Chemistry - An Asian Journal最新文献_第7页

Ligand Isomerism in Palladium(II)-Based Multi-Cavity Discrete Coordination Cages.

IF 3.5 3区化学

Chemistry - An Asian Journal Pub Date : 2025-03-11 DOI: 10.1002/asia.202401941

Shruti Sharma, Divya John, Dillip Kumar Chand

{"title":"Ligand Isomerism in Palladium(II)-Based Multi-Cavity Discrete Coordination Cages.","authors":"Shruti Sharma, Divya John, Dillip Kumar Chand","doi":"10.1002/asia.202401941","DOIUrl":"10.1002/asia.202401941","url":null,"abstract":"The term ligand isomerism stands for two or more isomeric coordination complexes having regioisomeric ligands coordinated around the metal center. Single-cavity discrete coordination cages (SCDCCs) and multi-cavity discrete coordination cages (MCDCCs) are exotic class of self-assembled complexes that should be suitable for exploration of ligand isomerism. This work describes rare varieties of double-cavity tetranuclear, triple-cavity pentanuclear and quadruple-cavity hexanuclear MCDCCs to exemplify ligand isomerism. Square planar Pd(II) and pyridine-based bis-, tris- and tetrakis-monodentate ligands are employed as the modular building blocks for constructing the cages. The frameworks of all the ten cages studied here (four reported and six new) contain trinuclear Pd3L6 type double-walled triangular core (or sub-framework) that is decorated with one, two and three units of Pd2L4 type entity or sub-framework resulting in tetra, penta and hexanuclear MCDCCs, respectively. Suitable incorporation of isomeric arms as part of the double-walled trinuclear core by sourcing from the basket of regioisomeric ligands would offer ligand isomerism in the MCDCCs. Our ligand design afforded four members for the tetra or pentanuclear and two for the hexanuclear architectures to demonstrate ligand isomerism in MCDCCs.","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401941"},"PeriodicalIF":3.5,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602956","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}

引用次数: 0

Nanoscale Metal-Organic Frameworks: An Emerging Versatile Tool for Next-Generation Photodynamic Therapy.

IF 3.5 3区化学

Chemistry - An Asian Journal Pub Date : 2025-03-11 DOI: 10.1002/asia.202500079

Gopal Singh Attar, Vandana Bhalla, Manoj Kumar

{"title":"Nanoscale Metal-Organic Frameworks: An Emerging Versatile Tool for Next-Generation Photodynamic Therapy.","authors":"Gopal Singh Attar, Vandana Bhalla, Manoj Kumar","doi":"10.1002/asia.202500079","DOIUrl":"10.1002/asia.202500079","url":null,"abstract":"Photodynamic therapy has emerged as a potent strategy for treatment of cancer due to its non-invasiveness, minimal toxicity, high spatial selectivity, and potential for combination therapies. However, self-aggregation of photosensitizers, tumour hypoxia and low penetration depth of excitation photons remain prominent challenges towards its clinical application. Nanoscale metal-organic frameworks have emerged as one of the most promising materials due to their tunable composition which allows the adjustment of optical and chemical properties by changing the metal ions or organic linkers. Due to their high porosity, they serve as carriers for photosensitizers and demonstrate high tumour accumulation rates, target specificity, and penetration depth with enhanced permeability and retention effect. This review aims to explore recent developments in nanoscale metal-organic frameworks focusing on the design strategies to enhance their effectiveness in tumour microenvironment. Specifically, we have examined the approaches to address challenges posed by hypoxic tumour environment and tissue penetration depth of the various light sources. Furthermore, this review provides insights into the targeting strategies that improve the overall efficacy through stimulus-activated release and sub-cellular internalization of photosensitizers. Finally, we discussed the on-going challenges and some future directions for harnessing their full potential as therapeutic agents for effective outcome of photodynamic therapy.","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500079"},"PeriodicalIF":3.5,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602972","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}

引用次数: 0

Application of NHC-Based Iridium Pincer Complexes in β-Alkylation of Alcohols and N-Alkylation of Amines: Mechanistic Studies on Precatalyst Activation.

