Pub Date : 2026-01-28DOI: 10.1016/j.carres.2026.109840
Matheus P. Freitas
The anomeric effect arises from a subtle balance between steric, electrostatic, and orbital interactions, yet its relative energetic origins remain debated. Here, we present a systematic computational study of substituted cyclohexanes, tetrahydropyrans, and thianes (YCH3, CF3, F, and Cl) to disentangle these contributions. Conformational energies were evaluated in the gas phase and in implicit water, and natural bond orbital (NBO) analyses were employed to decompose steric exchange, electrostatic (NCE), and electron-delocalization effects. While cyclohexane derivatives largely follow steric expectations, heterocycles containing oxygen or sulfur display pronounced axial stabilization for electronegative substituents, consistent with the anomeric effect. This stabilization is dominated by nX → σ∗C–Y hyperconjugation and supported by favorable electrostatics, whereas steric effects act mainly as a modulating factor and appear underestimated within the present partitioning scheme. Importantly, the qualitative balance between electrostatic and hyperconjugative contributions persists in polar solution, indicating that intramolecular dipolar interactions remain operative even under high-dielectric conditions.
{"title":"Anomeric effect in six-membered rings: An NBO perspective","authors":"Matheus P. Freitas","doi":"10.1016/j.carres.2026.109840","DOIUrl":"10.1016/j.carres.2026.109840","url":null,"abstract":"<div><div>The anomeric effect arises from a subtle balance between steric, electrostatic, and orbital interactions, yet its relative energetic origins remain debated. Here, we present a systematic computational study of substituted cyclohexanes, tetrahydropyrans, and thianes (Y<img>CH<sub>3</sub>, CF<sub>3</sub>, F, and Cl) to disentangle these contributions. Conformational energies were evaluated in the gas phase and in implicit water, and natural bond orbital (NBO) analyses were employed to decompose steric exchange, electrostatic (NCE), and electron-delocalization effects. While cyclohexane derivatives largely follow steric expectations, heterocycles containing oxygen or sulfur display pronounced axial stabilization for electronegative substituents, consistent with the anomeric effect. This stabilization is dominated by <em>n</em><sub>X</sub> → σ∗<sub>C</sub>–<sub>Y</sub> hyperconjugation and supported by favorable electrostatics, whereas steric effects act mainly as a modulating factor and appear underestimated within the present partitioning scheme. Importantly, the qualitative balance between electrostatic and hyperconjugative contributions persists in polar solution, indicating that intramolecular dipolar interactions remain operative even under high-dielectric conditions.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"562 ","pages":"Article 109840"},"PeriodicalIF":2.5,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074863","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 : 2026-01-28DOI: 10.1016/j.carres.2026.109842
Yuping Chen, Hanlei Wang, Xia Zhao, Kun Zhang, Yumei Zhang
This study optimized the hot-water extraction conditions of Wisteriopsis eurybotrya polysaccharides (WEP) using single-factor tests and response surface methodology, establishing optimal conditions as an extraction temperature of 92 °C, an extraction time of 241 min, and a liquid-solid ratio of 43 mL/g. Subsequently, a purified fraction named WEP-1-1 was isolated from WEP, followed by structural characterization and assessment of its in vitro activities. Structure analysis revealed that WEP-1-1, with a weight-average molecular weight of 130.3 kDa, was composed of Glc, Ara, Gal, Rha, Xyl, and Man in a molar ratio of 74.72:11.31:9.50:1.76:1.70:1.00, featuring a backbone predominantly of α-D-Glcp residues linked by (1 → 6) glycosidic bonds. Furthermore, WEP-1-1 could significantly enhance the glucose uptake in C2C12 myotubes and L02 cells. It also exhibited potent immunostimulatory activity in RAW264.7 cells, significantly enhancing phagocytosis and promoting production of NO and TNF-α. In conclusion, our findings demonstrate that WEP-1-1 is a promising candidate for natural functional materials due to its concurrent hypoglycemic and immunomodulatory activities.
