{"title":"Enhanced Photoluminescence Emission and Thermal Stability in Pt<sub>1</sub>Ag<sub>31</sub> nanocluster from Introduced Secondary Phosphine Oxide Functionalized ligand.","authors":"Zhuoyuan Li, Chuanjun Zhou, Kaiyang Kuang, Jiahao Liu, Shuang Chen, Shan Jin, Manzhou Zhu","doi":"10.1002/asia.202401819","DOIUrl":"10.1002/asia.202401819","url":null,"abstract":"<p><p>Surface ligands significantly influence the optical properties and stability of metal nanoclusters. In this study, we synthesized [Pt<sub>1</sub>Ag<sub>31</sub>(S-Adm)<sub>16</sub>(DPPM)<sub>3</sub>(DPPMO)Cl<sub>3</sub>](SbF<sub>6</sub>)<sub>4</sub> (Pt<sub>1</sub>Ag<sub>31</sub>-DPPMO). Compared to [Pt<sub>1</sub>Ag<sub>31</sub>(S-Adm)<sub>16</sub>(DPPM)<sub>3</sub>Cl<sub>3</sub>](SbF<sub>6</sub>)<sub>4</sub> (Pt<sub>1</sub>Ag<sub>31</sub>), the introduction of secondary phosphine oxide ligand, DPPMO, results in Pt<sub>1</sub>Ag<sub>31</sub>-DPPMO exhibiting enhanced photoluminescent properties in both solution and solid states, as well as improved stability and electron-withdrawing ability. This work presents a novel strategy to regulate the properties of metal nanoclusters, especially enhancing photoluminescence performance and stability, through the incorporation of secondary phosphine oxide ligand.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401819"},"PeriodicalIF":3.5,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143583915","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":"Intramolecular Diels-Alder Reaction of Benzo-Tethered Dienyl Cinnamates: Synthesis of the Tricyclic Core of Morusalisin A.","authors":"Poramate Songthammawat, Kasam Poonswat, Pisit Nithijarasrawee, Poonsakdi Ploypradith, Somsak Ruchirawat","doi":"10.1002/asia.202500258","DOIUrl":"10.1002/asia.202500258","url":null,"abstract":"<p><p>Herein, a three-step general strategy featuring a thermal intramolecular Diels-Alder (IMDA) reaction to prepare the tricyclic 9-methyl-7-aryl-tetrahydro-6H-benzo[c]chromen-6-one core of morusalisin A is reported. This developed chemistry is applicable to the synthesis of a variety of tricycles, including 9-silyloxy and 9-phenyl-7-aryl-tetrahydro-6H-benzo[c]chromen-6-ones. In addition, a one-pot dehydration/IMDA procedure was demonstrated. The positioning of substituents on the aryldiene moiety played a significant role in governing the endo/exo selectivity, while the overall yield and reaction rate were affected by the electronic properties of both cinnamates and aryldienes. Functional group manipulations of the resulting cycloadducts were performed to furnish synthetically useful derivatives.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500258"},"PeriodicalIF":3.5,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143583916","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":"Development of a Biodegradable BODIPY-ε-Caprolactone System for Rapid Colorimetric Detection of Fluoride Ions in Environmental Samples.","authors":"Chandan Kumar, Sangita Rajwar, Raja Shunmugam","doi":"10.1002/asia.202500383","DOIUrl":"10.1002/asia.202500383","url":null,"abstract":"<p><p>Fluoride ions (F<sup>-</sup>) are well-known for their beneficial effects on oral health and their involvement in acting osteoporosis. But it is crucial to understand that consuming too much fluoride can of several adverse health effects. Dental fluorosis, urolithiasis, and even cancer can result from excessive fluoride exposure. This is why monitoring fluoride levels is so important. A 2,4-dinitrophenyl hydrazine derivative of a BODIPY-based aldehyde system (BDNP) is a sensitive, ratiometric, and selective naked-eye sensor that we have developed for the quick detection of fluoride ions in biological and environment samples showed a significant color change from pink-to-grey and a significant redshift in absorbance maxima when interacting with fluoride ions. The notable color shift demonstrates the effectiveness of both BDNP and Poly-BDNP in detecting fluoride ions. Interestingly, here we also showed that the ring-opening polymerization (ROP) technique-synthesized biodegradable and biocompatible ε-Caprolactone homopolymer of BDNP (Poly-BDNP) is a great system that can detect fluoride ions colorimetrically with a higher limit of detection (LOD) value than the monomer and rapid detection ability. Using the UV-visible spectroscopy study and the <sup>1</sup>H NMR spectroscopic titration technique, the interaction between BDNP and fluoride ions was examined. It was determined that the deprotonation of N-H protons triggers the intermolecular charge transfer (ICT) reaction, which results in the system's dramatic color change. The precision of both BDNP and Poly-BDNP in detecting F<sup>-</sup> ions with LOD values of 7.73 µM and 87.9 nM, respectively, is determined by the ratiometric absorbance change of the sensor during the sensing process.