Jiawei Zhao, Wei Wei, Meihui Chen, Yanna Chen, Donghai An
{"title":"Syntheses, structures and characterization of noncentrosymmetric MZnPO<sub>4</sub> (M = K, NH<sub>4</sub>).","authors":"Jiawei Zhao, Wei Wei, Meihui Chen, Yanna Chen, Donghai An","doi":"10.1039/d4dt02530j","DOIUrl":"10.1039/d4dt02530j","url":null,"abstract":"<p><p>Two phosphates, KZnPO<sub>4</sub> and NH<sub>4</sub>ZnPO<sub>4</sub>, were successfully synthesized using a solid-state reaction method and characterized <i>via</i> single-crystal X-ray diffraction. Both of their structures feature a three-way skeleton composed of isolated PO<sub>4</sub> and ZnO<sub>4</sub> tetrahedra, with K<sup>+</sup>/NH<sub>4</sub><sup>+</sup> cations occupying the spaces within the frameworks to balance charges. These compounds are isostructural and crystallize in the noncentrosymmetric <i>P</i>6<sub>3</sub> space group. Their structures were compared, revealing that non-centrosymmetric (NCS) KZnPO<sub>4</sub> and NH<sub>4</sub>ZnPO<sub>4</sub> exhibit second harmonic generation (SHG) responses of 0.4 × KDP and 1 × KDP, respectively. Furthermore, by combining the electronic structure and SHG density calculations, we examined the effects of ZnO<sub>4</sub> tetrahedra on the SHG response of KZnPO<sub>4</sub> and NH<sub>4</sub>ZnPO<sub>4</sub>.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589576","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":"Bulk photovoltaic effect in a zero-dimensional room-temperature molecular ferroelectric [C8N2H22]1.5[Bi2I9]","authors":"Zhibo Chen, Tianhong Luo, Jinrong Wen, Zhanqiang Liu, Jingshan Hou, Yongzheng Fang, Ganghua Zhang","doi":"10.1039/d4dt02698e","DOIUrl":"https://doi.org/10.1039/d4dt02698e","url":null,"abstract":"Non-toxic molecular ferroelectrics have attracted significant interest due to their unique flexibility, low costs, and environmental friendliness. However, the variety of such materials with narrow bandgaps and above room temperature (RT) ferroelectricity is still scarce. Herein, we present a brand-new lead-free molecular ferroelectric [C8N2H22]1.5[Bi2I9] synthesized hydrothermally. [C8N2H22]1.5[Bi2I9] features a zero-dimensional (0D) structure with a polar space group of Pc, as confirmed by single-crystal X-ray diffraction and Second-Harmonic Generation (SHG) analyses. RT hysteresis loop reveals the intrinsic ferroelectricity of [C8N2H22]1.5[Bi2I9] with a spontaneous polarization (Ps) of 1.3 μC/cm². A visible-light optical bandgap has been confirmed by UV-vis spectrum and theoretical calculation. A notable ferroelectric photovoltaic (PV) effect has been revealed in [C8N2H22]1.5[Bi2I9]-based photoelectric device with an open-circuit voltage (Voc) of 0.39 V and a short-circuit current density (Jsc) of 2.3 μA/cm² under AM 1.5G illumination. The PV performance can be significantly enhanced by tuning the ferroelectric polarization, achieving a maximum Voc of 0.47 V and Jsc of about 50 μA/cm². This study offers a novel member of 0D lead-free hybrid organic-inorganic molecular ferroelectric family possessing great promise for optoelectronic devices.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580733","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}
Zhao-Guo Hong, Liangliang Zhang, Hong Liang, Fu-Ping Huang
{"title":"Recent advances in discrete Cu complexes for enhanced chemodynamic therapy","authors":"Zhao-Guo Hong, Liangliang Zhang, Hong Liang, Fu-Ping Huang","doi":"10.1039/d4dt02380c","DOIUrl":"https://doi.org/10.1039/d4dt02380c","url":null,"abstract":"Since the concept of metal ion stimulation-mediated chemodynamic therapy was proposed by Bu and Shi 's group in 2016, increasing attention has been directed toward fabricate efficient, safe and stable Fenton/Fenton-like catalysts to advance the clinical translation. In particular, metal-based complexes with inherent metal catalytic center have received extensive attention as potential alternatives/complements for traditional CDT agents. Among them, copper-based complexes, which possess excellent redox properties, extensive adaptability and abundant availability, enabling them to efficiently generate ROS through Fenton-like reactions in CDT, thereby causing oxidative damage to lipids, proteins, and DNA in cancer cells. In this brief review, we summarized the recent progress of various discrete copper-based metal complexes aimed at enhanced the therapeutic efficacy of CDT as well as their application in combination therapy. We hope that this review will attract active attention to metal complexes in advancing more accurate and efficient chemodynamic therapy, and encourage further in-depth research to facilitate clinical translation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580735","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 Cristina Resende Gonçalves, Silvia Helena Libardi, Júlio Cesar Borges, Ronaldo Junio de Oliveira, Carla Gotzmann, Olivier Blacque, Sergio Albuquerque, Carla Duque Lopes, Roger Alberto, Pedro Ivo da Silva Maia
