Rosa Maria Dell’Acqua, Veronica Schifano, Maria Vittoria Dozzi, Laura D’Alfonso, Monica Panigati, Paola Rusmini, Margherita Piccolella, Angelo Poletti, Silvia Cauteruccio, Daniela Maggioni
{"title":"Luminescent Iridium-Peptide Nucleic Acid Bioconjugate as Photosensitizer for Singlet Oxygen Production toward a Potential Dual Therapeutic Agent","authors":"Rosa Maria Dell’Acqua, Veronica Schifano, Maria Vittoria Dozzi, Laura D’Alfonso, Monica Panigati, Paola Rusmini, Margherita Piccolella, Angelo Poletti, Silvia Cauteruccio, Daniela Maggioni","doi":"10.1021/acs.inorgchem.4c05359","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05359","url":null,"abstract":"A novel bioorganometallic PNA conjugate (<b>Ir-PNA</b>) was synthesized by covalently bonding a model PNA tetramer to a luminescent bis-cyclometalated Ir(III) complex that acted as a photosensitizer under light irradiation to generate singlet oxygen (<sup>1</sup>O<sub>2</sub>). The conjugate was prepared using an Ir complex bearing the 1,10-phenanthroline ligand functionalized with either a free primary amine (<b>Ir-NH</b><sub><b>2</b></sub>) or a carboxyl group (<b>Ir-COOH</b>) for the conjugation to PNA. The photophysical studies on the <b>Ir-COOH</b> and the <b>Ir-PNA</b> demonstrated that the luminescent properties were maintained after the conjugation of the Ir fragment to PNA. Furthermore, the abilities to produce <sup>1</sup>O<sub>2</sub> of <b>Ir-COOH</b> and <b>Ir-PNA</b> were confirmed in a cuvette under visible light irradiation employing 1,5-dihydroxynaphthalene as a reporter, and the measured singlet oxygen quantum yield (Φ<sub>Δ</sub>) supported the <b>Ir-PNA</b> conjugate efficacy as a photosensitizer (Φ<sub>Δ</sub> = 0.54). Two-photon absorption microscopy on HeLa cells revealed that <b>Ir-PNA</b> localized in both the cytosol and nucleus, suggesting its potential as an intracellular carrier for PNA. Cytotoxicity assays by MTT tests showed that <b>Ir-PNA</b> was nontoxic in the absence of light, but induced cell death (EC<sub>50</sub> = 18 μM) after UV irradiation. Overall, the <b>Ir-PNA</b> conjugate represents a promising system for the intracellular delivery of the PNA and its application in PDT.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"70 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723801","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Enhanced Oxidative Coupling of Thiols to Disulfides Using the Visible-Light-Responsive POM@MOF Constructed with Ru Metalloligands","authors":"Luoning Li, Yanan Liu, Jing Wang, Minzhen Cai, Pengtao Ma, Jingping Wang, Jingyang Niu","doi":"10.1021/acs.inorgchem.5c00125","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00125","url":null,"abstract":"The photocatalytic oxidative coupling of thiols to disulfides by using visible light represents an economically viable and environmentally sustainable strategy. A novel POM@MOF photocatalyst (Ru–CdS–SiW) was synthesized through the encapsulation of Keggin-type [SiW<sub>12</sub>O<sub>40</sub>]<sup>4–</sup> within a MOF composed of Ru metalloligands and {Cd<sub>4</sub>S<sub>2</sub>O<sub>16</sub>} clusters. In this structure, the incorporation of POMs to the MOFs reduced the charge transport distance, facilitated the separation and transfer of photogenerated charges and holes, and prevented the recombination of electron–hole pairs. The Ru–CdS–SiW catalyst demonstrated exceptional catalytic performance, achieving a 98.1% yield in the S–S bond formation from 4-methylthiophenol coupling with an apparent quantum yield of 4.8% at 440 nm. Through comprehensive exploratory experiments and electron paramagnetic resonance (EPR) measurements, we elucidated the mechanism underlying the photoinduced oxidative coupling of thiols. Notably, this catalytic reaction operates under mild visible-light conditions and exhibits remarkable recyclability, presenting significant potential for applications in sensitive systems, such as protein disulfide bond formation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"81 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rose Jordan, Sam Kler, Iván Maisuls, Niklas Klosterhalfen, Benjamin Dietzek-Ivanšić, Cristian A. Strassert, Axel Klein