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500383"},"PeriodicalIF":3.5,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143583913","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 Charge Transportation in Type II WO<sub>3</sub>/ZnWO<sub>4</sub> Nanoflakes for Boosting Saline Water-splitting Reaction.","authors":"Prashant Choubey, Ritu Verma, Mrinmoyee Basu","doi":"10.1002/asia.202500292","DOIUrl":"10.1002/asia.202500292","url":null,"abstract":"<p><p>Photoelectrochemical (PEC) water-splitting is an energy-efficient and eco-friendly technique to produce green hydrogen (H<sub>2</sub>). Here, WO<sub>3</sub> is synthesized for saline water-splitting reaction. Initially, the activity of WO<sub>3</sub> is enhanced through morphology tuning. Nanoparticles (NPs), thick nanosheets (TSs), and nanoflakes (NFs) of WO<sub>3</sub> are synthesized, and their PEC activity is determined. The NFs show a photocurrent density of 1.53 mA/cm<sup>2</sup> at 1.2 V vs. Ag/AgCl, whereas TSs and NPs can generate 1.17 mA/cm<sup>2</sup> and 1.07 mA/cm<sup>2</sup> at 1.2 V vs. Ag/AgCl, respectively. The low charge transportation rate inhibits the PEC performance of these NFs in water-splitting reactions. To mitigate this problem, the type-II heterojunction is constructed with optimized deposition of ZnWO<sub>4</sub> on WO<sub>3,</sub> which favors the migration of charge-carriers in opposite directions, facilitating the charge-carrier separation and eventually enhancing the PEC activity. The optimized heterojunction shows a photocurrent density 1.5 times greater than bare WO<sub>3</sub> and 2.4 times enhanced carrier density, 2.16×10<sup>21</sup> cm<sup>-3</sup>. The heterostructure's rapid OCP decay and higher charge injection efficiency indicate an improved charge transport capability, the primary driving force for enhanced PEC activity. The stability of WO<sub>3</sub>/ZnWO<sub>4</sub> is studied for one hour.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500292"},"PeriodicalIF":3.5,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143583914","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":"Exploration into the Synthesis and Sodium Storage Characteristics of Hard Carbon Derived from Plastics.","authors":"Shuai Ruan, Xinping He, Hui Huang, Yongping Gan, Yang Xia, Jun Zhang, Fangfang Tu, Jiayuan Xiang, Wangjun Wan, Chen Wang, Xinhui Xia, Wenkui Zhang","doi":"10.1002/asia.202401804","DOIUrl":"10.1002/asia.202401804","url":null,"abstract":"<p><p>The crux for the advancement of high-performance sodium-ion batteries resides in the development of low-cost, high-performance hard carbon anode materials. In this study, waste plastics are utilized as precursors to prepare plastic-derived hard carbon materials through a simple high-temperature one-step carbonization method, which is particularly suitable for new energy storage devices such as sodium-ion batteries and supercapacitors. Through in-depth exploration, we discover that the initial coulombic efficiency of hard carbon is intimately associated with its structure, within which the PU material exhibits the attributes of high capacity, initial coulombic efficiency, and excellent cycle performance, meriting further optimization of hard carbon precursor materials. In this study, a novel idea of preparing a high-performance hard carbon anode by a low-carbon and environmentally friendly method is proposed, and the key factors influencing the electrochemical performance of hard carbon materials are revealed, providing a valuable experimental basis for the further development of sodium anodes.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401804"},"PeriodicalIF":3.