical structure was characterized by UPLC-ESI+-MS, GC–MS, HILIC-ESI--HCD-MS, and 1/2D-NMR spectroscopy. The structural features of AEFP-B1 are as follows: (i) its backbone consists of homogalacturonan (HG) and rhamnogalacturonan-I (RG-I) regions at a molar ratio of 3:2; (ii) complex side chains, i.e., arabinogalactooligosaccharide, glucuronoarabinogalactooligosaccharide, glucuronogalactooligosaccharide and arabinan, are attached to the C-4 positions of rhamnosyl residues in the RG-I domain; (iii) a repetitive structural fragment was deduced, including →2)-Rhap-(1→, →2,4)-Rhap-(1→, GalpA-(1→, →4)-GalpA-(1→, →4)-GalpA-6-OMe-(1→, Araf-(1→, →3)-Araf-(1→, →5)-Araf-(1→, →3,5)-Araf-(1→, Galp-(1→, →3)-Galp-1→, →4)-Galp-(1→, →6)-Galp-(1→, → 3,4)-Galp-(1→, →3,4,6)-Galp-(1→, and GlcpA-4-OMe-(1 → . Bioactivity assays demonstrated that AEFP-B1 could promote cytokine secretion and regulate immune responses. Surface plasmon resonance (SPR) analysis revealed that AEFP-B1 binds to toll-like receptor 2 (TLR2, dissociation constant KD = 8.99 × 10−6 M) and toll-like receptor 4 (TLR4, KD = 1.07 × 10−5 M), and this binding was further validated by molecular docking. To the best of our knowledge, this study is the first to isolate and structurally characterize pectic polysaccharides with immunomodulatory activity from A. elata fruits. It highlights the potential of AEFP-B1 for future applications both food and pharmaceutical industries.
{"title":"Structural characterization and immunomodulatory activity of a glucuronoarabinogalactooligosaccharide-complex pectin from the fruits of Aralia elata (Miq.) Seem","authors":"Tian-Yuan Wu , Yong-Xin Huang , Xu Liu , Yu Shen , Jun Liang , Hai-Xue Kuang , Yong-Gang Xia","doi":"10.1016/j.carres.2025.109763","DOIUrl":"10.1016/j.carres.2025.109763","url":null,"abstract":"<div><div>A novel glucuronoarabinogalactooligosaccharide-complex pectin, designated as <strong>AEFP-B<sub>1</sub></strong> (molecular weight: 7.352 × 10<sup>4</sup> g/mol), was isolated from the fruits of <em>Aralia elata</em> using multiple chromatographic techniques. Its chemical structure was characterized by UPLC-ESI<sup>+</sup>-MS, GC–MS, HILIC-ESI<sup>-</sup>-HCD-MS, and 1/2D-NMR spectroscopy. The structural features of <strong>AEFP-B<sub>1</sub></strong> are as follows: (i) its backbone consists of homogalacturonan (HG) and rhamnogalacturonan-I (RG-I) regions at a molar ratio of 3:2; (ii) complex side chains, i.e., arabinogalactooligosaccharide, glucuronoarabinogalactooligosaccharide, glucuronogalactooligosaccharide and arabinan, are attached to the <em>C</em>-4 positions of rhamnosyl residues in the RG-I domain; (iii) a repetitive structural fragment was deduced, including →2)-Rha<em>p</em>-(1→, →2,4)-Rha<em>p</em>-(1→, Gal<em>p</em>A-(1→, →4)-Gal<em>p</em>A-(1→, →4)<em>-</em>Gal<em>p</em>A-6-OMe-(1→, Ara<em>f</em>-(1→, →3)-Ara<em>f</em>-(1→, →5)-Ara<em>f</em>-(1→, →3,5)-Ara<em>f</em>-(1→, Gal<em>p</em>-(1→, →3)-Gal<em>p</em>-1→, →4)-Gal<em>p</em>-(1→, →6)-Gal<em>p</em>-(1→, → 3,4)-Gal<em>p</em>-(1→, →3,4,6)-Gal<em>p</em>-(1→, and Glc<em>p</em>A-4-OMe-(1 → . Bioactivity assays demonstrated that <strong>AEFP-B<sub>1</sub></strong> could promote cytokine secretion and regulate immune responses. Surface plasmon resonance (SPR) analysis revealed that <strong>AEFP-B<sub>1</sub></strong> binds to toll-like receptor 2 (TLR2, dissociation constant <em>K</em><sub>D</sub> = 8.99 × 10<sup>−6</sup> M) and toll-like receptor 4 (TLR4, <em>K</em><sub>D</sub> = 1.07 × 10<sup>−5</sup> M), and this binding was further validated by molecular docking. To the best of our knowledge, this study is the first to isolate and structurally characterize pectic polysaccharides with immunomodulatory activity from <em>A. elata</em> fruits. It highlights the potential of <strong>AEFP-B<sub>1</sub></strong> for future applications both food and pharmaceutical industries.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"560 ","pages":"Article 109763"},"PeriodicalIF":2.5,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145610606","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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