Pub Date : 2025-10-08DOI: 10.1016/j.carres.2025.109700
Olexandr I. Guzyr , Lyudmyla M. Potikha , Svitlana V. Shishkina , Volodymyr N. Fetyukhin , Yuriy G. Shermolovich , Julia P. Bas , Irina B. Kulyk , Polina Yu. Zaremba , Svitlana D. Zahorodnia
A one-step stereoselective synthesis of β-N-benzothiazolyl glycosides was developed by glycosylation of amino-2-pentafluorosulfanyl-1,3-benzothiazole and amino-2-trifluoromethyl-1,3-benzothiazole derivatives using unprotected d-glucose in ethanol solution. The structure of β-N-glycosides was confirmed by X-ray crystallography. Starting 4- and 6-amino substituted benzothiazoles bearing pentafluorosufanyl and trifluoromethyl groups were prepared from the corresponding nitro derivatives by the reduction with iron in NH4Cl/H2O media. The pKa values of the new aminobenzothiazoles were determined by potentiometric acid-base titration. Cytotoxicity in MDCK and Wish cell cultures was determined to evaluate the biological activity of the new compounds, and the antiviral activity against influenza virus type A (H1N1) was investigated. It was shown that 4-β-d-glucopyranosylamino-2-(trifluoromethyl)-1,3-benzothiazole shoved the ability to inhibit virus reproduction in cells.
利用无保护的d-葡萄糖在乙醇溶液中对氨基-2-五氟磺胺-1,3-苯并噻唑和氨基-2-三氟甲基-1,3-苯并噻唑衍生物进行糖基化，一步立体选择性合成了β- n -苯并噻唑糖苷。用x射线晶体学证实了β- n -糖苷的结构。在NH4Cl/H2O介质中，以相应的硝基衍生物为原料，用铁还原法制备了含五氟磺胺基和三氟甲基的4-和6-氨基取代苯并噻唑。采用电位酸碱滴定法测定了新型氨基苯并噻唑的pKa值。测定了新化合物在MDCK和Wish细胞培养中的细胞毒性，以评价其生物活性，并研究了其对甲型H1N1流感病毒的抗病毒活性。结果表明，4-β-d-glucopyranosylamino-2-（三氟甲基）-1,3-苯并噻唑具有抑制病毒在细胞内繁殖的能力。
{"title":"Synthesis, structure, and antiviral activity 4(6)-β-d-glucopyranosylamino-2-R-1,3-benzothiazoles","authors":"Olexandr I. Guzyr , Lyudmyla M. Potikha , Svitlana V. Shishkina , Volodymyr N. Fetyukhin , Yuriy G. Shermolovich , Julia P. Bas , Irina B. Kulyk , Polina Yu. Zaremba , Svitlana D. Zahorodnia","doi":"10.1016/j.carres.2025.109700","DOIUrl":"10.1016/j.carres.2025.109700","url":null,"abstract":"<div><div>A one-step stereoselective synthesis of <em>β</em>-<em>N</em>-benzothiazolyl glycosides was developed by glycosylation of amino-2-pentafluorosulfanyl-1,3-benzothiazole and amino-2-trifluoromethyl-1,3-benzothiazole derivatives using unprotected <span>d</span>-glucose in ethanol solution. The structure of <em>β</em>-<em>N</em>-glycosides was confirmed by X-ray crystallography. Starting 4- and 6-amino substituted benzothiazoles bearing pentafluorosufanyl and trifluoromethyl groups were prepared from the corresponding nitro derivatives by the reduction with iron in NH<sub>4</sub>Cl/H<sub>2</sub>O media. The pKa values of the new aminobenzothiazoles were determined by potentiometric acid-base titration. Cytotoxicity in MDCK and Wish cell cultures was determined to evaluate the biological activity of the new compounds, and the antiviral activity against influenza virus type A (H1N1) was investigated. It was shown that 4-<em>β</em>-d-glucopyranosylamino-2-(trifluoromethyl)-1,3-benzothiazole shoved the ability to inhibit virus reproduction in cells.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"558 ","pages":"Article 109700"},"PeriodicalIF":2.5,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145285661","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}
Tissue engineering has emerged as a potential area in regenerative medicine, leveraging biodegradable and biocompatible polymers to fabricate scaffolds for cell growth and tissue regeneration. Among biomaterials, plant-based polymers have garnered significant attention due to their sustainability, biocompatibility, and suitable mechanical properties. This review emphasises the innovative modifications in natural polymers such as fungal chitosan, nanocellulose composites, and hybrid plant-synthetic scaffolds-that address longstanding challenges in mechanical stability, degradation control, and bioactivity. By systematically comparing polysaccharides (e.g., cellulose, alginate) and proteins (soy, zein) across bone, cartilage, and wound healing applications, we identify structure-function relationships that enable tailored scaffold design. Finally, this review critically evaluates recent advances in plant-based polymers for tissue engineering, highlighting innovative modifications and unresolved challenges providing actionable strategies to advance plant derived biomaterials towards clinical transition.