{"title":"Synthesis and Photophysics of the Doubly Cyclometalated Pd(II) Complexes [Pd(C∧N∧C)(L)], L = PPh3, AsPh3, and SbPh3","authors":"Rose Jordan, Sam Kler, Iván Maisuls, Niklas Klosterhalfen, Benjamin Dietzek-Ivanšić, Cristian A. Strassert, Axel Klein","doi":"10.1021/acs.inorgchem.4c05436","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05436","url":null,"abstract":"While Pt(II) complexes containing doubly cyclometalated ligands as tridentate luminophores are well studied, the synthetic accessibility of their Pd(II) counterparts was lacking for a long time. Inspired by a recent report on the synthesis of [Pd(dpp)(PPh<sub>3</sub>)] involving the C<sup>∧</sup>N<sup>∧</sup>C coordination mode (with dpp<sup>2–</sup> = 2,6-di(phenid-2-yl)pyridine) and following our own work on closely related Pt(II)-based compounds, we produced the series of complexes [Pd(dpp)(PnPh<sub>3</sub>)] (Pn = P, As, Sb) by optimizing the synthetic procedure and exploring their reactivity in the process. Our study of the electrochemical (cyclic voltammetry) and photophysical (UV–vis absorption and emission, transient absorption (TA) spectroscopy) properties of the Pd(C<sup>∧</sup>N<sup>∧</sup>C) complexes represents the first report on their characterization. We observed UV–vis absorption bands down to 450 nm and electrochemical HOMO–LUMO gaps around 3.2 V, which show minimal variation with different PnPh<sub>3</sub> coligands. A more pronounced influence of the coligand was observed in time-resolved emission and TA spectroscopy. The highest photoluminescence quantum yield (Φ<sub>L</sub>) in the series was found for [Pd(dpp)(AsPh<sub>3</sub>)], reaching 0.06. The interpretation of the spectroscopic data is supported by (TD-)DFT calculations. Additionally, we report structural and spectroscopic data for several dinuclear Pd(II) complexes, including the precursor {[Pd(dppH)(μ-Cl)]}<sub>2</sub> and multiple decomposition products of the sensitive compounds [Pd(dpp)(PnPh<sub>3</sub>)].","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"125 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713619","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Seulgi Kim, Taehun Kim, Kyunghye Ju, Je Hyun Bae, In-Hyeok Park
{"title":"SCSC Transformation of Heterobimetallic 2D MOF to Homometallic 2D MOF via Solvent-Assisted Removal of Second Metal Component: An Add-and-Remove Strategy","authors":"Seulgi Kim, Taehun Kim, Kyunghye Ju, Je Hyun Bae, In-Hyeok Park","doi":"10.1021/acs.inorgchem.4c05422","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05422","url":null,"abstract":"Constructing high-dimensional metal–organic framework (MOF) materials that cannot be reached by direct methods is demanding. We herein report the construction of a two-dimensional (2D) copper(I) iodide MOF via an add-and-remove strategy of a second metal component (HgI<sub>2</sub>). The networking reaction of an O<sub>2</sub>S<sub>2</sub>-macrocycle (<b>L</b>) with CuI via a bridging exocyclic coordination under the direct condition was unsatisfactory because of its one-dimensional (1D) product {[(μ<sub>4</sub>-Cu<sub>3</sub>I<sub>3</sub>)(<b>L</b>)<sub>2</sub>]·2CH<sub>3</sub>CN·CH<sub>2</sub>Cl<sub>2</sub>}<sub><i>n</i></sub> (<b>1</b>) with low yield. Alternatively, the self-assembly of <b>L</b> with a mixture of CuI and HgI<sub>2</sub> allows the generation of a 2D heterobimetallic Cu(I)/Hg(II)-MOF {[Cu<sub>2</sub>(μ-Hg<sub>2</sub>I<sub>4</sub>)(<b>L</b>)<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub>I<sub>2</sub>]·toluene}<sub><i>n</i></sub> (<b>2</b>, brick wall) cross-linked by