{"title":"Fabrication of Biocompatible Helical Fibers Using an Optical Vortex Beam.","authors":"Kenta Homma, Yoshihisa Matsumoto, Yasushi Tanimoto, Kyoko Masui, Chie Hosokawa, Takashige Omatsu, Michiya Matsusaki","doi":"10.1002/asia.202500361","DOIUrl":"https://doi.org/10.1002/asia.202500361","url":null,"abstract":"<p><p>Helical structures are a fundamental characteristic of biological tissues, yet helical biomaterial scaffolds remain underdeveloped. Optical vortex beams, a unique class of light with helical wavefronts, carry optical angular momentum (OAM). Interestingly, it has been discovered that the OAM of optical vortex beams twists the irradiated photocurable resins to form helical fiber structures. This phenomenon opens up new possibilities that optical vortex beams enable the creation of photopolymerized structures for tissue engineering scaffolds. However, the fabrication of helical fibers formed of biocompatible polymers has not been established yet. In this study, we successfully fabricated helical gel fibers using poly(ethylene glycol) (PEG), a representative biocompatible polymer, through photopolymerization with an optical vortex beam. The helical wavefront of the optical vortex beam enabled the creation of twisted PEG gel microscale fibers with minimal branching, likely due to the OAM transferred to the gel precursors during photopolymerization. In contrast, PEG gel microscale fibers fabricated using a Gaussian beam with a planar wavefront exhibited significant branching. These findings demonstrate the potential of optical vortex beams for fabricating helical structures with biocompatible polymers, offering a promising approach for applications such as helical tissue engineering.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00361"},"PeriodicalIF":3.5,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256948","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":"HFIP-Assisted Relay Proton Transfer Facilitates Conjugate Addition of Amines to Vinyl Heteroarenes.","authors":"Arijit Mahana, Renuka Pradhan, Manas Kumar Sahu, Upakarasamy Lourderaj, Chidambaram Gunanathan","doi":"10.1002/asia.202500548","DOIUrl":"https://doi.org/10.1002/asia.202500548","url":null,"abstract":"<p><p>The Michael addition reaction of diverse acyclic and cyclic secondary amines towards 2-vinyl pyridine and vinyl quinoline was explored, using HFIP as the optimal potent solvent. Using this protocol, drug molecules with hypotensive and antivertigo properties were successfully synthesized, and ciprofloxacin was amenable in the reaction offering a pathway for drug modification. DFT studies reveal the role of HFIP during the solvent-assisted relay proton transfer step, leading to high product yields.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00548"},"PeriodicalIF":3.5,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256949","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}
Yulong Dai, Xinxin Wen, Wenxiao Yu, Xiaoxiao Huang, Jia Liu, Zhe Liu, Bingrong Guo, Yao Xu, Siwei Li
{"title":"Hydrolyzed MOFs-Derived IrO<sub>x</sub>/Co(OH)<sub>2</sub> for Highly Efficient Electrocatalytic Water Splitting.","authors":"Yulong Dai, Xinxin Wen, Wenxiao Yu, Xiaoxiao Huang, Jia Liu, Zhe Liu, Bingrong Guo, Yao Xu, Siwei Li","doi":"10.1002/asia.202500726","DOIUrl":"https://doi.org/10.1002/asia.202500726","url":null,"abstract":"<p><p>Electrocatalytic water splitting is a promising green energy conversion method. However, the high cost and limited availability of noble metals hinder their large-scale application. To enhance the efficiency of noble metal usage, we developed a facile and mild synthesis method for constructing bifunctional electrocatalysts. By using a metal-organic framework (MOF)-derived strategy, we synthesized IrO <sub>x</sub> clusters supported on Co(OH)<sub>2</sub> nanosheets on nickel foam (IrO<sub>x</sub>/Co(OH)<sub>2</sub>/NF). The mild conditions allowed the in situ loading of IrO<sub>x</sub> species without the need for high-temperature treatment. The resulting catalyst exhibits outstanding electrocatalytic performance for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), with a low overpotential of 215 and 36.8 mV, respectively, at 10 mA cm<sup>-2</sup>. Moreover, it maintains excellent stability, with negligible activity degradation observed over 500 h of OER, 200 h of HER, and 100 h of overall water splitting. This work provides a simple, effective strategy for synthesizing supported cluster catalysts with outstanding catalytic performance and stability in overall water splitting.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00726"},"PeriodicalIF":3.5,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256950","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}
