Pub Date : 2025-11-17DOI: 10.1016/j.carres.2025.109759
Jacob A. Clark , Agata Zykwinska , Sylvia Colliec-Jouault , Sergey A. Samsonov
Sulfated glycosaminoglycans (GAGs) are a large family of linear and highly negatively charged polysaccharides with many roles in tissue structure and physiology. Interest in glycosaminoglycans and molecules with mimetic properties has led to the discovery of a number of exopolysaccharides (EPS), such as the highly sulfated infernan (InfHS). Understanding of the bioactivity of these molecules depends on their structural features. Here, we constructed and simulated a model of InfHS, aiming to characterize its molecular properties. We observed increased intramolecular interactions as additional repeating units were added to the model, alongside folding of the structure. The branched structure and high sulfation also lead to a more pronounced polarization around the molecule in comparison to linear sulfated glycosaminoglycans. The findings demonstrate the unique properties of InfHS and provide a rationale for understanding its bioactivity.
{"title":"Modeling highly sulfated infernan","authors":"Jacob A. Clark , Agata Zykwinska , Sylvia Colliec-Jouault , Sergey A. Samsonov","doi":"10.1016/j.carres.2025.109759","DOIUrl":"10.1016/j.carres.2025.109759","url":null,"abstract":"<div><div>Sulfated glycosaminoglycans (GAGs) are a large family of linear and highly negatively charged polysaccharides with many roles in tissue structure and physiology. Interest in glycosaminoglycans and molecules with mimetic properties has led to the discovery of a number of exopolysaccharides (EPS), such as the highly sulfated infernan (Inf<sub>HS</sub>). Understanding of the bioactivity of these molecules depends on their structural features. Here, we constructed and simulated a model of Inf<sub>HS</sub>, aiming to characterize its molecular properties. We observed increased intramolecular interactions as additional repeating units were added to the model, alongside folding of the structure. The branched structure and high sulfation also lead to a more pronounced polarization around the molecule in comparison to linear sulfated glycosaminoglycans. The findings demonstrate the unique properties of Inf<sub>HS</sub> and provide a rationale for understanding its bioactivity.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109759"},"PeriodicalIF":2.5,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145573136","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 : 2025-11-14DOI: 10.1016/j.carres.2025.109757
A.K.M. Atique Ullah , Xuefei Huang
Aberrant glycosylation is a hallmark of cancer, producing tumor-associated carbohydrate antigens (TACAs) and altering cell-surface interactions that reshape adhesion, signaling, and immune recognition. These altered glycans, collectively referred to as the “cancer glyco-code”, represent unique glycan expression patterns that create actionable targets for diagnosis and therapy. The glycan-binding proteins that recognize and interpret these structures, termed the “readers” of the glyco-code, include lectin families such as Siglecs, galectins, selectins, and cluster of differentiation 44 (CD44). Glyco-nanoparticles (GlycoNPs) are inspired by glyco-code and designed to probe these readers by multivalently presenting tumor-relevant glycans on engineered cores (gold, iron oxide, polymers), thereby boosting avidity and selectivity in cancer targeting. This review distills design principles for GlycoNPs’ core selection, conjugation chemistry, glycan density/orientation, and multivalency control, and reviews applications in surface-enhanced Raman scattering (SERS), magnetic resonance imaging (MRI), high-throughput glycan binding screens, and targeted drug delivery. We highlight immune-modulatory strategies (e.g., Siglec decoying, galectin blockade, and glycan-guided macrophage reprogramming) that position GlycoNPs as “glycan immune checkpoints.” We also examine translational bottlenecks: inter- and intra-tumoral glycan heterogeneity; manufacturing reproducibility (density/orientation/valency); colloidal and biological stability; pharmacokinetics; and regulatory expectations for characterization and immunogenicity. Finally, we outline emerging applications that may accelerate bench-to-bedside translation. Overall, GlycoNPs offer a modular, multiplexable path to precision oncology, enabling reader-guided tumor profiling, imaging, and intervention through the language of glycans.
