Pub Date : 2025-03-24DOI: 10.1080/07328303.2025.2451825
Zoya Saifi , Tanya Ralli , Divya Vohora , Showkat R. Mir , Saima Amin
Effective oral drug delivery is highly desirable for a controlled drug release using various polymers. Among different polymers, chitosan is known to be a safe, nontoxic material that has served as an efficient drug carrier. It is biocompatible, biodegradable, and obtained by hydrolyzing the amino acetyl groups of chitins. Structurally chitosan does not possess any thiol group but is modified chemically to add free thiol groups to its structure. This derivatization makes it an ideal carrier with properties such as mucoadhesion and permeation of drugs. Recently it has been used for immune modulation and bone resorption because of the excessive charge on its surface that helps its binding with the charged surfaces. As a result, the current research thoroughly assesses the efficacy of chitosan and thiolated chitosan nanoparticles for oral drug administration in medicine, particularly in bone tissue regeneration for osteoporosis treatment.
{"title":"Formulation approaches and pharmaceutical applications of chitosan and thiolated chitosan nanoparticles","authors":"Zoya Saifi , Tanya Ralli , Divya Vohora , Showkat R. Mir , Saima Amin","doi":"10.1080/07328303.2025.2451825","DOIUrl":"10.1080/07328303.2025.2451825","url":null,"abstract":"<div><div>Effective oral drug delivery is highly desirable for a controlled drug release using various polymers. Among different polymers, chitosan is known to be a safe, nontoxic material that has served as an efficient drug carrier. It is biocompatible, biodegradable, and obtained by hydrolyzing the amino acetyl groups of chitins. Structurally chitosan does not possess any thiol group but is modified chemically to add free thiol groups to its structure. This derivatization makes it an ideal carrier with properties such as mucoadhesion and permeation of drugs. Recently it has been used for immune modulation and bone resorption because of the excessive charge on its surface that helps its binding with the charged surfaces. As a result, the current research thoroughly assesses the efficacy of chitosan and thiolated chitosan nanoparticles for oral drug administration in medicine, particularly in bone tissue regeneration for osteoporosis treatment.</div></div>","PeriodicalId":15311,"journal":{"name":"Journal of Carbohydrate Chemistry","volume":"44 1","pages":"Pages 1-30"},"PeriodicalIF":1.2,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-24DOI: 10.1080/07328303.2024.2418526
Haofei Hong , Kun Zhou , Han Lin , Zhimeng Wu
Enhancing the complement-dependent cytotoxicity (CDC) of monoclonal antibodies (mAbs) has the potential to improve their clinical performance. In this study, we describe an innovative antibody-hapten supramolecular complex strategy to amplify CDC activity. We selected Rituximab (RTX), an approved anti-CD20 mAb, and conjugated it with adamantane (Ada) to generate RTX-Ada. After targeting CD20-positive cells, this conjugate can interact with rhamnose (Rha)-modified β-cyclodextrin via host-guest interaction, in situ forming a supramolecular complex that can recruit anti-Rha antibodies onto CD20-positive cancer cells. This complex provides a larger number of Fc domains for complement system activation, leading to enhanced CDC. Our study demonstrates the potential of antibody-based supramolecular complexes for cancer immunotherapy, offering a promising approach to improve the efficacy of mAb-based cancer treatments.
