Sain Singh, Rajat Saini, Virendra Kumar Chaudhary, Kaushik Ghosh
{"title":"Organometallic Ru(III) Catalysts for α-Alkylation of Carbonyl Compounds using Alcohols: Mechanistic Insights via Detection of Key Intermediates.","authors":"Sain Singh, Rajat Saini, Virendra Kumar Chaudhary, Kaushik Ghosh","doi":"10.1002/asia.202400811","DOIUrl":"https://doi.org/10.1002/asia.202400811","url":null,"abstract":"<p><p>Three novel cyclometalated ruthenium complexes ([Ru.L(9)] [Ru.L(10)] and [Ru.L(11)]) featuring azo functionalities were synthesized and characterized using a variety of spectroscopic techniques, namely FT-IR, electronic absorption spectroscopy, and ESI-MS. Representative solid-state structures of the acquired complexes were determined through X-ray crystallography. These complexes were evidenced to be efficient catalysts for the synthesis of various α-alkylated compounds utilizing simple acetophenone derivatives with easily affordable and economically viable alcohols, which were isolated and characterized via 1H and 13C NMR spectroscopy. The optimum reaction conditions were found by employing toluene as solvent, potassium tert-butoxide as base at 115 oC temperature utilizing 0.8 mol% of catalyst [Ru.L(10)]. The yield of the desired compounds found to be in the range of 83 - 97%. Additionally, mass spectrometry provided insights into the in-situ generated ruthenium hydride and ruthenium alkoxy intermediates, shedding light on the catalytic mechanism.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400811"},"PeriodicalIF":3.5,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556517","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}
Md Badirujjaman, Rajkumar P Thummer, Krishna P Bhabak
{"title":"Esterase-Responsive Self-Immolative Prodrugs for the Sustained Delivery of the Anticancer Drug 5-Fluorouracil with Turn-On Fluorescence.","authors":"Md Badirujjaman, Rajkumar P Thummer, Krishna P Bhabak","doi":"10.1002/asia.202400846","DOIUrl":"10.1002/asia.202400846","url":null,"abstract":"<p><p>Stimuli-responsive prodrugs of anticancer drugs are advantageous for the selective delivery of drugs to cancer cells with minimized off-target side effects. In the present study, esterase-activatable fluorogenic prodrugs of the chemotherapeutic drug 5-fluorouracil (5-FU) have been rationally designed and synthesized using multi-step organic synthesis. While 5-FU was connected directly with the fluorophore via a C-N bond in the prodrug BJ-50, an additional self-immolative benzylic spacer with a carbonate linker was incorporated in the prodrug BJ-92. Although absorption and emission spectroscopic studies revealed the activation of both the prodrugs by porcine liver esterase (PLE), reverse-phase HPLC studies confirmed the inability of BJ-50 to release the active drug 5-FU. In contrast, a sustained release of 5-FU and Cou-OH was observed from BJ-92 in the presence of PLE. The endogenous esterase-mediated activation of the prodrug BJ-92 was validated by the turn-on fluorescence in A549 cells and the anti-proliferative activities in A549, and HEK-293 cells. Modulation of the expression of a few cancer marker proteins by BJ-92 and 5-FU was studied to evaluate their anticancer activities. As esterases are overexpressed in cancer cells, the prodrug in the present study would be helpful in selectively delivering 5-FU to cancer cells with reduced off-target side-effects.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400846"},"PeriodicalIF":3.5,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556516","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}
Zhongdong Tian, Yuan Gao, Peishu Tian, Silong Tian, Fengwei Shi, Jun Mei
{"title":"Polymer Electrolytes with High Ionic Conductivities at Freezing Temperature for Aqueous Hybrid Batteries.","authors":"Zhongdong Tian, Yuan Gao, Peishu Tian, Silong Tian, Fengwei Shi, Jun Mei","doi":"10.1002/asia.202401110","DOIUrl":"10.1002/asia.202401110","url":null,"abstract":"<p><p>Rechargeable and flexible aqueous batteries (ABs) have emerged as one of promising energy devices which is primarily due to the safety, environmental friendliness and economic efficiency. However, because of the freezing behavior of aqueous electrolytes, most ABs possess poor performance when the working temperature drops below zero. To solve this problem, a gel polymer electrolyte (GPE) with high ionic conductivity (IC) and frost-resistance is designed for aqueous Zn-Li hybrid batteries by a biomass-based polymers complex consisting of carboxyl modified sodium alginate (SA) and zwitterionic betaine (BA). Introducing iminodiacetic acid to enrich -COOH groups along the SA main chains could improve IC of the prepared GPEs to 41.27 and 20.96 mS cm<sup>-1</sup> at 20 and -20 °C, respectively. At -20 °C, the discharge capacity of the resultant cell is two times higher than that of the liquid electrolyte-based cell, and the cell presents a capacity retention of 91.6 % after 300 charge/discharge cycles at 1 C. This proposed strategy greatly improve the IC of GPEs at freezing temperature, which is expected to broaden the practical application of GPEs in wide range of temperature.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401110"},"PeriodicalIF":4.3,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142563338","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}
Xi-Yang Yu, Xue Su, Meng-Jia Xi, Zheng-Qing Huang, Chun-Ran Chang