{"title":"Recent advances in glyco-nanoparticles for probing the glyco-codes of cancer","authors":"A.K.M. Atique Ullah , Xuefei Huang","doi":"10.1016/j.carres.2025.109757","DOIUrl":"10.1016/j.carres.2025.109757","url":null,"abstract":"<div><div>Aberrant glycosylation is a hallmark of cancer, producing tumor-associated carbohydrate antigens (TACAs) and altering cell-surface interactions that reshape adhesion, signaling, and immune recognition. These altered glycans, collectively referred to as the “cancer glyco-code”, represent unique glycan expression patterns that create actionable targets for diagnosis and therapy. The glycan-binding proteins that recognize and interpret these structures, termed the “readers” of the glyco-code, include lectin families such as Siglecs, galectins, selectins, and cluster of differentiation 44 (CD44). Glyco-nanoparticles (GlycoNPs) are inspired by glyco-code and designed to probe these readers by multivalently presenting tumor-relevant glycans on engineered cores (gold, iron oxide, polymers), thereby boosting avidity and selectivity in cancer targeting. This review distills design principles for GlycoNPs’ core selection, conjugation chemistry, glycan density/orientation, and multivalency control, and reviews applications in surface-enhanced Raman scattering (SERS), magnetic resonance imaging (MRI), high-throughput glycan binding screens, and targeted drug delivery. We highlight immune-modulatory strategies (e.g., Siglec decoying, galectin blockade, and glycan-guided macrophage reprogramming) that position GlycoNPs as “glycan immune checkpoints.” We also examine translational bottlenecks: inter- and intra-tumoral glycan heterogeneity; manufacturing reproducibility (density/orientation/valency); colloidal and biological stability; pharmacokinetics; and regulatory expectations for characterization and immunogenicity. Finally, we outline emerging applications that may accelerate bench-to-bedside translation. Overall, GlycoNPs offer a modular, multiplexable path to precision oncology, enabling reader-guided tumor profiling, imaging, and intervention through the language of glycans.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109757"},"PeriodicalIF":2.5,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145573154","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 : 2025-11-14DOI: 10.1016/j.carres.2025.109758
Jessica Jung-Fittkau , Jascha Schmeh , Angelika Czajkowska , Sahin Özdemir , Josef Diebold , Magnus S. Schmidt
Bromalkyl glycosides are promising molecules for use as functionalised spacers in the production of glycomimetics. The here presented optimised process can serve as the basis for the technical synthesis of bromoalkyl glycosides in a microreactor. Therefore, we tested the influence of residence time and temperature on the synthesis of bromoalkyl glycosides in a microreactor. To determine the optimum temperature, the synthesis was investigated between 90 °C and 150 °C, in 10 °C increments. To determine the optimum residence time in the reactor, the residence time was varied between 1 and 10 min. The results show, that the product yield increases initially with increasing temperature or residence time. In both curves, there is limited growth before the yield drops again after the peak. It was found that at high temperatures and residence times, the number of undesirable by-products may also increase, which has a negative effect on product yield. We found the optimum temperature range is 120 °C–130 °C and the optimum residence time at 7.5 min.