μ-Hg<sub>2</sub>I<sub>4</sub> square dimers via the bridging exocoordination mode. When the crystals of <b>2</b> were immersed in methanol, the crystals were converted to a desired 2D Cu(I)-MOF [(μ<sub>4</sub>-Cu<sub>2</sub>I<sub>2</sub>)(<b>L</b>)<sub>2</sub>]<sub><i>n</i></sub> (<b>3</b>, square grid) by the replacement of the cross-linker μ-Hg<sub>2</sub>I<sub>4</sub> with μ<sub>4</sub>-Cu<sub>2</sub>I<sub>2</sub> via the solvent-assisted etching. Interestingly, this 2D–[1D]*–2D conversion process that proceeds in an SCSC mode is completed by the dimerization of open coordinating site CuI* to form a μ<sub>4</sub>-Cu<sub>2</sub>I<sub>2</sub> node (2CuI* → Cu<sub>2</sub>I<sub>2</sub>), preserving the 2D dimensionality. The conversion process is discussed based on PXRD, EDX, AFM, TGA, and NMR data.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Metal-Induced Amide Deprotonation and Binding Typical for Cu(II), Not Possible for Zn(II) and Fe(II)","authors":"Silvia Leveraro, Valentyn Dzyhovskyi, Kinga Garstka, Agnieszka Szebesczyk, Fabio Zobi, Denise Bellotti, Kamila Stokowa-Sołtys, Maurizio Remelli, Magdalena Rowińska-Żyrek","doi":"10.1021/acs.inorgchem.5c00672","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00672","url":null,"abstract":"Amide groups of the peptide backbone are very weak acids. In fact, their deprotonation in water solution is not a phenomenon usually observed in the measuring range of a glass electrode unless the proton is displaced by a metal such as Cu(II) or Ni(II). Other metals are not usually expected to deprotonate and bind to amide nitrogens, although, lately, some controversies have started to arise in the literature, suggesting that Zn(II) and Fe(II) may be capable of doing so. In order to clarify this phenomenon, we chose to study simple metal–peptide systems with Ala-to-Pro mutations, which excluded further amides from binding. A comparison of the metal-binding modes of Ac-AAAHAAA-NH<sub>2</sub>, Ac-AAPHAAA-NH<sub>2</sub>, and Ac-AAPHPAA-NH<sub>2</sub> complexes with Cu(II), Zn(II), and Fe(II) is a simple and elegant way of showing that neither Zn(II) nor Fe(II) is able to deprotonate and bind to amide nitrogens.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shoaib Azeem, Joaquín Soriano-López, Isaac Brotons-Alcázar, Christopher Allen, Ramón Torres-Cavanillas, Roger Sanchis-Gual, Eugenio Coronado
{"title":"Design of Core@Shell Nanoparticles Based on Gold and Magnetic NiFe Prussian-Blue Analogues Featuring Shape-Dependent Magnetic and Electrochemical Activity","authors":"Shoaib Azeem, Joaquín Soriano-López, Isaac Brotons-Alcázar, Christopher Allen, Ramón Torres-Cavanillas, Roger Sanchis-Gual, Eugenio Coronado","doi":"10.1021/acs.inorgchem.4c05320","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05320","url":null,"abstract":"Au@Prussian-Blue analogue (PBA) core@shell nanoparticles (NPs) are highly versatile nanostructures with complementary and shape-dependent properties of interest in the current technologies. However, due to the high reactivity of cyanides toward Au, scarce PBAs have been successfully synthesized in direct contact with Au NPs, leaving the formation of anisotropic Au@PBA NPs as a significant synthetic challenge. Here, we have developed a robust protocol for synthesizing core@shell NPs, composed of a magnetic CsNi[Fe(CN)<sub>6</sub>] PBA shell grown on individual Au NPs, regardless of the core morphology (spheres, rods, or stars). Specifically, the uniqueness of our protocol lies in the prior Au core functionalization with anchoring molecules that facilitate PBA growth while preventing Au etching and preserving the initial oxidation states of the metals. This has afforded direct growth of ferromagnetic Ni<sup>II</sup>Fe<sup>III</sup> PBAs on Au NPs. Moreover, by exploiting the structural mismatch at the Au/PBA interface and the curvature of anisotropic Au templates, we manage to induce a substantial structural strain within the PBA shell. When star-shaped Au nanoparticles are used, a maximum strain of 2.0% is reached. This strain combined with an increased polycrystallinity lead to modifications in the PBA catalytic properties, resulting in a 10-fold improvement in the intrinsic electrocatalytic activity.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ökten Üngör, Sara Termos, Robert W. Schurko, Joseph M. Zadrozny