{"title":"Plant-based biodegradable and biocompatible polymers for tissue engineering applications","authors":"Aditya Teja Guduru, Subramanian Sankaranarayanan, Dhiraj Bhatia","doi":"10.1016/j.carres.2025.109699","DOIUrl":"10.1016/j.carres.2025.109699","url":null,"abstract":"<div><div>Tissue engineering has emerged as a potential area in regenerative medicine, leveraging biodegradable and biocompatible polymers to fabricate scaffolds for cell growth and tissue regeneration. Among biomaterials, plant-based polymers have garnered significant attention due to their sustainability, biocompatibility, and suitable mechanical properties. This review emphasises the innovative modifications in natural polymers such as fungal chitosan, nanocellulose composites, and hybrid plant-synthetic scaffolds-that address longstanding challenges in mechanical stability, degradation control, and bioactivity. By systematically comparing polysaccharides (e.g., cellulose, alginate) and proteins (soy, zein) across bone, cartilage, and wound healing applications, we identify structure-function relationships that enable tailored scaffold design. Finally, this review critically evaluates recent advances in plant-based polymers for tissue engineering, highlighting innovative modifications and unresolved challenges providing actionable strategies to advance plant derived biomaterials towards clinical transition.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"558 ","pages":"Article 109699"},"PeriodicalIF":2.5,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145291210","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 : 2025-10-06DOI: 10.1016/j.carres.2025.109696
Neil P.J. Price , Karl E. Vermillion , Michael A. Jackson
A straightforward, aqueous-based procedure is described to determine the absolute configuration of aldose monosaccharides, a critical task in carbohydrate analysis. This approach leverages the reaction of aldose monosaccharide enantiomers with L-cysteine, a readily-available chiral amino acid, to form cyclic thiazolidine diastereomers. These derivatives can be analyzed using Heteronuclear Single Quantum Coherence (HSQC) NMR spectroscopy, specifically looking at the H-1 – C-1 proton-carbon single bond correlations. This NMR technique provides the necessary data to determine the absolute configuration of the parent monosaccharide. Several monosaccharide D-/L-enantiomeric pairs are analyzed as examples, and the technique is utilized to determine the compositional stereochemistry of complex polysaccharides (gellan and xanthan gums). We have also established the previously unknown stereochemistry of the arabinosyl residues found in frost grape polysaccharide (FGP) isolated from vines of the grape species, Vitis riparia Michx. The generalized method described is anticipated to be valuable to analytical carbohydrate chemists for the facile assignment of carbohydrate stereochemistry.
