Pub Date : 2024-10-11DOI: 10.1016/j.carres.2024.109288
Padmashri Rabha, Rajib Panchadhayee
Sulfonated graphene (GR-SO3H) was prepared and used as an efficient and sustainable catalyst to deprotect O-benzylidene and O-isopropylidene acetal of carbohydrates under ultrasound (US) irradiation. The solid catalyst can recovered by simple filtration and used several times without much loss in reactivity. This methodology not only reduces the reaction time but also increases the yield. Moreover, the work-up and purification procedure is very simple and also effective for large-scale preparation.
{"title":"Ultrasound-promoted removal of benzylidene and isopropylidene acetal protection of carbohydrates in presence of sulfonated graphene (GR-SO3H) as a sustainable acid catalyst","authors":"Padmashri Rabha, Rajib Panchadhayee","doi":"10.1016/j.carres.2024.109288","DOIUrl":"10.1016/j.carres.2024.109288","url":null,"abstract":"<div><div>Sulfonated graphene (GR-SO<sub>3</sub>H) was prepared and used as an efficient and sustainable catalyst to deprotect <em>O</em>-benzylidene and <em>O</em>-isopropylidene acetal of carbohydrates under ultrasound (US) irradiation. The solid catalyst can recovered by simple filtration and used several times without much loss in reactivity. This methodology not only reduces the reaction time but also increases the yield. Moreover, the work-up and purification procedure is very simple and also effective for large-scale preparation.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"545 ","pages":"Article 109288"},"PeriodicalIF":2.4,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142434223","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 : 2024-10-09DOI: 10.1016/j.carres.2024.109287
Haijuan Qin , Zhiwei Huang , Xue Mi , Shuai Zhang , Han-Yu Liu , Jia-Ning Wang , Mingming Xue , Zhiqi Lao , Yang Yang
A novel thioxoimidazolidin-linked sialoside bovine serum albumin (WM-BSA) conjugate was synthesized and evaluated as an inhibitor of influenza virus hemagglutinin (HA) and neuraminidase (NA). The multivalent conjugate was prepared by the attachment of thioxoimidazolidin-sialoside monomer (WM) to BSA via adipate linker. Surface plasmon resonance analysis revealed that WM-BSA exhibited potent binding to recombinant influenza HA and NA proteins, with dissociation constants in the submicromolar range. WM-BSA also demonstrated inhibitory activities in the low micromolar range against HA and NA proteins from multiple influenza strains. Investigation of cytopathic effects in infected MDCK cells indicated that WM-BSA possessed antiviral activity with EC50 values of 35–55 μM. The multivalent presentation of sialosides on the BSA scaffold significantly enhanced both the binding affinity and degree of inhibition compared to the monomeric compound WM. These results demonstrate the potential of multivalent sialoside-protein conjugate as a platform for developing novel anti-influenza agent.
研究人员合成了一种新型硫代咪唑啉连接的硅糖苷牛血清白蛋白（WM-BSA）共轭物，并将其作为流感病毒血凝素（HA）和神经氨酸酶（NA）的抑制剂进行了评估。这种多价共轭物是通过己二酸酯连接体将硫代咪唑烷-苷单体（WM）连接到 BSA 上制备而成的。表面等离子共振分析表明，WM-BSA 与重组流感 HA 和 NA 蛋白的结合力很强，解离常数在亚摩尔范围内。WM-BSA 还对多种流感病毒株的 HA 和 NA 蛋白具有低微摩尔范围的抑制活性。对受感染的 MDCK 细胞进行的细胞病理效应研究表明，WM-BSA 具有抗病毒活性，其 EC50 值为 35-55 μM。与单体化合物 WM 相比，在 BSA 支架上多价呈现的硅苷大大提高了结合亲和力和抑制程度。这些结果表明，多价硅藻糖苷-蛋白共轭物具有开发新型抗流感药物平台的潜力。