{"title":"A novel polysaccharide from Wisteriopsis eurybotrya: extraction optimization, structural characterization, and bioactivities.","authors":"Yuping Chen, Hanlei Wang, Xia Zhao, Kun Zhang, Yumei Zhang","doi":"10.1016/j.carres.2026.109842","DOIUrl":"https://doi.org/10.1016/j.carres.2026.109842","url":null,"abstract":"<p><p>This study optimized the hot-water extraction conditions of Wisteriopsis eurybotrya polysaccharides (WEP) using single-factor tests and response surface methodology, establishing optimal conditions as an extraction temperature of 92 °C, an extraction time of 241 min, and a liquid-solid ratio of 43 mL/g. Subsequently, a purified fraction named WEP-1-1 was isolated from WEP, followed by structural characterization and assessment of its in vitro activities. Structure analysis revealed that WEP-1-1, with a weight-average molecular weight of 130.3 kDa, was composed of Glc, Ara, Gal, Rha, Xyl, and Man in a molar ratio of 74.72:11.31:9.50:1.76:1.70:1.00, featuring a backbone predominantly of α-D-Glcp residues linked by (1 → 6) glycosidic bonds. Furthermore, WEP-1-1 could significantly enhance the glucose uptake in C2C12 myotubes and L02 cells. It also exhibited potent immunostimulatory activity in RAW264.7 cells, significantly enhancing phagocytosis and promoting production of NO and TNF-α. In conclusion, our findings demonstrate that WEP-1-1 is a promising candidate for natural functional materials due to its concurrent hypoglycemic and immunomodulatory activities.</p>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"563 ","pages":"109842"},"PeriodicalIF":2.5,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146117946","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 : 2026-01-27DOI: 10.1016/j.carres.2026.109839
Takaaki Kiryu, Koki Fujita, Motohiro Shizuma, Hiroaki Tatsuoka
Sixteen types of uronic acids are derived from aldohexoses. Except for a few examples, uronic acids are difficult to prepare and are not commercially available as reagents. Our previous study reported that C-6 oxidation of aldose (d-glucose) and aldonic acid (d-gluconic acid) by alcohol dehydrogenases from Pseudogluconobacter saccharoketogenes Rh47-3 produced the uronic acids (d-glucuronic acid and l-guluronic acid, respectively). Aldaric acid (d-glucaric acid) was also produced by further oxidation with aldehyde dehydrogenase from the same bacterium. The present study demonstrates that alcohol dehydrogenase widely oxidizes aldoses and aldonic acids, while aldehyde dehydrogenase extensively oxidizes aldoses and uronic acids; the alcohol dehydrogenase was named "aldose C-6 alcohol dehydrogenase" Except for commercially available d- and l-gulonic acid, all aldonic acids (14 types), uronic acids (16 types), and aldaric acids (10 types) derived from aldohexoses could be prepared using the alcohol dehydrogenase and resting cells. These sugar acids were obtained by oxidizing various aldoses and aldonic acids through either aldose C-1/C-6-inverting oxidation or aldose C-1/C-6-retaining oxidation, although the production of d-iduronic acid and d-idaric acid was low. The same reaction was also performed with Youhaiella spp., a registered strain in the Japan Collection of Microorganisms. The results provide comprehensive and simple methods for preparing sugar acids.
醛己糖衍生出十六种糖醛酸。除了少数例子外，糖醛酸很难制备，也不是商业上可用的试剂。我们之前的研究报道了来自假糖酸杆菌Rh47-3的乙醇脱氢酶对醛糖酸（d-葡萄糖）和醛糖酸（d-葡萄糖酸）的C-6氧化产生了糖醛酸（d-葡萄糖醛酸和l-糖醛酸）。用同一细菌的醛脱氢酶进一步氧化也可制得醛二酸（d-葡萄糖酸）。本研究表明，醇脱氢酶广泛氧化醛糖和醛糖酸，醛脱氢酶广泛氧化醛糖和醛酸；乙醇脱氢酶命名为“醛糖C-6醇脱氢酶”，除市售的d-谷醛酸和l-谷醛酸外，所有醛糖糖衍生的醛糖酸（14种）、糖醛酸（16种）和醛二酸（10种）均可通过乙醇脱氢酶和静息细胞制备。这些糖酸是通过醛糖C-1/ c -6反转氧化或醛糖C-1/ c -6保留氧化来氧化各种醛糖和醛糖酸得到的，尽管d-伊杜醛酸和d-伊达二酸的产量很低。同样的反应也发生在日本微生物收集的一种已登记菌株Youhaiella spp.上。结果为糖酸的制备提供了全面、简便的方法。
{"title":"Comprehensive preparation of uronic and aldaric acids by bacteria possessing aldose C-6 alcohol dehydrogenase activity.","authors":"Takaaki Kiryu, Koki Fujita, Motohiro Shizuma, Hiroaki Tatsuoka","doi":"10.1016/j.carres.2026.109839","DOIUrl":"https://doi.org/10.1016/j.carres.2026.109839","url":null,"abstract":"<p><p>Sixteen types of uronic acids are derived from aldohexoses. Except for a few examples, uronic acids are difficult to prepare and are not commercially available as reagents. Our previous study reported that C-6 oxidation of aldose (d-glucose) and aldonic acid (d-gluconic acid) by alcohol dehydrogenases from Pseudogluconobacter saccharoketogenes Rh47-3 produced the uronic acids (d-glucuronic acid and l-guluronic acid, respectively). Aldaric acid (d-glucaric acid) was also produced by further oxidation with aldehyde dehydrogenase from the same bacterium. The present study demonstrates that alcohol dehydrogenase widely oxidizes aldoses and aldonic acids, while aldehyde dehydrogenase extensively oxidizes aldoses and uronic acids; the alcohol dehydrogenase was named \"aldose C-6 alcohol dehydrogenase\" Except for commercially available d- and l-gulonic acid, all aldonic acids (14 types), uronic acids (16 types), and aldaric acids (10 types) derived from aldohexoses could be prepared using the alcohol dehydrogenase and resting cells. These sugar acids were obtained by oxidizing various aldoses and aldonic acids through either aldose C-1/C-6-inverting oxidation or aldose C-1/C-6-retaining oxidation, although the production of d-iduronic acid and d-idaric acid was low. The same reaction was also performed with Youhaiella spp., a registered strain in the Japan Collection of Microorganisms. The results provide comprehensive and simple methods for preparing sugar acids.</p>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"562 ","pages":"109839"},"PeriodicalIF":2.5,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146104086","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 : 2026-01-26DOI: 10.1016/j.carres.2026.109838
Antonio Lembo , Gian Luca Sardone , Michela Aurilia , Antonio Molinaro , Francesco Berti , Cristina De Castro , Massimiliano Biagini
Glycosylation is the most critical post-translational modification occurring on proteins and its specific pattern depends both on the cells used for their production, such as mammalian cells, insect cells and yeast, and the expression conditions (e.g., mannosidase inhibitors, gene deletion). The aim of this study is to characterize the glycans of recombinant glycoprotein B (gB) from Human Cytomegalovirus (HCMV), expressed in CHO cells, by using different hyphenated mass spectrometry techniques in order to enrich the knowledge about glycosylation pattern changes in the protein production process and to develop versatile analytical platforms for the rapid analysis of protein glycosylation. The settled workflows focus on two main classes of analytes originating from the glycoprotein studied: glycopeptides and glycans. The analysis of the first category of molecules relies on a bottom-up proteomic approach in which the glycosites and the correspondent glycan heterogeneity and occupancy have been investigated by using high resolution tandem mass spectrometry; the analysis of the second class of molecules occurs by glycan shaving followed by fluorescence-liquid chromatography and mass-spectrometry characterization. These analyzes have been performed on the same glycoprotein expressed in a different culture media to demonstrate the capability of these analytical methods to monitor in detail oligosaccharide pattern changes. Finally, the impact of changes in glycosylation pattern on antigen immunogenicity has been assessed, showing that the presence of only high mannose oligosaccharides elicits higher titer of neutralizing antibodies.