一个简单的，基于水的程序描述了确定醛糖单糖的绝对构型，在碳水化合物分析的关键任务。这种方法利用醛糖单糖对映体与l -半胱氨酸（一种容易获得的手性氨基酸）的反应，形成环噻唑烷非对映体。这些衍生物可以使用异核单量子相干（HSQC）核磁共振波谱分析，特别是观察H-1 - C-1质子-碳单键的相关性。这种核磁共振技术提供了必要的数据来确定母体单糖的绝对构型。以几种单糖D-/ l -对映体对为例进行了分析，并利用该技术确定了复合多糖（结冷胶和黄原胶）的组成立体化学。我们还建立了以前未知的立体化学，在从葡萄品种Vitis riparia micx的葡萄中分离的霜葡萄多糖（FGP）中发现阿拉伯糖基残基。所描述的广义方法预计对分析碳水化合物化学家来说是有价值的，可以方便地分配碳水化合物的立体化学。
{"title":"A simplified NMR-based method to assign the absolute configuration of aldose monosaccharides","authors":"Neil P.J. Price , Karl E. Vermillion , Michael A. Jackson","doi":"10.1016/j.carres.2025.109696","DOIUrl":"10.1016/j.carres.2025.109696","url":null,"abstract":"<div><div>A straightforward, aqueous-based procedure is described to determine the absolute configuration of aldose monosaccharides, a critical task in carbohydrate analysis. This approach leverages the reaction of aldose monosaccharide enantiomers with L-cysteine, a readily-available chiral amino acid, to form cyclic thiazolidine diastereomers. These derivatives can be analyzed using Heteronuclear Single Quantum Coherence (HSQC) NMR spectroscopy, specifically looking at the H-1 – C-1 proton-carbon single bond correlations. This NMR technique provides the necessary data to determine the absolute configuration of the parent monosaccharide. Several monosaccharide D-/L-enantiomeric pairs are analyzed as examples, and the technique is utilized to determine the compositional stereochemistry of complex polysaccharides (gellan and xanthan gums). We have also established the previously unknown stereochemistry of the arabinosyl residues found in frost grape polysaccharide (FGP) isolated from vines of the grape species, <em>Vitis riparia</em> Michx. The generalized method described is anticipated to be valuable to analytical carbohydrate chemists for the facile assignment of carbohydrate stereochemistry.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"558 ","pages":"Article 109696"},"PeriodicalIF":2.5,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145312488","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}
Mushroom-derived polysaccharides, particularly β-D-glucans, are valued for their biological activities and broad biotechnological applications. Although several conventional extraction methods have been established (cold-water, hot-water, and alkaline), the biomass that remains after exhaustive treatments is often discarded, despite its potential to retain valuable compounds. In this study, we evaluated whether residual laboratory materials from Pleurotus pulmonarius, Pholiota nameko, and Amanita muscaria still contain extractable polysaccharides by applying sequential autoclave extractions under aqueous, 5 % KOH, and 20 % KOH conditions. The extracts were precipitated with ethanol, quantified, and characterized by NMR, GC-MS, HPSEC-RI, and by total sugar and protein determinations. Significant yields were obtained, particularly with 5 % KOH, which produced up to 31.1 % in a single step, albeit with considerable protein content. Across extraction steps, a progressive decrease in molecular weight was observed, and monosaccharide analysis revealed that the extracts were composed predominantly of glucose. Structural characterization confirmed a predominance of β-D-glucans with (1→3)- and (1→6)-linkages, together with α-D-glucans with (1→3)- and (1→4)-linkages, as well as galactans and mannans. Overall, these findings demonstrate that autoclave extraction is a simple, efficient, and scalable approach to recover structurally diverse polysaccharides from mushroom residues, thereby enhancing resource utilization and opening new opportunities for fungal biomass valorization.
