Inorganic Chemistry Frontiers最新文献

{"title":"Fat or flat? The impact of dipole moment vectors on non-covalent interactions between aromatic tags and macromolecules.","authors":"Josef Holub,Adéla Jílková,Carina Lemke,Lorenzo Cianni,Petra Spiwoková,Martin Horn,Christian Breuer,Adrian Leontovyč,Jiří Brynda,Helena Mertlíková-Kaiserová,Marta Chanová,Fernanda Dos Reis Rocho,Carlos A Montanari,Nelly El-Sakkary,Conor R Caffrey,Michael Gütschow,Drahomír Hnyk,Michael Mareš,Jindřich Fanfrlík","doi":"10.1039/d5qi01546d","DOIUrl":"https://doi.org/10.1039/d5qi01546d","url":null,"abstract":"The closo-1,2-C2B10H12 carborane is a recognized 3D aromatic icosahedral building block, with an electron distribution governed by the outer hydridic BH and acidic CH vertices. We attached the carborane cage to a peptidomimetic scaffold to generate an active-site inhibitor of SmCB1, a protease drug target in the Schistosoma pathogen. The carborane-tagged compound exhibited superior inhibitor affinity and bioactivity compared to its conventional 2D aromatic phenyl analog. Quantum mechanical computations, based on the crystal structure of the protease-inhibitor complex, revealed that the carborane tag contributed to inhibitor binding not only through nonpolar interactions but also via a key hydrogen bond between its CH vertex and a negatively charged residue in the binding site. This interaction, driven by the large dipole moment of the carborane cage, resulted in a more favorable energy contribution than that of the phenyl group in the 2D analog. The carborane pharmacophore boosted affinity for SmCB1 and conferred specific anti-schistosomal activity, highlighting its potential in protein ligand design.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"56 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145339376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nitrogen-doped and Partly Graphitization Coal-based Hard Carbon Material for High-Performance Sodium-ion Storage in SIBs","authors":"Dong Wang, Li-rong Feng, Dejie Mo, Yutong Zhang, Xinru Zheng, Gang Xie, Xiaohui Guo","doi":"10.1039/d5qi01536g","DOIUrl":"https://doi.org/10.1039/d5qi01536g","url":null,"abstract":"Hard carbon materials are widely regarded as highly promising anode materials in sodium-ion batteries (SIBs) due to their distinctive disordered structure and high capacity. However, their practical applications are greatly limited due to high cost, as well as low conductivity and unsatisfied storage-sodium performances. In this work, we propose a cost-effective method for the preparation of nitrogen-doped and partially graphitized coal-based hard carbons (NHCs) as high-performance anode materials for SIBs. The resulting NHCs possess the structural advantages of a mesoporous structure, nitrogen doping, and homogeneous graphite domains, which facilitate rapid kinetics and electron transfer. When applied to anodes in SIBs, the NHCs can deliver a high reversible capacity of 291.45 mAh/g, a high initial Coulombic efficiency of 88.1%, as well as an impressive cycling stability of 132.7 mAh/g even after 500 cycles at 1 A/g. In a word, the coal-based hard carbon materials prepared using the straightforward yet effective method have the potential for large-scale energy-related applications in terms of economical precursors, simple synthesis process and excellent storage-energy performances.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145311494","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational Design of Helical Artificial Metallopeptides: From Sequence to Activity in Pd-Peptide Systems","authors":"Anton Domnin, Yaroslav V. Solovev, Denis S Syrko, Andrey V Golovin, Robert Alexandrovich Evarestov, Mikhail V. Polynski","doi":"10.1039/d5qi01794g","DOIUrl":"https://doi.org/10.1039/d5qi01794g","url":null,"abstract":"Artificial metallopeptides hold immense potential to combine enzymatic activity with the versatility of organometallic catalysts. However, computational de novo design is largely limited to theozyme models that may neglect second-sphere atomic structure, overlook hydrogen-bonding networks, and ignore metal-induced conformational selection. We overcome these limitations for the case of helical metallopeptides and metal-containing helical motifs by proposing a DFT-based bottom-up methodology applied to the design of Pd-binding (Met-X)<small>_n</small> sequences (X = Ala, Val, Ile). Line group symmetry theory is employed to accelerate the calculations by leveraging helical monoperiodicity for computational efficiency. The methodology (a) reproduces the geometric parameters of α-poly-Ala with near-experimental accuracy; (b) to the best of our knowledge, provides the first evidence that the α⟶π-transition may manifest as a first-order phase transition; (c) identifies (Met-Ala)<small>_n</small> π-helices as preferred matrices for canonical Pd(II) Suzuki coupling intermediates. In contrast, Pd incorporation in the α-helical matrix poses significant challenges, as shown by relaxed potential energy scans. From the periodic π-helix, we extract a cluster containing over 250 atoms and model it in aqueous solution at the ωB97X-V/def2-TZVP-gCP//B97-3c level to obtain reliable energetics for the free energy profile of the key oxidative addition step. The profile featured a low activation barrier and exergonic product formation, with reaction energy falling within the optimal window and barriers lower than those reported for bis-phosphine Pd(0) complexes. This methodology offers an efficient strategy for the de novo design of helical peptides and motifs and environmentally benign bioinorganic catalysts, from sequence to the reactivity of the metal center.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"47 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Improper Narrow Bandgap Molecular Ferroelectrics Enable Light-Excited Pyroelectricity for Broadband Self-Powered Photoactivities","authors":"Jialu Chen, liwei tang, Chen Gong, Linjie Wei, Jingtian Zhang, Xingguang Chen, Xiaoyu Zhang, Yi Liu, Junhua Luo, Zhihua Sun","doi":"10.1039/d5qi01797a","DOIUrl":"https://doi.org/10.1039/d5qi01797a","url":null,"abstract":"Narrow bandgap ferroelectrics are emerging as critical components for assembling high-performance optoelectronic devices with broadband spectral response, yet integrating narrow bandgap and robust ferroelectricity in a single-phase material system remains a huge challenge. Herein, we report a narrow bandgap improper molecular ferroelectric, (DMAPA)BiI<small>₅</small> (<strong>1</strong>; DMAPA = dimethylaminopropylammonium), which has the band gap of 1.94 eV and spontaneous polarization (<em>P</em><small>_s</small>) value of 1.38 µC cm<small>^-2</small>. It is notable that <strong>1</strong> exhibits unusual dielectric bistability near its Curie temperature (<em>T</em><small>_c</small>) = 372 K, along with only quite small variation in dielectric constants. This characteristic of improper ferroelectricity endows <strong>1</strong> with large pyroelectric figures-of-merit. Strikingly, light-induced change of its electric <em>P</em><small>_s</small> leads to ultraviolet-to-near-infrared pyroelectricity in a wide spectral region (266–980 nm), thus achieving broadband self-powered photoactivities. High-quality thin films of <strong>1</strong> fabricated <em>via</em> spin-coating process also exhibit excellent light-induced pyroelectric effects. The integration of photoactivities in narrow bandgap improper ferroelectrics offers a promising pathway toward scalable broadband optoelectronic device application.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"66 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306220","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Long-range disordered MoZn electrocatalyst with a synergistic AEM-LOM mechanism for efficient oxygen evolution","authors":"Xiaojun Wang, Huilin Zhao, Hongdong Li, Weiping Xiao, Guangrui Xu, Guangying Fu, Lei Wang, Zexing Wu","doi":"10.1039/d5qi01605c","DOIUrl":"https://doi.org/10.1039/d5qi01605c","url":null,"abstract":"Electrocatalysts for the oxygen evolution reaction (OER) have garnered substantial attention owing to their pivotal role in water splitting for hydrogen generation. In this study, corrosion engineering is employed to synthesize a long-range disordered MoZn-based catalyst on nickel foam (MoZn/NF). The synthesized catalyst features a superhydrophilic surface, long-range disordered nanosheet array, and porous channels, enabling effective active site exposure and favorable bubble diffusion during the OER. In addition, the incorporation of Zn optimizes the surface adsorption state of *OH and reaction kinetics, shifting the adsorbate evolution mechanism (AEM) of Mo/NF to the synergistic mechanism of adsorbate