{"title":"Preparation of a thioxoimidazolidin-linked sialoside BSA conjugate for the inhibition of influenza virus","authors":"Haijuan Qin , Zhiwei Huang , Xue Mi , Shuai Zhang , Han-Yu Liu , Jia-Ning Wang , Mingming Xue , Zhiqi Lao , Yang Yang","doi":"10.1016/j.carres.2024.109287","DOIUrl":"10.1016/j.carres.2024.109287","url":null,"abstract":"<div><div>A novel thioxoimidazolidin-linked sialoside bovine serum albumin (<strong>WM-BSA</strong>) conjugate was synthesized and evaluated as an inhibitor of influenza virus hemagglutinin (HA) and neuraminidase (NA). The multivalent conjugate was prepared by the attachment of thioxoimidazolidin-sialoside monomer (<strong>WM</strong>) to BSA <em>via</em> adipate linker. Surface plasmon resonance analysis revealed that <strong>WM-BSA</strong> exhibited potent binding to recombinant influenza HA and NA proteins, with dissociation constants in the submicromolar range. <strong>WM-BSA</strong> also demonstrated inhibitory activities in the low micromolar range against HA and NA proteins from multiple influenza strains. Investigation of cytopathic effects in infected MDCK cells indicated that <strong>WM-BSA</strong> possessed antiviral activity with EC<sub>50</sub> values of 35–55 μM. The multivalent presentation of sialosides on the BSA scaffold significantly enhanced both the binding affinity and degree of inhibition compared to the monomeric compound <strong>WM</strong>. These results demonstrate the potential of multivalent sialoside-protein conjugate as a platform for developing novel anti-influenza agent.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"545 ","pages":"Article 109287"},"PeriodicalIF":2.4,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142434222","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 : 2024-10-04DOI: 10.1016/j.carres.2024.109286
Shuvam Mukherjee , Mathias E. Chemen , Saikat Pal , Luana E. Piccini , Subrata Jana , Elsa B. Damonte , Bimalendu Ray , Cybele C. Garcia , Sayani Ray
In cultured cells, herpes simplex virus (HSV) infectivity is successfully inhibited by sulfated polysaccharides. Herein, we utilized an amalgamated extraction-sulfation procedure to produce two xylogalactofucan sulfates (S203 and S204) from Spatoglossum asperum using ClSO3H.Pyr/DMF and SO3.Pyr/DMF reagents, respectively. Among these xylogalactofucans, the 17 ± 12 kDa polymer (S203) with 14 % sulfate exhibited activity on several HSV variants, including an acyclovir-resistant HSV-1 strain. This is the first report of the anti-HSV activity of a sulfated xylogalactofucan of S. asperum. The effective concentration 50 % (EC50) value of S203 against HSV-1 strain F was 0.6 μg/mL with a selectivity index of 833. The backbone of this polymer (S203) is made up mostly of (1 → 4)-linked-α-l-Fucp units having sulfate groups typically at O–3 and sometimes at O–2 positions. Oligosaccharides containing Xyl, Gal and Fuc units confirms that they are an integral part of a single polymer, another novelty of this study.
The EC50 values of the native xylogalactofucan (S202) and the SO3.Pyr/DMF modified polymer (S204), containing 2 % and 6 % sulfates, were >100 and 3.3 μg/mL, respectively. Introduction of sulfate groups enhanced their capability to inhibit the infection of cells by HSV-1. These findings suggest feasibility of inhibiting HSV attachment to cells by blocking viral entry with polysaccharide having specific structure.