{"title":"Supramolecular assembly of antibody-rhamnose complex to enhance the complement-dependent cytotoxicity for cancer immunotherapy","authors":"Haofei Hong , Kun Zhou , Han Lin , Zhimeng Wu","doi":"10.1080/07328303.2024.2418526","DOIUrl":"10.1080/07328303.2024.2418526","url":null,"abstract":"<div><div>Enhancing the complement-dependent cytotoxicity (CDC) of monoclonal antibodies (mAbs) has the potential to improve their clinical performance. In this study, we describe an innovative antibody-hapten supramolecular complex strategy to amplify CDC activity. We selected Rituximab (RTX), an approved anti-CD20 mAb, and conjugated it with adamantane (Ada) to generate RTX-Ada. After targeting CD20-positive cells, this conjugate can interact with rhamnose (Rha)-modified β-cyclodextrin via host-guest interaction, <em>in situ</em> forming a supramolecular complex that can recruit anti-Rha antibodies onto CD20-positive cancer cells. This complex provides a larger number of Fc domains for complement system activation, leading to enhanced CDC. Our study demonstrates the potential of antibody-based supramolecular complexes for cancer immunotherapy, offering a promising approach to improve the efficacy of mAb-based cancer treatments.</div></div>","PeriodicalId":15311,"journal":{"name":"Journal of Carbohydrate Chemistry","volume":"44 1","pages":"Pages 31-42"},"PeriodicalIF":1.2,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The 4,6-O-cyclopropylmethylidene (CPMD) moiety of a methyl α-glucoside derivative can be regioselectively opened by trimethylaluminum to afford a corresponding 1-cyclopropylethyl (CPE) ether at C4 and a free alcohol at C6. This 1-CPE ether was found to be an acid-labile hydroxyl protecting group and can be readily cleaved using 10% trifluoracetic acid in dichloromethane at room temperature. The utilization of 1-CPE ether as a hydroxyl protecting group has been demonstrated in the efficient synthesis of a trisaccharide.
{"title":"Ring opening of cyclopropylmethylidene with trimethylaluminum: Synthesis of 1-cyclopropylethyl ether as an acid labile protecting group for hydroxyl Protection and carbohydrate synthesis","authors":"Madhav Poudel , Zainab Bustani , Xiaohua Li , Jianglong Zhu","doi":"10.1080/07328303.2025.2471354","DOIUrl":"10.1080/07328303.2025.2471354","url":null,"abstract":"<div><div>The 4,6-<em>O</em>-cyclopropylmethylidene (CPMD) moiety of a methyl α-glucoside derivative can be regioselectively opened by trimethylaluminum to afford a corresponding 1-cyclopropylethyl (CPE) ether at C4 and a free alcohol at C6. This 1-CPE ether was found to be an acid-labile hydroxyl protecting group and can be readily cleaved using 10% trifluoracetic acid in dichloromethane at room temperature. The utilization of 1-CPE ether as a hydroxyl protecting group has been demonstrated in the efficient synthesis of a trisaccharide.</div></div>","PeriodicalId":15311,"journal":{"name":"Journal of Carbohydrate Chemistry","volume":"44 1","pages":"Pages 81-93"},"PeriodicalIF":1.2,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716008","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The WHO classifies H. pylori as a critical public health issue. H. pylori is a gram-negative bacterium that causes infections in the stomach lining, contributing to conditions such as gastritis, peptic ulcers, and gastric cancer. The emergence of multidrug resistance in H. pylori presents a major obstacle in treatment, resulting in ineffective therapies and prolonged infections. The lipopolysaccharide biosynthesis pathway plays a crucial role in the survival of H. pylori. UDP-3-O-acyl-N-acetylglucosamine deacetylase (LpxC) is an essential enzyme, and its crucial role in disease pathogenesis has positioned LpxC as a highly promising druggable target for targeting H. pylori infection. In this study, we utilized structure-based virtual high-throughput screening of phytochemicals to discover potential inhibitors of LpxC. The selection of hits was initially based on their compliance with the Lipinski rule of 5, along with their toxicological, pharmacokinetic properties, and other drug-like attributes. This was followed by 100 ns molecular dynamics simulations in triplicate and MM/PBSA based binding free energy calculations. These findings indicated that Panicutine interacts strongly and enhances the stability of the LpxC structure, suggesting it as potential inhibitor of LpxC. The outcomes point to future studies to enhance their effectiveness as innovative and cost-effective treatments for H. pylori infections.