{"title":"Rhenium(I) and technetium(I) complexes with megazol derivatives: towards the development of a theranostic platform for Chagas disease","authors":"Ana Cristina Resende Gonçalves, Silvia Helena Libardi, Júlio Cesar Borges, Ronaldo Junio de Oliveira, Carla Gotzmann, Olivier Blacque, Sergio Albuquerque, Carla Duque Lopes, Roger Alberto, Pedro Ivo da Silva Maia","doi":"10.1039/d4dt02714k","DOIUrl":"https://doi.org/10.1039/d4dt02714k","url":null,"abstract":"The diagnosis and treatment of Chagas disease (CD) in the chronic phase remains a challenge. With that in mind, a potential theranostic device based on the trypanocidal agent known as megazol and the fac-M(CO)3+ (M = Re or 99mTc) fragment is proposed in the present work. The peripheral structure of megazol (LH,H) was modified to obtain the compounds LR1,R2 (R1 = H, R2 = Me and R1 = R2 = Me), which were used in the syntheses of complexes of composition [ReBr(CO)3LR1,R2]. These compounds were studied by elemental analysis, FTIR, UV-vis, NMR (1H and 13C), HR-ESI-MS, HPLC/UPLC and single-crystal XRD. The trypanocidal activity of the rhenium complexes was evaluated in vitro against the intracellular form of Trypanosoma cruzi. With exception of the [ReBr(CO)3LMe,Me] complex, all compounds are more active than the standard drug, benznidazole (Bzn), while [ReBr(CO)3LH,H] also exhibited a much higher selectivity index. In addition, the interaction of megazol and its ReI complex was evaluated with the T. cruzi Old Yellow Enzyme (TcOYE) by both experimental and computational methods. The data showed that megazol as well as its metal complex exhibited a higher affinity for TcOYE compared to Bzn. Finally, the labelling of megazol with 99mTc was successfully carried out. However, the results indicated that the Re complexes used as standards were not homologous with the 99mTc complexes. Despite this discrepancy, this research suggests that the investigation into Re and 99mTc complexes with megazol could lead to the development of a theranostic device for CD in a near future.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588788","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}
Chunmei Li, kan Mi, Kai Xu, Zhuo Jia, Xiaolei Jiang, Huili Peng, Xiuwen Zheng, Hongjiao Nie
{"title":"LDH-derived Co0.5Ni0.5Te2 Dispersed in 3D Carbon Sheets as Separator Modifier to Enable Kinetics-Accelerated Lithium-Sulfur Batteries","authors":"Chunmei Li, kan Mi, Kai Xu, Zhuo Jia, Xiaolei Jiang, Huili Peng, Xiuwen Zheng, Hongjiao Nie","doi":"10.1039/d4dt02619e","DOIUrl":"https://doi.org/10.1039/d4dt02619e","url":null,"abstract":"Lithium-sulfur battery is considered as a powerful candidate for the next generation of advanced energy storage systems relying on its high energy density and theoretical specific capacity. However, its practical commercial feasibility has been hampered by sluggish kinetics and severe shuttle effect. Hence, a novel hybrid that NiCo-LDH derived Co0.5Ni0.5Te2 nanoparticles grafted in 3D carbon sheets was rationally constructed by facile steps and acted as functional separator modifier for lithium sulfur battery. Therein, the 3D cross-linked conductive network structure is conductive to the continuous electron transfer. In addition, the well-dispersed Co0.5Ni0.5Te2 nanoparticles with hexahedral morphology offer ample sulfophilic surface to chemically anchor and catalyze the redox dynamic of sulfur species. It has been proved that the dynamic conversion of sulfur-involved reaction is effectively promoted and the utilizations of polysulfides are boosted. The related cells display attractive long cycling durability (784.8 mAh g-1 at 2C after 500 cycles) and excellent rate performance (699.5 mAh g-1 even at 7C). Furthermore, when sulfur loading is up to 6.89 mg cm-2, the areal capacity can still be maintained at 6.40 mAh cm-2 after 50 cycles at 0.2C. This work provides a promising strategy to design multifunctional separator modifier and promotes the exploration of metal tellurides to engineer advanced kinetics-accelerated lithium-sulfur batteries.