{"title":"Sulfated xylogalactofucans from Spatoglossum asperum: Production, structural features and antiviral activity","authors":"Shuvam Mukherjee , Mathias E. Chemen , Saikat Pal , Luana E. Piccini , Subrata Jana , Elsa B. Damonte , Bimalendu Ray , Cybele C. Garcia , Sayani Ray","doi":"10.1016/j.carres.2024.109286","DOIUrl":"10.1016/j.carres.2024.109286","url":null,"abstract":"<div><div>In cultured cells, herpes simplex virus (HSV) infectivity is successfully inhibited by sulfated polysaccharides. Herein, we utilized an amalgamated extraction-sulfation procedure to produce two xylogalactofucan sulfates (S203 and S204) from <em>Spatoglossum asperum</em> using ClSO<sub>3</sub>H.Pyr/DMF and SO<sub>3</sub>.Pyr/DMF reagents, respectively. Among these xylogalactofucans, the 17 ± 12 kDa polymer (S203) with 14 % sulfate exhibited activity on several HSV variants, including an acyclovir-resistant HSV-1 strain. This is the first report of the anti-HSV activity of a sulfated xylogalactofucan of <em>S. asperum</em>. The effective concentration 50 % (EC<sub>50</sub>) value of S203 against HSV-1 strain F was 0.6 μg/mL with a selectivity index of 833. The backbone of this polymer (S203) is made up mostly of (1 → 4)-linked-α-<em>l</em>-Fuc<em>p</em> units having sulfate groups typically at O–3 and sometimes at O–2 positions. Oligosaccharides containing Xyl, Gal and Fuc units confirms that they are an integral part of a single polymer, another novelty of this study.</div><div>The EC<sub>50</sub> values of the native xylogalactofucan (S202) and the SO<sub>3</sub>.Pyr/DMF modified polymer (S204), containing 2 % and 6 % sulfates, were >100 and 3.3 μg/mL, respectively. Introduction of sulfate groups enhanced their capability to inhibit the infection of cells by HSV-1. These findings suggest feasibility of inhibiting HSV attachment to cells by blocking viral entry with polysaccharide having specific structure.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"545 ","pages":"Article 109286"},"PeriodicalIF":2.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142434221","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 : 2024-10-02DOI: 10.1016/j.carres.2024.109285
Naoko Osada , Masamichi Nagae , Takahiro Yamasaki , Anne Harduin-Lepers , Yasuhiko Kizuka
N-Glycan branching critically regulates glycoprotein functions and is involved in various diseases. Among the glycosyltransferases involved in N-glycan branching is the human N-acetylglucosaminyltransferase-IV (GnT-IV) family, which has four members: GnT-IVa, GnT-IVb, GnT-IVc, and GnT-IVd. GnT-IVa and GnT-IVb have glycosyltransferase activity that generates the type-2 diabetes-related β1,4-GlcNAc branch on the α1,3-Man arm of N-glycans, whereas GnT-IVc and GnT-IVd do not. Recently, this enzyme family was found to have a unique lectin domain in the C-terminal region, which is essential for enzyme activity toward glycoprotein substrates but not toward free N-glycans. Furthermore, interaction between the lectin domain of GnT-IV and N-glycan attached to GnT-IV enables self-regulation of GnT-IV activity, indicating that the lectin domain plays a unique and pivotal role in the regulation of GnT-IV activity. In this review, we summarize the GnT-IV family's biological functions, selectivity for glycoprotein substrates, and regulation of enzymatic activity, with a focus on its unique C-terminal lectin domain.
{"title":"Regulation of human GnT-IV family activity by the lectin domain","authors":"Naoko Osada , Masamichi Nagae , Takahiro Yamasaki , Anne Harduin-Lepers , Yasuhiko Kizuka","doi":"10.1016/j.carres.2024.109285","DOIUrl":"10.1016/j.carres.2024.109285","url":null,"abstract":"<div><div><em>N</em>-Glycan branching critically regulates glycoprotein functions and is involved in various diseases. Among the glycosyltransferases involved in <em>N</em>-glycan branching is the human <em>N</em>-acetylglucosaminyltransferase-IV (GnT-IV) family, which has four members: GnT-IVa, GnT-IVb, GnT-IVc, and GnT-IVd. GnT-IVa and GnT-IVb have glycosyltransferase activity that generates the type-2 diabetes-related β1,4-GlcNAc branch on the α1,3-Man arm of <em>N</em>-glycans, whereas GnT-IVc and GnT-IVd do not. Recently, this enzyme family was found to have a unique lectin domain in the C-terminal region, which is essential for enzyme activity toward glycoprotein substrates but not toward free <em>N</em>-glycans. Furthermore, interaction between the lectin domain of GnT-IV and <em>N</em>-glycan attached to GnT-IV enables self-regulation of GnT-IV activity, indicating that the lectin domain plays a unique and pivotal role in the regulation of GnT-IV activity. In this review, we summarize the GnT-IV family's biological functions, selectivity for glycoprotein substrates, and regulation of enzymatic activity, with a focus on its unique C-terminal lectin domain.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"545 ","pages":"Article 109285"},"PeriodicalIF":2.4,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142380086","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 : 2024-09-26DOI: 10.1016/j.carres.2024.109283
Nikita M. Podvalnyy , Lisa Crone , Daniela Paganini , Michael B. Zimmermann , Thierry Hennet
Deoxy-hexose sugars, such as rhamnose and quinovose, and the dideoxy-hexoses colitose, abequose, and tyvelose are highly antigenic given that they are absent from animal glycoconjugates. To investigate the specificity of antibodies towards structurally similar carbohydrate epitopes found in bacteria, we synthesized trisaccharides containing colitose, abequose, and fucose motifs. Each trisaccharide was designed with a spacer ending with a primary amino group. These trisaccharide constructs were immobilized on O-succinimide coated glass slides alongside bacterial lipopolysaccharides (LPS) containing colitose, abequose, and fucose residues. We compared the recognition of the synthetic trisaccharides and natural LPS including structurally related epitopes by monoclonal and polyclonal antibodies targeting bacterial LPS. Additionally, we used arrays displaying the synthetic trisaccharides and natural LPS to assess the variability of IgA reactivity from breast milk samples towards the carbohydrate antigens. The results obtained underlined the cross-reactivity of polyclonal antibodies towards structurally related carbohydrate antigens and revealed a broad reactivity of breast milk-derived IgA towards the carbohydrate antigens tested. The significant cross-reactivity of antibodies towards structurally related LPS antigens may lead to false-positive detection of bacterial serotypes when used for diagnostic purposes.
