{"title":"β1,6-Selective Enzymatic N-Acetylglucosamination Catalyzed by the Family GH84 N-Acetyl-β-D-glucosaminidase from Bacteroides thetaiotaomicron and its Glycosyl Acceptor Specificity.","authors":"Rika Okuno, Shunsuke Nakada, Kisuke Tonomura, Yuji Aso, Daijiro Takeshita, Takayuki Ohnuma, Tomonari Tanaka","doi":"10.1002/asia.202500142","DOIUrl":"https://doi.org/10.1002/asia.202500142","url":null,"abstract":"<p><p>The chemoenzymatic synthesis of oligosaccharides presents a highly attractive methodology with significant potential for diverse applications, particularly through using various glycosidases. In this study, the O-glycan core 6 disaccharide moiety, GlcNAcβ1-6GalNAc, was successfully synthesized via enzymatic glycosylation using an N-acetyl-β-D-glucosaminidase from Bacteroides thetaiotaomicron (BtOGA), a member of glycoside hydrolase family 84 (GH84), alongside an N-acetyl-D-glucosamine oxazoline derivative (GlcNAc-oxa) as the glycosyl donor. Furthermore, an investigation into glycosyl acceptor recognition in BtOGA-catalyzed enzymatic glycosylation indicated that the presence of an aromatic group at the anomeric position and an axial hydroxy group at the 4-position of the saccharide moiety is crucial for effective recognition of BtOGA as a glycosyl acceptor. The protecting-group-free chemoenzymatic synthesis of the core 6 disaccharide moiety was achieved by integrating the direct synthesis of GlcNAc-oxa thorough Shoda activation method using a water-soluble dehydration condensing agent in an aqueous medium, followed by BtOGA-catalyzed enzymatic glycosylation.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500142"},"PeriodicalIF":3.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802172","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}
{"title":"Characterization of Cyclic [n]Spirobifluorenylene Compounds and Electron Delocalization in Their Radical Cation Species.","authors":"Tomoya Imai, Toru Amaya","doi":"10.1002/asia.202500320","DOIUrl":"https://doi.org/10.1002/asia.202500320","url":null,"abstract":"<p><p>Charge delocalization through spiro-conjugation provides insights for the rational design of next-generation charge transport materials. We have previously conducted studies using terminally alkyl-protected cyclic [3]spirobifluorenylene compound 1-[3], which features a cyclic structure composed of bifluorenyl units. ESR studies on this radical cation species have shown that its electron is delocalized over approximately three bifluorenyl units, meaning that it is delocalized across the entire molecule. In this study, we newly synthesized cyclic [n]spirobifluorenylene compounds 1-[4] and 1-[5] and investigated their spectroscopic and electrochemical properties, and chemical oxidation behavior. Additionally, DFT calculations were performed not only for the neutral species but also for the radical cation species. Furthermore, we examined the influence of the number of perpendicular π-conjugated units on electron delocalization in their radical cation species. As a result, ESR spectral analysis of the radical cation species 1-[4]<sup>·+</sup> and 1-[5]<sup>·+</sup> revealed that electrons were delocalized over 3.37 and 3.87 units, respectively, when considering bifluorenyl as the unit structure.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500320"},"PeriodicalIF":3.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143810346","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}
{"title":"Room Temperature Operation of All-Solid-State Potassium-Ion Battery Enabled by Unconventional Ionic Solid Electrolyte K<sub>6</sub>[Rh<sub>4</sub>Zn<sub>4</sub>(l-cys)<sub>12</sub>O]·nH<sub>2</sub>O.","authors":"Ryo Sakamoto, Kosuke Nakamoto, Atsushi Inoishi, Masato Ito, Nobuto Yoshinari, Takumi Konno, Yukihiro Hara, Takafumi Fujii, Shigeto Okada","doi":"10.1002/asia.202401781","DOIUrl":"https://doi.org/10.1002/asia.202401781","url":null,"abstract":"<p><p>The unconventional ionic solid, K<sub>6</sub>[Rh<sub>4</sub>Zn<sub>4</sub>(L-cys)<sub>12</sub>O]·nH<sub>2</sub>O, exhibited excellent formability as well as high ionic conductivity. These features enabled a straightforward assembly of all-solid-state potassium-ion battery: A cold-pressed solid sample of K<sub>6</sub>[Rh<sub>4</sub>Zn<sub>4</sub>(L-cys)<sub>12</sub>O]·nH<sub>2</sub>O, which was sandwiched by solid samples of K<sub>2</sub>Ni[Fe(CN)<sub>6</sub>] and chloranil as cathode, and anode, respectively, displayed an initial discharge capacity of 21.6 mAh g<sup>-1</sup>-electrodes at 25 °C at a current density of 0.5 mA cm<sup>-2</sup> (∼0.34C). Energy dispersive X-ray spectroscopy analysis confirmed that K<sup>+</sup> ions swiftly conduct through K<sub>6</sub>[Rh<sub>4</sub>Zn<sub>4</sub>(L-cys)<sub>12</sub>O]·nH<sub>2</sub>O between the cathode and anode during charge-discharge cycles.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401781"},"PeriodicalIF":3.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802135","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}