{"title":"Parameter optimisation of a microreactor based continuous synthesis of bromooctyl glucoside by Fischer glycosylation","authors":"Jessica Jung-Fittkau , Jascha Schmeh , Angelika Czajkowska , Sahin Özdemir , Josef Diebold , Magnus S. Schmidt","doi":"10.1016/j.carres.2025.109758","DOIUrl":"10.1016/j.carres.2025.109758","url":null,"abstract":"<div><div>Bromalkyl glycosides are promising molecules for use as functionalised spacers in the production of glycomimetics. The here presented optimised process can serve as the basis for the technical synthesis of bromoalkyl glycosides in a microreactor. Therefore, we tested the influence of residence time and temperature on the synthesis of bromoalkyl glycosides in a microreactor. To determine the optimum temperature, the synthesis was investigated between 90 °C and 150 °C, in 10 °C increments. To determine the optimum residence time in the reactor, the residence time was varied between 1 and 10 min. The results show, that the product yield increases initially with increasing temperature or residence time. In both curves, there is limited growth before the yield drops again after the peak. It was found that at high temperatures and residence times, the number of undesirable by-products may also increase, which has a negative effect on product yield. We found the optimum temperature range is 120 °C–130 °C and the optimum residence time at 7.5 min.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109758"},"PeriodicalIF":2.5,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145562879","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}
Pyrimidine nucleoside phosphorylase (PyNP) catalyzes phosphorolysis and base exchange reactions, providing an eco-friendly and stereoselective approach for synthesizing unnatural nucleosides. This study investigates PyNP substrate specificity, particularly the effects of functional group modifications at the 6-position of purine nucleobases on enzymatic base exchange reactions using thymidine (Thd) or uridine (Urd) as ribose donors. The reaction rate with the two ribose donors varied significantly depending on the 6-substituent on purine bases. Compounds with 6-monoalkylamino groups preferentially reacted with uridine (Thd/Urd values lower than 1.0), while 6-dialkylamino groups favored thymidine (Thd/Urd values greater than 1). When an ether or alkyl group was introduced at the 6-position, the corresponding purine was found to react preferentially with thymidine as a ribose donor. Docking simulations suggested that the steric hindrance of a 6-dialkylamino group affected substrate positioning, leading to a preferential reaction with thymidine, while increasing the steric hindrance of the 2′-hydroxyl group of uridine. On the other hand, 6-monoalkylaminopurines were less sterically hindered, and the ribose moiety was located away from the pocket surface of the enzyme, suggesting that the presence or absence of the 2′-hydroxyl group of the ribose form had minimal impact. Thus, selectivity (Thd/Urd value) showed a slight preference for uridine, albeit not significant. These results demonstrate that, in the bi-substrate enzymatic reaction of PyNP, one substrate recognizes the structure of the other, thereby altering its reactivity. Specifically, it was revealed that the positioning of one substrate within the enzyme pocket induces conformational changes in the other substrate, consequently influencing the nucleophilic reaction.
{"title":"Impact of 6-purine modifications on the ribose substrate selectivity of pyrimidine nucleoside phosphorylase (PyNP) in base exchange reactions","authors":"Akihiko Hatano , Riki Matsuzaka , Rai Hamano , Genki Shimane , Toranosuke Fukatsu , Hibiki Okumoto , Masatoshi Kidowaki , Toshifumi Konishi","doi":"10.1016/j.carres.2025.109739","DOIUrl":"10.1016/j.carres.2025.109739","url":null,"abstract":"<div><div>Pyrimidine nucleoside phosphorylase (PyNP) catalyzes phosphorolysis and base exchange reactions, providing an eco-friendly and stereoselective approach for synthesizing unnatural nucleosides. This study investigates PyNP substrate specificity, particularly the effects of functional group modifications at the 6-position of purine nucleobases on enzymatic base exchange reactions using thymidine (Thd) or uridine (Urd) as ribose donors. The reaction rate with the two ribose donors varied significantly depending on the 6-substituent on purine bases. Compounds with 6-monoalkylamino groups preferentially reacted with uridine (Thd/Urd values lower than 1.0), while 6-dialkylamino groups favored thymidine (Thd/Urd values greater than 1). When an ether or alkyl group was introduced at the 6-position, the corresponding purine was found to react preferentially with thymidine as a ribose donor. Docking