Dalton Transactions最新文献

{"title":"Novel Zn(II), Co(II) and Cu(II) diflunisalato complexes with neocuproine and their exceptional antiproliferative activity against cancer cell lines","authors":"Romana Smolková, Lukáš Smolko, Erika Samolova, Ibrahim Morgan, Robert Rennert, Goran Kaluđerović","doi":"10.1039/d4dt01736f","DOIUrl":"https://doi.org/10.1039/d4dt01736f","url":null,"abstract":"Three novel complexes of deprotonated diflunisal (dif) with neocuproine (neo) were synthesized and characterized by elemental, spectral (UV-Vis, FTIR, fluorescence, mass spectrometry) and single-crystal X-ray diffraction analysis. Although, the compounds have a similar composition of [MCl(dif)(neo)], where M represents Zn(II) (1), Co(II) (2) and Cu(II) (3), respectively, only 1 and 2 are isostructural, while 3 differs in both molecular and supramolecular structure. In all three complex molecules, the central atom is coordinated by two nitrogen atoms of neo in bidentate chelate mode, one chlorido ligand and dif is bonded in either monodentate mode via one oxygen atom of the carboxylate in 1 and 2 or in bidentate chelate mode via both carboxylate oxygen atoms in 3. All three compounds demonstrated remarkable antiproliferative activity against human prostate (PC-3), colon (HCT116) and breast (MDA-MB-468) cancer cell lines with IC50 values in the nanomolar range, with the lowest values observed in case of PC-3 and MDA-MB-468 with 2 (20.0 nM) and 3 (31.1 nM), respectively. Moreover, complex 2, as the most active, was further investigated for its potential to induce perturbations in the cell cycle of PC-3 cells. The results indicate an induction of caspase-independent apoptosis. The interaction of the complexes with genomic DNA isolated from the respective cancer cell lines was evaluated for the intercalative mode, with the binding strength correlating with the antiproliferative activity against the PC-3 and MDA-MB-468 cancer cell lines.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324941","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":"Gradual spin crossover behavior encompassing room temperature in an Iron(II) complex based on heteroscorpionate ligand","authors":"Oleksandr Horniichuk, Laure Vendier, Lionel Salmon, Azzedine Bousseksou","doi":"10.1039/d4dt02244k","DOIUrl":"https://doi.org/10.1039/d4dt02244k","url":null,"abstract":"In this paper, we report the synthesis of six novel triazol-based heteroscorpionate ligands based on heterocycle metathesis reactions and their Iron(II) complexes. Single crystal structural analyses, spectroscopic and magnetic properties of the obtained complexes were studied and their spin crossover-structural relationships compared to those obtained for their pyrazole-based analogues reported in the literature. In particular, the amino derivative complex Bis[hydrobis(pyrazol-1-yl)(3-amino-1,2,4-triazol-1-yl)]iron(II) obtained by post synthetic catalytic nitro-group reduction under pressure of hydrogen in an autoclave presents a scarce gradual spin crossover behavior encompassing room temperature. The profile of the SCO curve can be explain by the presence of only relatively weak H-bondings spreading only in one dimension. Among the interesting spin transition behaviors observed for the different complexes, such stable, complete and gradual spin crossover at room temperature makes this neutral complex a good candidate for sublimation and future investigation as active element notably for thermoreflectance-based surface microthermometry applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324940","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":"Gelatin and sodium alginate derived carbon/silicon composites as high-performance anode materials for lithium-ion batteries","authors":"Liyang Lin, Mengjun Li, Ying Yan, Yuanhao Tian, Juan Qing, Susu Chen","doi":"10.1039/d4dt02623c","DOIUrl":"https://doi.org/10.1039/d4dt02623c","url":null,"abstract":"The volume expansion and poor conductivity greatly limit the application of silicon as an anode for lithium-ion batteries. Although nanocrystallization of silicon and its surface carbon coating can be improved to some extent, the serious problems of particle aggregation and structural instability have not been effectively solved. In this paper, gelatin and sodium alginate (GE+SA) derived carbon/silicon composites are successfully prepared by liquid-phase method, freeze-drying technique, and heat treatment. Si nanoparticles (NPs) are uniformly encapsulated in a