Yi Wang, Le Liu, Yutao Rao, Ling Xu, Mingbo Zhou, Bangshao Yin, Atsuhiro Osuka, Jianxin Song
{"title":"m-Pyrenisubporphyrins and Their B<sup>III</sup> Complexes and Reduced Congeners.","authors":"Yi Wang, Le Liu, Yutao Rao, Ling Xu, Mingbo Zhou, Bangshao Yin, Atsuhiro Osuka, Jianxin Song","doi":"10.1002/asia.202500693","DOIUrl":"https://doi.org/10.1002/asia.202500693","url":null,"abstract":"<p><p>m-Pyrenisubporphyrins were synthesized by Pd-catalyzed cross-coupling of α,α'-diboryl-m-pyrenitripyrrane with 9,10-bis(1,1-dibromomethylenyl)anthracene followed by oxidation with DDQ. Reaction of the m-pyrenisubporphyrin with BBr<sub>3</sub> and triethylamine gave a B-hydroxy complex and an oxygen-atom-inserted product. Reaction of the m-pyrenisubporphyrin with PhBCl<sub>2</sub> and triethylamine gave a B-phenyl complex. These m-pyrenisubporphyrins show red-shifted absorption bands, reflecting the incorporated pyrene segment, but are all nonaromatic. Reduction of m-pyrenisubporphyrin with p-tosylhydrazide and K<sub>2</sub>CO<sub>3</sub> gave m-pyrenisubchlorin and m-pyrenisubbacteriochlorin, depending upon the reaction conditions. These reduced products have also been shown to be nonaromatic by the low-field shifted chemical shifts of the inner pyrrolic protons, broad and non-structured absorption bands, and small NICS values.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00693"},"PeriodicalIF":3.5,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256953","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 and Characterization of New Hydrolytic Resistant Antibacterial Pyridinium and N-Alkyl Ammonium-Containing Methacrylamides for Dental Resin Adhesives.","authors":"Arthit Pikulngam, Supitcha Talungchit, Somjin Ratanasathien, Piangkwan Saiprasert, Prompat Promphet, Chittreeya Tansakul","doi":"10.1002/asia.202401643","DOIUrl":"https://doi.org/10.1002/asia.202401643","url":null,"abstract":"<p><p>Resin-based composites have relatively short lifetime mainly attributed to hydrolytic and enzymatic degradation of easily hydrolyzed methacrylates in the dental resin adhesive. To address these problems, a series of antibacterial and hydrolytic resistant methacrylamide monomers containing quaternary ammonium salts and long alkyl chains, MAPs, MADAs, and BMADPB were synthesized. Synthesized methacrylamides exhibited antibacterial activities against S. mutans and E. faecalis. Factors that affect the antibacterial activities are intermolecular hydrogen bonding and alkyl chain length. Some synthesized methacrylamides expressed equal or lower cytotoxic activities against mouse dental papilla cell lines than those of bis-GMA and MDPB, common methacylates used in dental resin adhesives. Degree of conversion at 30 s, the clinically relevant exposure time for tooth restoration, of methacrylamides (51%-83%) were lower than that of the reference antibacterial methacrylate, MDPB (98%) due to lower reactivity of methacrylamide compared with methacrylate. Addition of selected methacrylamides in the resins remarkably improved flexural modulus after water storage. Hydrolysis experiment in acidic condition of the synthesized monomers and their corresponding polymers proved their hydrolytic stability. Antibacterial activities, cell viability, mechanical strength, and hydrolytic stability of new methacrylamides represent alternative antibacterial and durable monomers for resin adhesives.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e01643"},"PeriodicalIF":3.5,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256960","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":"Design of Chirality-Controlled Ketorolac-Peptide Conjugates for Selective COX-2 Inhibition and Localized Drug Release.","authors":"Srinivasa Rao Nelli, Yue-Ming Xing, Satish Kumar Talloj, Abdelreheem Abdelfatah Saddik, Mohiuddin Mohammed, Mei-Yu Yeh, Hsin-Chieh Lin","doi":"10.1002/asia.202500189","DOIUrl":"https://doi.org/10.1002/asia.202500189","url":null,"abstract":"<p><p>Ketorolac (Ket), a widely used nonsteroidal anti-inflammatory drug (NSAID), alleviates pain and inflammation in chronic diseases by inhibiting cyclooxygenase (COX) enzymes. However, its non-selectivity for COX-1 and COX-2 often leads to adverse effects. In this study, a series of Ket-tripeptide