simulations suggested that the steric hindrance of a 6-dialkylamino group affected substrate positioning, leading to a preferential reaction with thymidine, while increasing the steric hindrance of the 2′-hydroxyl group of uridine. On the other hand, 6-monoalkylaminopurines were less sterically hindered, and the ribose moiety was located away from the pocket surface of the enzyme, suggesting that the presence or absence of the 2′-hydroxyl group of the ribose form had minimal impact. Thus, selectivity (Thd/Urd value) showed a slight preference for uridine, albeit not significant. These results demonstrate that, in the bi-substrate enzymatic reaction of PyNP, one substrate recognizes the structure of the other, thereby altering its reactivity. Specifically, it was revealed that the positioning of one substrate within the enzyme pocket induces conformational changes in the other substrate, consequently influencing the nucleophilic reaction.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109739"},"PeriodicalIF":2.5,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145534390","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 : 2025-11-13DOI: 10.1016/j.carres.2025.109742
Monika Tvrdoňová , Peter Michalčin , Tatiana Pončáková , Yuliia Zuzak , Martina Bago Pilátová , Juraj Kuchár , Miroslava Litecká , Miroslava Martinková
Two approaches leading to 2-C-tridecyl piperidine-containing 1-N-iminosugars from the chiral pool were accomplished. The pivotal steps for completing the construction of these azasugars were aza-Claisen rearrangements as a powerful tool for the formation of carbon-nitrogen bonds, cyclisation protocols and an olefin cross-metathesis. The versatility of the developed concept permits access to other stereoisomeric partners of this class of compounds by varying the sugar unit used as the starting material. Moreover, the late-stage introduction of an alkyl branch could provide high flexibility for novel side chain analogues. Last but not least, carbohydrates are a cost-effective, environmentally biocompatible starting material for the chiral pool strategy. The preliminary cytotoxic evaluation indicates that the designed piperidines have a promising capacity to alter the viability of cancer cell lines.
完成了从手性池中得到含2- c -三烷基哌啶- 1- n -亚氨基糖的两种方法。完成这些偶氮糖构建的关键步骤是偶氮糖- clisen重排作为形成碳-氮键的有力工具，环化协议和烯烃交叉复分解。所开发概念的多功能性允许通过改变用作起始材料的糖单位来获得该类化合物的其他立体异构体伙伴。此外，烷基分支的后期引入可以为新的侧链类似物提供高的灵活性。最后但并非最不重要的是，碳水化合物是一种具有成本效益，环境生物相容性的手性池策略起始材料。初步的细胞毒性评价表明，所设计的哌啶具有改变癌细胞存活能力的前景。
{"title":"A ‘chiron’ approach to divergent synthesis of 2-C-tridecyl 1-N-iminosugar mimetics and their anticancer profile","authors":"Monika Tvrdoňová , Peter Michalčin , Tatiana Pončáková , Yuliia Zuzak , Martina Bago Pilátová , Juraj Kuchár , Miroslava Litecká , Miroslava Martinková","doi":"10.1016/j.carres.2025.109742","DOIUrl":"10.1016/j.carres.2025.109742","url":null,"abstract":"<div><div>Two approaches leading to 2-<em>C</em>-tridecyl piperidine-containing 1-<em>N</em>-iminosugars from the chiral pool were accomplished. The pivotal steps for completing the construction of these azasugars were <em>aza</em>-Claisen rearrangements as a powerful tool for the formation of carbon-nitrogen bonds, cyclisation protocols and an olefin cross-metathesis. The versatility of the developed concept permits access to other stereoisomeric partners of this class of compounds by varying the sugar unit used as the starting material. Moreover, the late-stage introduction of an alkyl branch could provide high flexibility for novel side chain analogues. Last but not least, carbohydrates are a cost-effective, environmentally biocompatible starting material for the chiral pool strategy. The preliminary cytotoxic evaluation indicates that the designed piperidines have a promising capacity to alter the viability of cancer cell lines.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109742"},"PeriodicalIF":2.5,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145534438","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 : 2025-11-12DOI: 10.1016/j.carres.2025.109745
Anna M. Shpirt , Zakhar V. Serpokrylov , Andrei V. Perepelov , Andrei S. Dmitrenok , Mikhail M. Shneider , Anastasiya V. Popova , Philip V. Toukach , Yuriy A. Knirel
Structure of the Acinetobacter baumannii MAR20-4513 (K104) capsular polysaccharide (CPS) was established using Smith degradation, 1H and 13C NMR spectroscopy, including two-dimensional homonuclear 1Н,1Н COSY, TOCSY, ROESY and heteronuclear 1Н,13C HSQC and HMBC experiments, and modeling. The K104 CPS is composed of a branched pentasaccharide K unit containing two d-Glcp residues, and one residue each of d-GalpNAc, d-GlcpNAc and d-Galp. The following structure of the pentasaccharide repeating unit of the CPS was established.