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580731","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":"Structural and Mechanistic Insights into Oxidative Biaryl Coupling to form Arylomycin Core by an Engineered CYP450","authors":"Vandana Kardam, Vaibhav Bhatt, Kshatresh Dubey","doi":"10.1039/d4dt02197e","DOIUrl":"https://doi.org/10.1039/d4dt02197e","url":null,"abstract":"Arylomycin, a potent antibiotic targeting bacterial signal peptidases, is difficult to synthesize experimentally due to its poor to moderate yields and the formation of a mixture of compounds. A recent experimental bioengineering work shows that the core of Arylomycin can be efficiently synthesized by engineering Cytochrome P450 enzyme Streptomyces sp; however, the mechanism of the same was not elucidated. Herein, we have thoroughly investigated the mechanism behind the evolution of the enzyme for the synthesis of Arylomycin core via C-C bond formation in CYP450 enzyme using hybrid QM/MM calculations, MD simulations, and DFT calculations. We show that strategic mutations such as a) G-101A facilitate biaryl coupling by subtly pushing the substrate and b) Q-306→H mutation creates a strong pi-pi interaction with the substrate that brings the two phenol rings of the substrate closer to undergo C-C coupling. Importantly, our QM/MM calculations show that for an efficient C-C formation, the reaction should undergo via biradical mechanism over hydroxylation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580732","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}
Alexey Bilyachenko, Victor N Khrustalev, Zhibin Huang, Lidia S. Shul'pina, Pavel Dorovatovskii, Elena Shubina, Nikolay S. Ikonnikov, Nikolai N. Lobanov, Karim G. Rahimov, Di Sun
{"title":"An octanuclear 3-phenyl-5-(2-pyridyl)pyrazolate/phenylsilsesquioxane complex: synthesis, unique structure, and catalytic activity","authors":"Alexey Bilyachenko, Victor N Khrustalev, Zhibin Huang, Lidia S. Shul'pina, Pavel Dorovatovskii, Elena Shubina, Nikolay S. Ikonnikov, Nikolai N. Lobanov, Karim G. Rahimov, Di Sun","doi":"10.1039/d4dt02690j","DOIUrl":"https://doi.org/10.1039/d4dt02690j","url":null,"abstract":"First metallasilsesquioxane bearing pyrazolylpyridine ligands, Cu8-based complex 1, adopts cage structure with two zigzag-like copper tetramers sandwiched by two cyclic Si5 silsesquioxane ligands. Four 3-phenyl-5-(2-pyridyl)pyrazolate ligands in 1 exhibit dual (chelating and bridging) principle of ligation. Compound 1 is very active in the oxidation of alkanes and alcohols.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588786","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":"Two amino-functionalized metal-organic frameworks with different topologies for C2H2/C2H4 separation","authors":"Yue Li, Mingming Xu, Hongyan Liu, Xiaokang Wang, Yutong Wang, Meng Sun, Weidong Fan, Daofeng Sun","doi":"10.1039/d4dt02592j","DOIUrl":"https://doi.org/10.1039/d4dt02592j","url":null,"abstract":"The rational design of metal-organic framework adsorbents is crucial for target gas separation. Herein, we report two three-dimensional MOFs with different topologies by regulating metal ions with amino-functionalized V-type ligands. Adsorption isotherms and Grand Canonical Monte Carlo simulation reveal that UPC-122 with channel-cavity structure has the potential to separate C2H2/C2H4 at room temperature with a separation ratio of 2.35 (50/50).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142588789","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":"Reactions of a Geminal Sc/P Lewis Pair with Pyridotetrazole and Beyond","authors":"Yiwen Guan, Xian Xu, Xin Xu","doi":"10.1039/d4dt02838d","DOIUrl":"https://doi.org/10.1039/d4dt02838d","url":null,"abstract":"Frustrated Lewis pair (FLP) chemistry has undergone remarkable growth, among which rare-earth metal-based Lewis pairs have exhibited unique reactivity in recent years. Herein, treatment of the intramolecular Sc/P Lewis pair, i.e., (ArO)2ScN(tBu)PPh2 (1, Ar = 2,6-tBu2-C6H3), with pyridotetrazole resulted in the formation of an FLP nitrene adduct with N2 elimination, offering additional insights into the mechanism of transition-metal-catalyzed denitrogenative annulation of pyridotetrazole. Reactions of complex 1 with 1,3,5-triazine and benzo[c]cinnoline generated FLP-type products via Sc/P 1,2-addition to the C=N bond and the N=N bond, respectively. Furthermore, treatments of 1 with phenylacetylene, diazo, and azide compounds were also investigated, leading to the formation of a variety of metallacyclic complexes displaying typical FLP behaviors.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580734","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}
David T Jenkins, Elizabeth C Trodden, John Andresen, Stephen M Mansell, Ruaraidh D McIntosh
{"title":"Switchable, Chiral Aluminium Catalysts for Ring Opening Polymerisations","authors":"David T Jenkins, Elizabeth C Trodden, John Andresen, Stephen M Mansell, Ruaraidh D McIntosh","doi":"10.1039/d4dt02831g","DOIUrl":"https://doi.org/10.1039/d4dt02831g","url":null,"abstract":"A switchable, solvent-free catalytic system was developed in which Al methyl aminebis(phenolate) catalysts selectively initiate the formation of a polyether from cyclohexene oxide under CO2 atmosphere or the ROCoP of cyclohexene oxide and CO2 through the addition of a PPNCl cocatalyst to form poly(cyclohexene carbonate).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580729","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}