{"title":"59Co Thermal Sensitivity in Co(III) Trisdithiocarbamate Complexes","authors":"Ökten Üngör, Sara Termos, Robert W. Schurko, Joseph M. Zadrozny","doi":"10.1021/acs.inorgchem.4c05385","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05385","url":null,"abstract":"Understanding temperature sensitivity in magnetic resonance is key to novel molecular probes for noninvasive temperature mapping. Herein, we report an investigation of the effects of heavy-donor-atom dithiocarbamate ligands on the variable-temperature <sup>59</sup>Co nuclear magnetic resonance (NMR) properties of six Co(III) complexes: Co(et<sub>2</sub>-dtc)<sub>3</sub> (<b>1</b>), Co(bu<sub>2</sub>-dtc)<sub>3</sub> (<b>2</b>), Co(hex<sub>2</sub>-dtc)<sub>3</sub> (<b>3</b>), Co(pyrr-dtc)<sub>3</sub> (<b>4</b>), Co(benzyl<sub>2</sub>-dtc)<sub>3</sub> (<b>5</b>) and Co(2,6-dmpip-dtc)<sub>3</sub> (<b>6</b>) (et<sub>2</sub>-dtc = diethyldithiocarbamate; bu<sub>2</sub>-dtc = dibutyldithiocarbamate; hex<sub>2</sub>-dtc = dihexyldithiocarbamate; pyrr-dtc = pyrrolidine-dithiocarbamate; benzyl<sub>2</sub>-dtc = dibenzyldithiocarbamate; and 2,6-dmpip-dtc = 2,6-dimethylpiperidine-dithiocarbamate). This study reveals <sup>59</sup>Co chemical-shift temperature dependences of 1.17(3)–1.73(4) ppm/°C as a function of ligand substituents. Solid-state Raman spectroscopic analyses show that more Raman-active Co–S<sub>6</sub> vibrational modes correlate to higher thermal sensitivities for these compounds, in line with our current model for temperature sensitivity. Short spin–lattice relaxation <i>T</i><sub>1</sub> times in solution (<i>ca</i>. 200 μs) were observed, and correlation with <i>T</i><sub>2</sub>* times and solid-state <sup>59</sup>Co NMR analyses reveal that the solution-phase line widths are attributable to quadrupolar relaxation processes, which ultimately lower temperature-sensing resolution.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"57 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713653","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nils Ansmann, Jakob H. Alberts, Finn Hagen, Immanuel E. Blaum, Lutz Greb
{"title":"Co-Ligand-Dependent Rh(I)–Si(IV) Interactions in Silicon Z-Type Complexes","authors":"Nils Ansmann, Jakob H. Alberts, Finn Hagen, Immanuel E. Blaum, Lutz Greb","doi":"10.1021/acs.inorgchem.5c00368","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00368","url":null,"abstract":"Rh(I) Z-type complexes featuring σ-accepting group 13 Lewis acids have been well established over recent years and proven efficient in catalytic transformations. In this work, we report the isolation and characterization of the first Rh(I) silane Z-type complexes. Distinct properties compared to their group 13 counterparts are exhibited due to the high effective Lewis acidity of Si(IV), which leads to remarkably strong Rh(I)–Si(IV) bonding. The nature of this interaction is found to be highly dependent on the choice of coligands at Rh(I) (e.g., Cl, Me, Cp, H, and CNCy). Through a combination of experimental techniques and quantum chemical analyses (NBO, QTAIM, and ETS-NOCV), we systematically investigate this coligand dependency. These findings provide valuable insights into the design and optimization of catalytically active Rh(I) Z-type complexes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Lanthanide-Incorporated PIII–SbIII-Heteroatom-Templated Tetrahedral Heteropolyoxometalate Cluster for Detecting Early Tumor Marker