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143571791","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-Induced Energy Transfer Mediated Regioselective C-3 Thiolation of Imidazoheterocycles using Bunte Salts.","authors":"Sehdev Kumar, Anoop Sharma, Raman Kumar, Anuj Sharma","doi":"10.1002/asia.202401875","DOIUrl":"https://doi.org/10.1002/asia.202401875","url":null,"abstract":"<p><p>An external-photocatalyst-free visible light-induced regioselective C-3 sulfenylation of imidazo[1,2-a]pyridines using Bunte salts has been accomplished via C(sp2)-H functionalization. This protocol allows the coupling of a wide range of imidazoheterocycles with alkyl-, benzyl-, and aryl Bunte salts under ambient air as the sole oxidant. The radical scavenging, UV-visible spectroscopic studies, and Stern‒Volmer experiments revealed that the reaction occurs through energy transfer followed by a radical SET pathway. In this work, the dual role of imidazopyridines as photoexciting species and as energy transfer vehicle is proposed. Activation of the triplet oxygen as a result of energy transfer, which acts on somophlic Bunte salts to generate thiyl radical, eventually resulting in the C(sp2)-H functionalization.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401875"},"PeriodicalIF":3.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143575608","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}
José Leonardo Gómez Chávez, Matías Orlando Miranda, Emilio Luis Angelina, Silvana Carina Pamies, Nélida María Peruchena, Andre Nicolai Petelski
{"title":"Supramolecular Polymers of Amino Triazines vs. Amino Pyrimidines in Aqueous Solution: How Key Interactions Control their Thermodynamic Stability.","authors":"José Leonardo Gómez Chávez, Matías Orlando Miranda, Emilio Luis Angelina, Silvana Carina Pamies, Nélida María Peruchena, Andre Nicolai Petelski","doi":"10.1002/asia.202401905","DOIUrl":"https://doi.org/10.1002/asia.202401905","url":null,"abstract":"<p><p>Supramolecular polymers (SPs) based on the stacking of hydrogen-bonded rosettes are attracting increasing attention due to their potential applications as soft materials. However, a detailed description of the interactions that give rise to these one-dimensional architectures is still scarce in the literature. In this work, we use molecular dynamics to analyze in aqueous solution the stability of two SPs based on amino triazines (AT) and amino pyrimidines (AP) modified with a hydrophilic chain of succinic acid (-saH). Our results reveal that the AT-based polymers are stable in both their neutral and anionic (succinate -sa-) forms. In contrast, the anionic AP-based polymer is completely dissociated in the presence of sodium cations. While chloride anions can stabilize AT polymers and even induce helical coordination, sodium cations destabilize the AP polymer by penetrating its structure and coordinating with the N atoms, thereby disrupting the hydrogen bonds of the rosettes. On the contrary, the AT-sa- monomers are able to hold back sodium cations due to their extra endocyclic N atom. The side chains are also essential for the formation of these SPs. In summary, we show how non-covalent interactions can be strategically used to control the stability of these systems.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401905"},"PeriodicalIF":3.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143571794","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":"The Z-enoate Assisted Meyer-Schuster Rearrangement with Thiol Nucleophiles. An Approach for the Functionalized Vinyl Sulfides, and Sulfones.","authors":"Beeraiah Baire, Sumran Raikwar","doi":"10.1002/asia.202500080","DOIUrl":"https://doi.org/10.1002/asia.202500080","url":null,"abstract":"<p><p>Vinyl sulfides and their sulfones act as very important building blocks in organic synthesis. Further they are prevalent in bioactive natural and unnatural products and exhibit diverse bioactivities. Here in we report a Z-enoate assisted Meyer-Schuster rearrangement approach for the rapid generation of 1,4-ketoester based vinyl sulfides. The thiols were employed as nucleophiles during this versatile transformation the propargylic alcohols. The process exhibited broader scope for thiols (aryl and alkyl), and propargylic alcohols. Further these vinyl sulfides were efficiently converted into the corresponding vinyl sulfones by employing a Mo-based oxidizing agent. Sodium borohydride reduction of the 1,4-ketoester based vinyl sulfides directly gave the butyrolactones having the vinyl sulfide unit. The phenols, alcohols and amines were found to be inefficient as nucleophiles to give the corresponding vinyl ethers.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500080"},"PeriodicalIF":3.