鼠李糖和喹诺酮糖等脱氧己糖以及可乐糖、阿贝糖和岩藻糖等双脱氧己糖具有很强的抗原性，因为动物糖结合物中没有这些糖。为了研究抗体对细菌中结构相似的碳水化合物表位的特异性，我们合成了含有可乐糖、阿贝果糖和岩藻糖基团的三糖。每种三糖都设计了一个以伯氨基结尾的间隔。将这些三糖构建体固定在涂有 O-琥珀酰亚胺的玻璃载玻片上，同时固定的还有含有可立糖、阿贝库糖和岩藻糖残基的细菌脂多糖（LPS）。我们比较了针对细菌 LPS 的单克隆和多克隆抗体对合成三糖和天然 LPS（包括结构相关的表位）的识别率。此外，我们还使用显示合成三糖和天然 LPS 的阵列来评估母乳样本中 IgA 对碳水化合物抗原反应性的变异性。研究结果表明，多克隆抗体对结构相关的碳水化合物抗原具有交叉反应性，并显示母乳中的 IgA 对测试的碳水化合物抗原具有广泛的反应性。在用于诊断时，抗体对结构相关的 LPS 抗原的明显交叉反应可能会导致对细菌血清型的假阳性检测。
{"title":"Synthesis of trisaccharide antigens featuring colitose, abequose and fucose residues and assessment of antibody binding on antigen arrays","authors":"Nikita M. Podvalnyy , Lisa Crone , Daniela Paganini , Michael B. Zimmermann , Thierry Hennet","doi":"10.1016/j.carres.2024.109283","DOIUrl":"10.1016/j.carres.2024.109283","url":null,"abstract":"<div><div>Deoxy-hexose sugars, such as rhamnose and quinovose, and the dideoxy-hexoses colitose, abequose, and tyvelose are highly antigenic given that they are absent from animal glycoconjugates. To investigate the specificity of antibodies towards structurally similar carbohydrate epitopes found in bacteria, we synthesized trisaccharides containing colitose, abequose, and fucose motifs. Each trisaccharide was designed with a spacer ending with a primary amino group. These trisaccharide constructs were immobilized on O-succinimide coated glass slides alongside bacterial lipopolysaccharides (LPS) containing colitose, abequose, and fucose residues. We compared the recognition of the synthetic trisaccharides and natural LPS including structurally related epitopes by monoclonal and polyclonal antibodies targeting bacterial LPS. Additionally, we used arrays displaying the synthetic trisaccharides and natural LPS to assess the variability of IgA reactivity from breast milk samples towards the carbohydrate antigens. The results obtained underlined the cross-reactivity of polyclonal antibodies towards structurally related carbohydrate antigens and revealed a broad reactivity of breast milk-derived IgA towards the carbohydrate antigens tested. The significant cross-reactivity of antibodies towards structurally related LPS antigens may lead to false-positive detection of bacterial serotypes when used for diagnostic purposes.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"545 ","pages":"Article 109283"},"PeriodicalIF":2.4,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142342163","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-26DOI: 10.1016/j.carres.2024.109284
Oliver Müller, Daniel Wefers
Several lactic acid bacteria are capable of producing water-soluble exopolysaccharides such as dextran from sucrose by using glucansucrases. Several recombinant glucansucrases were described, however, yields were often limited and most dextrans were branched at position O3. In this study, the dextransucrase from Ligilactobacillus animalis TMW 1.971 was recombinantly produced without its N-terminal variable region and used for dextran synthesis. The enzyme expressed well and showed very high total as well as transferase activities compared to other glucansucrases. It was able to transfer nearly all glucose from sucrose to oligo- and polymeric products under certain conditions (about 95 % of glucose transferred). The high efficiency of the enzyme made it possible to obtain absolute dextran yields of up to 214.9 g/L from a 1.5 M sucrose solution. Structural characterization of the products showed that the dextrans produced have a rather low molecular weight, a narrow size distribution, and are completely linear. Furthermore, we showed that various low molecular weight dextrans or 1,6-linked isomalto-oligosaccharides can be efficiently produced by acid hydrolysis. Overall, we demonstrated that Ligilactobacillus animalis TMW 1.971 dextransucrase can be used to efficiently synthesize dextrans with a quite unique structural composition. The dextrans produced have a high potential for further applications such as synthesis of copolymers or size standards with a very defined molecular structure.