蘑菇来源的多糖，特别是β- d -葡聚糖，因其生物活性和广泛的生物技术应用而受到重视。虽然已经建立了几种传统的提取方法（冷水、热水和碱性），但经过彻底处理后剩下的生物质往往被丢弃，尽管它可能保留有价值的化合物。在这项研究中，我们通过在水、5% KOH和20% KOH条件下的顺序高压灭菌法提取，评估了从肺侧耳菌（Pleurotus pulmonarius）、菲洛塔（Pholiota nameko）和毒伞菌（Amanita muscaria）中提取的残留实验材料是否仍含有可提取的多糖。提取液用乙醇沉淀，定量，并通过NMR， GC-MS, HPSEC-RI，总糖和蛋白质测定进行表征。获得了显著的产量，特别是在5% KOH的情况下，单步产量高达31.1%，尽管蛋白质含量相当高。在整个提取步骤中，观察到分子量逐渐减少，单糖分析表明提取物主要由葡萄糖组成。结构表征证实了（1→3）-和（1→6）-键的β- d -葡聚糖、（1→3）-和（1→4）-键的α- d -葡聚糖以及半乳聚糖和甘露聚糖的优势。总之，这些发现表明，高压灭菌法是一种简单、高效、可扩展的方法，可以从蘑菇残留物中回收结构多样的多糖，从而提高资源利用率，并为真菌生物量增值开辟新的机会。
{"title":"Autoclave extraction applied to residual mushroom biomass: An efficient method for high-yield polysaccharide recovery","authors":"Matheus Zavadinack , Hellen Abreu , Dib Mady Diniz Gomes , Shayane da Silva Milhorini , Fhernanda Ribeiro Smiderle , Lucimara M.C. Cordeiro , Marcello Iacomini","doi":"10.1016/j.carres.2025.109698","DOIUrl":"10.1016/j.carres.2025.109698","url":null,"abstract":"<div><div>Mushroom-derived polysaccharides, particularly β-D-glucans, are valued for their biological activities and broad biotechnological applications. Although several conventional extraction methods have been established (cold-water, hot-water, and alkaline), the biomass that remains after exhaustive treatments is often discarded, despite its potential to retain valuable compounds. In this study, we evaluated whether residual laboratory materials from <em>Pleurotus pulmonarius</em>, <em>Pholiota nameko</em>, and <em>Amanita muscaria</em> still contain extractable polysaccharides by applying sequential autoclave extractions under aqueous, 5 % KOH, and 20 % KOH conditions. The extracts were precipitated with ethanol, quantified, and characterized by NMR, GC-MS, HPSEC-RI, and by total sugar and protein determinations<strong>.</strong> Significant yields were obtained, particularly with 5 % KOH, which produced up to 31.1 % in a single step, albeit with considerable protein content. Across extraction steps, a progressive decrease in molecular weight was observed, and monosaccharide analysis revealed that the extracts were composed predominantly of glucose. Structural characterization confirmed a predominance of β-D-glucans with (1→3)- and (1→6)-linkages, together with α-D-glucans with (1→3)- and (1→4)-linkages, as well as galactans and mannans. Overall, these findings demonstrate that autoclave extraction is a simple, efficient, and scalable approach to recover structurally diverse polysaccharides from mushroom residues, thereby enhancing resource utilization and opening new opportunities for fungal biomass valorization.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"558 ","pages":"Article 109698"},"PeriodicalIF":2.5,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145291218","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}
Seafood waste especially crustacean shells are often discarded at sea or landfilled. Therefore, the extraction of valuable biomolecules such as chitin and the synthesis of chitosan and its nanoparticles are considered a beneficial solution to reduce crustacean shell waste. In the present study, chitosan (ACs) was extracted from the shells of anomuran crab Albunea symmysta and chitosan nanoparticles (CsNP) were synthesized using the ionic gelation method. The degree of deacetylation of chitosan was found to be 82.85 %. FTIR analysis of ACs and CsNP depicted similar functional groups at corresponding peaks compared to commercial chitosan (CCs). XRD analysis confirmed the semi crystalline nature of CCs, ACs, while CsNP exhibited reduced crystallinity and more amorphous structure. DLS studies evidenced that the mean diameter of CsNP was 144.3 ± 11.8 nm and the zeta potential of both ACs and CsNP was found to be positive. SEM imaging of ACs exhibited rough, porous surface morphology whereas the CsNP exhibited smooth, spherical granular nanostructures. Elemental analysis via EDX confirmed the presence of key elements such as carbon (C), oxygen (O) and nitrogen (N) in both ACs and CsNP. TGA studies further demonstrated the thermal stability of CCs, ACs and CsNP. Moreover, CsNP exhibited significant antibacterial and anticoagulant activity and were effective in extending the shelf life of fruits through surface coating. Overall, the synthesis of ACs and CsNP presents a sustainable approach to crustacean shell waste utilization. These findings underscore the potential applications of CsNP in biomedical and food preservation fields.