{"title":"Dissecting the glycoprofile of the human cytomegalovirus protein gB by comprehensive mass spectrometry analysis","authors":"Antonio Lembo , Gian Luca Sardone , Michela Aurilia , Antonio Molinaro , Francesco Berti , Cristina De Castro , Massimiliano Biagini","doi":"10.1016/j.carres.2026.109838","DOIUrl":"10.1016/j.carres.2026.109838","url":null,"abstract":"<div><div>Glycosylation is the most critical post-translational modification occurring on proteins and its specific pattern depends both on the cells used for their production, such as mammalian cells, insect cells and yeast, and the expression conditions (<em>e.g.,</em> mannosidase inhibitors, gene deletion). The aim of this study is to characterize the glycans of recombinant glycoprotein B (gB) from Human Cytomegalovirus (HCMV), expressed in CHO cells, by using different hyphenated mass spectrometry techniques in order to enrich the knowledge about glycosylation pattern changes in the protein production process and to develop versatile analytical platforms for the rapid analysis of protein glycosylation. The settled workflows focus on two main classes of analytes originating from the glycoprotein studied: glycopeptides and glycans. The analysis of the first category of molecules relies on a bottom-up proteomic approach in which the glycosites and the correspondent glycan heterogeneity and occupancy have been investigated by using high resolution tandem mass spectrometry; the analysis of the second class of molecules occurs by glycan shaving followed by fluorescence-liquid chromatography and mass-spectrometry characterization. These analyzes have been performed on the same glycoprotein expressed in a different culture media to demonstrate the capability of these analytical methods to monitor in detail oligosaccharide pattern changes. Finally, the impact of changes in glycosylation pattern on antigen immunogenicity has been assessed, showing that the presence of only high mannose oligosaccharides elicits higher titer of neutralizing antibodies.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"562 ","pages":"Article 109838"},"PeriodicalIF":2.5,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074862","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 : 2026-01-21DOI: 10.1016/j.carres.2026.109836
Marcelo L.K. Marchioro , Gabrielly C.G. Xavier , Thaís F.M. Mota , Robert F.H. Dekker , Mário A.A. Cunha
β-glucans are polysaccharides with remarkable biological properties, including antioxidants, anticoagulants, antimicrobials, and immunomodulatory activities. However, their low solubility limits industrial applications, making chemical modification a key strategy to enhance solubility, biocompatibility, and biological performance. This scientometric study analyzed research on the chemical modification of β-glucans from 1986 to 2025, using data from Web of Science, Scopus, and PubMed. After refinement, 321 articles were evaluated through Excel, OriginPro 2025, and CiteSpace software. Results revealed a marked increase in publications and citations over the last decade, with China, Japan, the United States, and Brazil leading in productivity. Carbohydrate Polymers and the International Journal of Biological Macromolecules were the most influential journals in this field. Keyword analysis revealed three developmental stages: an initial phase centered on structural studies, an intermediate phase focused on biomedical applications (including antitumor and anticoagulant properties), and a recent phase emphasizing the antioxidant potential and integration of modified β-glucans in drug delivery and nanotechnology. Despite significant progress, challenges persist regarding the standardization of synthesis, structural characterization, and clinical validation. Strengthening regioselective synthesis, consistent analytical methods, and sustainable approaches is essential to consolidate modified β-glucans as promising biopolymers for pharmaceuticals, functional foods, and biomaterials.