有几种乳酸菌能够利用葡聚糖琥珀酸酶从蔗糖中生产葡聚糖等水溶性外多糖。目前已描述了几种重组葡聚糖琥珀酸酶，但产量往往有限，而且大多数葡聚糖在 O3 位发生支化。在这项研究中，重组生产了来自动物舌杆菌 TMW 1.971 的葡聚糖粘多糖酶，去除了其 N 端可变区，并将其用于葡聚糖合成。与其他葡聚糖琥珀酸酶相比，该酶表达良好，显示出极高的总活性和转移酶活性。在特定条件下，它几乎能将所有葡萄糖从蔗糖转移到低聚物和聚合产物中（转移的葡萄糖约占 95%）。该酶的高效率使其能够从 1.5 M 的蔗糖溶液中获得高达 214.9 g/L 的绝对葡聚糖产量。产物的结构特征显示，生成的葡聚糖分子量相当低，粒度分布窄，且完全呈线性。此外，我们还发现通过酸水解法可以有效地生产出各种低分子量的葡聚糖或 1,6 连接的异麦芽寡糖。总之，我们证明了动物假丝酵母 TMW 1.971 葡聚糖酶可用于高效合成具有独特结构组成的葡聚糖。生产出的葡聚糖具有很大的进一步应用潜力，如合成共聚物或具有非常明确分子结构的尺寸标准。
{"title":"High-yield production of completely linear dextrans and isomalto-oligosaccharides by a truncated dextransucrase from Ligilactobacillus animalis TMW 1.971","authors":"Oliver Müller, Daniel Wefers","doi":"10.1016/j.carres.2024.109284","DOIUrl":"10.1016/j.carres.2024.109284","url":null,"abstract":"<div><div>Several lactic acid bacteria are capable of producing water-soluble exopolysaccharides such as dextran from sucrose by using glucansucrases. Several recombinant glucansucrases were described, however, yields were often limited and most dextrans were branched at position <em>O</em>3. In this study, the dextransucrase from <em>Ligilactobacillus animalis</em> TMW 1.971 was recombinantly produced without its <em>N</em>-terminal variable region and used for dextran synthesis. The enzyme expressed well and showed very high total as well as transferase activities compared to other glucansucrases. It was able to transfer nearly all glucose from sucrose to oligo- and polymeric products under certain conditions (about 95 % of glucose transferred). The high efficiency of the enzyme made it possible to obtain absolute dextran yields of up to 214.9 g/L from a 1.5 M sucrose solution. Structural characterization of the products showed that the dextrans produced have a rather low molecular weight, a narrow size distribution, and are completely linear. Furthermore, we showed that various low molecular weight dextrans or 1,6-linked isomalto-oligosaccharides can be efficiently produced by acid hydrolysis. Overall, we demonstrated that <em>Ligilactobacillus animalis</em> TMW 1.971 dextransucrase can be used to efficiently synthesize dextrans with a quite unique structural composition. The dextrans produced have a high potential for further applications such as synthesis of copolymers or size standards with a very defined molecular structure.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"545 ","pages":"Article 109284"},"PeriodicalIF":2.4,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142364497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-24DOI: 10.1016/j.carres.2024.109282
Robert J. Nicholas, Nosa B. Idahagbon, Alexander Wei
Trifluoroacetic anhydride (TFAA) reacts smoothly with low molecular weight carbohydrates and cellulose nanofibers (CNFs) under base-free conditions. Methyl α- and β-d-glucopyranoside were used as model compounds to optimize reaction conditions, which were then applied to lyophilized CNFs for surface modification. ATR-IR spectroscopy and powder X-ray diffraction were employed to characterize the modified CNFs. Trifluoroacetylation for 4 h yields a degree of substitution (DS) of 0.4 acyl groups per anhydroglucose unit while maintaining a crystallinity index near 50 %. DS values were quantified by gravimetry, acid–base titration after saponification, and a novel approach utilizing solution 19F NMR spectroscopy which offers greater accuracy than the other techniques. This study presents an efficient, base-free method for derivatizing carbohydrates as well as surface functionalization of CNFs with trifluoroacetyl groups, potentially expanding their application in fiber-reinforced thermoplastic composites.
