Jiyang Tian, Jiajun Wan, Qian Zhang, Huibo Zhang, Jie Liu
Rational electrocatalyst design is an effective approach to accelerate Li₂S deposition kinetics and suppress polysulfide shuttling in Li-S batteries. Increasing the sulfur loading and cathode area is crucial to inspect their effectiveness in practical applications. However, concentrated polysulfide intermediates remain a great challenge to the cycling performance. Herein, to fast consume polysulfide intermediates, we provide a novel design strategy based on low-valent cation substitution to build highly active catalytic surfaces with massive active sites. As a proof of concept, a trimetallic perovskite oxide LaCu₀.₅Co₀.₅O₃₋ₓ (LCCO) electrocatalyst is constructed via low-valent Cu²⁺ substitution. This induces lattice self-adaptation and considerable oxygen vacancy, shifting the d-band center toward the Fermi level. Notably, the fast Li₂S deposition rate but slow Li₂S diffusion rate induces 3D electrodeposition of dense Li₂S nanoparticles, homogenizing the electric field for continuous Li₂S deposition. Consequently, Li-S batteries with LCCO-functionalized separator exhibit a high areal capacity of 5.92 mAh cm⁻² at a current density of 0.5 mA cm⁻² under a high sulfur loading (7.54 mg cm⁻²) and lean electrolyte (7 μL mg⁻¹). Furthermore, high-loading large-size pouch cells (64 cm²) with a capacity of 1024 mAh g⁻¹ at 10 mA show stable cycling. This study highlights the low-valent cation substitution strategy to modulate d-electrons for practical electrocatalysts in Li-S batteries.
{"title":"Low-valent cation substitution engineering regulates Li₂S durable electrodeposition in practical lithium-sulfur batteries","authors":"Jiyang Tian, Jiajun Wan, Qian Zhang, Huibo Zhang, Jie Liu","doi":"10.1039/d6dt00136j","DOIUrl":"https://doi.org/10.1039/d6dt00136j","url":null,"abstract":"Rational electrocatalyst design is an effective approach to accelerate Li₂S deposition kinetics and suppress polysulfide shuttling in Li-S batteries. Increasing the sulfur loading and cathode area is crucial to inspect their effectiveness in practical applications. However, concentrated polysulfide intermediates remain a great challenge to the cycling performance. Herein, to fast consume polysulfide intermediates, we provide a novel design strategy based on low-valent cation substitution to build highly active catalytic surfaces with massive active sites. As a proof of concept, a trimetallic perovskite oxide LaCu₀.₅Co₀.₅O₃₋ₓ (LCCO) electrocatalyst is constructed via low-valent Cu²⁺ substitution. This induces lattice self-adaptation and considerable oxygen vacancy, shifting the d-band center toward the Fermi level. Notably, the fast Li₂S deposition rate but slow Li₂S diffusion rate induces 3D electrodeposition of dense Li₂S nanoparticles, homogenizing the electric field for continuous Li₂S deposition. Consequently, Li-S batteries with LCCO-functionalized separator exhibit a high areal capacity of 5.92 mAh cm⁻² at a current density of 0.5 mA cm⁻² under a high sulfur loading (7.54 mg cm⁻²) and lean electrolyte (7 μL mg⁻¹). Furthermore, high-loading large-size pouch cells (64 cm²) with a capacity of 1024 mAh g⁻¹ at 10 mA show stable cycling. This study highlights the low-valent cation substitution strategy to modulate d-electrons for practical electrocatalysts in Li-S batteries.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"146 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489418","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}
The high-entropy concept has driven technological innovation in the field of rechargeable batteries, providing novel solutions for the design of material composition, structure, and electronic properties. This review systematically summarizes the development and application of high-entropy sulfides, selenides, and phosphides as anode materials in rechargeable batteries. These materials benefit from advantages such as tunable composition, structural diversity, high conductivity, and entropy-driven stability. It offers a systematic overview of the current research status and challenges to these high-entropy anode materials, focusing on synthesis strategies, characterization, structural features, electrical properties, multi-element synergism, and electrochemical performances. Future research directions, persistent challenges, and potential methodologies are identified, aiming to accelerate the fundamental understanding and practical applications of high-entropy sulfides, selenides, and phosphides in energy storage.