Functions of genes in the K locus of A. baumannii K104 were assigned by a comparison with sequences in the available databases and found to be in agreement with the CPS structure.
{"title":"Structure and gene cluster of the capsular polysaccharide of Acinetobacter baumannii K104","authors":"Anna M. Shpirt , Zakhar V. Serpokrylov , Andrei V. Perepelov , Andrei S. Dmitrenok , Mikhail M. Shneider , Anastasiya V. Popova , Philip V. Toukach , Yuriy A. Knirel","doi":"10.1016/j.carres.2025.109745","DOIUrl":"10.1016/j.carres.2025.109745","url":null,"abstract":"<div><div>Structure of the <em>Acinetobacter baumannii</em> MAR20-4513 (K104) capsular polysaccharide (CPS) was established using Smith degradation, <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy, including two-dimensional homonuclear <sup>1</sup>Н,<sup>1</sup>Н COSY, TOCSY, ROESY and heteronuclear <sup>1</sup>Н,<sup>13</sup>C HSQC and HMBC experiments, and modeling. The K104 CPS is composed of a branched pentasaccharide K unit containing two <span>d</span>-Glc<em>p</em> residues, and one residue each of <span>d</span>-Gal<em>p</em>NAc, <span>d</span>-Glc<em>p</em>NAc and <span>d</span>-Gal<em>p</em>. The following structure of the pentasaccharide repeating unit of the CPS was established.</div><div>Functions of genes in the K locus of <em>A. baumannii</em> K104 were assigned by a comparison with sequences in the available databases and found to be in agreement with the CPS structure.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109745"},"PeriodicalIF":2.5,"publicationDate":"2025-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145548461","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}
The Acinetobacter genus comprises a multitude of species that have been isolated from both environmental and clinical samples. In recent years, the scientific community has expended considerable effort in characterising the structures of the capsular polysaccharides and lipooligoaccharides (LOS) of A. baumannii, given the increasing mortality rate caused by this species. Comparatively little research has been undertaken for the non-pathogenic species.
In the present study, we describe the first case of isolation and identification of the LOS molecule of Acinetobacter modestus CM11G, a Gram-negative bacterium colonising the intestinal crypts of a healthy mouse. By combining spectroscopic and spectrometric analyses with chemical derivatisations, we were able to determine the structure of the entire LOS. The lipid A moiety is composed mainly of hepta-acylated species, a characteristic also observed in other Acinetobacter species. It is extended with a disaccharide of Kdo, which acts as a bridge between the lipid A and the oligosaccharide portion. Indeed, the internal Kdo residue is linked at position O-5 with a novel tetrasaccharide composed of βGlcN(1→2)-βGal(1→6)-αGlc(1→, where the glucose is further substituted at position O-4 with a terminal β-Glc. In contrast, the external Kdo residue does not undergo further substitution, contrary to what generally occurs in the LOS of A. baumannii.