{"title":"Inhibition of lipopolysaccharide layer by plant-derived molecules: A novel approach to combat Helicobacter pylori","authors":"Abhishek Sharma , Pragati Mahur , Amit Kumar Singh , Jayaraman Muthukumaran , Monika Jain","doi":"10.1080/07328303.2025.2459914","DOIUrl":"10.1080/07328303.2025.2459914","url":null,"abstract":"<div><div>The WHO classifies <em>H. pylori</em> as a critical public health issue. <em>H. pylori</em> is a gram-negative bacterium that causes infections in the stomach lining, contributing to conditions such as gastritis, peptic ulcers, and gastric cancer. The emergence of multidrug resistance in <em>H. pylori</em> presents a major obstacle in treatment, resulting in ineffective therapies and prolonged infections. The lipopolysaccharide biosynthesis pathway plays a crucial role in the survival of <em>H. pylori</em>. UDP-3-<em>O</em>-acyl-<em>N</em>-acetylglucosamine deacetylase (LpxC) is an essential enzyme, and its crucial role in disease pathogenesis has positioned LpxC as a highly promising druggable target for targeting <em>H. pylori</em> infection. In this study, we utilized structure-based virtual high-throughput screening of phytochemicals to discover potential inhibitors of LpxC. The selection of hits was initially based on their compliance with the Lipinski rule of 5, along with their toxicological, pharmacokinetic properties, and other drug-like attributes. This was followed by 100 ns molecular dynamics simulations in triplicate and MM/PBSA based binding free energy calculations. These findings indicated that Panicutine interacts strongly and enhances the stability of the LpxC structure, suggesting it as potential inhibitor of LpxC. The outcomes point to future studies to enhance their effectiveness as innovative and cost-effective treatments for <em>H. pylori</em> infections.</div></div>","PeriodicalId":15311,"journal":{"name":"Journal of Carbohydrate Chemistry","volume":"44 1","pages":"Pages 43-62"},"PeriodicalIF":1.2,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-24DOI: 10.1080/07328303.2025.2468188
Na. Li , Bin Hu , Kexin Du , Yi. Cao , Zhongzhe Zhang , Binhao Guo , Chuanchuan Liu , Songshen Chu , Jinhua Gao , Chaojie Wang , Jing Ma , Lingling Di , Songqiang Xie
For patients with hepatocellular carcinoma (HCC), recurrence and metastasis lead to approximately 90% deaths, even after various standard therapies, indicating the need for novel therapies and antimetastatic drugs. Recently, mitochondrial dysfunction has been shown to be closely associated with HCC recurrence and metastasis. Herein, a novel glycosylated naphthalimide conjugate 4a was explored to target HCC and HCC metastasis by inducing ROS-mediated mitochondrial metabolic programs in HCC, remarkably improving the efficacy of amonafide and prolonging the survival of mice. Mechanistically, 4a, as a potential fluorescent chemical probe, could target mitochondria, which is completely different from amonafide. Preliminary investigation into the mechanism of 4a indicates that it localizes in the mitochondria and selectively causes reactive oxygen species (ROS) overproduction in HCC instead of the matched normal liver cells, leading to HCC cell apoptosis and migration inhibition via multiple ROS-mediated signaling pathways. In addition to exposing a previously undefined mitochondrial metabolic program in HCC, our study further illuminates an unrecognized naphthalimide-based tumor therapeutic strategy to prolong the life of terminal HCC in a completely new field.
{"title":"A glycosylated naphthalimide conjugate preferentially accumulates in metastatic hepatocellular carcinoma as ROS-mediated mitochondrial-targeted antimetastatic agent","authors":"Na. Li , Bin Hu , Kexin Du , Yi. Cao , Zhongzhe Zhang , Binhao Guo , Chuanchuan Liu , Songshen Chu , Jinhua Gao , Chaojie Wang , Jing Ma , Lingling Di , Songqiang Xie","doi":"10.1080/07328303.2025.2468188","DOIUrl":"10.1080/07328303.2025.2468188","url":null,"abstract":"<div><div>For patients with hepatocellular carcinoma (HCC), recurrence and metastasis lead to approximately 90% deaths, even after various standard therapies, indicating the need for novel therapies and antimetastatic drugs. Recently, mitochondrial dysfunction has been shown to be closely