IF 3.5 3区化学

Chemistry - An Asian Journal Pub Date : 2025-03-10 DOI: 10.1002/asia.202401665

Miguel González-Lainez, M Victoria Jiménez, F Javier Modrego, Jesus J Pérez-Torrente

{"title":"Application of NHC-Based Iridium Pincer Complexes in β-Alkylation of Alcohols and N-Alkylation of Amines: Mechanistic Studies on Precatalyst Activation.","authors":"Miguel González-Lainez, M Victoria Jiménez, F Javier Modrego, Jesus J Pérez-Torrente","doi":"10.1002/asia.202401665","DOIUrl":"https://doi.org/10.1002/asia.202401665","url":null,"abstract":"The iridium(I) complexes [IrBr(cod)(κC-tBuImCH2PyCH2NRR')] (NRR' = NEt2, NHtBu) have been prepared by reaction of the corresponding functionalized imidazolium salt with the appropriate dinuclear compound [Ir(µ-OR)(cod)]2 (R = OMe, OEt). These compounds react with H2(g) (5 bar) to afford the pincer iridium(III) dihydrido complexes [IrBrH2(κ3C,N,N'-tBuImCH2PyCH2NRR')] in good yields. The complexes [IrBr(cod)(κC-tBuImCH2PyCH2NRR')] efficiently catalyzed the β-alkylation of a series of secondary alcohols and the N-alkylation of a range of aniline derivatives with primary alcohols, with good selectivities for the β-alkylated alcohol and monoalkylated secondary amine products, respectively, at low catalyst loading, typically 0.1 mol%, and sub-stoichiometric amount of base in toluene at 383 K. The pincer iridium(III) dihydrido complexes show a catalytic performance similar to that of the iridium(I) complexes in model alkylation reactions. Mechanistic studies on the activation of the catalyst precursors have shown that both type of complexes have the ability to activate benzyl alcohol through the dearomatization of the pyridine ring by selective deprotonation of the methylene linker between the pyridine and the imidazole-2-ylidene fragment. DFT calculations suggest that activation of both catalytic precursors could lead to th common pincer iridium(I) species [IrH(κ3C,N,N-tBuImCH2PyCH2NEt2)], which may be key to the borrowing hydrogen reaction mechanism.","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401665"},"PeriodicalIF":3.5,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143595994","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}

引用次数: 0

Vacancy Ordered Double Perovskites [N(CH₃)₄]₂SnX₆ (X=Cl, Br, I): Thermal Phase Transition and Wide Range Optical Absorption.

IF 3.5 3区化学

Chemistry - An Asian Journal Pub Date : 2025-03-10 DOI: 10.1002/asia.202401483

Nagale S Vishwajith, Ajay J Prasad, Digvijay Narayan Singh, Pratap Vishnoi

{"title":"Vacancy Ordered Double Perovskites [N(CH3)4]2SnX6 (X=Cl, Br, I): Thermal Phase Transition and Wide Range Optical Absorption.","authors":"Nagale S Vishwajith, Ajay J Prasad, Digvijay Narayan Singh, Pratap Vishnoi","doi":"10.1002/asia.202401483","DOIUrl":"10.1002/asia.202401483","url":null,"abstract":"(TMA)2SnX6 (TMA=tetramethylammonium; X=Cl, Br, I) compounds form vacancy-ordered halide double perovskites (VODPs) with TMA+ cation in the A-site, Sn4+ cation in the M-site and X- anion in the halide site. This study reports the synthesis and the structural phase transition of (TMA)₂SnCl₆, (TMA)2SnCl0.7Br5.3, (TMA)₂SnBr₆, and (TMA)₂SnI₆. All four halides crystallize in a cubic Fd <math> <semantics><mover><mn>3</mn> <mo>‾</mo></mover> <annotation>${bar{3}}$</annotation> </semantics> </math> c symmetry at room temperature. At elevated temperatures, (TMA)2SnCl6 and (TMA)2SnBr6 show phase transition to a cubic Fm <math> <semantics><mover><mn>3</mn> <mo>‾</mo></mover> <annotation>${bar{3}}$</annotation> </semantics> </math> m symmetry at 364 K and 369 K, respectively. While the phase transition of (TMA)2SnCl6 was reported earlier, that of (TMA)2SnBr6 is reported for the first time in this study. The synthesis and structures of (TMA)2SnCl0.7Br5.3 and (TMA)2SnI6 are reported for the first time in this study, with calorimetry data showing a reversible transition at 363 K and 325 K, respectively. Further, the choice of halide ligand influences the bandgap and the colour of the compounds. The absorption edge lies at 3.60 eV for (TMA)2SnCl6, at 2.64 eV for (TMA)2SnBr6, and at 1.12 eV for (TMA)2SnI6. Such a wide tunability of bandgap across the ultraviolet to infrared regions in combination with the thermal phase change makes these perovskites interesting materials for thermal and solar energy storage applications.","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401483"},"PeriodicalIF":3.5,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143583919","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}