{"title":"Lipooligosaccharide architecture in Acinetobacter modestus CM11G: a non-pathogenic strain","authors":"Immacolata Speciale , Luisa Sturiale , Angelo Palmigiano , Anna Notaro","doi":"10.1016/j.carres.2025.109743","DOIUrl":"10.1016/j.carres.2025.109743","url":null,"abstract":"<div><div>The <em>Acinetobacter</em> genus comprises a multitude of species that have been isolated from both environmental and clinical samples. In recent years, the scientific community has expended considerable effort in characterising the structures of the capsular polysaccharides and lipooligoaccharides (LOS) of <em>A. baumannii</em>, given the increasing mortality rate caused by this species. Comparatively little research has been undertaken for the non-pathogenic species.</div><div>In the present study, we describe the first case of isolation and identification of the LOS molecule of <em>Acinetobacter modestus</em> CM11G, a Gram-negative bacterium colonising the intestinal crypts of a healthy mouse. By combining spectroscopic and spectrometric analyses with chemical derivatisations, we were able to determine the structure of the entire LOS. The lipid A moiety is composed mainly of hepta-acylated species, a characteristic also observed in other <em>Acinetobacter</em> species. It is extended with a disaccharide of Kdo, which acts as a bridge between the lipid A and the oligosaccharide portion. Indeed, the internal Kdo residue is linked at position <em>O</em>-5 with a novel tetrasaccharide composed of βGlcN(1→2)-βGal(1→6)-αGlc(1→, where the glucose is further substituted at position <em>O</em>-4 with a terminal β-Glc. In contrast, the external Kdo residue does not undergo further substitution, contrary to what generally occurs in the LOS of <em>A. baumannii</em>.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109743"},"PeriodicalIF":2.5,"publicationDate":"2025-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145522983","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}
Allii macrostemonis Bulbus (Xiebai) is an important medicinal and edible homologous plant belonging to the genus Allium in the family Liliaceae. Its polysaccharide components (XBPS) are regarded as one of its principal bioactive constituents. Although significant progress has been made in the extraction, structural characterization, and pharmacological evaluation of XBPS, its detailed structural features, biological mechanisms of action, and structure-activity relationships remain insufficiently elucidated. This review summarizes recent advances in the extraction, purification, structural analysis, biological activities, and structural modification of XBPS, aiming to provide a theoretical foundation for its further development and application.
Studies have shown that, compared with traditional hot-water extraction, emerging techniques such as ultrasound-assisted extraction offer significant advantages in enhancing extraction yield and preserving the native bioactive structures of XBPS. Structural analyses reveal that XBPS mainly comprises two types of polysaccharides: acidic polysaccharides and neutral fructans. The acidic polysaccharides are rich in uronic acids, which confer high target affinity and bioavailability, whereas the fructans primarily consist of β-(2 → 1) and β-(2 → 6) glycosidic linkages, forming a highly branched, chain-like network that serves as an important structural model for investigating structure-activity relationships.
Pharmacological studies have demonstrated that XBPS exhibits a broad spectrum of biological activities, including anti-atherosclerotic, cardioprotective, anti-inflammatory, antioxidant, hepatoprotective, and antitumor effects. These biological functions are synergistically influenced by factors such as molecular weight, monosaccharide composition, glycosidic linkage type, and spatial conformation. Future research should focus on standardizing extraction and characterization methodologies, elucidating structure-function correlations, and exploring the potential applications of XBPS in the development of functional foods and pharmaceutical agents.