{"title":"Ionic gelation based synthesis of chitosan nanoparticles from the waste shells of anomuran crab Albunea symmysta (Linnaeus, 1758) exhibits potential applications","authors":"Francis Abisha Adline , Jinna Dowlath Nisa , Rangasamy Shanthi , Mullaivanam Ramasamy Sivakumar","doi":"10.1016/j.carres.2025.109697","DOIUrl":"10.1016/j.carres.2025.109697","url":null,"abstract":"<div><div>Seafood waste especially crustacean shells are often discarded at sea or landfilled. Therefore, the extraction of valuable biomolecules such as chitin and the synthesis of chitosan and its nanoparticles are considered a beneficial solution to reduce crustacean shell waste. In the present study, chitosan (ACs) was extracted from the shells of anomuran crab <em>Albunea symmysta</em> and chitosan nanoparticles (CsNP) were synthesized using the ionic gelation method. The degree of deacetylation of chitosan was found to be 82.85 %. FTIR analysis of ACs and CsNP depicted similar functional groups at corresponding peaks compared to commercial chitosan (CCs). XRD analysis confirmed the semi crystalline nature of CCs, ACs, while CsNP exhibited reduced crystallinity and more amorphous structure. DLS studies evidenced that the mean diameter of CsNP was 144.3 ± 11.8 nm and the zeta potential of both ACs and CsNP was found to be positive. SEM imaging of ACs exhibited rough, porous surface morphology whereas the CsNP exhibited smooth, spherical granular nanostructures. Elemental analysis via EDX confirmed the presence of key elements such as carbon (C), oxygen (O) and nitrogen (N) in both ACs and CsNP. TGA studies further demonstrated the thermal stability of CCs, ACs and CsNP. Moreover, CsNP exhibited significant antibacterial and anticoagulant activity and were effective in extending the shelf life of fruits through surface coating. Overall, the synthesis of ACs and CsNP presents a sustainable approach to crustacean shell waste utilization. These findings underscore the potential applications of CsNP in biomedical and food preservation fields.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"558 ","pages":"Article 109697"},"PeriodicalIF":2.5,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145243785","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 : 2025-10-03DOI: 10.1016/j.carres.2025.109695
Ting Yang , Yang Yang , Rong Chen , Pinyi Gao , Danqi Li , Xuegui Liu
This study investigates the structural features and lipid-regulating mechanisms of hawthorn leaf polysaccharides (HLPs). Three acidic polysaccharides (HLP-1, HLP-2, and HLP-3) were isolated from hawthorn leaves and characterized via high-performance gel permeation chromatography (HPGPC), ion chromatography (IC), methylation analysis, and nuclear magnetic resonance (NMR) spectroscopy. Structural analyses revealed their molecular weights were 10.19 kDa, 400.38 kDa, and 435.52 kDa, respectively, with primary composition of galacturonic acid, galactose, and rhamnose. The Congo red assay indicated potential ordered aggregation with molecular weight-dependent thermal stability. Among the three, HLP-1 demonstrated the most potent in vitro bioactivity, including superior antioxidant capacity; in HepG2 cells, it most effectively reduced TG, TC, and LDL-c levels and increased HDL-c, outperforming HLP-2 and HLP-3. Mechanistically, HLP-1's hypolipidemic effect was linked to suppression of the SREBP-1c pathway. Furthermore, this study establishes the structure-activity relationship between HLPs' structural properties and lipid-lowering effects, laying a foundation for future HLP-based therapeutic interventions in metabolic diseases.