{"title":"Natural Surface Frustrated Lewis Pairs: The Concept and Beyond.","authors":"Xi-Yang Yu, Xue Su, Meng-Jia Xi, Zheng-Qing Huang, Chun-Ran Chang","doi":"10.1002/asia.202401155","DOIUrl":"10.1002/asia.202401155","url":null,"abstract":"<p><p>The reusable and separable surface frustrated Lewis pairs (SFLPs) open up a novel approach to efficient small-molecule activation and conversion in heterogeneous catalysis. However, SFLPs have only been reported on limited systems due to the difficulty in the design and synthesis process. The inherent Lewis pairs on various solid materials offer promising opportunities for finding natural SFLPs, providing a straightforward and efficient strategy to overcome the current limitations. In this concept, we retrospect the concept of natural SFLPs proposed on wurtzite crystal surfaces and identify other natural SFLPs that probably exist on solid materials, including reduced oxide surfaces, corrugated graphene, and perovskite quantum dots. Having focused on the reactivity of natural SFLPs in small-molecule activation, we discuss the current challenges, propose possible research directions, and highlight potential applications of natural SFLPs in heterogeneous catalysis.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401155"},"PeriodicalIF":3.5,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542245","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":"A Fluorescent Probe with Large Stokes Shift Based on Benzothiadiazole Scaffolds for Selective Detection of Hg<sup>2+</sup> in Lysosomes and Its Application in Biological Imaging.","authors":"Lin Wang, Ning Zhang, Yuan He, Jian-Yong Wang","doi":"10.1002/asia.202401067","DOIUrl":"10.1002/asia.202401067","url":null,"abstract":"<p><p>Mercury is highly toxic, and appropriate amounts of the mercury-selenium complex can protect plasma. However, when excessive mercury (II) ions (Hg<sup>2+</sup>) are exposed to human skin or ingested directly, it can lead to irreversible accumulation in the body. Therefore, detecting the presence of Hg<sup>2+</sup> in cells is important. A novel fluorescent probe BTD-Hg-Lyso was designed and constructed based on the intramolecular charge transfer mechanism. Thiotaldehyde could specifically recognize Hg<sup>2+</sup> so that the probe could produce a fluorescence enhancement effect. In addition, the fluorescent probe BTD-Hg-Lyso exhibited the advantages of large Stokes shift (210 nm) and good selectivity. More importantly, the probe BTD-Hg-Lyso could be used for the determination of Hg<sup>2+</sup> in cellular lysosomes. BTD-Hg-Lyso was able to image Hg<sup>2+</sup> in HeLa cells, zebrafish, and tobacco seedlings (rhizome and stem) successfully.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401067"},"PeriodicalIF":3.5,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556515","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 Catalyzed Growth of Carbon Nanotube with Asphalt Cladding as a Bicarbon Synergistic Framework of Silicon Anodes for Lithium-ion Batteries.","authors":"Yiming Liu, Jianzheng Duan, Pengfei Chen, Peihua Li, Wanggang Zhang, Xiaohong Li, Jian Wang","doi":"10.1002/asia.202400838","DOIUrl":"10.1002/asia.202400838","url":null,"abstract":"<p><p>Silicon, as the most promising advanced anode material for lithium-ion batteries, faces challenges in large-scale industrial production due to the significant volume expansion effect. In this investigation, Si/CNTs/C composite materials were effectively produced through high-temperature carbonization utilizing asphalt, silicon, hexahydrate ferric chloride, and melamine as primary elements. The distinctive dual-carbon framework of asphalt-derived carbon and carbon nanotubes alleviates the volume expansion of silicon, thereby stabilizing the composite material's structure. Testing the electrochemical performance reveals that the Si/CNTs/C composite material exhibits a reversible specific capacity of 1187 mAh g<sup>-1</sup> with a capacity retention rate of 92.6 % after 150 cycles at a current density of 0.2 A g<sup>-1</sup>. Even after 500 cycles at a current density of 1 A g<sup>-1</sup>, it sustains a specific capacity of 879.4 mAh g<sup>-1</sup> with a capacity retention rate of 87.9 %, showcasing outstanding electrochemical performance.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400838"},"PeriodicalIF":3.5,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542243","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 and Development of Infiltration Resins: From Base Monomer Structure to Resin Properties.","authors":"Shuo Yang, Ting Zhao, Xiaoqiu Liu, Haibo Zhang, Bo Yang, Zheng Chen","doi":"10.1002/asia.202401157","DOIUrl":"10.1002/asia.202401157","url":null,"abstract":"<p><p>The resin infiltration concept is one of the most widely used minimally invasive restorative techniques in restorative dentistry with the most outstanding therapeutic effect, and it is also one of the key research directions in restorative dentistry. \"Infiltration resin\" is the specialty restorative material for the technology, which is the key factor to success. The specialized restorative material is commonly known as \"infiltrant/infiltration resins\" \"resins infiltrant\" \"infiltrant\" or \"resins,\" which will be consistently referred to as \"infiltration resins\" throughout the article. The paper aims to provide a comprehensive overview of infiltration resins by introducing the development of their therapeutic mechanisms, basic components, current challenges, and future trends, Based on existing literature, we analyze and compare how changes in the base monomer's structure and ratio affect the effectiveness of infiltration resins, from the material's structure-effective relationship. After compiling the information, the existing solution strategies have been listed to offer substantial support and guidance for future research endeavors.