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First total synthesis of cyanopterin, a pterin glycoside isolated from a cyanobacterium 首次合成了从一种蓝藻菌中分离出来的蝶呤苷
IF 2.5 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-10-21 DOI: 10.1016/j.carres.2025.109710
Tadashi Hanaya, Yuta Maeda, Kazumasa Ejiri
The first total synthesis and structural identification of cyanopterin, a pterin glycoside isolated from the cyanobacterium Synechocystis sp. PCC 6803, has been accomplished. The synthesis was achieved by convergent coupling of three key derivatives: d-glucuronate, d-galactose, and 6-hydroxymethylpterin. An α-selective glycosylation enabled efficient construction of the glucuronate–galactose disaccharide, while subsequent β-exclusive glycosylation with the 6-hydroxymethylpterin derivative furnished the desired pterin–disaccharide glycoside. Final deprotection provided cyanopterin in its natural form, allowing confirmation of its precise structure.
本文首次合成并鉴定了从藻胞菌中分离得到的一种蝶呤苷类化合物蓝翅素。通过三个关键衍生物:d-葡萄糖醛酸盐、d-半乳糖和6-羟甲基蝶呤的聚合偶联实现了合成。α-选择性糖基化可以有效地构建葡萄糖醛酸-半乳糖双糖,而随后与6-羟甲基蝶呤衍生物进行β-特异性糖基化可以得到所需的蝶呤-双糖糖苷。最后的去保护提供了自然形态的蓝翅虫素,从而确认了其精确的结构。
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引用次数: 0
Comparison of the physical and chemical features of composites produced from textile waste and cellulose plants 纺织废料与纤维素植物合成复合材料的理化特性比较。
IF 2.5 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-10-21 DOI: 10.1016/j.carres.2025.109706
Norbert Lipka , Paulina Żarnowiec , Karolina Soja , Wiesław Kaca
One of the most pressing unresolved environmental challenges is the massive accumulation of unrecycled textile waste. In this study, we demonstrate that reinforcing recycled textile materials with plant-based cellulose fibers can yield functional composite materials. The following natural fibers were investigated: sisal, cotton, linen, coconut, wood, abaca, jute, and hemp. Both the textiles and plant fibers were ground into fragments ranging from 2 to 15 mm in length. Plant–textile composites were produced using an extruder at temperatures up to 195 °C, allowing for the plasticization of the polymer components in the textile waste. Plant fibers were incorporated into the recycled textile matrix at concentrations ranging from 3 % to 6 % by weight. A total of 19 different composite samples were fabricated and tested for their mechanical properties, including tensile strength, flexural strength, and compressive resistance.
FTIR spectra of all cellulose fibers exhibited characteristic cellulose absorption bands, with notable differences in intensity and distribution. The O–H stretching band (3600–3200 cm−1), indicative of hydrogen bonding within cellulose, varied significantly across the different fiber types. SEM micrographs revealed that the surface of the sisal-reinforced composite was relatively smooth and uniform, while the fiberglass composite exhibited a rough and crinkled surface morphology.
In conclusion, composites made from recycled textiles and plant-based fibers represent a promising class of eco-friendly materials with potential as sustainable alternatives to conventional composites.
一个最紧迫的尚未解决的环境挑战是大量堆积的不可回收的纺织废料。在这项研究中,我们证明了用植物基纤维素纤维增强再生纺织材料可以产生功能性复合材料。研究了以下天然纤维:剑麻、棉花、亚麻、椰子、木材、abaca、黄麻和大麻。纺织品和植物纤维都被磨成2至15毫米长的碎片。植物-纺织复合材料是在195°C的温度下使用挤出机生产的,允许纺织废料中的聚合物成分塑化。植物纤维以重量3%至6%的浓度掺入回收的纺织基质中。共制备了19种不同的复合材料样品,并测试了它们的力学性能,包括拉伸强度、弯曲强度和抗压性。所有纤维素纤维的FTIR光谱均表现出特有的纤维素吸收带,其强度和分布有显著差异。O-H拉伸带(3600-3200 cm-1)在不同纤维类型中差异显著,表明纤维素内部的氢键。SEM显微形貌显示,剑麻增强复合材料表面相对光滑均匀,而玻璃纤维增强复合材料表面形貌粗糙、皱褶。总之,由回收纺织品和植物纤维制成的复合材料代表了一类有前途的环保材料,具有替代传统复合材料的可持续发展潜力。
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引用次数: 0
Resveratrol-loaded nanoparticles based on the self-assembly behavior of Sparassis latifolia polysaccharides: Preparation, characterization, release behavior under in vitro digestion and synergistic hypoglycemic effects 白藜芦醇负载纳米粒子的自组装行为:制备、表征、体外消化释放行为和协同降糖作用。