{"title":"Structural characterization, in vitro antioxidant and lipid-lowering activities of purified polysaccharides from hawthorn leaf","authors":"Ting Yang , Yang Yang , Rong Chen , Pinyi Gao , Danqi Li , Xuegui Liu","doi":"10.1016/j.carres.2025.109695","DOIUrl":"10.1016/j.carres.2025.109695","url":null,"abstract":"<div><div>This study investigates the structural features and lipid-regulating mechanisms of hawthorn leaf polysaccharides (HLPs). Three acidic polysaccharides (HLP-1, HLP-2, and HLP-3) were isolated from hawthorn leaves and characterized via high-performance gel permeation chromatography (HPGPC), ion chromatography (IC), methylation analysis, and nuclear magnetic resonance (NMR) spectroscopy. Structural analyses revealed their molecular weights were 10.19 kDa, 400.38 kDa, and 435.52 kDa, respectively, with primary composition of galacturonic acid, galactose, and rhamnose. The Congo red assay indicated potential ordered aggregation with molecular weight-dependent thermal stability. Among the three, HLP-1 demonstrated the most potent <em>in vitro</em> bioactivity, including superior antioxidant capacity; in HepG2 cells, it most effectively reduced TG, TC, and LDL-c levels and increased HDL-c, outperforming HLP-2 and HLP-3. Mechanistically, HLP-1's hypolipidemic effect was linked to suppression of the <em>SREBP-1c</em> pathway. Furthermore, this study establishes the structure-activity relationship between HLPs' structural properties and lipid-lowering effects, laying a foundation for future HLP-based therapeutic interventions in metabolic diseases.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"558 ","pages":"Article 109695"},"PeriodicalIF":2.5,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145238056","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 : 2025-10-03DOI: 10.1016/j.carres.2025.109693
Grzegorz Detlaff , Artur Sikorski , Jarosław Chojnacki , Beata Liberek
Bromoacetates of α-d-xylose and α-l-xylose, compounds from the group of extensively explored carbohydrate substrates, were synthesised and structurally characterised. Crystallographic studies performed for both compounds respectively indicate that this pair of enantiomers crystallises in the pair of enantiomorphic space groups, P41212 and P43212, respectively. The chirality of these space groups is induced by the helical arrangement of the bromides in the crystals. Geometry of the synthesised bromoacetates is discussed based on crystallographic data and calculations performed using DFT methods. It was proved that the anomeric effect acts and that the acetyl groups are characteristically arranged in the bromoacetates.
{"title":"Crystallisation of 2,3,4-tri-O-acetyl-α-d- and α-l-xylopyranosyl bromides in enantiomorphic space groups","authors":"Grzegorz Detlaff , Artur Sikorski , Jarosław Chojnacki , Beata Liberek","doi":"10.1016/j.carres.2025.109693","DOIUrl":"10.1016/j.carres.2025.109693","url":null,"abstract":"<div><div>Bromoacetates of α-<span>d</span>-xylose and α-<span>l</span>-xylose, compounds from the group of extensively explored carbohydrate substrates, were synthesised and structurally characterised. Crystallographic studies performed for both compounds respectively indicate that this pair of enantiomers crystallises in the pair of enantiomorphic space groups, <em>P</em>4<sub>1</sub>2<sub>1</sub>2 and <em>P</em>4<sub>3</sub>2<sub>1</sub>2, respectively. The chirality of these space groups is induced by the helical arrangement of the bromides in the crystals. Geometry of the synthesised bromoacetates is discussed based on crystallographic data and calculations performed using DFT methods. It was proved that the anomeric effect acts and that the acetyl groups are characteristically arranged in the bromoacetates.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"558 ","pages":"Article 109693"},"PeriodicalIF":2.5,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145291260","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 : 2025-10-03DOI: 10.1016/j.carres.2025.109692
Florent Pelus, Mikael Bols
A series of partially silylated and unsymmetrical α-, β- and γ-cyclodextrins were prepared and the NMR spectra in CDCl3 were analyzed. All unsymmetrical compounds showed a complex pattern of OH signals similarly to what has previously been seen for 6A−F,2A-hepta-O-tertbutyldimethylsilyl α-cyclodextrin. The compounds ability to form hydrogen bond network is discussed.