β-葡聚糖是具有显著生物学特性的多糖，包括抗氧化剂、抗凝血剂、抗菌剂和免疫调节活性。然而，它们的低溶解度限制了工业应用，使化学改性成为提高溶解度，生物相容性和生物性能的关键策略。本科学计量学研究使用Web of Science、Scopus和PubMed的数据，分析了1986年至2025年间β-葡聚糖化学修饰的研究。精细化后，通过Excel、OriginPro 2025和CiteSpace软件对321篇文章进行评估。结果显示，在过去十年中，中国、日本、美国和巴西的出版物和引用量显著增加。《碳水化合物聚合物》和《国际生物大分子杂志》是该领域最具影响力的期刊。关键词分析揭示了三个发展阶段：以结构研究为中心的初始阶段，专注于生物医学应用（包括抗肿瘤和抗凝血特性）的中间阶段，以及强调抗氧化潜力和修饰β-葡聚糖在药物传递和纳米技术中的整合的最新阶段。尽管取得了重大进展，但在合成标准化、结构表征和临床验证方面仍然存在挑战。加强区域选择性合成、一致的分析方法和可持续的方法是巩固修饰β-葡聚糖作为有前途的生物聚合物用于药物、功能食品和生物材料的必要条件。
{"title":"Functionalization of β-glucans as a tool for enhancing biological properties: A scientometric approach","authors":"Marcelo L.K. Marchioro , Gabrielly C.G. Xavier , Thaís F.M. Mota , Robert F.H. Dekker , Mário A.A. Cunha","doi":"10.1016/j.carres.2026.109836","DOIUrl":"10.1016/j.carres.2026.109836","url":null,"abstract":"<div><div>β-glucans are polysaccharides with remarkable biological properties, including antioxidants, anticoagulants, antimicrobials, and immunomodulatory activities. However, their low solubility limits industrial applications, making chemical modification a key strategy to enhance solubility, biocompatibility, and biological performance. This scientometric study analyzed research on the chemical modification of β-glucans from 1986 to 2025, using data from Web of Science, Scopus, and PubMed. After refinement, 321 articles were evaluated through Excel, OriginPro 2025, and CiteSpace software. Results revealed a marked increase in publications and citations over the last decade, with China, Japan, the United States, and Brazil leading in productivity. Carbohydrate Polymers and the International Journal of Biological Macromolecules were the most influential journals in this field. Keyword analysis revealed three developmental stages: an initial phase centered on structural studies, an intermediate phase focused on biomedical applications (including antitumor and anticoagulant properties), and a recent phase emphasizing the antioxidant potential and integration of modified β-glucans in drug delivery and nanotechnology. Despite significant progress, challenges persist regarding the standardization of synthesis, structural characterization, and clinical validation. Strengthening regioselective synthesis, consistent analytical methods, and sustainable approaches is essential to consolidate modified β-glucans as promising biopolymers for pharmaceuticals, functional foods, and biomaterials.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"562 ","pages":"Article 109836"},"PeriodicalIF":2.5,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146036016","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 : 2026-01-21DOI: 10.1016/j.carres.2026.109837
Özlem Kaplan , Kevser Bal , Sibel Küçükertuğrul Çeli̇k , Nazan Gökşen Tosun , Mehmet Koray Gök
In this study, a novel chitosan-based nanocarrier system was developed through dual modification with α-lipoic acid and l-serine (ChiLipo–Ser) to enhance its physicochemical and biological properties for drug delivery applications. FTIR and 1H NMR spectroscopy verified the successful conjugation of functional groups onto the chitosan backbone, while GPC analysis confirmed an increase in molecular weight consistent with the modification. Compared with native chitosan, the ChiLipo–Ser exhibited improved solubility at physiological pH and enhanced buffering capacity. Nanoparticles prepared via ionotropic gelation demonstrated favorable characteristics, including an average particle size of ∼150 nm, low polydispersity, and a positive surface charge. Redox sensitivity was evidenced by DLS analysis, which revealed particle destabilization in the presence of 10–20 mM DTT, resulting from disulfide bond cleavage. Importantly, ChiLipo–Ser modification significantly enhanced the encapsulation efficiency of curcumin compared to unmodified chitosan, while the resulting formulations also exhibited effective release behavior at pH 5, mimicking the tumor intracellular environment. Furthermore, in vitro cytotoxicity assays showed that CUR-loaded ChiLipo–Ser nanoparticles exerted cytotoxic effects against HeLa and HT29 cancer cells while maintaining acceptable biocompatibility in BJ fibroblasts. Collectively, these results highlight the potential of ChiLipo–Ser nanoparticles as a promising platform for stimuli-responsive anticancer drug delivery.