{"title":"Base-free trifluoroacetylation: From methyl glucopyranoside to cellulose nanofibers","authors":"Robert J. Nicholas, Nosa B. Idahagbon, Alexander Wei","doi":"10.1016/j.carres.2024.109282","DOIUrl":"10.1016/j.carres.2024.109282","url":null,"abstract":"<div><div>Trifluoroacetic anhydride (TFAA) reacts smoothly with low molecular weight carbohydrates and cellulose nanofibers (CNFs) under base-free conditions. Methyl α- and β-<span>d</span>-glucopyranoside were used as model compounds to optimize reaction conditions, which were then applied to lyophilized CNFs for surface modification. ATR-IR spectroscopy and powder X-ray diffraction were employed to characterize the modified CNFs. Trifluoroacetylation for 4 h yields a degree of substitution (DS) of 0.4 acyl groups per anhydroglucose unit while maintaining a crystallinity index near 50 %. DS values were quantified by gravimetry, acid–base titration after saponification, and a novel approach utilizing solution <sup>19</sup>F NMR spectroscopy which offers greater accuracy than the other techniques. This study presents an efficient, base-free method for derivatizing carbohydrates as well as surface functionalization of CNFs with trifluoroacetyl groups, potentially expanding their application in fiber-reinforced thermoplastic composites.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"545 ","pages":"Article 109282"},"PeriodicalIF":2.4,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324103","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 : 2024-09-23DOI: 10.1016/j.carres.2024.109281
Emmanilo Delar , Yanis Tigherghar , Laurie Girard , Mohamed Haddad , Charles Ramassamy , Jean Legault , Charles Gauthier
Phenylethanoid glycosides are a well-studied class of bioactive compounds found throughout the plant kingdom. In contrast, research on the synthesis and pharmacological activity of phenacyl glycosides, a specific subgroup of phenylethanoid glycosides with a ketone functionality at the alpha position of the phenol ring, has been limited. In this study, we report the synthesis, cytotoxic, antiviral, and anti-inflammatory evaluation of a series of 18 4′-hydroxyphenacyl glycosides. These compounds consist of six different sugar residues (β-d-glucose, β-d-galactose, α-l-arabinose, β-d-xylose, α-l-rhamnose, and β-d-glucuronic acid) and display three distinct methoxylation patterns at the phenacyl ring, similar to the substitution motifs of anthocyanins. We obtained the target phenacyl glycosides in high yield and stereoselectivity through the coupling of benzoyl-protected trichloroacetimidate glycosyl donors and corresponding acetophenones. Our work represents the first total synthesis of the natural products 4′-hydroxyphenacyl-β-d-glucopyranoside (1) and 4′-hydroxy-3′-methoxyphenacyl-β-d-glucopyranoside (2). None of the phenacyl glycosides showed cytotoxicity against the tested cell lines. Notably, several of the synthesized compounds exhibited antiviral activity, with natural product 2 being the most active against herpes simplex virus type 1, while phenacyl arabinoside 9 and natural product 2 were the most active against human coronavirus OC43. Natural product 2 significantly inhibited the production of interleukin-6 in lipopolysaccharide-stimulated microglia cells. Overall, our findings highlight the importance of the sugar residue and phenacyl ring substitution pattern in modulating the antiviral activity of phenacyl glycosides. Natural product 2 and phenacyl arabinoside 9 emerge as promising leads for the development of antiviral agents.