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143571795","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":"Novel Sb₂S₃-3,4,9,10-Perylene Tetracarboxylic Acid Composite for Enhanced Photocatalytic Reduction of Cr(VI) in Aqueous Media.","authors":"Yongshan Ma, Qingxiang Guan, Qingbo Huang, Xuewu Zhu, Fengxia Zhang, Tianyi Jiang, Yanyan Zhu, Xuemei Li","doi":"10.1002/asia.202401708","DOIUrl":"10.1002/asia.202401708","url":null,"abstract":"<p><p>The construction of organic-inorganic semiconductor heterojunctions is an important way to improve the photocatalytic performance of semiconductors and inhibit the recombination of photogenerated charge carriers. In this paper, a novel Sb₂S₃-3,4,9,10-perylene tetracarboxylic acid (Sb<sub>2</sub>S<sub>3</sub>-PTCA) heterojunction was prepared by hydrothermal method. Compared with Sb<sub>2</sub>S<sub>3</sub> and PTCA, Sb<sub>2</sub>S<sub>3</sub>-PTCA composite catalyst had better photocatalytic reduction ability for Cr(VI) in aqueous solution under visible light conditions. The optimized Sb<sub>2</sub>S<sub>3</sub>-1.0 wt.% PTCA heterostructures exhibited significantly enhanced photocatalytic activity compared to pure Sb₂S₃ and PTAC, achieving a complete Cr(VI) reduction rate of 100 % in just 50 min. This will lead to cleaner effluent water being discharged into the environment, thereby reducing pollution and protecting aquatic ecosystems. The enhanced photocatalytic efficacy exhibited by the Sb<sub>2</sub>S<sub>3</sub>-PTCA heterostructure stems from the creation of a type II heterojunction, which facilitates a more proficient dissociation and transportation of the electron-hole pairs, thus contributing to its superior performance.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401708"},"PeriodicalIF":3.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143571793","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}
Nijita Mathew, Radha Rathod, Sougata Saha, Pralay K. Santra, Swapan K. Pati, Muthusamy Eswaramoorthy
{"title":"Engineering Ni(OH)2 with Pd for Efficient Electrochemical Urea Oxidation","authors":"Nijita Mathew, Radha Rathod, Sougata Saha, Pralay K. Santra, Swapan K. Pati, Muthusamy Eswaramoorthy","doi":"10.1002/asia.202401188","DOIUrl":"10.1002/asia.202401188","url":null,"abstract":"<p>Urea-assisted water electrolysis is a promising and energy-efficient alternative to electrochemical water splitting due to its low thermodynamic potential of 0.37 V, which is 860 mV less than that needed for water splitting (1.23 V). Ni(OH)<sub>2</sub> has proven to be an efficient catalyst for this reaction. However, the non-spontaneous desorption of CO<sub>2</sub> molecules from the catalyst surface leads to active site poisoning, which significantly impacts its long-term stability. Herein, we have demonstrated that Pd incorporated NiOH<sub>2</sub> (Pd/Ni(OH)<sub>2</sub>) results in a significant decrease in the overpotential by 40 mV at 10 mA cm<sup>−2</sup> as compared to Ni(OH)<sub>2</sub>. The decrease in the Tafel slope and charge transfer resistance of Pd/Ni(OH)<sub>2</sub> indicates an improvement in the kinetics of the reaction, resulting in a maximum current density of 380 mA cm<sup>−2</sup> at 1.5 V, which is higher than that observed for Ni(OH)<sub>2</sub> (180 mA cm<sup>−2</sup>). XAS analysis was utilized to determine the nature of the metal species in the catalyst. It revealed that while Pd predominantly exists in its metallic state within the bulk of the catalyst, the surface is enriched with the oxide phase. The presence of Pd prevents the strong adsorption of CO<sub>2</sub> at the active site in Pd/Ni(OH)<sub>2</sub>, resulting in a substantial improvement of stability of up to 300 h as compared to Ni(OH)<sub>2</sub>. DFT calculations were performed to explore the detailed reaction mechanism of urea oxidation on Ni(OH)<sub>2</sub> and Pd/Ni(OH)<sub>2</sub>. These calculations provided further insight into the experimental observations and evaluated the contribution of Pd in enhancing the catalytic efficiency of Ni(OH)<sub>2</sub>. Additionally, the operando Raman and IR spectroscopy were used to understand the formation of the active sites and the intermediates during urea electrooxidation.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":"20 7","pages":""},"PeriodicalIF":3.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143571790","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}