{"title":"Recent advances in high-entropy metal sulfides, selenides, and phosphides for use in lithium/sodium-ion batteries.","authors":"Chen Sun,Yingzhe Gong,Yukun Zhang,Shaopeng Zheng,Xiao Zhang,Jinxue Guo","doi":"10.1039/d5dt02722e","DOIUrl":"https://doi.org/10.1039/d5dt02722e","url":null,"abstract":"The high-entropy concept has driven technological innovation in the field of rechargeable batteries, providing novel solutions for the design of material composition, structure, and electronic properties. This review systematically summarizes the development and application of high-entropy sulfides, selenides, and phosphides as anode materials in rechargeable batteries. These materials benefit from advantages such as tunable composition, structural diversity, high conductivity, and entropy-driven stability. It offers a systematic overview of the current research status and challenges to these high-entropy anode materials, focusing on synthesis strategies, characterization, structural features, electrical properties, multi-element synergism, and electrochemical performances. Future research directions, persistent challenges, and potential methodologies are identified, aiming to accelerate the fundamental understanding and practical applications of high-entropy sulfides, selenides, and phosphides in energy storage.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"27 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147483685","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}
An efficient one-step synthesis of 1,3- and 1,1’-diarylferrocenes has been developed via the reaction of ferrocene with anilines. This practical method enables gram-scale preparation of the diarylsubstituted ferrocene derivatives. Furthermore, the 1,1’-diarylferrocene served as a key building block for the concise construction of a main-chain ferrocene-based macrocycle (main-Fc[11]CPP) in only two additional steps. The structure of main-Fc[11]CPP was unambiguously confirmed by single-crystal X-ray diffraction, revealing a strained ellipsoidal geometry. Photophysical and electrochemical studies demonstrate that the macrocycle exhibits intramolecular charge-transfer behavior and possesses a lower strain energy compared to its side-chain analog.
通过二茂铁与苯胺的反应，一步合成了1,3-和1,1 ' -二芳基二茂铁。这种实用的方法使二芳基取代二茂铁衍生物的克级制备成为可能。此外，1,1′-二芳基二茂铁作为一个关键的构建块，仅在两个额外的步骤中就可以简洁地构建主链二茂铁基大环（main-Fc[11]CPP）。主- fc [11]CPP的结构被单晶x射线衍射明确证实，显示出一个应变椭球几何形状。光物理和电化学研究表明，与侧链类似物相比，大环具有分子内电荷转移行为，并且具有较低的应变能。
{"title":"One-Step Synthesis of 1,3-and 1,1'-Diarylated Ferrocenes toward Main-Chain Metallomacrocycles","authors":"Wenjuan Li, Yuanping Li, Yanting Shi, Hui Xu, Ling-Yun Zhu, Xinyu Chen, Xiaopei Li, Jian-Feng Yan, Lantao Liu, Yuanming Li","doi":"10.1039/d6dt00371k","DOIUrl":"https://doi.org/10.1039/d6dt00371k","url":null,"abstract":"An efficient one-step synthesis of 1,3- and 1,1’-diarylferrocenes has been developed via the reaction of ferrocene with anilines. This practical method enables gram-scale preparation of the diarylsubstituted ferrocene derivatives. Furthermore, the 1,1’-diarylferrocene served as a key building block for the concise construction of a main-chain ferrocene-based macrocycle (main-Fc[11]CPP) in only two additional steps. The structure of main-Fc[11]CPP was unambiguously confirmed by single-crystal X-ray diffraction, revealing a strained ellipsoidal geometry. Photophysical and electrochemical studies demonstrate that the macrocycle exhibits intramolecular charge-transfer behavior and possesses a lower strain energy compared to its side-chain analog.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478628","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}
Itzel Gutiérrez-Barroso, Kevin A. Quintanilla, Merced Martínez, Eduardo Pena-Cabrera, Adriana Galvan, Miguel A. Vazquez