{"title":"Synthesis and pharmacological evaluation of nature-inspired phenacyl glycosides","authors":"Emmanilo Delar , Yanis Tigherghar , Laurie Girard , Mohamed Haddad , Charles Ramassamy , Jean Legault , Charles Gauthier","doi":"10.1016/j.carres.2024.109281","DOIUrl":"10.1016/j.carres.2024.109281","url":null,"abstract":"<div><div>Phenylethanoid glycosides are a well-studied class of bioactive compounds found throughout the plant kingdom. In contrast, research on the synthesis and pharmacological activity of phenacyl glycosides, a specific subgroup of phenylethanoid glycosides with a ketone functionality at the alpha position of the phenol ring, has been limited. In this study, we report the synthesis, cytotoxic, antiviral, and anti-inflammatory evaluation of a series of 18 4′-hydroxyphenacyl glycosides. These compounds consist of six different sugar residues (<em>β</em>-<span>d</span>-glucose, <em>β</em>-<span>d</span>-galactose, <em>α</em>-<span>l</span>-arabinose, <em>β</em>-<span>d</span>-xylose, <em>α</em>-<span>l</span>-rhamnose, and <em>β</em>-<span>d</span>-glucuronic acid) and display three distinct methoxylation patterns at the phenacyl ring, similar to the substitution motifs of anthocyanins. We obtained the target phenacyl glycosides in high yield and stereoselectivity through the coupling of benzoyl-protected trichloroacetimidate glycosyl donors and corresponding acetophenones. Our work represents the first total synthesis of the natural products 4′-hydroxyphenacyl-<em>β</em>-<span>d</span>-glucopyranoside (<strong>1</strong>) and 4′-hydroxy-3′-methoxyphenacyl-<em>β</em>-<span>d</span>-glucopyranoside (<strong>2</strong>). None of the phenacyl glycosides showed cytotoxicity against the tested cell lines. Notably, several of the synthesized compounds exhibited antiviral activity, with natural product <strong>2</strong> being the most active against herpes simplex virus type 1, while phenacyl arabinoside <strong>9</strong> and natural product <strong>2</strong> were the most active against human coronavirus OC43. Natural product <strong>2</strong> significantly inhibited the production of interleukin-6 in lipopolysaccharide-stimulated microglia cells. Overall, our findings highlight the importance of the sugar residue and phenacyl ring substitution pattern in modulating the antiviral activity of phenacyl glycosides. Natural product <strong>2</strong> and phenacyl arabinoside <strong>9</strong> emerge as promising leads for the development of antiviral agents.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"545 ","pages":"Article 109281"},"PeriodicalIF":2.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142356698","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Stereoselective synthesis of 2,3-diazido-2,3-dideoxy-β-d-mannosides has been accomplished via Cs2CO3-mediated anomeric O-alkylation of 2,3-diazido-2,3-dideoxy-β-d-mannoses with primary electrophiles. Selective oxidation of the C6 primary alcohol of the 2,3-diazido-2,3-dideoxy-β-d-mannoside successfully produced corresponding 2,3-diazido-2,3-dideoxy-β-d-mannuronic acid.