{"title":"In Situ Electrochemical Reduction of Imidacloprid involving a Nitroso-Intermediate-Trapped DWCNT and Its Biomimetic Cellular Oxidative Stress-Related Mediated Oxidation of Thiols.","authors":"Kandavel Preethika Andal, Annamalai Senthil Kumar","doi":"10.1002/asia.202401779","DOIUrl":"https://doi.org/10.1002/asia.202401779","url":null,"abstract":"<p><p>Imidacloprid (IMP) is a widely used pesticide and insecticide known for its effectiveness in controlling pests and increasing crop yields. Exposure of the compound to water bodies has led to environmental pollution and adverse effects on human health. One major concern is the generation of oxidative-stress in the cellular system, which is often a result of IMP exposure. Although the exact mechanism of toxicity is not fully understood, it is believed that the nitroso-intermediate of IMP (IMP-NO) binds to acetylcholine receptors, disrupting neural function. Thiol pools in the blood serum act as antioxidants to mitigate the toxicity. This study presents an in situ electrochemical conversion of IMP into its key intermediate, IMP-NO, and its subsequent entrapment on a double-walled carbon nanotube-modified glassy carbon electrode (GCE/DWCNT@IMP-NO) as a surface confined redox-peak in a physiological solution. It was characterized by SEM, FTIR, Raman, SECM, and LC-MS techniques. The system exhibited excellent mediated oxidation of the thiol group, using cysteine as a model. The findings presented in this work correlate with observations related to cellular oxidative-stress and its thiol-assisted mitigation. Employing a Michaelis-Menten-type enzyme-substrate reaction mechanism and estimated the kinetic parameters. Chronoamperometric techniques were used to demonstrate the oxidative detection of thiol.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401779"},"PeriodicalIF":3.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802104","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}
{"title":"Recent Advances in Crystalline Porous Materials for Antibacterial Applications.","authors":"Peijie Wu, Luofei Wei, Rui Yao, Bingyu Liu, Shuai-Liang Yang, Liang Qiao, Xiao Wang, Wei Gong, Yan Liu, Yong Cui, Jinqiao Dong","doi":"10.1002/asia.202401961","DOIUrl":"https://doi.org/10.1002/asia.202401961","url":null,"abstract":"<p><p>Bacterial infections remain a significant and escalating threat to global health, exacerbated by multidrug-resistant strains that undermine the efficacy of conventional antibiotics. This pressing issue underscores the urgent need for the development of new antimicrobial materials. Among these, molecular-based crystalline porous materials, such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and supramolecular assembly frameworks (SAFs), have emerged as a promising class of antibacterial agents. These materials exhibit well-defined crystallinity and tunable structures, offering exceptional versatility for antibacterial applications. Notably, their high surface area, adjustable pore size, and potential for functionalization enable efficient loading and controlled release of antibacterial agents, including metal ions and antibacterial molecules. This review provides a comprehensive analysis of recent advancements in this field, highlighting design strategies, structural diversity, antibacterial mechanisms, and applications. Finally, we discuss the current challenges and outline future opportunities for the practical development and deployment of antibacterial porous materials.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401961"},"PeriodicalIF":3.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802106","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}