IF 2.5 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-10-20 DOI: 10.1016/j.carres.2025.109707
Pengya Du , Shuyu Bi , Fangming Cui , Lixia He , Jiangyan Hou , Jinling Cao , Yanfen Cheng , Feier Cheng , Wenfei Zhao , Cuiping Feng , Shaojun Yun
Resveratrol (Res) is a naturally occurring polyphenolic compound exhibiting a wide range of biological activities. However, its application is limited due to the instability, poor water solubility, and low bioavailability. Therefore, this study aimed to prepare Sparassis latifolia polysaccharides (SLPs) nanoparticles loaded with Res (SLPs-Res NPs) through the self-assembly behavior of SLPs. Our findings revealed that SLPs underwent a conformational transition from triple helix to single strand when exposed to varying concentrations of dimethyl sulfoxide (DMSO). By virtue of this self-assembly characteristic, the spherical or subspherical nanoparticles loaded with Res were successfully fabricated. The optimal preparation conditions included an 80 % volume ratio of DMSO, a mass ratio of Res to SLPs at 1:32, and magnetic stirring for 2 h. Under these conditions, the average particle size of SLPs-Res NPs was 230.4 ± 7.8 nm, and the encapsulation efficiency of Res reached (66.69 ± 0.10)%. Hydrogen bonding and hydrophobic forces were involved in the formation of nanoparticles. SLP-Res NPs demonstrated enhanced photothermal stability and desirable sustained-release properties. It also exerted significant inhibitory effects on α-glucosidase activity in vitro and glucose-lowering effects in mice during glucose tolerance tests. This study presents an approach for delivering Res using self-assembled SLPs, demonstrating their potential as effective functional carriers for the encapsulation of hydrophobic bioactive molecules.
白藜芦醇是一种天然存在的多酚类化合物,具有广泛的生物活性。然而,由于不稳定、水溶性差、生物利用度低,其应用受到限制。因此,本研究旨在通过木犀草多糖(SLPs)的自组装行为制备载Res纳米粒子(SLPs-Res NPs)。我们的研究结果表明,当暴露于不同浓度的二甲亚砜(DMSO)时,slp经历了从三螺旋到单链的构象转变。利用这种自组装特性,成功制备了负载稀土的球形或亚球形纳米颗粒。最佳制备条件为:DMSO体积比为80%,Res与SLPs质量比为1:32,磁搅拌2 h。在此条件下,SLPs-Res NPs的平均粒径为230.4±7.8 nm, Res包封率为(66.69±0.10)%。氢键和疏水力参与了纳米颗粒的形成。SLP-Res NPs表现出增强的光热稳定性和理想的缓释性能。对体外α-葡萄糖苷酶活性有明显抑制作用,对小鼠糖耐量试验有明显降糖作用。本研究提出了一种使用自组装slp递送Res的方法,证明了它们作为包封疏水生物活性分子的有效功能载体的潜力。
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引用次数: 0
Stereoselective synthesis of LacdiNAc N-glycan based on remote neighboring group participation 基于远邻基参与的LacdiNAc n -聚糖立体选择性合成。
IF 2.5 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-10-20 DOI: 10.1016/j.carres.2025.109709
Kenta Iino , Nozomi Ishii , Kanata Yoshida , Hideki Ishida , Yuji Matsuzaki , Ichiro Matsuo
LacdiNAc (GalNAcβ1-4GlcNAc) is a distinctive epitope found at the non-reducing termini of both N- and O-glycans. In recent years, the physiological functions of LacdiNAc have attracted increasing attention. Consequently, there is a significant demand for pure glycans for use in biochemical experiments. In this study, a concise and practical synthetic approach was developed for biantennary complex-type nonasaccharide 1, which contains LacdiNAc structures at the non-reducing end. Specifically, nonasaccharide 2 was initially constructed in a stereoselective manner via the condensation of trisaccharide donor 3 with trisaccharide acceptor 4, which bears hydroxy groups at the 3- and 6-positions of the β-mannose residue. Notably, this was achieved via the remote neighboring group participation of a pivaloyl group. Subsequent conversion of the N-phthalimido group into an acetamido group, followed by global deprotection, furnished the target compound, 1. The developed synthetic route represents a valuable tool for future investigations into LacdiNAc-modified N-glycans.