引用次数: 0

Significant Insights into the Origins of Reaction Barriers Governing the Addition Reactions of Olefins with Singly Bonded G13/P-Based (G13=Group 13 Element) and Al/G15-Based (G15=Group 15 Element) Molecules.

IF 3.5 3区化学

Chemistry - An Asian Journal Pub Date : 2025-03-10 DOI: 10.1002/asia.202500016

Shi-Hao Wu, Ming-Der Su

{"title":"Significant Insights into the Origins of Reaction Barriers Governing the Addition Reactions of Olefins with Singly Bonded G13/P-Based (G13=Group 13 Element) and Al/G15-Based (G15=Group 15 Element) Molecules.","authors":"Shi-Hao Wu, Ming-Der Su","doi":"10.1002/asia.202500016","DOIUrl":"10.1002/asia.202500016","url":null,"abstract":"The addition reactions of propylene with singly bonded G13/P-based (G13=Group 13 element) and B/G15-based (G15=Group 15 element) molecules, all yielding the >G13-G15< geometrical structure, have been analyzed theoretically using density functional theory (DFT). The current DFT findings indicate that, of all singly bonded G13/P-based and Al/G15-based molecules, only Al/P-Rea can reversibly carry out the [2+2] addition reaction with propylene, both from kinetic and thermodynamic viewpoints. The activation strain model suggests that the deformation energy of the singly bonded >G13-G15< fragment is pivotal in determining the barrier heights that allow for optimal orbital interactions between G13/P-Rea, Al/G15-Rea, and propylene. Our theoretical analyses demonstrates that donor-acceptor bonding (singlet-singlet) has a greater impact compared to electron-sharing bonding (triplet-triplet) in the transition states G13/P-TS and Al/G15-TS. Sophisticated analytical frameworks suggest that the forward interaction (lone pair (G15)→p-π* of C=C in propylene) predominantly affects the addition reactions of singly bonded G13/P-Rea and Al/G15-Rea with propylene, whereas the backward interaction (p-π*(G13) ← p-π of C=C in propylene) is less influential. Our current DFT calculations, focusing on the structures and relative energetics of stationary points analyzed through the earlier mentioned advanced methods, conform to the Hammond postulate.","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202500016"},"PeriodicalIF":3.5,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143583918","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}

引用次数: 0

Zinc Sensing by a Janus-Faced Fluorophore and its Application in the Cellular Microenvironment.

IF 3.5 3区化学

Chemistry - An Asian Journal Pub Date : 2025-03-10 DOI: 10.1002/asia.202401726

Ajit G Wadkar, Savita Choudhary, Pravinkumar Vipparthi, Adarash Kumar Shukla, Onkar Prakash Kulkarni, Anupam Bhattacharya