Retro-Aldol Condensation has emerged as a powerful strategy to produce high-value carbonyl derivatives from complex substrates. In this study, a heterogeneous catalyst was developed by immobilising a Keggin heteropoly anion on an ionic-liquid-functionalised mesocellular foam silica (HPW@MIM–MCF). The catalyst was synthesised through covalent grafting of methylimidazolium groups onto the silica surface, followed by anion metathesis with H₃PW₁₂O₄₀. The material was characterised by N₂ adsorption–desorption, FT-IR, ²⁹Si and ³¹P CP-MAS NMR, SEM-EDS, and XPS analyses. The catalytic activity was evaluated in the reaction between 2H-chromenes and amines, affording Schiff bases via retro-aldol condensation. No nucleophilic activation or recyclization typical products were detected. When o-phenylenediamine and related nucleophiles were employed, the reaction yielded benzimidazole and benzothiazole derivatives, demonstrating the system's dual catalytic behaviour. Finally, catalyst recovery and reuse were investigated over ten consecutive cycles, showing a gradual decrease in activity
{"title":"Supported Keggin Anion Catalyst: A Study of its Multifunctionality in Retro-Aldol Condensation of 2H-chromenes","authors":"Itzel Gutiérrez-Barroso, Kevin A. Quintanilla, Merced Martínez, Eduardo Pena-Cabrera, Adriana Galvan, Miguel A. Vazquez","doi":"10.1039/d6dt00223d","DOIUrl":"https://doi.org/10.1039/d6dt00223d","url":null,"abstract":"Retro-Aldol Condensation has emerged as a powerful strategy to produce high-value carbonyl derivatives from complex substrates. In this study, a heterogeneous catalyst was developed by immobilising a Keggin heteropoly anion on an ionic-liquid-functionalised mesocellular foam silica (HPW@MIM–MCF). The catalyst was synthesised through covalent grafting of methylimidazolium groups onto the silica surface, followed by anion metathesis with H<small><sub>₃</sub></small>PW<small><sub>₁₂</sub></small>O<small><sub>₄₀</sub></small>. The material was characterised by N<small><sub>₂</sub></small> adsorption–desorption, FT-IR, <small><sup>²⁹</sup></small>Si and <small><sup>³¹</sup></small>P CP-MAS NMR, SEM-EDS, and XPS analyses. The catalytic activity was evaluated in the reaction between 2H-chromenes and amines, affording Schiff bases via retro-aldol condensation. No nucleophilic activation or recyclization typical products were detected. When o-phenylenediamine and related nucleophiles were employed, the reaction yielded benzimidazole and benzothiazole derivatives, demonstrating the system's dual catalytic behaviour. Finally, catalyst recovery and reuse were investigated over ten consecutive cycles, showing a gradual decrease in activity","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"27 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489417","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}
Herein, we successfully obtained a two-dimensional (2D) Co(II) metal–organic framework with [Co2(PDPA)(H2O)8]n (XAIU-4) by using Co(NO3)2·6H2O and 5,5'-(phenazine-5,10-diyl)diisophthalic acid (H4PDPA). Single-crystal X-ray diffraction revealed its staggered ABAB-layered arrangement, with interpenetration between layers forming a 2D + 2D → three-dimensional (3D) supramolecular architecture. XAIU-4 demonstrated remarkable photocatalytic activity for thioether oxidation and benzyl alcohol dehydrogenation under red light irradiation. Ultrasonic XAIU-4 crystals yielded nanoparticles (XAIU-4-NP) with enhanced photocatalytic activity, attributed to exposed Co(II) active sites and reduced charge-transfer resistance, which facilitated efficient electron-hole separation and substrate activation. This work not only presents a sustainable strategy for synthesizing sulfoxides and aromatic aldehydes under red light but also underscores the critical role of catalyst nanoparticles in optimizing photo-redox performance.