LacdiNAc (GalNAcβ1-4GlcNAc)是一个独特的表位,位于N-和o -聚糖的非还原末端。近年来,LacdiNAc的生理功能越来越受到人们的关注。因此,对用于生化实验的纯聚糖有很大的需求。本研究开发了一种简洁实用的双天线络合型非糖精1的合成方法,该非还原端含有LacdiNAc结构。具体来说,非糖2最初是通过三糖给体3和三糖受体4的缩合以立体选择性的方式构建的,三糖受体4在β-甘露糖残基的3位和6位上具有羟基。值得注意的是,这是通过远邻基参与的一个戊酰基实现的。随后n -邻苯二胺基转化为乙酰氨基基,然后进行全局脱保护,得到目标化合物,1。开发的合成路线为今后研究lacdinac修饰的n -聚糖提供了有价值的工具。
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引用次数: 0
Molecular dynamics study of the impact of glycosylation on conformational properties of trimeric N-terminal domain of human copper transporter 1 糖基化对人体铜转运体三聚体n端结构域构象性质影响的分子动力学研究[j]。
IF 2.5 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-10-18 DOI: 10.1016/j.carres.2025.109708
Sergey A. Samsonov , Tomasz Frączyk , Iwona Ufnalska , Wojciech Bal
In this study, we investigate how N- and O-glycosylation affect the structure and dynamics of the disordered N-terminal extracellular domain of human copper transporter 1 (hCtr1), a trimeric transmembrane protein responsible for cellular copper uptake. Copper is an essential trace element, with both deficiency and excess linked to severe disorders. In mammals, its homeostasis is tightly regulated by proteins involved in copper transport and storage. The N-terminal region of hCtr1, comprising 65 amino acids, contains specific copper-binding motifs critical for its function but remains structurally uncharacterized due to its intrinsically disordered nature. This domain can be N- and O-glycosylated at Asn15 and Thr27, respectively, with the latter potentially influencing its physiological function. However, the structural consequences of these modifications remain unclear. We built a trimeric model of the hCtr1 N-terminal domain and performed microsecond-scale molecular dynamics simulations for both glycosylated and non-glycosylated forms. The resulting conformational ensembles revealed unimodal distributions across structural and dynamical descriptors, consistent with disordered behaviour and showing no significant impact of glycosylation. These findings enhance our understanding of the structural flexibility of hCtr1 and provide a foundation for future studies into its structure, function and regulation.
在这项研究中,我们研究了N-和o -糖基化如何影响人类铜转运蛋白1 (hCtr1)的无序N端胞外结构域的结构和动力学,hCtr1是一种负责细胞铜摄取的三聚体跨膜蛋白。铜是一种必需的微量元素,缺乏和过量都会导致严重的疾病。在哺乳动物中,它的体内平衡受到参与铜运输和储存的蛋白质的严格调节。hCtr1的n端区域包含65个氨基酸,包含对其功能至关重要的特定铜结合基序,但由于其内在无序性,其结构仍未表征。该结构域可分别在Asn15和Thr27位点进行N-和o -糖基化,后者可能影响其生理功能。然而,这些变化的结构性后果仍不清楚。我们建立了hCtr1 n端结构域的三聚体模型,并对糖基化和非糖基化形式进行了微秒尺度的分子动力学模拟。由此产生的构象集合揭示了结构和动力学描述符之间的单峰分布,与无序行为一致,并且没有显示糖基化的显著影响。这些发现增强了我们对hCtr1结构灵活性的认识,为进一步研究其结构、功能和调控提供了基础。
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引用次数: 0
1H NMR studies of molecular interaction of d-glucosamine and N-acetyl-D-glucosamine with curcumin and caffeic acid phenethyl ester in DMSO DMSO中d-氨基葡萄糖和n -乙酰- d-氨基葡萄糖与姜黄素和咖啡酸苯乙酯分子相互作用的1H NMR研究。
IF 2.5 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-10-13 DOI: 10.1016/j.carres.2025.109704
Evelin Martínez-Benavidez , Analilia Sánchez , Zaira Domínguez , Magali Salas-Reyes , Gustavo Adolfo Castillo-Herrera , Inocencio Higuera-Ciapara , Ofelia Yadira Lugo-Melchor , Motomichi Inoue , Claudia Virués
Chitosan (Cs)-based polymers have been explored as potential drug-delivery systems that could enhance the practical applications of bioactive phenolic (Ph) substances, such as curcumin (CUR) and caffeic acid phenethyl ester (CAPE). In this study, we focused on designing CS-based drug carriers by examining the intermolecular interactions between the polymer components, d-glucosamine (Gn) and N-acetyl-d-glucosamine (AGn), and the target substances CUR and CAPE through 1H NMR titration in dimethyl sulfoxide (DMSO‑d6). The observed changes in chemical shifts indicated that Gn cation (GnH+) forms molecular complexes, whereas AGn does not exhibit any intermolecular interaction. We developed a titration curve for the complexation, which competes with the self-association of GnH+ (Gnz) in DMSO. Least-squares analyses concluded that molecular complex represented as Ph·Gnz (z = 3 or 4) is formed through a reaction between a Gnz aggregate and a Ph molecule. The formation constant, K = [Ph·Gnz]/[Ph][Gnz], falls within the range of 50–300 M−1. The complex is stabilized by intermolecular interactions at multiple sites within the glucosamine aggregate Gnz, although the non-covalent interactions at each binding site are relatively weak. These findings suggest that chitosan can capture CAPE or CUR exclusively at segments composed of adjacent cationic glucosamine units.