本研究通过α-硫辛酸和l-丝氨酸（ChiLipo-Ser）的双重修饰，构建了一种新型的壳聚糖纳米载体体系，以提高其物理化学和生物学性能，用于药物递送。FTIR和1H NMR验证了壳聚糖骨架上官能团的成功偶联，而GPC分析证实了分子量的增加与改性一致。与天然壳聚糖相比，ChiLipo-Ser在生理pH下的溶解度提高，缓冲能力增强。通过离子化凝胶法制备的纳米颗粒表现出良好的特性，包括平均粒径约150 nm，低多分散性和表面带正电荷。DLS分析证实了氧化还原敏感性，发现在10-20 mM DTT存在下，由于二硫键断裂导致颗粒不稳定。重要的是，与未修饰的壳聚糖相比，ChiLipo-Ser修饰显著提高了姜黄素的包封效率，同时所得到的溶液在pH 5下也表现出有效的释放行为，模拟肿瘤细胞内环境。此外，体外细胞毒性实验表明，cur负载的ChiLipo-Ser纳米颗粒对HeLa和HT29癌细胞具有细胞毒性作用，同时在BJ成纤维细胞中保持可接受的生物相容性。总的来说，这些结果突出了chilibo - ser纳米颗粒作为刺激反应性抗癌药物递送的有前途的平台的潜力。
{"title":"α-lipoic acid and L-serine conjugated chitosan as a stimuli-responsive drug delivery platform","authors":"Özlem Kaplan , Kevser Bal , Sibel Küçükertuğrul Çeli̇k , Nazan Gökşen Tosun , Mehmet Koray Gök","doi":"10.1016/j.carres.2026.109837","DOIUrl":"10.1016/j.carres.2026.109837","url":null,"abstract":"<div><div>In this study, a novel chitosan-based nanocarrier system was developed through dual modification with α-lipoic acid and <span>l</span>-serine (Chi<sub>Lipo–Ser</sub>) to enhance its physicochemical and biological properties for drug delivery applications. FTIR and <sup>1</sup>H NMR spectroscopy verified the successful conjugation of functional groups onto the chitosan backbone, while GPC analysis confirmed an increase in molecular weight consistent with the modification. Compared with native chitosan, the Chi<sub>Lipo–Ser</sub> exhibited improved solubility at physiological pH and enhanced buffering capacity. Nanoparticles prepared via ionotropic gelation demonstrated favorable characteristics, including an average particle size of ∼150 nm, low polydispersity, and a positive surface charge. Redox sensitivity was evidenced by DLS analysis, which revealed particle destabilization in the presence of 10–20 mM DTT, resulting from disulfide bond cleavage. Importantly, Chi<sub>Lipo–Ser</sub> modification significantly enhanced the encapsulation efficiency of curcumin compared to unmodified chitosan, while the resulting formulations also exhibited effective release behavior at pH 5, mimicking the tumor intracellular environment. Furthermore, <em>in vitro</em> cytotoxicity assays showed that CUR-loaded Chi<sub>Lipo–Ser</sub> nanoparticles exerted cytotoxic effects against HeLa and HT29 cancer cells while maintaining acceptable biocompatibility in BJ fibroblasts. Collectively, these results highlight the potential of Chi<sub>Lipo–Ser</sub> nanoparticles as a promising platform for stimuli-responsive anticancer drug delivery.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"562 ","pages":"Article 109837"},"PeriodicalIF":2.5,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146036015","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 : 2026-01-20DOI: 10.1016/j.carres.2026.109835
Anbang Li , Chang Liu , Ronge Xing , Song Liu , Kecheng Li
Phenol-sulfuric acid method, a classical approach for total sugar quantification, suffers from substantial variation in the colorimetric efficiency among different monosaccharides, which may result in significant measurement bias. In this study, we investigated the colorimetric efficiency of 14 monosaccharides across three different systems and found that the colorimetric efficiency followed the pattern: neutral > acidic > amino monosaccharides. Notably, the colorimetric efficiency of mannose was over 800-fold higher than that of glucosamine. Principal coordinate analysis (PCoA) revealed that functional groups (carboxyl, amino) were the major determinants of colorimetric efficiency. Based on these findings, we assessed three quantitative models for five polysaccharides. The traditional model was suitable for homogeneous glucans (e.g., starch, recovery ∼101.0 %). The dominant monosaccharide model was effective for neutral polysaccharides with a single monosaccharide composition (e.g., mannan, recovery ∼100.5 % in the optimized system). In contrast, the weighted model, which integrates molar ratios and individual efficiencies, failed to improve accuracy for complex heterogeneous acidic polysaccharides (e.g., fucoidans, recovery <40.0 %). Furthermore, amino groups in polysaccharides (e.g., chitosan) strongly inhibited the reaction, precluding accurate quantification. This study provides a theoretical basis for the precise application of the phenol-sulfuric acid method and offers methodological guidance for the standardization of polysaccharide analysis.
{"title":"Investigation of monosaccharide colorimetric efficiency by phenol-sulfuric acid method and optimization of quantitative models for polysaccharides","authors":"Anbang Li , Chang Liu , Ronge Xing , Song Liu , Kecheng Li","doi":"10.1016/j.carres.2026.109835","DOIUrl":"10.1016/j.carres.2026.109835","url":null,"abstract":"<div><div>Phenol-sulfuric acid method, a classical approach for total sugar quantification, suffers from substantial variation in the colorimetric efficiency among different monosaccharides, which may result in significant measurement bias. In this study, we investigated the colorimetric efficiency of 14 monosaccharides across three different systems and found that the colorimetric efficiency followed the pattern: neutral > acidic > amino monosaccharides. Notably, the colorimetric efficiency of mannose was over 800-fold higher than that of glucosamine. Principal coordinate analysis (PCoA) revealed that functional groups (carboxyl, amino) were the major determinants of colorimetric efficiency. Based on these findings, we assessed three quantitative models for five polysaccharides. The traditional model was suitable for homogeneous glucans (e.g., starch, recovery ∼101.0 %). The dominant monosaccharide model was effective for neutral polysaccharides with a single monosaccharide composition (e.g., mannan, recovery ∼100.5 % in the optimized system). In contrast, the weighted model, which integrates molar ratios and individual efficiencies, failed to improve accuracy for complex heterogeneous acidic polysaccharides (e.g., fucoidans, recovery <40.0 %). Furthermore, amino groups in polysaccharides (e.g., chitosan) strongly inhibited the reaction, precluding accurate quantification. This study provides a theoretical basis for the precise application of the phenol-sulfuric acid method and offers methodological guidance for the standardization of polysaccharide analysis.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"562 ","pages":"Article 109835"},"PeriodicalIF":2.5,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074864","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 : 2026-01-16DOI: 10.1016/j.carres.2026.109813
Bijoy Rudra , Subrata Das , Balaram Mukhopadhyay
Total chemical synthesis of the tetrasaccharide repeating unit of the O-antigen from the halophilic bacterium Salinicola salarius HO-14 in the form of its 2-aminoethyl glycoside is reported. Partially protected monosaccharide synthons are prepared from the commercially available d-mannose and l-rhamnose through rational protecting group manipulations. Sequential stereoselective glycosylations through activation of the thioglycoside using NIS and TMSOTf gave the target tetrasaccharide. The crucial 1,2-cis rhamnosidic linkage is formed by the use of hydrogen bond assisted aglycon delivery. The conjugation ready target tetrasaccharide is attractive for further glycoconjugate formation.