three-dimensional network of N-doped carbon that is enriched with rich pore structure. The reversible capacity of the particular Si@C composite electrode was maintained at 580 mAh g−1 after 300 cycles at a current density of 1 A g−1, showing good cycling stability. Meanwhile, the anode also has excellent rate performance with reversible capacities of 2230, 1458, 1101, and 686.6 mAh g−1 at current densities of 0.1, 0.5, 1, and 2 A g−1, respectively. The GE+SA derived carbon/silicon composites effectively solve the problems of particle aggregation and unstable carbon/silicon interface structure, and can become one of the candidates for anode materials in lithium-ion batteries.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321500","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":"ZnVO3: an ilmenite-type vanadium oxide hosting robust V–V dimers","authors":"Hajime Yamamoto, Takumi Nishikubo, Shintaro Kobayashi, Kazuki Takahashi, Masaki Azuma, Shogo Kawaguchi, Tadashi Abukawa","doi":"10.1039/d4dt02239d","DOIUrl":"https://doi.org/10.1039/d4dt02239d","url":null,"abstract":"Ilmenite-type vanadium oxides exhibit a distinctive cation-dimerization behavior. Here, we report a novel ilmenite-type compound, ZnVO<small>₃</small>. Polycrystalline ZnVO<small>₃</small> samples are synthesized under conditions of 10 GPa and 1573 K. The obtained sample crystallizes in the triclinic <em>P</em><img alt=\"[1 with combining macron]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_0031_0304.gif\"> space group. Both V–V and Zn–Zn dimers (dimer-like displacement) are present in the structure, arranged in a ladder-like pattern on each honeycomb lattice. Notably, the V–V dimer persists up to 625 K, surpassing the stability of the V–V dimer state in other ilmenite-type vanadium oxides. Magnetic susceptibility measurements corroborate the formation of direct V–V bond in the dimer. The off-centered position of the Zn<small>²⁺</small> ion at the octahedral site, driven by Zn–O covalency and its sp<small>³</small> nature, promotes the Zn–Zn dimer-like displacement. Cooperative distortions between honeycomb layers further reinforce the V–V dimers. This finding offers insights into controlling cation-dimer strength in crystalline compounds <em>via</em> crystal structure distortions.</img>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321505","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":"Temperature tunable terahertz metamaterial device based on VO2 phase transition principle","authors":"Hao Sun, Tangyou Sun, Qianju Song, Liang Bian, Zao Yi, Jianguo Zhang, Zhiqiang hao, Chaojun Tang, Pinghui Wu, Qingdong Zeng","doi":"10.1039/d4dt02412e","DOIUrl":"https://doi.org/10.1039/d4dt02412e","url":null,"abstract":"Terahertz devices play an irreplaceable role in the development of terahertz technology. The bad thing is that many natural materials are difficult to respond in terahertz band, so the devices made of them have single function. In order to realize the diversity and tunability of device functions, we designed a terahertz metamaterial device composed of thermally induced phase change material VO2. The device structure is composed of Au bottom layer, SiO2 dielectric layer and VO2 top layer. We use the three-dimensional electromagnetic simulation, and use Bruggeman effective medium theory to clarify the phase transition characteristics of vanadium dioxide, while the Drude model establishes the functional relationship between the conductivity of vanadium dioxide and temperature. The basic principle behind high absorptivity is expounded by using impedance matching theory. Through software simulation, we know that when T=313 K, the device has complete reflection ability in the whole terahertz band. When T=342 K, the average absorption rate is above 95% in the ultra wideband range of 4.71~9.41 THz, and the absorption rate reaches an amazing 0.99999 at 6.31 THz, so the maximum thermal modulation range of the device is 0.001-0.99999, which exceeds the vast majority of current absorbers. By illustrating the electric field intensity distribution on the device surface pre and post the phase transition temperature during the heating process, we substantiate the vanadium dioxide phase transition and elucidate the transformation of device performance. Furthermore, absorptivity diagrams for the device with distinct structures are depicted to further exemplify the impact of each structure on the device's absorption characteristics. We explored the influence of the geometric size of the device on the absorptivity, which provides a certain reference value for practical application. In a word, we have designed a tunable terahertz device with simple structure, high absorption rate, wide absorption bandwidth, which can be used in the fields of energy collection, electromagnetic stealth, modulation and so on.