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401157"},"PeriodicalIF":3.5,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542242","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":"Low-valent Main-group Catalysis Under Ambient Conditions Using a Germylene Cation*.","authors":"Hemant Kumar, Pritam Mahawar, Purva Dua, Vivek Kumar Singh, Pratima Shukla, Prakash Chandra Joshi, Gopalan Rajaraman, Selvarajan Nagendran","doi":"10.1002/asia.202400692","DOIUrl":"https://doi.org/10.1002/asia.202400692","url":null,"abstract":"<p><p>Catalysis using low-valent main-group compounds is usually done under inert conditions; no example of such catalysis has been doable entirely in ambient conditions until now. This aspect is addressed in this work through an air- and water-stable germylene cation ([DPMGe][(OH)B(C6F5)3] (2) (DPM = dipyrromethene); it efficiently catalyzes aldehyde and ketone hydrosilylations under ambient conditions. Detailed theoretical studies reveal that compound 2's stability is bolstered by the interaction between the anion and germanium's frontier orbitals. However, the detachment of the anion (in the solution) alters the capability of compound 2 to render exceptional catalytic efficiency. Compound 2 was synthesized under ambient conditions by the equimolar reaction of DPMGeOH (1) with B(C6F5)3.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400692"},"PeriodicalIF":3.5,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542244","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":"Visible Light-Driven Metal- and Photocatalyst-Free Synthesis of β-Trifluoromethylated Enamines via Trifluoromethyl Thianthrenium Salts.","authors":"Liang Jiang, Yisong Tang, Shaxuan Li, Xing Peng, Rim Saffar Andaloussi, Xiao Yun Chen","doi":"10.1002/asia.202401129","DOIUrl":"10.1002/asia.202401129","url":null,"abstract":"<p><p>A novel protocol for the visible-light-driven synthesis of β-trifluoromethylated enamines has been developed, which operates without the use of transition metals or any photocatalysts, utilizing trifluoromethylthiosulfonium salts as the source of trifluoromethyl groups under mild conditions. According to this new protocol, more than 40 products have been prepared in moderate to good yields. In addition to eliminating the need for expensive or toxic transition metals and photocatalysts, this new methodology proves its potential scalability through air-stability, the use of safe and readily available reagents, a two-step one-pot procedure, and effective gram-scale reactions. This innovative approach not only demonstrates promise for green chemical synthesis but also offers a new pathway for the advancement of fluorine chemistry in sustainable organic synthesis.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401129"},"PeriodicalIF":4.3,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142520499","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}
Ana L A Simões, Lílian A de Carvalho, Rochel M Lago, Célia M Ronconi, Sara S Vieira, Maria H Araujo
{"title":"3D Graphene-like Carbon Structures from Poly(Acrylic Acid): A Novel Synthetic Route.","authors":"Ana L A Simões, Lílian A de Carvalho, Rochel M Lago, Célia M Ronconi, Sara S Vieira, Maria H Araujo","doi":"10.1002/asia.202400832","DOIUrl":"https://doi.org/10.1002/asia.202400832","url":null,"abstract":"<p><p>Emerging contaminants, such as the hormone 17α-ethynylestradiol (EE), in aquatic environments pose a serious risk to both human and environmental health, making efficient removal essential. This study evaluated the effectiveness of three-dimensional porous carbon structures derived from poly(acrylic acid) (PAAc, Carbopol 990) as adsorbents for removing EE from aqueous solutions. Activated carbon materials were prepared using varying ratios of KOH as an activating agent (PAAc:KOH; 1:0 AAC, 1:1 AC1, 1:2 AC2, and 1:3 AC3). Adsorption tests were conducted by adding 10 mg of the adsorbent to 40 mL of an EE solution (100 ppm, 20% acetonitrile in water). Analyses including TGA, XRD, and Raman spectroscopy were performed to evaluate the materials' structural properties and adsorption capacities. Among the materials, AC3 exhibited the highest adsorption capacity for EE (238 mg g-1), followed by AC2 (153 mg g-1) and AC1 (82 mg g-1). The superior efficiency of AC3 can be attributed to its larger surface area and pore volume, enabling greater interaction with EE molecules. These materials demonstrated higher adsorption capacities compared to commercial activated carbons and single-walled carbon nanotubes. This work opens new possibilities for developing efficient adsorbents, contributing to more effective and sustainable solutions for water purification and environmental protection.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400832"},"PeriodicalIF":3.5,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542241","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}