{"title":"Chemical synthesis of the tetrasaccharide repeating unit of the O-antigen from halophilic Salinicola salarius HO-14","authors":"Bijoy Rudra , Subrata Das , Balaram Mukhopadhyay","doi":"10.1016/j.carres.2026.109813","DOIUrl":"10.1016/j.carres.2026.109813","url":null,"abstract":"<div><div>Total chemical synthesis of the tetrasaccharide repeating unit of the O-antigen from the halophilic bacterium <em>Salinicola salarius</em> HO-14 in the form of its 2-aminoethyl glycoside is reported. Partially protected monosaccharide synthons are prepared from the commercially available <span>d</span>-mannose and <span>l</span>-rhamnose through rational protecting group manipulations. Sequential stereoselective glycosylations through activation of the thioglycoside using NIS and TMSOTf gave the target tetrasaccharide. The crucial 1,2-<em>cis</em> rhamnosidic linkage is formed by the use of hydrogen bond assisted aglycon delivery. The conjugation ready target tetrasaccharide is attractive for further glycoconjugate formation.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"562 ","pages":"Article 109813"},"PeriodicalIF":2.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146017484","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 : 2026-01-16DOI: 10.1016/j.carres.2026.109833
Nurettin Yaylı , Büşra Korkmaz , Gozde Bozdal , Büşra Şahin , Şeyma Arıcı , Yasemin Altun Ali , Sermet Yıldırmış , Gökçe Seyhan , Ahmet Buğra Aksel , Kamil Coşkunçelebi , Serdar Makbul , Arif Bozdeveci
<div><div>In this study, the phytochemical investigation of <em>Scorzonera yildirimlii</em> and <em>S. zorkunensis</em> led to the isolation and identification of eight new oligosaccharide constituents (<strong>1</strong>–<strong>8</strong>). Their structures were elucidated through comprehensive spectroscopic analysis (NMR, FT-IR, and mass spectrometry) and comparison with literature data. The structure of isolated compounds were <em>O</em>-<em>α</em>-D-Glc<em>p-</em>(1 → 2)-<em>O</em>-<em>β</em>-D-Fru<em>f</em>-(3 → 1)-<em>O</em>-<em>myo</em>-inositol (<strong>1</strong>), <em>O</em>-<em>α</em>-D-Glc<em>p-</em>(1 → 2)-<em>O</em>-<em>β</em>-D-Fru<em>f</em>-(3 → 1)-<em>O</em>-<em>epi</em>-inositol (<strong>2</strong>), <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-<em>O</em>-<em>α</em>-D-Glc<em>p</em>-(1 → 1)-<em>O</em>-<em>β</em>-D-Glc<em>p</em> (<strong>3</strong>), <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-<em>O</em>-α-D-Glc<em>p</em>-(1 → 1)-<em>O</em>-<em>β</em>-D-Gal<em>p</em> (<strong>4</strong>), <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-<em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-<em>O</em>-<em>α</em>-D-Glc<em>p</em>-(1 → 1)-<em>O</em>-<em>β</em>-D-Glc<em>p</em> (<strong>5</strong>), <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-[<em>O</em>-<em>β</em>-D-Glc<em>p-</em>(1 → 4)]-<em>O</em>-<em>α</em>-D-Glc<em>p</em>-(1 → 1)-<em>O</em>-<em>β</em>-D-Glc<em>p</em> (<strong>6</strong>), <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-[<em>O</em>-<em>β</em>-D-Glc<em>p</em>-(1 → 4)]-3-OCH<sub>3</sub>-<em>O</em>-<em>α</em>-D-Glc<em>p</em>-(1 → 1)-<em>O</em>-<em>β</em>-D-Glc<em>p</em> (<strong>7</strong>), and <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-[<em>O</em>-<em>β</em>-D-Glc<em>p</em>-(1 → 4)]-<em>O</em>-<em>α</em>-D-Glc<em>p</em>-(1 → 4)-<em>O</em>-<em>α</em>-D-Glc<em>p-</em>(1 → 2)-O-<em>β</em>-D-Fru<em>f</em> (<strong>8</strong>). The antimicrobial activities of all the isolated compounds (<strong>1</strong>–<strong>8</strong>) were investigated against six microorganisms. Compounds <strong>2</strong> and <strong>3</strong> were effective against <em>Mycobacterium smegmatis</em> at minimum inhibitory concentrations (MICs) of 3.13 μg/mL and 3.44 μg/mL, respectively, compared with streptomycin (MIC = 4.0 μg/mL). The enzyme-inhibitory properties of the isolated compounds (<strong>1</strong>–<strong>8</strong>) were evaluated against tyrosinase and <em>α</em>-glucosidase. Among the tested compounds, <strong>4</strong> (39.78 ± 10.29 %) exhibited inhibitory activity against tyrosinase, while compound <strong>2</strong> (68.04 ± 4.68 %) exhibited inhibitory activity against α-glucosidase. <em>In silico</em> studies of <strong>1</strong>–<strong>8</strong> showed the best predicted binding affinities for the Trehalose-LpqY complex in the range of −11.088 kcal/mol to −14.297 kcal/mol, compared to streptomycin (−6.638 kcal/mol). Compounds <strong>1</strong>–<strong>8</strong> exhibited almost no cytotoxic activity against L-929 cells, fu