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321502","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":"Ligand triggered antenna effect and dual emissions in Eu(III) MOF and its application in multi-mode sensing of 1,4-dioxane","authors":"Madhulekha Gogoi, Sanmilan Jyoti Kalita, Jyotirmoy Deb, Ankur Gogoi, Lakshi Saikia","doi":"10.1039/d4dt01709a","DOIUrl":"https://doi.org/10.1039/d4dt01709a","url":null,"abstract":"A new set of metal organic frameworks were designed by functionalizing g-C3N4 with benzoic acid and using them as structure directing ligand during metal-organic framework (MOF) formation. One such MOF exhibited dual emissions, both metal- and ligand-centered, enabling ratiometric sensing of the carcinogenic industrial solvent dioxane. The fabricated MOFs possessed a unique fluffy spherical morphology that enabled atomic level resolution in transmission electron microscopy—a rarity in MOFs due to the 'Knock-on' effect. Sensor experiments showed a rapid response within 5 seconds of analyte introduction and achieved a low limit of detection (LOD) of 0.026 ppm, well below the FDA-approved level of 10 ppm. In addition, the sensor exhibited exceptional selectivity, discriminating 1,4-dioxane from a pool of 16 solvents. This increased sensing capability was attributed to the formation of complexes and precise alignment of energy levels between the host and analyte, facilitating photoinduced electron transfer (PET). This material is equally efficient for colorimetric detection of the same solvent under excitation of UV light as well as gas phase detection of this volatile organic compound through I-V characteristics. Density functional theory (DFT) analysis supported the crucial role of Eu and the ligand system in the efficient detection of 1,4-dioxane by fluorescence spectroscopy, as shown in the energy level diagram. Future research could focus on optimizing these metal-organic frameworks for enhanced industrial applications in the detection of dioxane and exploring their potential applications in real-world environmental monitoring and public health safety.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321501","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":"Cation Induced Changes to the Structure of Cryptophane Cages","authors":"Oscar H. Lloyd Williams, Claudia S. Cox, Meng Y. Zhang, Martina Lessio, Olivia Rusli, William Donald, Lachlan Jekimovs, David Marshall, Michael Craig Pfrunder, Berwyck Poad, Thierry Brotin, Nicole Joy Rijs","doi":"10.1039/d4dt01824a","DOIUrl":"https://doi.org/10.1039/d4dt01824a","url":null,"abstract":"Here the monocation complexes of seven anti-cryptophanes are examined with high-resolution ion-mobility mass spectrometry. The relative size of the [cation+cryptophane]<small>⁺</small> complexes were compared based on their measured mobilities and derived collisional cross sections. A paradoxical trend of structural contraction was observed for complexes of increasing cation size. Density functional theory confirmed encapsulation occurs for cation = Na<small>⁺</small>, K<small>⁺</small>, Rb<small>⁺</small>, Cs<small>⁺</small> and NH<small>₄</small><small>⁺</small>. However, cation = Li<small>⁺</small> preferred oxygen coordination at a linker over encapsulation within the cavity, leading to a slightly larger gas phase structure overall. Protonated cryptophanes yielded much larger collision cross sections via imploded cryptophane structures. Thus, competing physical effects led to the observed non-periodic size trend of the complexes. Trends in complexation from isothermal titration calorimetry and other condensed phase techniques were borne out by the gas phase studies. Further, predicted cavity sizes compared with the gas phase experimental findings reveal more about the encapsulation mechanisms themselves.