{"title":"Frozen Natural Orbitals-Based Coupled-Cluster Singles, Doubles, and (full) Triples - A Computational Study.","authors":"Manisha, Prashant Uday Manohar","doi":"10.1002/asia.202500472","DOIUrl":"https://doi.org/10.1002/asia.202500472","url":null,"abstract":"<p><p>Frozen (F) natural orbitals (NO) approach in coupled cluster (CC) singles and doubles (SD) and equation-of-motion (EOM) CCSD methods is well-known for provide cost-effective yet accurate alternative for energy computation. In this article, we extend the FNO approach to CCSDT (CC with singles, doubles, and triples) implemented within Q-CHEM. This can be employed within both the (conventional) double precision (DP) as well as the single precision (SP) algorithms. Errors due to employing SP algorithm instead of DP are insignificant and therefore are not discussed. However, for computational timings, we present the performance of FNO-CCSDT versus conventional CCSDT methods with both SP and DP algorithms using water molecule as a test system. FNO-CCSDT results at different thresholds can be extrapolated to give the XFNO-CCSDT approach, which provides an enhanced accuracy. To illustrate this, we present total energies of a few molecules, adiabatic triplet-singlet gaps of a few chromophores and bond-stretching trends in total energies and vertical triplet-singlet gaps of hydrogen fluoride molecule. We also examine these methods for numerical estimation of spectroscopic parameters - force constants and vibrational frequencies of some diatomic molecules.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00472"},"PeriodicalIF":3.5,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232800","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 Luminescence Resonance Energy Transfer (LRET)-Based Nanoprobe for Ascorbic Acid Detection in Living Cells and Real Samples.","authors":"Siyu Pan, Yonggen Hong, Yuehan Jian, Pei Shen, Xuanyi Lu, Yuhan Chen, Ying Lin, Shuai Zha, Lijun Jiang, Xueyang Fang","doi":"10.1002/asia.202500124","DOIUrl":"https://doi.org/10.1002/asia.202500124","url":null,"abstract":"<p><p>Ascorbic acid (AA) is a ubiquitous and essential, water-soluble electron donor in living organisms which must be obtained from the diet. AA deficiency is closely associated with the pathogenesis and/or progression of various diseases, including diabetes and neurodegenerative disorders affecting hippocampal neurogenesis and cognitive function. Thus, it is beneficial to monitor AA in living cells and real samples. However, few probes have been developed for AA monitoring in both living cells and real samples. Here, we developed an LRET-based nanoprobe for AA detection, leveraging the near-infrared (NIR) excitation properties and spectral tunability of up-conversion nanoparticles (UCNPs). Upon exposure to AA, the MnO<sub>2</sub> layer undergoes gradual decomposition, leading to a significant decrease in absorption. The detection limit was determined to be 0.097 µg/mL. As the MnO<sub>2</sub> layer decomposes, the quenching effect on UCNPs is inhibited, leading to a 5.2-fold enhancement in up-conversion emission. The detection limit for this luminescence-based approach was determined to be 2.48 µg/mL. Moreover, UCNP@MnO<sub>2</sub> exhibits low cytotoxicity and efficiently enters cells, making it suitable for application in both living cells and real samples. This research demonstrates the dual-sensing capabilities of UCNP@MnO<sub>2</sub> to AA, and validates its application in both living cells and real samples.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00124"},"PeriodicalIF":3.5,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232798","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}
Chang Ge, Mingzhe Wang, Xiaoqi Tian, Lei Ye, Zhe Sun