associated with HCC recurrence and metastasis. Herein, a novel glycosylated naphthalimide conjugate <strong>4a</strong> was explored to target HCC and HCC metastasis by inducing ROS-mediated mitochondrial metabolic programs in HCC, remarkably improving the efficacy of amonafide and prolonging the survival of mice. Mechanistically, <strong>4a</strong>, as a potential fluorescent chemical probe, could target mitochondria, which is completely different from amonafide. Preliminary investigation into the mechanism of <strong>4a</strong> indicates that it localizes in the mitochondria and selectively causes reactive oxygen species (ROS) overproduction in HCC instead of the matched normal liver cells, leading to HCC cell apoptosis and migration inhibition <em>via</em> multiple ROS-mediated signaling pathways. In addition to exposing a previously undefined mitochondrial metabolic program in HCC, our study further illuminates an unrecognized naphthalimide-based tumor therapeutic strategy to prolong the life of terminal HCC in a completely new field.</div></div>","PeriodicalId":15311,"journal":{"name":"Journal of Carbohydrate Chemistry","volume":"44 1","pages":"Pages 63-80"},"PeriodicalIF":1.2,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143716018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-23DOI: 10.1080/07328303.2024.2399506
Tao Xiong , Zhen Cao , Jiarui Gu , Nengzhong Wang , Mingguo Liu , Hui Yao
We report herein the stereoselective synthesis of 3-sulfone sugars in good yields from glycals and sodium arylsulfinates. Various 3,4-O-carbonate glycals were sulfonylated directly by a range of benzene- and naphthalene-sulfinic acid sodium salts catalyzed by cobalt species, demonstrating a broad substrate scope. The mechanism of cobalt-catalyzed decarboxylative allylation from the bottom face of the sugar ring due to the steric effect from the C3 group of glycals was proposed. Moroever, cobalt catalysis tends to favor branched allylation, resulting in excellent regioselectivity. This synthetic strategy features the green sulfone source, good functional group tolerance, exclusive regioselectivity, and excellent stereoselectivity.
{"title":"Stereoselective synthesis of 3-sulfone sugars via cobalt catalysis","authors":"Tao Xiong , Zhen Cao , Jiarui Gu , Nengzhong Wang , Mingguo Liu , Hui Yao","doi":"10.1080/07328303.2024.2399506","DOIUrl":"10.1080/07328303.2024.2399506","url":null,"abstract":"<div><div>We report herein the stereoselective synthesis of 3-sulfone sugars in good yields from glycals and sodium arylsulfinates. Various 3,4-<em>O</em>-carbonate glycals were sulfonylated directly by a range of benzene- and naphthalene-sulfinic acid sodium salts catalyzed by cobalt species, demonstrating a broad substrate scope. The mechanism of cobalt-catalyzed decarboxylative allylation from the bottom face of the sugar ring due to the steric effect from the C3 group of glycals was proposed. Moroever, cobalt catalysis tends to favor branched allylation, resulting in excellent regioselectivity. This synthetic strategy features the green sulfone source, good functional group tolerance, exclusive regioselectivity, and excellent stereoselectivity.</div></div>","PeriodicalId":15311,"journal":{"name":"Journal of Carbohydrate Chemistry","volume":"43 3","pages":"Pages 70-89"},"PeriodicalIF":1.2,"publicationDate":"2024-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142416350","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-23DOI: 10.1080/07328303.2024.2366770
Modulating the reactivity of glycosyl acceptors has become a key in promoting the chemical synthesis of complex glycans. Herein, computational chemistry was employed to explore the impacts of protecting groups on the non-covalent interactions and electronic properties of glycosyl acceptors. Wavefunction analyses showed that substituting benzoyl groups with benzyl groups and introducing a benzyl group to the C2 amine of a D-GlcpNAc residue can eliminate intra-/intermolecular hydrogen bonds, thereby altering the charge distribution significantly. This protecting group-induced charge distribution increases the nucleophilicity of hydroxyl group. This study may contribute to understanding the assistance of computational chemistry in glycan synthesis.