制备了一系列部分硅基化和不对称的α-、β-和γ-环糊精，并对其在CDCl3中的NMR谱进行了分析。所有不对称的化合物都显示出复杂的OH信号模式，类似于之前在6A−F， 2a -庚- o -叔丁基二甲基硅基α-环糊精中所看到的。讨论了化合物形成氢键网络的能力。
{"title":"New partially silylated cyclodextrins with complex hydrogen bond networks","authors":"Florent Pelus, Mikael Bols","doi":"10.1016/j.carres.2025.109692","DOIUrl":"10.1016/j.carres.2025.109692","url":null,"abstract":"<div><div>A series of partially silylated and unsymmetrical α-, β- and γ-cyclodextrins were prepared and the NMR spectra in CDCl<sub>3</sub> were analyzed. All unsymmetrical compounds showed a complex pattern of OH signals similarly to what has previously been seen for 6<sup>A−F</sup>,2<sup>A</sup>-hepta-<em>O</em>-tertbutyldimethylsilyl α-cyclodextrin. The compounds ability to form hydrogen bond network is discussed.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"558 ","pages":"Article 109692"},"PeriodicalIF":2.5,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145217001","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 : 2025-10-03DOI: 10.1016/j.carres.2025.109694
Si-si Jia , Zi-wei Han , Hui-yang Wang , Yv-jie Wu , Mei-juan Zhao , Hong-wei Qiu , He-he Li , Fei Chen , Guang-ping Lv
Polysaccharides from 18 batches of Atractylodes lancea (AL), A. chinensis (AC) and A. macrocephala (AM) were compared based on molecular weight (MW) distribution, monosaccharide composition and content, and glycosidic linkage type. Results showed that polysaccharides from AL, AC and AM mainly exhibited three molecular weight fractions, and the average Mw of fraction 1 and 2 in AM is 4.0–1.8 times of AL and AC. Therefore, AM could be distinguished from AL and AC based on large Mw. 7 kinds of monosaccharides were released from AL, AC and AM, and the average content of released monosaccharides in AC (141.2 mg/g) was obviously higher than that in AL (106.4 mg/g) and AM (121.0 mg/g). AC could be distinguished from AL based on monosaccharides content. 1,2-Fruf is the dominant type of glycosidic linkage, which indicated that fructan is abundant. The higher proportion of 1,4-Galp residues after reduction in AM revealed that pectin-type polysaccharides are relatively abundant in AM. Combined with chemometric analysis, the glycosidic linkage can distinguish AL, AC and AM clearly, and 1, 4-Galp and 1,2,4-Rhap residues were confirmed as the differential glycosidic linkages. This study was helpful in understanding the varied functions of different Atractylodes spp. based on chemical composition.
{"title":"Characterization and discrimination of polysaccharides from three Atractylodes spp. based on multiple structural information","authors":"Si-si Jia , Zi-wei Han , Hui-yang Wang , Yv-jie Wu , Mei-juan Zhao , Hong-wei Qiu , He-he Li , Fei Chen , Guang-ping Lv","doi":"10.1016/j.carres.2025.109694","DOIUrl":"10.1016/j.carres.2025.109694","url":null,"abstract":"<div><div>Polysaccharides from 18 batches of <em>Atractylodes lancea</em> (AL), <em>A. chinensis</em> (AC) and <em>A. macrocephala</em> (AM) were compared based on molecular weight (MW) distribution, monosaccharide composition and content, and glycosidic linkage type. Results showed that polysaccharides from AL, AC and AM mainly exhibited three molecular weight fractions, and the average Mw of fraction 1 and 2 in AM is 4.0–1.8 times of AL and AC. Therefore, AM could be distinguished from AL and AC based on large Mw. 7 kinds of monosaccharides were released from AL, AC and AM, and the average content of released monosaccharides in AC (141.2 mg/g) was obviously higher than that in AL (106.4 mg/g) and AM (121.0 mg/g). AC could be distinguished from AL based on monosaccharides content. 1,2-Fru<em>f</em> is the dominant type of glycosidic linkage, which indicated that fructan is abundant. The higher proportion of 1,4-Gal<em>p</em> residues after reduction in AM revealed that pectin-type polysaccharides are relatively abundant in AM. Combined with chemometric analysis, the glycosidic linkage can distinguish AL, AC and AM clearly, and 1, 4-Gal<em>p</em> and 1,2,4-Rha<em>p</em> residues were confirmed as the differential glycosidic linkages. This study was helpful in understanding the varied functions of different <em>Atractylodes</em> spp. based on chemical composition.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"558 ","pages":"Article 109694"},"PeriodicalIF":2.5,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145263124","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 : 2025-10-02DOI: 10.1016/j.carres.2025.109691
Nahoko Yagami, Fatma Eljabu, Manas Jana, Elisa G. Carvajal, Christopher W. Cairo
There is increasing interest in carbohydrate analogs for drug development, and the polar nature of these targets presents a challenge for medicinal chemistry. Multiple substrate hydroxy groups are typically required for enzyme active site recognition. Not all of these polar groups will have the same importance in recognition. A common strategy is to replace or remove these groups and compare the activity of the resulting analogs. If hydroxy groups are non-essential, or if their removal results in increased potency they may form the basis of improved inhibitors or substrates. In our studies of human neuraminidase enzymes (NEU), we have identified modifications at the C5 and C9 positions of the 2-deoxy-2,3-didehydro-N-acetyl neuraminic (DANA) scaffold that provide potent and selective inhibitors. In this study, we sought to test the requirements of each of the four human NEU isoenzymes for the presence of O4, O7, O8, or O9 hydroxy groups found in DANA. We synthesized the corresponding mono- (4, 7, 8, and 9) and di-deoxy (7,9; 7,8; and 8,9) analogs of DANA and tested their potency against human NEU. We found that 8-deoxy compounds increased potency against NEU2 and NEU3. Additionally, several di-deoxy analogs were tolerated by NEU1, NEU2, and NEU3. Finally, we generated known selective inhibitors of NEU3 and NEU4 and tested their 8-deoxy analogs. Combination of these features did not improve overall potency, suggesting deoxygenated analogs will require additional optimization.