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321846","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":"Activation of uranyl peroxides by ionizing radiation prior to uranyl carbonate formation","authors":"Zoe Emory, Peter C Burns, Jay LaVerne","doi":"10.1039/d4dt01841a","DOIUrl":"https://doi.org/10.1039/d4dt01841a","url":null,"abstract":"The solid form of the uranyl peroxide cage (UPC) cluster LiU28 (Li28[(UO2)28(O2)42]) was irradiated by 5 MeV He2+ ions to achieve doses up to 42 MGy. An intermediate compound formed that reacts with atmospheric CO2 to form uranyl carbonates. The role of water in the UPC to uranyl carbonate transformation was studied by flowing either dry or hydrated Ar over samples during He2+ irradiation, and by storing samples in dry and humid environments before and after irradiation. Raman, infrared, and X-ray photoelectron spectroscopies and electrospray ionization mass spectrometry were used to characterize solid Li-U28 salts before and after He2+ irradiation. The highest yield of uranyl carbonates occurred when hydrated Ar gas was flowed across the sample during He2+ irradiation. Electron paramagnetic resonance spectroscopy provided evidence of hydroxyl and superoxide radicals in both unirradiated and -irradiated Li-U28.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324912","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":"Influence of annealing temperature on persistent luminescence in BaAl2O4:Eu2+/Eu3+ nanocrystals and its application for latent fingerprint detection","authors":"Shivaramu N J, Divya Janardhana, Lucas Erasmus, Elizabeth Coetsee, David Edmond Motaung, Hendrik Christoffel Swart","doi":"10.1039/d4dt01680g","DOIUrl":"https://doi.org/10.1039/d4dt01680g","url":null,"abstract":"The luminescent properties of Europium (Eu) doped BaAl2O4 phosphors were strongly influenced by post-annealing temperatures for blue-green persistent luminescence and latent fingerprints (LFPs). The X-ray powder diffraction patterns of the BaAl2O4: 1 mol% Eu nanophosphor, annealed between 1000 and 1300 °C, indicated a hexagonal ferroelectric phase. The X-ray photoelectron spectroscopy (XPS) revealed that the Ba atoms occupied two different sites in the BaAl2O4. The XPS and photoluminescence (PL) results revealed the presence of Eu3+ and Eu2+ states. The Eu-doped BaAl2O4 showed the characteristic red emission of Eu3+ at 251 and 464 nm excitations, while excitations at 340 and 380 nm showed yellowish-green emission. Strong evidence of energy transfer between a charge transfer band and the different energy levels of Eu2+ and Eu3+ ions was obtained. The existence of the Cr ion impurity in the aluminates was confirmed with UV-VIS diffuse reflectance and PL spectroscopy. The present results suggested that [Eu3+]Ba, • [Eu3+]Ba' and Oiʹʹ defects have introduced electron and hole traps in the host that acted as luminescent centers for persistent luminescence. LFPs detection using BaAl2O3:Eu2+/Eu3+ phosphor showed an excellent marking agent for applications in forensic science.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317633","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":"(Imidazol-2-ylidene)→S Coordination Interaction and its Modulation Upon S-Oxidation","authors":"Joy Mukhopadhyay, Prasad V. Bharatam, Subash Chandra Sahoo","doi":"10.1039/d4dt02286f","DOIUrl":"https://doi.org/10.1039/d4dt02286f","url":null,"abstract":"(NHC)→E coordination interactions are being explored in many chemical species, including carbones, and nitreones. (NHC)→S interactions are rare, but increasing attention is being paid to the compounds containing such interactions. The electron deficiency at the S centre is responsible for triggering electron donation from the NHC unit in (NHC)→SR(+) systems. It is well known that the positive charge at the sulfur centre increases upon single oxidation and further increases upon double oxidation. This implies that (NHC)→S interactions may get explicit after S-oxidation in (NHC)→SR(+) systems. To explore this hypothesis, we performed quantum chemical design and synthesis of (NHC)→SR(+), (NHC)→S(O)R(+), (NHC)→S(O)2R(+) complexes in which the ligands are imidazol-2-ylidene derivatives. Eight derivatives of (imidazol-2-ylidene)→SR(+) systems were generated, and their sulfoxide and sulfone derivatives were obtained by oxidising using (Urea-H2O2 and mCPBA, respectively). The crystal structures of three compounds belonging to a series were obtained. A comparison of the geometric, energetic and electronic characteristics confirmed the hypothesis that the (NHC)→S coordination interaction becomes comparatively stronger with an increase in oxygen atoms at the sulfur centre.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317634","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}