{"title":"The impacts of benzoyl and benzyl groups on the non-covalent interactions and electronic properties of glycosyl acceptors","authors":"","doi":"10.1080/07328303.2024.2366770","DOIUrl":"10.1080/07328303.2024.2366770","url":null,"abstract":"<div><div>Modulating the reactivity of glycosyl acceptors has become a key in promoting the chemical synthesis of complex glycans. Herein, computational chemistry was employed to explore the impacts of protecting groups on the non-covalent interactions and electronic properties of glycosyl acceptors. Wavefunction analyses showed that substituting benzoyl groups with benzyl groups and introducing a benzyl group to the C2 amine of a D-Glc<em>p</em>NAc residue can eliminate intra-/intermolecular hydrogen bonds, thereby altering the charge distribution significantly. This protecting group-induced charge distribution increases the nucleophilicity of hydroxyl group. This study may contribute to understanding the assistance of computational chemistry in glycan synthesis.</div></div>","PeriodicalId":15311,"journal":{"name":"Journal of Carbohydrate Chemistry","volume":"43 3","pages":"Pages 51-69"},"PeriodicalIF":1.2,"publicationDate":"2024-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141341451","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-23DOI: 10.1080/07328303.2024.2399517
Guozhu Zhang , Yuan Guan , Xin Zhang , Jing Li , Haishan Chen , Li Zhou , Jun Liang , Xia Li
The absorption and metabolism of indigestible dietary glycans play a crucial role in maintaining the integrity of the intestinal barrier and shaping the gut microbiota. Three chemically modified products of xylan, including carboxymethylated xylan, xylan–zinc complex, and carboxymethylated xylan–zinc complex, were synthesized using xylan from sugarcane bagasse. The potential effects of xylan before and after modification on the intestinal barriers and intestinal microbiota of mice were subsequently investigated and compared, revealing distinct changes in the gut microbiota of mice. The results suggest that the chemically modified xylan products have the potential to induce specific regulatory functions on the gut microbiota.
{"title":"Chemical modifications of xylan from sugarcane bagasse and their regulatory effects on gut microbiota in mice","authors":"Guozhu Zhang , Yuan Guan , Xin Zhang , Jing Li , Haishan Chen , Li Zhou , Jun Liang , Xia Li","doi":"10.1080/07328303.2024.2399517","DOIUrl":"10.1080/07328303.2024.2399517","url":null,"abstract":"<div><div>The absorption and metabolism of indigestible dietary glycans play a crucial role in maintaining the integrity of the intestinal barrier and shaping the gut microbiota. Three chemically modified products of xylan, including carboxymethylated xylan, xylan–zinc complex, and carboxymethylated xylan–zinc complex, were synthesized using xylan from sugarcane bagasse. The potential effects of xylan before and after modification on the intestinal barriers and intestinal microbiota of mice were subsequently investigated and compared, revealing distinct changes in the gut microbiota of mice. The results suggest that the chemically modified xylan products have the potential to induce specific regulatory functions on the gut microbiota.</div></div>","PeriodicalId":15311,"journal":{"name":"Journal of Carbohydrate Chemistry","volume":"43 3","pages":"Pages 90-111"},"PeriodicalIF":1.2,"publicationDate":"2024-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142416349","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-12DOI: 10.1080/07328303.2024.2366789
Zeguo Fang , Nawaf Al-Maharik
The current body of research on the health implications of isoflavone phytoestrogens still presents unsolved matters pertaining to absorption, metabolism, and bioavailability. To conduct research in this particular domain, it is important to possess the means to obtain samples of both isoflavone 7-O-glucosides, which are naturally occurring in plants, and 7-O-glucuronides, which are major metabolites present in mammals. To comprehensively examine the potential health advantages, it is important to precisely measure the concentrations of phytoestrogens present in various food sources and bodily fluids. The use of C-labeled isoflavones was critical to the development of a methodology that allows for precise measurement. 2,3,4-13C-Labeled isoflavone 7-O-glucosides, namely 2,3,4-13C-labeled daidzin, genestin and glycitin, were efficiently prepared via BF3·Et2O catalyzed glycosylation at the 7-O-position of 13C-labeled 4′-O-hexanoyldaidzein, 4′-O-hexanoylglycitein and 5,4′-O-dihexannoylgenestein with 2,2,2-trifluoro-N-(p-methoxyphenyl)acetamidates as glycosyl donors. It was found that protecting all of the OH groups in the isoflavones with hexanoyl groups, with the exception of the 7-OH group, resulted in an increase in both their solubility in organic solvents and the reaction efficiency.