壳聚糖(Cs)基聚合物作为潜在的药物递送系统,可以增强姜黄素(CUR)和咖啡酸苯乙酯(CAPE)等生物活性酚类物质的实际应用。在本研究中,我们重点设计了基于cs的药物载体,通过1H NMR滴定法研究了聚合物组分d-氨基葡萄糖(Gn)和n -乙酰-d-氨基葡萄糖(AGn)与靶物质CUR和CAPE在二甲亚砜(DMSO - d6)中的分子间相互作用。观察到的化学位移变化表明,Gn阳离子(GnH+)形成分子复合物,而AGn不表现出任何分子间相互作用。我们开发了一个络合滴定曲线,它与GnH+ (Gnz)在DMSO中的自结合相竞争。最小二乘分析得出,分子复合物表示为Ph·Gnz(z = 3或4),是由Gnz聚集体与Ph分子之间的反应形成的。形成常数K = [Ph·Gnz]/[Ph][Gnz]在50-300 M-1之间。该复合物通过葡萄糖胺聚集体Gnz内多个位点的分子间相互作用来稳定,尽管每个结合位点的非共价相互作用相对较弱。这些发现表明,壳聚糖可以捕获由相邻阳离子氨基葡萄糖单元组成的片段上的CAPE或CUR。
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引用次数: 0
Azobenzene-modified chitosan composites harnessing high-efficiency photosensitive shape memory behaviors 利用高效光敏形状记忆行为的偶氮苯改性壳聚糖复合材料。
IF 2.5 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-10-13 DOI: 10.1016/j.carres.2025.109705
Ziyun Li , Shuai Yang , Menghua Hou , Sitong Wang , Jiaying Liu , Zhichao He , Zijian Song , Yingchun Li
Chitosan-based shape memory polymers (SMPs) represent a promising class of smart materials for biomedical and packaging applications, yet their development is often limited by the reliance on solutions and thermal stimuli. To enable remote and precise control, this study focuses on developing photosensitive SMPs by conferring light responsiveness to chitosan. Azobenzene-modified chitosan (CSM) was synthesized via a three-step process involving maleic anhydride modification of chitosan followed by free radical grafting with 4-acryloyloxyazobenzene. Composite films (CSMCFs) were then prepared by blending the CSM with poly(vinyl alcohol) (PVA) at varying mass ratios. The chemical structures of the intermediates and the final composite were confirmed by 1H NMR and FTIR spectroscopy. The incorporation of azobenzene groups was verified by UV–vis spectroscopy, and the thermal properties were assessed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The photosensitive shape memory behavior was quantitatively evaluated by measuring the shape fixation rate (Rf) and shape recovery rate (Rr) under 365 nm UV light irradiation. The optimal composites (CSMCF-3), with a CSM/PVA ratio of 3/7 and 0.5 % azobenzene derivative, exhibited a high shape fixation rate of 97.2 % and an exceptional shape recovery rate of 93.3 % within 300 s. These results demonstrate the high potential of these composite films for applications in smart packaging and biomedical devices where remote, light-triggered actuation is desired.