{"title":"Synthesis, Biological Evaluation, Molecular Docking, and In Silico ADME Predictions of Huperzine: A Derivative for the Novel Protective Application Against Neurodegenerations.","authors":"Benjaporn Homkajorn, Thanasan Nilsu, Sumitra Suntararuks, Patchreenart Saparpakorn, Kornkanok Ingkaninan, Nanteetip Limpeanchob, Jutamaad Satayavivad, Somsak Ruchirawat, Nopporn Thasana","doi":"10.1002/asia.202401950","DOIUrl":"https://doi.org/10.1002/asia.202401950","url":null,"abstract":"<p><p>To date, there has been no effective treatment available for the Alzheimer's disease (AD); hence, novel compounds with AD inhibitory effects are highly desirable. Huperzine A (HupA), a natural Lycopodium alkaloid, is a potent acetylcholinesterase (AChE) inhibitor for AD treatment. In this study, HupA derivatives, huperzil, N-hippurylhuperzine A, pyrrolhuperzine A, maleicamide-huperzine A and phthaleicamide-huperzine A, were synthesized and their in silico computation as the central nervous system (CNS) drug was performed. All derivatives exhibited lower anti-AChE activity than HupA. However, we found other non-cholinergic functions in AD-mimicking models using differentiated SH-SY5Y. HupA and derivatives significantly suppressed the Aβ<sub>25-35</sub> cytotoxicity and showed recovery effects against arsenic- induced AD pathologies including reactive oxygen species generation, neurite outgrowth shortening, amyloid precursor protein suppression and the elevation of β-secretase, endogenous Aβ peptide, and Tau and neurofilament light proteins. In summary, we prepared three potential compounds with dual-AChE cholinergic and non-cholinergic functions. Further development of these compounds will be beneficial for the future use as an alternate compound against AD.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401950"},"PeriodicalIF":3.5,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802169","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}
{"title":"Phosphonocarboxylates in Mixed-Ligated Approach with Diverse Structural Features (0D to 3D), and Studies of Non-Covalent Interactions for Revealed Proton Conduction.","authors":"Syed Meheboob Elahi","doi":"10.1002/asia.202401887","DOIUrl":"https://doi.org/10.1002/asia.202401887","url":null,"abstract":"<p><p>Coordination compounds are an essential group of functional materials with different dimensionalities (0D, 1D, 2D, and 3D) depending on the metal atoms or organic linkers/ligands used. In this study, two different phosphonocarboxylates were combined with 4,4'-bipyridine (bpy) to create mixed-ligated coordination frameworks, resulting in three distinct coordination compounds with different dimensionalities: [Co(H<sub>2</sub>O)<sub>4</sub>(4,4'-bpy)<sub>2</sub>][H<sub>3</sub>L1]<sub>2</sub>∙10H<sub>2</sub>O (1) with 0D, {[Zn(H<sub>2</sub>L1)(4,4'-bpy)]·H<sub>2</sub>O}<sub>n</sub> (2) with 2D, and [Co(H<sub>2</sub>O)Co<sub>2</sub>(H<sub>2</sub>L2)<sub>2</sub>(4,4'-bpy)<sub>3</sub>]<sub>n</sub> (3) with 3D structure. Here, H<sub>4</sub>L1 = 5-Phosphonoisophthalic acid, and H<sub>5</sub>L2 = 3,5-Diphosphonobenzoic acid. Compound 1 had the most guest water molecules connected to the protonated phosphonate moieties and coordinated water molecules, creating extended hydrogen-bonding interactions among these three structures. Thereby, compound 1 was subjected to proton conductivity (PC) measurement, and revealed a PC value of 0.84 × 10<sup>-4</sup> S cm<sup>-1</sup> at 50 °C and 95% relative humidity (RH). A structural correlation was conducted with the previously reported similar guest-framework system, and a single point energy (with counterpoise = 2, basis set superposition error <0.003%) was calculated for the supramolecular architecture formed by the guest organic moiety and lattice water. Furthermore, non-covalent interactions were checked and compared.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401887"},"PeriodicalIF":3.5,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794262","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}
Analia Young Hwa Cho, Matias Carrasco-Bozo, Christian Soto-Piñeira, Christian Silva, Rodrigo Ormazábal-Toledo, Catalina Sandoval-Altamirano, German Gunther