{"title":"Synthesis of 2,3-diazido-2,3-dideoxy-β-d-mannosides and 2,3-diazido-2,3-dideoxy-β-d-mannuronic acid via stereoselective anomeric O-alkylation","authors":"Rama Banjara, Prakash Thapa, Shailja Hitesh Kela, Fenglang Wu, Jianglong Zhu","doi":"10.1016/j.carres.2024.109279","DOIUrl":"10.1016/j.carres.2024.109279","url":null,"abstract":"<div><div>Stereoselective synthesis of 2,3-diazido-2,3-dideoxy-β-<span>d</span>-mannosides has been accomplished via Cs<sub>2</sub>CO<sub>3</sub>-mediated anomeric <em>O</em>-alkylation of 2,3-diazido-2,3-dideoxy-β-<span>d</span>-mannoses with primary electrophiles. Selective oxidation of the C6 primary alcohol of the 2,3-diazido-2,3-dideoxy-β-<span>d</span>-mannoside successfully produced corresponding 2,3-diazido-2,3-dideoxy-β-<span>d</span>-mannuronic acid.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"545 ","pages":"Article 109279"},"PeriodicalIF":2.4,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142320210","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 : 2024-09-19DOI: 10.1016/j.carres.2024.109280
Louis J. Liotta, Jessica Antoine, Leighanne A. Brammer Basta, Andrew S. Campbell, Gabrielle Y. Cole, Kristen A. Demick Brazile, Natalie M. Dogal Gardner, Megan E. Fitzgerald, Jean E.K. Francois, Brian M. French, Sara L. Garafola, Catherine A. Giannetti, Eve A. Granatosky, Alycen M. Harney, James T. Hummel, Andrew P. Joyce, Mitchell H. Keylor, Jasmine A. Khubchandani, Claudia Korzeniecki, Diana C. Lieberman, Kerstin L. Tougas
Herein, we describe the efficient, diastereoselective syntheses of the iminosugars 1,4-dideoxy-1,4-imino-D-arabinitol (DAB) 1b, lentiginosine 3a, and the seven stereoisomers of each of these iminosugars starting from 4-benzoyl-6-deoxy-6-iodoglycopyranosides 47 with yields ranging from 38 % to 68 % for the DAB and isomers 1a-1h and from 44 % to 89 % for the lentiginosine and isomers 3a-3h. We also report the syntheses of the eight stereoisomers of the 4-benzoyl-6-deoxy-6-iodoglycopyranosides 47 from commercially available sugars. Key to the iminosugar syntheses is a single multistep reaction that converts the 4-benzoyl-6-deoxy-6-iodoglycopyranosides 47 to a vinyl pyrrolidine through a one-pot zinc mediated reductive elimination, followed by a reductive amination and finally an intramolecular nucleophilic substitution. Strategic selection of the amine utilized in the reductive amination and the functionalization of the intermediate carbon-carbon double bond provides access to a vast array of iminosugars.
{"title":"Efficient synthesis for each of the eight stereoisomers of the iminosugars lentiginosine and 1,4-dideoxy-1,4-imino-D-arabinitol (DAB)","authors":"Louis J. Liotta, Jessica Antoine, Leighanne A. Brammer Basta, Andrew S. Campbell, Gabrielle Y. Cole, Kristen A. Demick Brazile, Natalie M. Dogal Gardner, Megan E. Fitzgerald, Jean E.K. Francois, Brian M. French, Sara L. Garafola, Catherine A. Giannetti, Eve A. Granatosky, Alycen M. Harney, James T. Hummel, Andrew P. Joyce, Mitchell H. Keylor, Jasmine A. Khubchandani, Claudia Korzeniecki, Diana C. Lieberman, Kerstin L. Tougas","doi":"10.1016/j.carres.2024.109280","DOIUrl":"10.1016/j.carres.2024.109280","url":null,"abstract":"<div><div>Herein, we describe the efficient, diastereoselective syntheses of the iminosugars 1,4-dideoxy-1,4-imino-D-arabinitol (DAB) <strong>1b</strong>, lentiginosine <strong>3a</strong>, and the seven stereoisomers of each of these iminosugars starting from 4-benzoyl-6-deoxy-6-iodoglycopyranosides <strong>47</strong> with yields ranging from 38 % to 68 % for the DAB and isomers <strong>1a-1h</strong> and from 44 % to 89 % for the lentiginosine and isomers <strong>3a-3h</strong>. We also report the syntheses of the eight stereoisomers of the 4-benzoyl-6-deoxy-6-iodoglycopyranosides <strong>47</strong> from commercially available sugars. Key to the iminosugar syntheses is a single multistep reaction that converts the 4-benzoyl-6-deoxy-6-iodoglycopyranosides <strong>47</strong> to a vinyl pyrrolidine through a one-pot zinc mediated reductive elimination, followed by a reductive amination and finally an intramolecular nucleophilic substitution. Strategic selection of the amine utilized in the reductive amination and the functionalization of the intermediate carbon-carbon double bond provides access to a vast array of iminosugars.</div></div>","PeriodicalId":9415,"journal":{"name":"Carbohydrate Research","volume":"545 ","pages":"Article 109280"},"PeriodicalIF":2.4,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142320209","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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