人们对用于药物开发的碳水化合物类似物越来越感兴趣，这些目标的极性性质对药物化学提出了挑战。酶活性位点识别通常需要多个底物羟基。并不是所有这些极性群体在识别中都具有同样的重要性。一种常见的策略是替换或删除这些基团，并比较产生的类似物的活性。如果羟基不是必需的，或者如果它们的去除导致效力增加，它们可以形成改进的抑制剂或底物的基础。在我们对人类神经氨酸酶（NEU）的研究中，我们已经在2-脱氧-2,3-二脱氢- n -乙酰神经氨酸（DANA）支架的C5和C9位置发现了修饰，这些修饰提供了有效的选择性抑制剂。在这项研究中，我们试图测试四种人类NEU同工酶对DANA中发现的O4、O7、O8或O9羟基的存在的要求。我们合成了相应的单-（4,7,8和9）和双脱氧（7,9,7,8和8,9）类似物，并测试了它们对人NEU的效力。我们发现8-脱氧化合物增加了对NEU2和NEU3的效力。此外，NEU1、NEU2和NEU3耐受几种双脱氧类似物。最后，我们生成了NEU3和NEU4的已知选择性抑制剂，并测试了它们的8-脱氧类似物。这些特征的组合并没有提高整体效力，这表明脱氧类似物需要额外的优化。
{"title":"Deoxygenated analogs of 2-deoxy-2,3-didehydro-N-acetyl neuraminic acid as inhibitors of human neuraminidase enzymes","authors":"Nahoko Yagami, Fatma Eljabu, Manas Jana, Elisa G. Carvajal, Christopher W. Cairo","doi":"10.1016/j.carres.2025.109691","DOIUrl":"10.1016/j.carres.2025.109691","url":null,"abstract":"<div><div>There is increasing interest in carbohydrate analogs for drug development, and the polar nature of these targets presents a challenge for medicinal chemistry. Multiple substrate hydroxy groups are typically required for enzyme active site recognition. Not all of these polar groups will have the same importance in recognition. A common strategy is to replace or remove these groups and compare the activity of the resulting analogs. If hydroxy groups are non-essential, or if their removal results in increased potency they may form the basis of improved inhibitors or substrates. In our studies of human neuraminidase enzymes (NEU), we have identified modifications at the C5 and C9 positions of the 2-deoxy-2,3-didehydro-<em>N</em>-acetyl neuraminic (DANA) scaffold that provide potent and selective inhibitors. In this study, we sought to test the requirements of each of the four human NEU isoenzymes for the presence of O4, O7, O8, or O9 hydroxy groups found in DANA. We synthesized the corresponding mono- (4, 7, 8, and 9) and di-deoxy (7,9; 7,8; and 8,9) analogs of DANA and tested their potency against human NEU. We found that 8-deoxy compounds increased potency against NEU2 and NEU3. Additionally, several di-deoxy analogs were tolerated by NEU1, NEU2, and NEU3. Finally, we generated known selective inhibitors of NEU3 and NEU4 and tested their 8-deoxy analogs. Combination of these features did not improve overall potency, suggesting deoxygenated analogs will require additional optimization.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"558 ","pages":"Article 109691"},"PeriodicalIF":2.5,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145312489","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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