conjugates with controlled chirality were synthesized and systematically analyzed to enhance COX-2 selectivity. These amphiphilic Ket-capped peptides self-assemble in water, forming supramolecular hydrogels at pH 7.0 that showed drug-release properties. Among them, Ket-Gly-<sub>D</sub>-Phe-<sub>D</sub>-Phe demonstrated significantly higher selectivity for COX-2, an enzyme upregulated during inflammation. While Ketorolac and most Ket-peptides in this study exhibited a COX-2/COX-1 ratio below 1, Ket-Gly-<sub>D</sub>-Phe-<sub>D</sub>-Phe achieved a remarkable COX-2/COX-1 ratio of 5.8. This result underscores the critical role of chirality control in improving COX-2 selectivity, offering a promising strategy to develop safer and more effective anti-inflammatory therapeutics. The findings suggest that supramolecular hydrogels of Ket-Gly-<sub>D</sub>-Phe-<sub>D</sub>-Phe could serve as potential candidates for topical and drug-release applications, minimizing systemic toxicity while maximizing therapeutic efficacy.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00189"},"PeriodicalIF":3.5,"publicationDate":"2025-06-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144245438","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}
Surajit Das, Jayanta Bag, Sayan Sarkar, Anindita Das, Kuntal Pal
{"title":"Influence of the Ligand's Electronic Effect on iClick Reaction of Ni(II)-Azido Complexes with Alkynes: Synthesis, Structure, Characterization, and Kinetic Studies.","authors":"Surajit Das, Jayanta Bag, Sayan Sarkar, Anindita Das, Kuntal Pal","doi":"10.1002/asia.202500597","DOIUrl":"https://doi.org/10.1002/asia.202500597","url":null,"abstract":"<p><p>The synthesis and characterization of two new square planer Ni(II)-azido complexes [Ni(N<sub>3</sub>)(L)]<sup>-1</sup> of 1-N<sub>3</sub> and 2-N<sub>3</sub> using electronically varied N/S/O donor tridentate ligands (where H<sub>2</sub>L<sup>OMe</sup>: (E)-2-(((2-mercaptophenyl)imino)methyl)-6-methoxyphenol), H<sub>2</sub>L<sup>t</sup> <sup>Bu</sup>: (E)-2,4-di-tert-butyl-6-(((2-mercaptophenyl)imino)methyl)phenol) were reported. Azido moiety in Ni-azido complexes was found as more dipolar than free azide ion. Six number of [3+2] cycloaddition coupling product of 1-N<sub>3</sub>/2-N<sub>3</sub> and three different alkynes were isolated and well characterized as [Ni(triazolate)(L)]<sup>-1</sup> (1<sup>/</sup> <sup>t</sup> <sup>Bu</sup>-T) complexes. In triazolate complexes originated from terminal alkyne, the triazolate ligand was coordinated via the N1-T atom whose (1-T<sup>2</sup>) crystal structure was presented. The triazolato products of symmetrical and unsymmetrical nonterminal alkynes were isolated as N2-T mode of binding. The conversion of N1-T/N3-T to N2-T as well as the stability in a particular mode of binding was proposed as thermal control of their equilibrium based on the variable temperature <sup>19</sup>F NMR studies on 1-T<sup>3</sup>/2-T<sup>3</sup>. The detail kinetic studies resulted that the reaction with methyl propiolate follows zero-order rate law, whereas other two alkynes showed first-order rate. Mostly, the electron-poor ethyl-4,4,4-trifluorobut-2-ynoate always react faster than dimethyl but-2-ynedioate, and Ni(II)-azido complex with L<sup>t</sup> <sup>Bu</sup> ligated always react with a particular alkyne in a faster rate than the same of L<sup>OMe</sup>.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00597"},"PeriodicalIF":3.5,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232801","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":"Kinetic Network Models to Elucidate the Kinetic-Controlled Molecular Assembly Processes.","authors":"Lingyu Zhang, Yijia Wang, Xiaoyan Zheng","doi":"10.1002/asia.202500283","DOIUrl":"https://doi.org/10.1002/asia.202500283","url":null,"abstract":"<p><p>Organic molecular assembly is a fundamental protocol for constructing organic functional materials at time and length scales beyond individual molecules. Following a bottom-up strategy, organic nanostructures with diverse morphologies and specific functionalities could be obtained. However, the flexible conformations and the cooperative interplay of different noncovalent interactions, lead to countless kinetically metastable states and make the precise prediction of assembled nanostructures extremely challenging. In this review, the theoretical backgrounds and a general theoretical protocol of kinetic network models (KNMs) are first introduced. Then, the molecular assembly mechanism and its regulation