MicroRNA-155","authors":"Yu Liu, Zhigang Tang, Yanfeng Pu, Junwei Zhao, Lijuan Chen","doi":"10.1021/acs.inorgchem.5c00279","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00279","url":null,"abstract":"Heteropolyoxometalates have garnered widespread attention owing to their diverse structures and intriguing physicochemical properties. Herein, we successfully synthesized a unique lanthanide-incorporated P<sup>III</sup>–Sb<sup>III</sup>-heteroatom-templated tetrahedral polyoxometalate cluster [H<sub>2</sub>N(CH<sub>3</sub>)<sub>2</sub>]<sub>20</sub>Na<sub>7</sub>H<sub>7</sub>{[Er<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>][W<sub>4</sub>O<sub>16</sub>][HPSbW<sub>15</sub>O<sub>54</sub>]<sub>4</sub>}·132H<sub>2</sub>O (<b>1</b>). The polyoxoanion of <b>1</b> can be perceived as four trilacunary Dawson [HPSbW<sub>15</sub>O<sub>54</sub>]<sup>11–</sup> {PSbW<sub>15</sub>} building blocks encapsulating a deca-nuclear heterometallic [Er<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>W<sub>4</sub>O<sub>16</sub>]<sup>10+</sup> cluster. This heterometallic cluster comprises an inner tetrahedral [W<sub>4</sub>O<sub>16</sub>]<sup>8–</sup> ({W<sub>4</sub>}) core surrounded by an octahedral [Er<sub>6</sub>(H<sub>2</sub>O)<sub>6</sub>]<sup>18+</sup> ({Er<sub>6</sub>}) shell. Consequently, the polyoxoanion of <b>1</b> exhibits the distinctive ({W<sub>4</sub>} ⊂ {Er<sub>6</sub>} ⊂ [{PSbW<sub>15</sub>}]<sub>4</sub>) three-shell structure. Considering the electron transfer characteristics of <b>1</b>, it was coelectropolymerized with <i>N</i>-methylpyrrole (NMPy) to fabricate the <b>1</b>–PNMPy film (PNMPy = polyNMPy). Notably, the incorporation of <b>1</b> improves the electron distribution within the PNMPy backbone, thereby narrowing the band gap of PNMPy and enhancing the conductive performance of the <b>1</b>–PNMPy film. Therefore, the <b>1</b>–PNMPy film is utilized as the modified electrode material to construct an electrochemical biosensor for the sensitive detection of the tumor marker microRNA-155. This research not only provides a viable approach for the fabrication of multishell heteropolyoxometalates but also promotes the exploration and application of multicomposition polyoxometalates in electrochemical biosensing microRNA.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"110 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713657","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Host–Guest Approach to Enhancing Photocatalysis via Photoinduced Energy and Electron Transfer from a Photoactive Triphenylamine-Based Metal–Organic Cage to Bound Guests","authors":"Hechuan Li, Jing Wang, Wenting Zhu, Danyang Li, Xuezhao Li, Cheng He","doi":"10.1021/acs.inorgchem.5c00145","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00145","url":null,"abstract":"The host–guest strategy presents an ideal way to construct versatile supramolecular systems that mimic the structure and functionality of natural enzymes and, therefore, achieve efficient chemical conversions. An emissive triphenylamine-based cage-like host donor was constructed as an energy or electron donor to achieve efficient photoinduced energy or electron transfer (PEnT or PET) by encapsulating the energy or electron acceptor into the cavity of the cage. The host–guest complexes, which served as enzyme-mimicking supramolecular systems, were successfully used as photocatalysts for the selective aerobic oxidation of sulfides and the efficient photocatalytic reduction of aryl halides with high reduction potentials. This work details a promising approach for creating a host–guest system via a host–guest encapsulation strategy to enhance the efficiency of the PEnT or PET process. The resulting designed artificial supramolecular systems achieve efficient chemical conversions by mimicking the structure and functionality of natural enzymes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}