{"title":"Cycloparaphenylene-Helicene Conjugates with Donor-Acceptor Structure for Bioimaging.","authors":"Chang Ge, Mingzhe Wang, Xiaoqi Tian, Lei Ye, Zhe Sun","doi":"10.1002/asia.202500655","DOIUrl":"https://doi.org/10.1002/asia.202500655","url":null,"abstract":"<p><p>Two cycloparaphenylene-helicene conjugates with one or two [7]helicene moieties are designed and synthesized using a highly efficient cyclocondensation reaction. Configurationally stable enantiomers with P/M-configurations or P,P/M,M-configurations were isolated using high-performance liquid chromatography technique. The reported conjugates exhibit remarkable chiroptical properties and bright emission at long wavelength beyond 600 nm, as a result of the combination of cycloparaphenylene and helicene units, and the presence of a donor-acceptor structure. It is discovered that the nanoparticles prepared from one of the conjugates could be stably present in A549 cells with minimal cytotoxicity, and lysosomally colocalized for live cell imaging. This study may shed light on the application of chiral carbon nanohoops in the biological systems.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00655"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223822","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}
Yongquan Zhang, Shuo Fan, Tao Ding, Lin Bo, Jingrun Hu, Jingshun Wang, Changhai Zhang, Tiandong Zhang, Yue Zhang
{"title":"Hydrothermally Synthesized ZnMn<sub>2</sub>O<sub>4</sub>@GO Cathode Enhances Zinc-Ion Kinetics and Cycling Stability for Aqueous Zinc-Ion Batteries.","authors":"Yongquan Zhang, Shuo Fan, Tao Ding, Lin Bo, Jingrun Hu, Jingshun Wang, Changhai Zhang, Tiandong Zhang, Yue Zhang","doi":"10.1002/asia.202500181","DOIUrl":"https://doi.org/10.1002/asia.202500181","url":null,"abstract":"<p><p>Spinel-type ZnMn<sub>2</sub>O<sub>4</sub> has been identified as a cathode that demonstrates considerable potential material for zinc-ion batteries (ZIBs). In this study, the synthesis of ZnMn<sub>2</sub>O<sub>4</sub>@GO composite material was conducted using a hydrothermal method. The electrochemical performance of the composite material was found to be significantly enhanced, a phenomenon that was primarily ascribed to the substantial specific surface area and exceptional conductivity of graphene, which improved the diffusion kinetics of zinc ions at the electrode-electrolyte interface. At a current density of 50 mA g<sup>-1</sup>, the discharge capacity of the ZnMn<sub>2</sub>O<sub>4</sub>@GO composite electrode was 186.4 mAh g<sup>-1</sup>, much higher than that of ZnMn<sub>2</sub>O<sub>4</sub> (133.3 mAh g<sup>-1</sup>). Moreover, after 1000 charge-discharge cycles at a current density of 1000 mA g<sup>-1</sup>, the discharge capacity of ZnMn<sub>2</sub>O<sub>4</sub>@GO composite electrode was 50% higher than that of ZnMn<sub>2</sub>O<sub>4</sub>.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00181"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223827","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":"Distal Heteroaryl Ipso-Migration of Unactivated Alkenes via Cobalt/Photoredox-Catalyzed Hydrogen/Deuterium Atom Transfer.","authors":"Masaaki Yamashita, Akihiko Suzuki, Tatsuhiko Yoshino, Kosuke Higashida, Masahiro Kojima, Shigeki Matsunaga","doi":"10.1002/asia.202500448","DOIUrl":"https://doi.org/10.1002/asia.202500448","url":null,"abstract":"<p><p>A structural isomerization of alkenyl alcohols via 1,4- or 1,5-heteroaryl migration initiated by metal-hydride hydrogen atom transfer (MHAT) under cobalt/photoredox dual catalysis is described. The remote migration method provided various heteroaryl-containing ketones inaccessible through conventional MHAT 1,2-migration pathways. The cobalt/photoredox catalysis was further applied to the synthesis of deuterium-labeled heteroaryl-containing ketones.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00448"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223824","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":"Effects of Bases on the Mechanism of Ag(I)-Catalyzed Selectivity of CO<sub>2</sub> Incorporation into Conjugated Ynones: A Computational Study.","authors":"Binfang Yuan, Junyi Ma, Guangzhao Wang, Xiaogang Guo, Huisheng Huang, Jinyang Chen, Bing Li, Rongxing He","doi":"10.1002/asia.202401903","DOIUrl":"https://doi.org/10.1002/asia.202401903","url":null,"abstract":"<p><p>The mechanisms of AgOAc-catalyzed CO<sub>2</sub> incorporation into conjugated ynones are studied using density functional theory (DFT) calculations to explore the selectivity of reaction (5-exo-dig P1 versus 6-endo-dig P2) and to understand the effects of bases (MTBD versus TMG versus DMAP) on the reactions. The bases have the function of proton-shuttle, assisting the transfer of H1 (H2) from C4 (C4) to C1 (O1) by the four-step proton-transfer strategy. More importantly, the differences of base strength are revealed to be the primary factor that determines the catalytic activities of MTBD, TMG, and DMAP, and the order of catalytic activity is MTBD > TMG > DMAP, which does match with the increased trend of base strength MTBD > TMG > DMAP. Moreover, the selectivity of Ag(I)-catalyzed reaction is controlled via the intramolecular cyclization to selectively generate 5-exo-dig P1, which could be reasonably explained by the analysis of electronic interactions and bond lengths on the base of theoretical calculations. In a word, the studies provide indispensable understanding for the transition-metals catalyzed CO<sub>2</sub> conversion with assistance of bases to synthesize various high-value chemicals.