{"title":"A review of Allii macrostemonis Bulbus polysaccharides: Extraction, purification, structural characterization, and biological activity","authors":"Hua Huang, Xiaolan Liu, Yiqiao Ding, Xuebin Xu, Guoyou Chen, Jianqiang Ma, Meng Wang, Haixue Kuang, Zhibin Wang","doi":"10.1016/j.carres.2025.109747","DOIUrl":"10.1016/j.carres.2025.109747","url":null,"abstract":"<div><div><em>Allii macrostemonis</em> Bulbus (Xiebai) is an important medicinal and edible homologous plant belonging to the genus <em>Allium</em> in the family Liliaceae. Its polysaccharide components (XBPS) are regarded as one of its principal bioactive constituents. Although significant progress has been made in the extraction, structural characterization, and pharmacological evaluation of XBPS, its detailed structural features, biological mechanisms of action, and structure-activity relationships remain insufficiently elucidated. This review summarizes recent advances in the extraction, purification, structural analysis, biological activities, and structural modification of XBPS, aiming to provide a theoretical foundation for its further development and application.</div><div>Studies have shown that, compared with traditional hot-water extraction, emerging techniques such as ultrasound-assisted extraction offer significant advantages in enhancing extraction yield and preserving the native bioactive structures of XBPS. Structural analyses reveal that XBPS mainly comprises two types of polysaccharides: acidic polysaccharides and neutral fructans. The acidic polysaccharides are rich in uronic acids, which confer high target affinity and bioavailability, whereas the fructans primarily consist of <em>β</em>-(2 → 1) and <em>β</em>-(2 → 6) glycosidic linkages, forming a highly branched, chain-like network that serves as an important structural model for investigating structure-activity relationships.</div><div>Pharmacological studies have demonstrated that XBPS exhibits a broad spectrum of biological activities, including anti-atherosclerotic, cardioprotective, anti-inflammatory, antioxidant, hepatoprotective, and antitumor effects. These biological functions are synergistically influenced by factors such as molecular weight, monosaccharide composition, glycosidic linkage type, and spatial conformation. Future research should focus on standardizing extraction and characterization methodologies, elucidating structure-function correlations, and exploring the potential applications of XBPS in the development of functional foods and pharmaceutical agents.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109747"},"PeriodicalIF":2.5,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145511690","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 : 2025-11-08DOI: 10.1016/j.carres.2025.109741
Shuyu Yue, Jishun Shi, Changyu Cai, Yanxiong Ke
QS-21 is a highly effective vaccine adjuvant that is purified from the bark of the Quillaja saponaria tree. However, due to the complex structure of saponins and the existence of multiple isomers with similar structures, obtaining high-purity QS-21 is extremely challenging. This study describes the development of a chromatographic process for purifying QS-21xyl and QS-21Api using commercially available Q. saponaria bark extract as the starting material. First, the sample was purified using Polyvinyl pyrrolidone-divinylbenzene (PVP-DVB) copolymer resin to remove highly polar compounds and obtain a saponin-enriched component. Then, the fraction containing QS-21 was obtained using a C18 column. Impurities in the sample were identified using Matrix-Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) mass spectrometry, including structurally analogous impurities such as S1, S2, S3 and S5. Analysis using an amide column in hydrophilic interaction chromatography (HILIC) mode exhibited different separation selectivity compared to analysis using a C18 column in reverse phase mode. The HILIC separation condition of QS-21xyl and QS-21Api was optimized and then the compounds were purified using a semi-preparative chromatographic column. The resulting QS-21Xyl and QS-21Api had a purity greater than 97 %. This process provides an efficient method of obtaining highly pure QS-21 isomers from Q. Saponaria bark extract.