本研究通过对Scorzonera yildirimlii和S. zorkunensis的植物化学研究，分离鉴定了8个新的低聚糖成分（1-8）。通过综合光谱分析（NMR、FT-IR和质谱）和文献资料对比，对其结构进行了鉴定。孤立的结构化合物O -α-D-Glcp -(1→2)- O -β-D-Fruf -(3→1)-O-myo-inositol (1), O -α-D-Glcp -(1→2)- O -β-D-Fruf -(3→1)-O-epi-inositol (2), O -β-D-Fruf -(2→6)- O -α-D-Glcp -(1→1)- O -β-D-Glcp (3), O -β-D-Fruf -(2→6)- O -α-D-Glcp -(1→1)- O -β-D-Galp (4), O -β-D-Fruf -(2→6)- O -β-D-Fruf -(2→6)- O -α-D-Glcp -(1→1)- O -β-D-Glcp (5), O -β-D-Fruf -(2→6)[O -β-D-Glcp -(1→4)- O -α-D-Glcp -(1→1)- O -β-D-Glcp (6), O -β-D-Fruf -(2→6)[O -β-D-Glcp -(1→4)]3-och3-o -α-D-Glcp -(1→1)- O -β-D-Glcp (7),和O -β-D-Fruf -(2→6)[O -β-D-Glcp -(1→4)- O -α-D-Glcp -(1→4)- O -α-D-Glcp -(1→2)- O -β-D-Fruf(8)。研究了分离得到的化合物（1 ~ 8）对6种微生物的抑菌活性。化合物2和3对耻垢分枝杆菌的最低抑制浓度（MIC）分别为3.13 μg/mL和3.44 μg/mL，而链霉素的最低抑制浓度为4.0 μg/mL。分离得到的化合物（1-8）对酪氨酸酶和α-葡萄糖苷酶的酶抑制性能进行了评价。化合物4（39.78±10.29%）对酪氨酸酶具有抑制活性，化合物2（68.04±4.68%）对α-葡萄糖苷酶具有抑制活性。硅实验结果表明，海藻糖- lpqy复合物的结合亲和力在- 11.088 kcal/mol至- 14.297 kcal/mol之间，而链霉素的结合亲和力为- 6.638 kcal/mol。化合物1-8对L-929细胞几乎没有细胞毒活性，进一步支持其治疗用途的潜力。
{"title":"Oligosaccharides from Scorzonera yildirimlii and S. zorkunensis, and their potential antimicrobial, enzyme inhibition, cytotoxic effect, and in silico study","authors":"Nurettin Yaylı , Büşra Korkmaz , Gozde Bozdal , Büşra Şahin , Şeyma Arıcı , Yasemin Altun Ali , Sermet Yıldırmış , Gökçe Seyhan , Ahmet Buğra Aksel , Kamil Coşkunçelebi , Serdar Makbul , Arif Bozdeveci","doi":"10.1016/j.carres.2026.109833","DOIUrl":"10.1016/j.carres.2026.109833","url":null,"abstract":"<div><div>In this study, the phytochemical investigation of <em>Scorzonera yildirimlii</em> and <em>S. zorkunensis</em> led to the isolation and identification of eight new oligosaccharide constituents (<strong>1</strong>–<strong>8</strong>). Their structures were elucidated through comprehensive spectroscopic analysis (NMR, FT-IR, and mass spectrometry) and comparison with literature data. The structure of isolated compounds were <em>O</em>-<em>α</em>-D-Glc<em>p-</em>(1 → 2)-<em>O</em>-<em>β</em>-D-Fru<em>f</em>-(3 → 1)-<em>O</em>-<em>myo</em>-inositol (<strong>1</strong>), <em>O</em>-<em>α</em>-D-Glc<em>p-</em>(1 → 2)-<em>O</em>-<em>β</em>-D-Fru<em>f</em>-(3 → 1)-<em>O</em>-<em>epi</em>-inositol (<strong>2</strong>), <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-<em>O</em>-<em>α</em>-D-Glc<em>p</em>-(1 → 1)-<em>O</em>-<em>β</em>-D-Glc<em>p</em> (<strong>3</strong>), <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-<em>O</em>-α-D-Glc<em>p</em>-(1 → 1)-<em>O</em>-<em>β</em>-D-Gal<em>p</em> (<strong>4</strong>), <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-<em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-<em>O</em>-<em>α</em>-D-Glc<em>p</em>-(1 → 1)-<em>O</em>-<em>β</em>-D-Glc<em>p</em> (<strong>5</strong>), <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-[<em>O</em>-<em>β</em>-D-Glc<em>p-</em>(1 → 4)]-<em>O</em>-<em>α</em>-D-Glc<em>p</em>-(1 → 1)-<em>O</em>-<em>β</em>-D-Glc<em>p</em> (<strong>6</strong>), <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-[<em>O</em>-<em>β</em>-D-Glc<em>p</em>-(1 → 4)]-3-OCH<sub>3</sub>-<em>O</em>-<em>α</em>-D-Glc<em>p</em>-(1 → 1)-<em>O</em>-<em>β</em>-D-Glc<em>p</em> (<strong>7</strong>), and <em>O</em>-<em>β</em>-D-Fru<em>f</em>-(2 → 6)-[<em>O</em>-<em>β</em>-D-Glc<em>p</em>-(1 → 4)]-<em>O</em>-<em>α</em>-D-Glc<em>p</em>-(1 → 4)-<em>O</em>-<em>α</em>-D-Glc<em>p-</em>(1 → 2)-O-<em>β</em>-D-Fru<em>f</em> (<strong>8</strong>). The antimicrobial activities of all the isolated compounds (<strong>1</strong>–<strong>8</strong>) were investigated against six microorganisms. Compounds <strong>2</strong> and <strong>3</strong> were effective against <em>Mycobacterium smegmatis</em> at minimum inhibitory concentrations (MICs) of 3.13 μg/mL and 3.44 μg/mL, respectively, compared with streptomycin (MIC = 4.0 μg/mL). The enzyme-inhibitory properties of the isolated compounds (<strong>1</strong>–<strong>8</strong>) were evaluated against tyrosinase and <em>α</em>-glucosidase. Among the tested compounds, <strong>4</strong> (39.78 ± 10.29 %) exhibited inhibitory activity against tyrosinase, while compound <strong>2</strong> (68.04 ± 4.68 %) exhibited inhibitory activity against α-glucosidase. <em>In silico</em> studies of <strong>1</strong>–<strong>8</strong> showed the best predicted binding affinities for the Trehalose-LpqY complex in the range of −11.088 kcal/mol to −14.297 kcal/mol, compared to streptomycin (−6.638 kcal/mol). Compounds <strong>1</strong>–<strong>8</strong> exhibited almost no cytotoxic activity against L-929 cells, fu","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"562 ","pages":"Article 109833"},"PeriodicalIF":2.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146036014","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 : 2026-01-16DOI: 10.1016/j.carres.2026.109831
Eleanor Dodd , Simon J. Coles , William Fraser
The X-ray crystal structure of methyl 2-deoxy-3,5-di-O-p-toluoyl-α-d-ribofuranoside (5) presented here, is a unique example of an alpha-configured, methyl 2-deoxyribofuranoside with the same protecting group at positions C3 and C5. Methyl 2-deoxy-3,5-di-O-p-toluoyl-α/β-d-ribofuranoside (3), exists as a mixture of alpha and beta anomers from which we isolated a single anomer on recrystallization from acetone. TLC analysis indicated the presence of a single compound with NMR analysis in support of the alpha anomer. SC-XRD analysis showed that methyl glycoside (5) crystallizes from acetone as the alpha anomer in the monoclinic space group I2. Methyl glycoside (5) possesses a glycosidic bond length of 1.408 Å with pseudorotational analysis showing the conformation of the five-membered ring to be 0E (O4-endo) with P = 89.9° and φm = 64.4°.
本文介绍的甲基2-脱氧-3,5-二- o -对甲苯基-α-d-核呋喃苷(5)的x射线晶体结构是一个独特的α配置的例子，甲基2-脱氧核呋喃苷在C3和C5位置具有相同的保护基团。甲基2-脱氧-3,5-二- o -对甲苯基-α/β-d-核呋喃苷(3)，存在于α和β的混合物中，我们从丙酮重结晶中分离到一个单一的异头物。薄层色谱分析表明存在单一化合物，核磁共振分析支持α异位。SC-XRD分析表明，甲基糖苷(5)在单斜空间群I2中作为α异头物由丙酮结晶而成。甲基糖苷(5)的糖苷键长为1.408 Å，伪旋转分析表明其五元环的构象为0E (O4-endo), P = 89.9°，φm = 64.4°。
{"title":"Methyl 2-deoxy-3,5-di-O-p-toluoyl-α-d-ribofuranoside: isolation, crystal structure and conformation","authors":"Eleanor Dodd , Simon J. Coles , William Fraser","doi":"10.1016/j.carres.2026.109831","DOIUrl":"10.1016/j.carres.2026.109831","url":null,"abstract":"<div><div>The X-ray crystal structure of methyl 2-deoxy-3,5-<em>di</em>-<em>O</em>-<em>p</em>-toluoyl-<em>α</em>-<span>d</span>-ribofuranoside (<strong>5</strong>) presented here, is a unique example of an alpha-configured, methyl 2-deoxyribofuranoside with the same protecting group at positions C3 and C5. Methyl 2-deoxy-3,5-<em>di</em>-<em>O</em>-<em>p</em>-toluoyl-<em>α/β</em>-<span>d</span>-ribofuranoside (<strong>3</strong>), exists as a mixture of alpha and beta anomers from which we isolated a single anomer on recrystallization from acetone. TLC analysis indicated the presence of a single compound with NMR analysis in support of the alpha anomer. SC-XRD analysis showed that methyl glycoside (<strong>5</strong>) crystallizes from acetone as the alpha anomer in the monoclinic space group <em>I</em>2. Methyl glycoside (<strong>5</strong>) possesses a glycosidic bond length of 1.408 Å with pseudorotational analysis showing the conformation of the five-membered ring to be <sup>0</sup><em>E</em> (O4-<em>endo</em>) with <em>P</em> = 89.9° and <em>φ</em><sub><em>m</em></sub> = 64.4°.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"562 ","pages":"Article 109831"},"PeriodicalIF":2.5,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145997287","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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