{"title":"Oxazol-Fused Phenalenones: Tuning Fluorescence and Singlet Oxygen Generation with Solvent and Substituent.","authors":"Analia Young Hwa Cho, Matias Carrasco-Bozo, Christian Soto-Piñeira, Christian Silva, Rodrigo Ormazábal-Toledo, Catalina Sandoval-Altamirano, German Gunther","doi":"10.1002/asia.202500060","DOIUrl":"https://doi.org/10.1002/asia.202500060","url":null,"abstract":"<p><p>Typically, singlet oxygen is generated by photosensitization, with 1H-phenalen-1-one (PN) being an efficient photosensitizer that achieves nearly unity quantum yield across various solvents. However, the molecule lacks the ability to fluoresce, which could otherwise provide spatiotemporal information for potential theranostic applications. Moreover, its absorption spectrum should be red-shifted to move toward the visible range, ideally approaching the therapeutic window without compromising ability to generate singlet oxygen. We resolved to explore the option of fusing new aromatic rings to the tricyclic PN structure. A series of 9-substituted 7H-phenaleno[2,1-d]oxazol-7-one were synthesized and characterized. The results indicate that introduction of an oxazole ring does not significantly disturb the efficient photosensitization of the core 1H-phenalen-1-one, as evidenced by 9-methyl-7H-phenaleno[2,1-d]oxazol-7-one) which presented Φ<sub>Δ</sub> near unity across various solvents; albeit it lacked fluorescence. In contrast, aromatic derivatives exhibit a balanced behavior between fluorescence and photosensitization. In polar protic media, fluorescence is preferred, while in apolar media, photosensitization is favored. The substituent effect was analyzed with electron-donating groups favoring non-radiative processes, particularly in polar media. Electron-attracting/neutral groups exhibited a mixed behavior between fluorescence, intersystem crossing (ISC), and non-radiative processes. Theoretical calculations suggest that observed excitation profiles and photochemical behavior correlates with electron density remotion from PN core.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500060"},"PeriodicalIF":3.5,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143794261","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}
{"title":"Enhanced Long-Term Stability of Perovskite Solar Cells Employing a Benzodithiophene Derivative-Based Dopant-Free Hole Transporting Layer.","authors":"Gyuri Yu, Jeonghwan Han, Sanghyun Paek","doi":"10.1002/asia.202500077","DOIUrl":"https://doi.org/10.1002/asia.202500077","url":null,"abstract":"<p><p>Perovskite solar cell (PSC) is characterized by high photoelectric conversion efficiency (PCE) and low material cost compared to the silicon solar cell that has already been commercialized. Many researchers are conducting various studies to improve efficiency and stability. To increase power conversion efficiency, hole transporting materials (HTMs) are one of the most important factors for achieving high performance in PSCs. HTMs exhibit an important role in PSCs to transfer the positive charges in between perovskite and counter electrodes. Among the various HTMs, Spiro-OMeTAD has been widely used in PSCs. However, due to its reliance on additives to enhance hole mobility, Spiro-OMeTAD suffers from degradation issues that compromise its long-term stability. So, it is necessary to develop new HTMs to replace Spiro-OMeTAD for their low stability and expensiveness in future application of PSCs. Therefore, we designed and synthesized the materials named PEH-23 and PEH-24 incorporating dialkoxyphenyl and dialkoxybenzodithiophene. As the conjugation length increases, the material demonstrates improved stability, suggesting its potential as an effective HTM with long-term reliability.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500077"},"PeriodicalIF":3.5,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802097","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}
{"title":"Cover Feature: Endoplasmic Reticulum-Targeting Delayed Fluorescent Probe for Dual-mode Nitroreductase Sensing (Chem. Asian J. 6/2025)","authors":"V. T. K. Shradha, Subhadeep Das, Abhijit Patra","doi":"10.1002/asia.202580603","DOIUrl":"https://doi.org/10.1002/asia.202580603","url":null,"abstract":"<p>The study highlights an innovative approach to developing a highly selective delayed fluorescent probe for the dual-mode detection of a cancer hallmark within the endoplasmic reticulum (ER, depicted as a greenish-blue structure). The ER-specific probe, designed for selective detection of nitroreductase (NTR, shown in orange), is initially in a non-fluorescent state (grey). Upon interacting with NTR, the probe activates, emitting green fluorescence and long-lived emission, enabling intracellular detection through luminescence and time-resolved imaging modes symbolized by clock icons. More details can be found in article number e202401226 by Abhijit Patra and co-workers.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":"20 6","pages":""},"PeriodicalIF":3.5,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/asia.202580603","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143638700","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}