{"title":"Zinc Sensing by a Janus-Faced Fluorophore and its Application in the Cellular Microenvironment.","authors":"Ajit G Wadkar, Savita Choudhary, Pravinkumar Vipparthi, Adarash Kumar Shukla, Onkar Prakash Kulkarni, Anupam Bhattacharya","doi":"10.1002/asia.202401726","DOIUrl":"10.1002/asia.202401726","url":null,"abstract":"In this work, we have investigated the metal sensing capabilities of dimeric fused heterocycles, PQ-BCN and PQN-BCN, bearing a pyrrole-pyridine chelating unit. PQ-BCN displayed selectivity towards Zn2+ in micromolar levels by steady-state absorbance and fluorescence-assisted screening experiments. The binding stoichiometry of the complex was determined to be a 1 : 2 probe-to-metal ratio. PQN-BCN, however, did not show any preferences towards any metal. NMR titration experiments provided insights into the differing behaviors of PQ-BCN and PQN-BCN, highlighting the role of pyrrolic NH in Zn2+ coordination. Different binding affinities obtained using absorbance and fluorescence titrations indicated that the first Zn2+ binds strongly in the ground state, but the second Zn2+ coordination contributes significantly to fluorescence enhancement. Computational experiments revealed the preference for PQ-BCN compared to PQN-BCN, possibly originating from the difference in the Mulliken charges of the respective chelating nitrogens. A lifetime study on the PQ-BCN-Zn2+ complex gave a bi-exponential fit with an enhancement of its slower component upon interaction with Zn2+ compared to the free probe. It is the slower component that significantly contributes to the enhancement of fluorescence. Cellular studies were further performed with PQ-BCN using MOC-2 (oral cancer cells), revealing the probe's non-toxic nature and its capability to monitor zinc in cells in the presence/absence of zinc transporter ZnPT. Visualization of zinc was also successful without its external supplementation when cells were under peroxide-induced oxidative stress, thereby demonstrating the innate capability of the probe to detect zinc.","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401726"},"PeriodicalIF":3.5,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143583920","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}

引用次数: 0

K/Cl Dual-Mediated Spatial Charge Separation in Carbon Nitride Boosts Piezocatalytic Pure Water Splitting.

IF 3.5 3区化学

Chemistry - An Asian Journal Pub Date : 2025-03-09 DOI: 10.1002/asia.202500026

Qirong Zhu, Fan Wu, Jie Yuan, Chengyu Huang, Huaibao Qiu, Yingfeng Zhou, Difa Xu, Shiying Zhang, Hui Wan, Wenhui Feng

引用次数: 0

Enhanced Photoluminescence Emission and Thermal Stability in Pt₁Ag₃₁ nanocluster from Introduced Secondary Phosphine Oxide Functionalized ligand.

IF 3.5 3区化学

Chemistry - An Asian Journal Pub Date : 2025-03-08 DOI: 10.1002/asia.202401819

Zhuoyuan Li, Chuanjun Zhou, Kaiyang Kuang, Jiahao Liu, Shuang Chen, Shan Jin, Manzhou Zhu

引用次数: 0

Intramolecular Diels-Alder Reaction of Benzo-Tethered Dienyl Cinnamates: Synthesis of the Tricyclic Core of Morusalisin A.

IF 3.5 3区化学

Chemistry - An Asian Journal Pub Date : 2025-03-08 DOI: 10.1002/asia.202500258

Poramate Songthammawat, Kasam Poonswat, Pisit Nithijarasrawee, Poonsakdi Ploypradith, Somsak Ruchirawat

引用次数: 0

Enhanced Charge Transportation in Type II WO₃/ZnWO₄ Nanoflakes for Boosting Saline Water-splitting Reaction.

IF 3.5 3区化学

Chemistry - An Asian Journal Pub Date : 2025-03-08 DOI: 10.1002/asia.202500292

Prashant Choubey, Ritu Verma, Mrinmoyee Basu

{"title":"Enhanced Charge Transportation in Type II WO3/ZnWO4 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":"Photoelectrochemical (PEC) water-splitting is an energy-efficient and eco-friendly technique to produce green hydrogen (H2). Here, WO3 is synthesized for saline water-splitting reaction. Initially, the activity of WO3 is enhanced through morphology tuning. Nanoparticles (NPs), thick nanosheets (TSs), and nanoflakes (NFs) of WO3 are synthesized, and their PEC activity is determined. The NFs show a photocurrent density of 1.53 mA/cm2 at 1.2 V vs. Ag/AgCl, whereas TSs and NPs can generate 1.17 mA/cm2 and 1.07 mA/cm2 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 ZnWO4 on WO3, 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 WO3 and 2.4 times enhanced carrier density, 2.16×1021 cm-3. 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 WO3/ZnWO4 is studied for one hour.","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}

引用次数: 0