are presented for various molecular assembly systems ranging from small molecules (e.g., surfactants, lipids, metal complexes, and ice nuclei) to block copolymers and patchy particles, and further to peptides. For each assembly system, the distribution of metastable structures and the kinetically assembled pathways of the assembly process, as well as the relationship between kinetic pathways preferences and the finally assembled nanostructures are presented. Therefore, it is crucial for a deeper understanding of assembly mechanism and it paves an effective way for the precise control of assembled nanostructures kinetically, which benefits the fabrication of advanced organic functional materials.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00283"},"PeriodicalIF":3.5,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232802","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}
Wenhao Zhao, Shifu Wang, El Mehdi Chatir, Xuning Li, Yanqiang Huang
{"title":"Design Principles of Single-Atom Catalysts for Electrocatalytic CO<sub>2</sub> Reduction to High-Value Hydrocarbons.","authors":"Wenhao Zhao, Shifu Wang, El Mehdi Chatir, Xuning Li, Yanqiang Huang","doi":"10.1002/asia.202500545","DOIUrl":"https://doi.org/10.1002/asia.202500545","url":null,"abstract":"<p><p>The CO<sub>2</sub> electrochemical reduction (CO<sub>2</sub>RR) is regarded as a promising approach to mitigate carbon emissions while producing valuable chemical feedstocks and fuels. Among the possible products, multi-carbon (C<sub>2+</sub>) compounds such as ethylene and ethanol are highly desirable due to their higher energy density and industrial relevance. Recently, single-atom catalysts (SACs) have emerged as a powerful class of electrocatalysts in CO<sub>2</sub>RR, offering high atomic efficiency and tunable active sites. However, challenges such as sluggish C─C coupling kinetics, dynamic evolution of the catalytic sites, limited understanding of reaction mechanism, and difficulties at controlling product selectivity hinder their further development for large-scale application. Hence, this review explores the underlying mechanisms for CO<sub>2</sub> to C<sub>2+</sub> product conversion, emphasizing catalyst design strategies to enhance C─C coupling efficiency and selectivity. Furthermore, recent advances in in situ characterization techniques that provide atomic-level insights into reaction intermediates and active site evolution are discussed. Finally, the potential of machine learning approaches in accelerating catalysts discovery by optimizing SACs structures, identifying key design parameters, and predicting catalytic performance is highlighted. Overall, this study aims to provide a comprehensive reference for the rational design of SACs for effective and selective CO<sub>2</sub> conversion into C<sub>2</sub> products.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00545"},"PeriodicalIF":3.5,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232799","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":"Sucrose-Derived Functionalized Layer Carbon with Excellent Proton Conductive Properties.","authors":"Xinyao Liu, Md Saidul Islam, Lutfia Isna Ardhayanti, Shakiba Salehpour, Yoshihiro Sekine, Shinya Hayami","doi":"10.1002/asia.202500288","DOIUrl":"https://doi.org/10.1002/asia.202500288","url":null,"abstract":"<p><p>Sucrose-derived layered carbon materials hold promise for energy storage applications, but their synthesis is challenging due to sucrose's molecular structure and pyrolysis behavior. This work demonstrates the successful synthesis of layered carbon from sucrose using FeCl₃ as a catalyst. The resulting layered carbon was then functionalized via Hummer's oxidation and Fenton reaction methods to enhance proton conductivity. Characterization by SEM, FTIR, and XPS confirmed the layered structure and the presence of oxygenated functional groups after oxidation. Electrochemical measurements revealed significantly improved proton conductivity, with the Fenton-modified layered carbon exhibiting the highest conductivity of 3.27 × 10<sup>-</sup> <sup>3</sup> S cm<sup>-</sup>¹ in the in-plane direction at 90% relative humidity and 55 °C. These results suggest the potential of this sucrose-derived, functionalized layered carbon material for use in advanced energy storage technologies.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500288"},"PeriodicalIF":3.5,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232803","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}