evolution and lattice oxygen participation (AEM-LOM) of the MoZn/NF catalyst, thereby enhancing the catalyst's OER activity and stability. Remarkably, at a current density of 10 mA cm<small>⁻²</small>, it achieves an overpotential of 241 mV and maintains stability for 50 hours without significant degradation in 1 M KOH. Moreover, with its outstanding performance in overall water splitting (1.58 V@10 mA cm<small>⁻²</small>), the MoZn/NF electrode can be powered by sustainable energy sources, showcasing its potential for practical applications in renewable energy conversion systems. Therefore, this work provides a feasible approach for simultaneously enhancing the activity and stability of the OER process by activating the dual synergistic mechanisms, and this approach provides favorable conditions for efficient water electrolysis to generate hydrogen.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"54 64 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Immunogenic cell death-inducing Rh(I) and Ir(I) complexes with bis(imino)acenaphthene-derived ligands: Insights into the role of the metal center and the ligands","authors":"Chengnan Wu, Nikolay Filippovich Romashev, Veronica I. Komlyagina, Tamara Petrović, Ivan V. Bakaev, Pavel A. Abramov, Yuan Wang, Alexey A. Ryadun, Iakov S. Fomenko, Taotao Zou, Artem Gushchin, Maria V Babak","doi":"10.1039/d5qi00868a","DOIUrl":"https://doi.org/10.1039/d5qi00868a","url":null,"abstract":"While various metal complexes demonstrated immunogenic cell death (ICD)-inducing properties, there is a lack of studies comparing ICD properties in structurally similar complexes with different metal centers. In this study, we synthesized four structurally similar Rh(I) and Ir(I) complexes with redox-active 1,2-bis(arylimino)acenaphthene (Ar-bian) ligands and assessed their anticancer and ICD-inducing properties. Analysis of danger-associated molecular patterns (DAMPs) and dying cell populations highlighted the distinct role of the metal center, with the contribution of the ligand being less evident. Specifically, only Rh(I) complexes induced the release of the three essential DAMPs and high levels of late apoptotic cells, while the Ir(I) complexes failed to trigger crucial \"eat-me\" signals. This work offers valuable insights into understanding of structure-activity relationships in metal complexes in the context of ICD.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306216","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The impact of albumin conjugation on the cytotoxic properties of cisplatin, oxaliplatin and auranofin in cancer cells","authors":"Valentina Vitali, Lorenzo Chiaverini, Mirko Severi, Maria Letizia Trincavelli, Luigi Messori, Lara Massai, Tiziano Marzo, Chiara Giacomelli","doi":"10.1039/d5qi01487e","DOIUrl":"https://doi.org/10.1039/d5qi01487e","url":null,"abstract":"The role of human serum albumin (HSA) in the delivery of anticancer metallodrugs remains unclear and requires further investigation. To this end, bioconjugates of HSA with the metallodrugs cisplatin (CIS), oxaliplatin (OXA) and auranofin (AF) were prepared, characterised by ESI-MS and ICP, and tested for their cytotoxic properties in A2780 and HCT116 cancer cells. Significant differences in the biological activity of the two Pt bioconjugates compared to the Au bioconjugate emerged, which are interpreted and discussed in the context of the available literature.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"25 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145311688","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"NiII complex supported by an iminophosphorane ONP ligand: Synthesis and catalytic C=C and C=O bonds hydrosilylation","authors":"Ingrid Popovici, Thomas F. Akwright Arcilla, Sophie Bourcier, Nicolas Casaretto, Vincent Gandon, Audrey Auffrant","doi":"10.1039/d5qi01895a","DOIUrl":"https://doi.org/10.1039/d5qi01895a","url":null,"abstract":"An original ONP iminophosphorane ligand was synthesised and coordinated to [NiX2(DME)] (X=Cl, Br). The corresponding complexes (2X, X=Cl, Br) were isolated and characterised among others by multinuclear NMR spectroscopy and X-ray crystallography. The collected data suggest that different geometries coexist in solution at room temperature. 