{"title":"Synthesis of 2,3,4-13C-labeled isoflavone 7-O-glucosides","authors":"Zeguo Fang , Nawaf Al-Maharik","doi":"10.1080/07328303.2024.2366789","DOIUrl":"10.1080/07328303.2024.2366789","url":null,"abstract":"<div><p>The current body of research on the health implications of isoflavone phytoestrogens still presents unsolved matters pertaining to absorption, metabolism, and bioavailability. To conduct research in this particular domain, it is important to possess the means to obtain samples of both isoflavone 7-<em>O</em>-glucosides, which are naturally occurring in plants, and 7-<em>O</em>-glucuronides, which are major metabolites present in mammals. To comprehensively examine the potential health advantages, it is important to precisely measure the concentrations of phytoestrogens present in various food sources and bodily fluids. The use of C-labeled isoflavones was critical to the development of a methodology that allows for precise measurement. 2,3,4-<sup>13</sup>C-Labeled isoflavone 7-<em>O</em>-glucosides, namely 2,3,4-<sup>13</sup>C-labeled daidzin, genestin and glycitin, were efficiently prepared via BF<sub>3</sub>·Et<sub>2</sub>O catalyzed glycosylation at the 7-<em>O</em>-position of <sup>13</sup>C-labeled 4′-<em>O</em>-hexanoyldaidzein, 4′-<em>O</em>-hexanoylglycitein and 5,4′-<em>O</em>-dihexannoylgenestein with 2,2,2-trifluoro-<em>N</em>-(<em>p</em>-methoxyphenyl)acetamidates as glycosyl donors. It was found that protecting all of the OH groups in the isoflavones with hexanoyl groups, with the exception of the 7-OH group, resulted in an increase in both their solubility in organic solvents and the reaction efficiency.</p></div>","PeriodicalId":15311,"journal":{"name":"Journal of Carbohydrate Chemistry","volume":"43 1","pages":"Pages 37-50"},"PeriodicalIF":1.2,"publicationDate":"2024-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142228943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-02-12DOI: 10.1080/07328303.2024.2366774
Lvfeng Zhang , Youling Liang , Xiaona Li , Rongkun Liu , Jibin Zheng , Peng Xu , Biao Yu , You Yang
Gold-catalyzed glycosylation using alkyne donors is a versatile approach for the efficient assembly of diverse types of glycosides due to its catalytic and mild glycosylation properties. Minor structural alterations might significantly affect the glycosylation reaction when the alkyne-based leaving groups are simplified. By mapping the glycosylation reactivities of a series of structurally simplified alkyne donors, herein we demonstrate the role of each characteristic functional group of glycosyl ynenoates. Based on the isolation and the X-ray diffraction characterization of the pyran-5-ylgold(I) complex generated from the leaving group, a plausible mechanism of the gold(I)-catalyzed glycosylation with glycosyl ynenoates as donors was proposed.
由于金催化糖基化具有催化性和温和的糖基化特性，因此使用炔烃供体进行金催化糖基化是高效合成各种类型糖苷的通用方法。简化炔基离去基团时，微小的结构变化可能会严重影响糖基化反应。通过绘制一系列结构简化的炔烃供体的糖基化反应图，我们在此证明了炔苷酸糖基化物中每个特征官能团的作用。根据分离和 X 射线衍射表征从离去基团生成的吡喃-5-基金（I）复合物，我们提出了以炔酸酯为给体的金(I)催化糖基化的合理机制。
{"title":"Insight into gold-catalyzed glycosylation of glycosyl ynenoates","authors":"Lvfeng Zhang , Youling Liang , Xiaona Li , Rongkun Liu , Jibin Zheng , Peng Xu , Biao Yu , You Yang","doi":"10.1080/07328303.2024.2366774","DOIUrl":"10.1080/07328303.2024.2366774","url":null,"abstract":"<div><p>Gold-catalyzed glycosylation using alkyne donors is a versatile approach for the efficient assembly of diverse types of glycosides due to its catalytic and mild glycosylation properties. Minor structural alterations might significantly affect the glycosylation reaction when the alkyne-based leaving groups are simplified. By mapping the glycosylation reactivities of a series of structurally simplified alkyne donors, herein we demonstrate the role of each characteristic functional group of glycosyl ynenoates. Based on the isolation and the X-ray diffraction characterization of the pyran-5-ylgold(I) complex generated from the leaving group, a plausible mechanism of the gold(I)-catalyzed glycosylation with glycosyl ynenoates as donors was proposed.</p></div>","PeriodicalId":15311,"journal":{"name":"Journal of Carbohydrate Chemistry","volume":"43 1","pages":"Pages 21-36"},"PeriodicalIF":1.2,"publicationDate":"2024-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142229041","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"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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