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e01903"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223825","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":"Examining the Role of Internal Electric Fields in Reducing Reaction Barriers in Cycloaddition Reactions of Oxygen-Bridged Al/P- and Si/P-Based Frustrated Lewis Pairs with Heterocumulenes.","authors":"Zheng-Feng Zhang, Ming-Der Su","doi":"10.1002/asia.202500431","DOIUrl":"https://doi.org/10.1002/asia.202500431","url":null,"abstract":"<p><p>In this investigation, computational methods were employed to study the transition-metal-free trapping reactions of small organic molecules using two distinct intramolecular frustrated Lewis pairs (FLPs) via cycloaddition mechanisms. The reactivity of oxygen-bridged geminal FLP-type molecules Al/P-Rea (1) and Si/P-Rea (2) with CS<sub>2</sub>, PhN═C═S, SO<sub>2</sub>, and PhN═S═O was evaluated. Experimental results reported by Mitzel and coworkers indicate that FLPs 1 and 2 alone exhibit limited ability to activate these four small molecules, being hindered by endergonic barriers, reaction thresholds, or potential structural degradation. Evidence from activation strain model (ASM) analysis suggests that the interaction of a larger FLP-type molecule with a chemical bond in a smaller organic molecule, or its binding to a single bond within a heterocumulene, induces enhanced motion within the smaller molecule (or heterocumulene). This increased motion leads to a significant rise in structural strain energy, which substantially affects the activation energy required for bonding. Alternatively, our ASM findings emphasize that when an FLP-type molecule binds simultaneously to both ends of a similar-sized organic molecule, the activation barrier is primarily governed by the strain energies of both reactants. Notably, this study further suggests that introducing cations (e.g., Li⁺) or anions (e.g., Cl⁻) into the reaction system of otherwise unreactive or weakly reactive FLP-type molecules induces an internal electric field that dramatically reduces the activation energy and enhances the exergonicity of the process, thereby facilitating the overall reaction. We hope that this study provides experimental synthetic chemists with novel insights and valuable guidance for future synthetic efforts.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00431"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223826","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":"New Exciplex-forming Cohost Systems Harnessing Acceptors With Phenanthrene and Phenanthroline Core for Near-Infrared OLEDs.","authors":"Guan-Cheng Liu, Tzu-Hao Huang, Yi-Yun Chen, Yu-Cheng Kung, Yuan-Chih Lo, Wen-Yi Hung, Ken-Tsung Wong","doi":"10.1002/asia.202500357","DOIUrl":"https://doi.org/10.1002/asia.202500357","url":null,"abstract":"<p><p>Two new acceptors, C-BPhCN and N-BPhCN, with 2,3-dicyanopyrazinophenanthrene and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile core and ortho-linked biphenyl peripherals were synthesized and characterized. The exciplex formation of C-BPhCN and N-BPhCN as acceptor (A) and SBFC-G1 as donor (D) was examined. Through optimization, the device using a D:A (2:1) blend in emitting layer (EML) exhibited maximum external quantum efficiency (EQE<sub>max</sub>) of 8.26% and 5.25% with electroluminescence peak (EL λ<sub>max</sub>) centered at 581 and 595 nm, respectively. A new D-A-D configured near-infrared (NIR) fluorescent emitter DMACBBT was introduced as a dopant in the exciplex-forming cohost system. By tuning the thickness of the electron transporting layer (ETL), the EQE<sub>max</sub> of the device employing SBFC-G1:C-BPhCN (2:1): 9 wt % DMACBBT as the EML reached 1.03% with EL λ<sub>max</sub> at 808 nm. The counterpart device utilizing SBFC-G1:N-BPhCN (2:1): 9 wt % DMACBBT as the EML exhibited an EQE<sub>max</sub> of 1.01% and EL λ<sub>max</sub> at 817 nm. The stability of the NIR OLED device was measured, yielding lifetimes (T<sub>60</sub>) of 182 and 126 h for SBFC-G1:C-BPhCN and SBFC-G1:N-BPhCN cohost-based devices, respectively. This work highlights the high efficiency of NIR OLEDs that can be practically realized by using the exciplex cohost systems with a tailor-made NIR fluorescent emitter.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00357"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223828","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}