{"title":"Purification of Quillaja saponins QS-21Xyl and QS-21Api by hydrophilic interaction chromatography","authors":"Shuyu Yue, Jishun Shi, Changyu Cai, Yanxiong Ke","doi":"10.1016/j.carres.2025.109741","DOIUrl":"10.1016/j.carres.2025.109741","url":null,"abstract":"<div><div>QS-21 is a highly effective vaccine adjuvant that is purified from the bark of the <em>Quillaja saponaria</em> tree. However, due to the complex structure of saponins and the existence of multiple isomers with similar structures, obtaining high-purity QS-21 is extremely challenging. This study describes the development of a chromatographic process for purifying QS-21<sub>xyl</sub> and QS-21<sub>Api</sub> using commercially available <em>Q. saponaria</em> bark extract as the starting material. First, the sample was purified using Polyvinyl pyrrolidone-divinylbenzene (PVP-DVB) copolymer resin to remove highly polar compounds and obtain a saponin-enriched component. Then, the fraction containing QS-21 was obtained using a C18 column. Impurities in the sample were identified using Matrix-Assisted Laser Desorption/Ionization Time of Flight (MALDI-TOF) mass spectrometry, including structurally analogous impurities such as S1, S2, S3 and S5. Analysis using an amide column in hydrophilic interaction chromatography (HILIC) mode exhibited different separation selectivity compared to analysis using a C18 column in reverse phase mode. The HILIC separation condition of QS-21<sub>xyl</sub> and QS-21<sub>Api</sub> was optimized and then the compounds were purified using a semi-preparative chromatographic column. The resulting QS-21<sub>Xyl</sub> and QS-21<sub>Api</sub> had a purity greater than 97 %. This process provides an efficient method of obtaining highly pure QS-21 isomers from <em>Q. Saponaria</em> bark extract.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109741"},"PeriodicalIF":2.5,"publicationDate":"2025-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145502080","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 : 2025-11-07DOI: 10.1016/j.carres.2025.109744
Shuai Wang , Mingxuan Li , Xiaomeng Gong , Zhi Chen , Huagang Sheng , Fengxia Xu , Yanru Ren , Chao Zhang , Fei Guo , Zhiyuan Zhang
Ophiopogonis Radix and Liriopes Radix (Maidong), a traditional Chinese medicine esteemed for its yin-nourishing and lung-moistening properties, is a rich source of bioactive polysaccharides (Maidong polysaccharides, MDPs). This review systematically consolidates recent advances (from 2018 to October 2025) in the extraction, purification, structural characterization, and diverse bioactivities of MDPs. Modern research reveals that MDPs exhibit a broad spectrum of pharmacological activities, including antioxidant, anti-inflammatory, immunomodulatory, and gut microbiota-regulating effects. These properties underpin their potential therapeutic applications in managing conditions like diabetes, cardiovascular disorders, and inflammatory diseases. Despite promising findings, a clear understanding of the precise structural information and structure-activity relationships of MDPs remains limited. This comprehensive summary aims to lay a foundation for future research, highlighting the therapeutic potential of MDPs while identifying key areas requiring further investigation to fully exploit their health-promoting functions.
{"title":"A systematic review on polysaccharides from Ophiopogonis Radix and Liriopes Radix: Advances in the preparation, structural characterization and pharmacological activities","authors":"Shuai Wang , Mingxuan Li , Xiaomeng Gong , Zhi Chen , Huagang Sheng , Fengxia Xu , Yanru Ren , Chao Zhang , Fei Guo , Zhiyuan Zhang","doi":"10.1016/j.carres.2025.109744","DOIUrl":"10.1016/j.carres.2025.109744","url":null,"abstract":"<div><div>Ophiopogonis Radix and Liriopes Radix (Maidong), a traditional Chinese medicine esteemed for its yin-nourishing and lung-moistening properties, is a rich source of bioactive polysaccharides (Maidong polysaccharides, MDPs). This review systematically consolidates recent advances (from 2018 to October 2025) in the extraction, purification, structural characterization, and diverse bioactivities of MDPs. Modern research reveals that MDPs exhibit a broad spectrum of pharmacological activities, including antioxidant, anti-inflammatory, immunomodulatory, and gut microbiota-regulating effects. These properties underpin their potential therapeutic applications in managing conditions like diabetes, cardiovascular disorders, and inflammatory diseases. Despite promising findings, a clear understanding of the precise structural information and structure-activity relationships of MDPs remains limited. This comprehensive summary aims to lay a foundation for future research, highlighting the therapeutic potential of MDPs while identifying key areas requiring further investigation to fully exploit their health-promoting functions.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"559 ","pages":"Article 109744"},"PeriodicalIF":2.5,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145534392","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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