2Cl proved to be an efficient hydrosilylation catalyst able to perform at a loading of 1 mol % in presence of one equivalent SiH2Ph2 and 1 mol % of tBuOK, the reduction of C=C and C=O bonds in high yield in 1 h for most substrates. Moreover, the selective conversion of C=O bond to silylether linkage was observed for nine enones. Therefore, 2Cl presents a rather unique catalytic behaviour compared to previously described Ni catalysts. Both experimental and theoretical investigations regarding the mechanism suggest the involvement of a Ni-H complex. The computed mechanism presents a highest-lying transition state at only 19.0 kcal mol-1 and shows that the reaction is driven by the favorable thermodynamics.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145295960","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anomalous redshift emission in Pt(II) vs Ir(III) complexes with identical ligands and the application of these complexes in high-efficiency OLED.","authors":"Wenping Liu, Shipan Xu, Xuyang Du, Yan An, Shengli Li, Xiaolong Yang, Jun Xi, Yousong Ding, Guijiang Zhou, Yuanhui Sun","doi":"10.1039/d5qi01849h","DOIUrl":"https://doi.org/10.1039/d5qi01849h","url":null,"abstract":"Conventionally, Ir(III) complexes typically show longer emission wavelengths compared to their Pt(II) complexes with identical ligands. In this work, a series of Pt(II) and Ir(III) complexes based on identical benzothiophene ligands were designed. Experimental results demonstrate that the Pt(II) complexes exhibit red-shifted emission compared to the Ir(III) complexes. This is caused by the stronger ligand field and lower T1 energy level of the Pt(II) complexes. The device efficiency prepared by vapor deposition can reach up to 20.3% with very small efficiency roll-off, demonstrating superior performance among Ir(III) complexes bearing thiophene and related structures. Furthermore, the broader spectrum of Pt(II) complexes is suitable for the application of white light devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"92 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145295638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In situ nitrogen-doped double-shell SiOx nanospheres: a novel approach for enhancing lithium-ion battery performance","authors":"Yang Chen, Yu Tang, Leiyun Han, Yingjie Hua, Xudong Zhao, Xiaoyang Liu","doi":"10.1039/d5qi01215e","DOIUrl":"https://doi.org/10.1039/d5qi01215e","url":null,"abstract":"Effectively alleviating the volume change of silicon oxide (SiO<small>_<em>x</em></small>) anodes and improving their conductivity are crucial for enhancing the structural integrity and cycling stability of lithium-ion batteries (LIBs). In this study, ZIF-67 hollow nanospheres (ZIF-67 HNSs) were synthesized for the first time and used as templates to achieve a hollow structure, nanostructuring, and <em>in situ</em> nitrogen doping in SiO<small>_<em>x</em></small> anodes, resulting in the successful preparation of N/SiO<small>_<em>x</em></small>@N/SiO<small>_<em>x</em></small>@C double-shell layer hollow nanospheres. The material features a robust nitrogen-doped SiO<small>_<em>x</em></small> double-shell structure, which, combined with oxygen content regulation, effectively alleviates the volume expansion of high-capacity SiO<small>_<em>x</em></small> anodes. Additionally, <em>in situ</em> nitrogen doping into the SiO<small>_<em>x</em></small> matrix further optimizes the electronic conductivity and ion diffusivity. Electrochemical impedance spectroscopy and distribution of relaxation time analyses indicate that the anode exhibits excellent charge transfer kinetics and a stable solid electrolyte interfacial layer, which remains stable even after prolonged cycling. <em>In situ</em> Raman spectroscopy further confirms that the double-shell structure effectively preserves the integrity of the electrode. The anode achieves a high specific capacity of 893.1 mAh g<small>⁻¹</small> after 1000 cycles at 1 A g<small>⁻¹</small> and demonstrates excellent rate capability (447.4 mAh g<small>⁻¹</small> at 3 A g<small>⁻¹</small>). This study presents a novel approach for designing SiO<small>_<em>x</em></small> anodes with <em>in situ</em> nitrogen doping and spatially engineered double-shell structures, offering new insights into the design of high-performance LIB anodes with enhanced cycling stability and capacity retention.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145288766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}