Jing Wang, Danyang Qi, Caiyun Shao, Qian Guo, Lirong Yang
{"title":"Two Ln-MOFs Based on 4,4',4''-nitrilotrisbenzoic Acid as Multi-Response Luminescence Sensors With High Selectivity and Sensitivity Toward Fe<sup>3+</sup> and Cr<sub>2</sub>O<sub>7</sub> <sup>2</sup>.","authors":"Jing Wang, Danyang Qi, Caiyun Shao, Qian Guo, Lirong Yang","doi":"10.1002/asia.202500418","DOIUrl":"https://doi.org/10.1002/asia.202500418","url":null,"abstract":"<p><p>Lanthanide metal-organic frameworks (Ln-MOFs) have been widely developed for sensing due to their inherent structural properties and unique lanthanide luminescence characteristics. Herein, a series of Ln-MOFs (Ln = Nd (1), Eu (2), Gd (3), Tb (4), Ho (5)) were successfully synthesized using the ligand 4,4',4''-nitrilotrisbenzoic acid (H<sub>3</sub>NTB) under hydrothermal conditions. The fluorescence experiments demonstrate that compounds 2 and 4 can specifically recognize Fe<sup>3+</sup> and Cr<sub>2</sub>O<sub>7</sub> <sup>2-</sup> ions in aqueous solutions through significant fluorescence quenching, respectively. This process not only exhibits high selectivity for the target ions but also shows a low detection limit, excellent anti-interference capability, and relatively fast response time (less than 45 s). The distinct emission changes of 2/4 enable multifunctional, rapid, convenient, and visible detection by the naked eye under 365 nm UV light. Finally, the potential sensing mechanisms were elucidated based on experimental evaluation in detail.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00418"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223829","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}
Komal Ali Rao, Muhammad Ehsan Mazhar, Javed Ahmad, Muhammad Bilal, Saqlain Haider, Muhammad Imran Khan, Waseem Abbas, Naeem Akhtar, Muhammad Suleman Ahmad, Rafael Luque
{"title":"Development of NiCo<sub>2</sub>O<sub>4</sub>/rGO Nanocomposites for High Performance Supercapacitors.","authors":"Komal Ali Rao, Muhammad Ehsan Mazhar, Javed Ahmad, Muhammad Bilal, Saqlain Haider, Muhammad Imran Khan, Waseem Abbas, Naeem Akhtar, Muhammad Suleman Ahmad, Rafael Luque","doi":"10.1002/asia.202500388","DOIUrl":"https://doi.org/10.1002/asia.202500388","url":null,"abstract":"<p><p>Transition metal oxide nanocomposites featuring diverse structures have garnered significant attention in the realm of supercapacitors. This interest is attributed to their cost-effectiveness, high surface area, rapid transport of ions and electrons, and the ability to deliver high specific capacitance. In this work, sea-urchin shaped NiCo<sub>2</sub>O<sub>4</sub> reduced graphene oxide (NCO/rGO) nanocomposites were synthesized via facile hydrothermal route. NCO/rGO nanocomposite was subsequently loaded on nickel foam (NF) using the drop casting method to build NCO/rGO electrodes. The structural and morphological characteristics of our designed electrodes such as NCO and NCO/rGO electrodes were investigated by scanning electron microscope (SEM), energy dispersive spectroscopy (EDX), X-ray diffraction (XRD), and Fourier infrared transform spectroscopy (FTIR) while cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) techniques were performed to address the electrochemical efficacy of our designed electrodes which reveal redox-mediated charge storage in NCO-rGO. As-prepared NCO/rGO electrode exhibited high specific capacitance of 875 F g<sup>-1</sup> at current density of 1 A g<sup>-1</sup> which demonstrates the potential of NCO/rGO as a suitable candidate in supercapacitor applications.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00388"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223823","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}