壳聚糖基形状记忆聚合物(SMPs)代表了一类有前途的智能材料,用于生物医学和包装应用,但它们的发展往往受到依赖解决方案和热刺激的限制。为了实现远程和精确控制,本研究着重于通过赋予壳聚糖光响应性来开发光敏SMPs。采用顺丁二酸酐对壳聚糖进行改性,然后与4-丙烯氧基偶氮苯进行自由基接枝,三步法合成了偶氮苯改性壳聚糖。然后将CSM与聚乙烯醇(PVA)按不同的质量比共混制备复合膜(CSMCFs)。通过1H NMR和FTIR对中间体和最终合成物的化学结构进行了表征。通过紫外可见光谱验证了偶氮苯基的掺入,并通过热重分析(TGA)和差示扫描量热法(DSC)评估了热性能。通过测量365 nm紫外光照射下的形状固定率(Rf)和形状恢复率(Rr),定量评价光敏形状记忆行为。最佳复合材料(CSMCF-3) CSM/PVA比为3/7,偶氮苯衍生物含量为0.5%,在300 s内具有97.2%的形状固定率和93.3%的形状恢复率。这些结果证明了这些复合薄膜在智能包装和生物医学设备中应用的巨大潜力,这些设备需要远程、光触发驱动。
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引用次数: 0
Corrigendum to“Kiryu hexose and pentose matrix: A comprehensive model of epimers, structures, and C-1/C-6 inversion products for hexoses and pentoses” [Carbohydr. Res. (2025) 109683] 对“Kiryu己糖和戊糖基质:己糖和戊糖的外显体、结构和C-1/C-6转化产物的综合模型”的更正[碳水化合物]。Res.(2025) 109683]。
IF 2.5 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-10-12 DOI: 10.1016/j.carres.2025.109702
Takaaki Kiryu, Hiroaki Tatsuoka, Motohiro Shizuma
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引用次数: 0
A new UDP-glycosyltransferase for rare ginsenoside biosynthesis from Gynostemma pentaphyllum (Thunb.) 一种新的用于绞股蓝合成稀有人参皂苷的udp -糖基转移酶。
IF 2.5 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-10-09 DOI: 10.1016/j.carres.2025.109703
Qiaoxiang Wu , Yangyang Chen , Mingxing Ye , Yuanping Chen , Xiaoxuan Yuan , Xiaofen Liu , Zehao Huang , Shaohua Xu , Wei Xu , Hua Li , Yaqian Feng
Heterologous biosynthesis of ginsenosides, which possess remarkable therapeutic potential as drug candidates, is currently a research hotspot. The insufficient mining of UDP-glycosyltransferases (UGTs), which are key downstream enzymes in their biosynthetic pathway, limits the variety and yield of ginsenosides that can be bio-produced. As the only medicinal plant outside the Araliaceae family currently discovered to contain ginsenosides, the enzymes involved in ginsenoside synthesis in the Cucurbitaceae plant Gynostemma pentaphyllum (Thunb.) have great development value. In this study, a new glycosyltransferase was mined from G. pentaphyllum and was classified into the UGT74 family based on sequence homology, named GpUGT74A1. GpUGT74A1 exhibits relatively low sequence homology compared to other UGTs that have been reported. Although GpUGT74A1 was almost entirely insoluble when cloned and expressed in Escherichia coli, its soluble expression was successfully achieved by fusion with the MBP solubility tag. In vitro enzyme activity experiments found that it could catalyze the C-20 glycosylation of ginsenosides PPD, PPT, and Rh2 to produce ginsenosides CK, F1, and F2, respectively. This study further enriched the sequence of plant-derived glycosyltransferase genes and provided new candidate elements for the heterologous synthesis of rare ginsenosides.
人参皂苷的异源生物合成作为候选药物具有显著的治疗潜力,是目前的研究热点。作为生物合成途径中关键的下游酶,udp -糖基转移酶(UGTs)的开采不足,限制了人参皂苷生物生产的品种和产量。绞股蓝(Gynostemma pentaphyllum, Thunb.)是目前发现的除五加科外唯一含有人参皂苷的药用植物,其合成人参皂苷的酶具有很大的开发价值。本研究从G. pentaphyllum中分离到一种新的糖基转移酶,根据序列同源性将其归入UGT74家族,命名为GpUGT74A1。与其他已报道的ugt相比,GpUGT74A1的序列同源性相对较低。虽然GpUGT74A1在大肠杆菌中克隆表达时几乎完全不溶,但通过与MBP溶解度标签融合,成功实现了其可溶性表达。体外酶活性实验发现,它可以催化人参皂苷PPD、PPT和Rh2的C-20糖基化,分别生成人参皂苷CK、F1和F2。该研究进一步丰富了植物源性糖基转移酶基因序列,为稀有人参皂苷的异源合成提供了新的候选元件。
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引用次数: 0
Dedicated issue of ‘Carbohydrate Research’ as part of celebration of 90th birth anniversary of Prof. (em.) Dr. Richard R. Schmidt 《碳水化合物研究》专刊,庆祝理查德·r·施密特教授(em.)博士诞辰90周年。
IF 2.5 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2025-10-09 DOI: 10.1016/j.carres.2025.109701
Vinod K. Tiwari
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引用次数: 0
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Carbohydrate Research
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