{"title":"Ultrasonication-induced Co-based metal–organic frameworks nanoparticle for red light photocatalytic aerobic oxidation","authors":"Xiong-Feng Ma, Zhuang Miao, Xiaodun Deng, Hongping Hou, Wenke Li, Yangyang Liu, Chengyu Xi, Rong Zhang, Zhihuan Zhou, Chaoqian Ai, Hongliang Du","doi":"10.1039/d5dt01720c","DOIUrl":"https://doi.org/10.1039/d5dt01720c","url":null,"abstract":"Herein, we successfully obtained a two-dimensional (2D) Co(II) metal–organic framework with [Co2(PDPA)(H2O)8]n (XAIU-4) by using Co(NO3)2·6H2O and 5,5'-(phenazine-5,10-diyl)diisophthalic acid (H4PDPA). Single-crystal X-ray diffraction revealed its staggered ABAB-layered arrangement, with interpenetration between layers forming a 2D + 2D → three-dimensional (3D) supramolecular architecture. XAIU-4 demonstrated remarkable photocatalytic activity for thioether oxidation and benzyl alcohol dehydrogenation under red light irradiation. Ultrasonic XAIU-4 crystals yielded nanoparticles (XAIU-4-NP) with enhanced photocatalytic activity, attributed to exposed Co(II) active sites and reduced charge-transfer resistance, which facilitated efficient electron-hole separation and substrate activation. This work not only presents a sustainable strategy for synthesizing sulfoxides and aromatic aldehydes under red light but also underscores the critical role of catalyst nanoparticles in optimizing photo-redox performance.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471116","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}
Samith B. Jayawardana, Collin B Gabel, Arya A Bhosale, Aruzhan Abdikaiym, Gbolagade Olajide, Shanuk Rajapakse, Tibor Szilvasi, Brad S Pierce, Gayan B Wijeratne
Reactivity studies of synthetic heme–peroxo complexes with excess NO⁺ uncover an unprecedented reaction pathway that diverges sharply from the canonical nitric oxide dioxygenase (NOD) chemistry observed under 1 equiv of NO⁺. When exposed to excess NO⁺ (4 equiv), heme–peroxo adducts generate two stoichiometric equivalents of •NO₂ radicals and concurrently yield “naked” ferric heme products. Comprehensive spectroscopic and computational analyses support this distinctive interconversion, and the resulting •NO₂ radicals are shown to drive nitration and oxidation of a series of bioinspired substrates. This stoichiometry-dependent reactivity shift highlights a long-proposed, but experimentally elusive principle governing interactions between heme-oxygen intermediates and nitrogen oxides, providing new mechanistic insight into nitrosative stress pathways relevant to analogous biological systems.
{"title":"Stoichiometry Dependent Modifications in Synthetic Heme Peroxo Reactivity with Nitrosonium: A New Paradigm for Understanding Heme Mediated Nitration Chemistry","authors":"Samith B. Jayawardana, Collin B Gabel, Arya A Bhosale, Aruzhan Abdikaiym, Gbolagade Olajide, Shanuk Rajapakse, Tibor Szilvasi, Brad S Pierce, Gayan B Wijeratne","doi":"10.1039/d6dt00522e","DOIUrl":"https://doi.org/10.1039/d6dt00522e","url":null,"abstract":"Reactivity studies of synthetic heme–peroxo complexes with excess NO⁺ uncover an unprecedented reaction pathway that diverges sharply from the canonical nitric oxide dioxygenase (NOD) chemistry observed under 1 equiv of NO⁺. When exposed to excess NO⁺ (4 equiv), heme–peroxo adducts generate two stoichiometric equivalents of •NO₂ radicals and concurrently yield “naked” ferric heme products. Comprehensive spectroscopic and computational analyses support this distinctive interconversion, and the resulting •NO₂ radicals are shown to drive nitration and oxidation of a series of bioinspired substrates. This stoichiometry-dependent reactivity shift highlights a long-proposed, but experimentally elusive principle governing interactions between heme-oxygen intermediates and nitrogen oxides, providing new mechanistic insight into nitrosative stress pathways relevant to analogous biological systems.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478630","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}
Sarah Kromer, Liam J Dress, Evgeny O. Danilov, Livia I Cohen, Adrienne Faulkner, Felix N Castellano
Thiol-pyridine and thiol-quinoline bridging ligands have previously been shown to reduce the metal-metal separation in Pt(II) dimers. Additionally, coordination complexes of the tridentate cyclometalating ligand 4-tolyl-6-phenyl-2,2’-bipyridine (4tpbpy) exhibit enhanced Pt dz2 orbital overlap through improved π-stacking of the cyclometalating ligands (CMLs), lengthening the Pt-Pt distance at which metal-metal-to-ligand charge transfer (MMLCT) transitions can be observed. To collectively study these phenomena, a series of molecules using the 4tpbpy CML with thiol-containing bridges: 2-benzothiazolethiol (2), 2-quinolinethiol (3), 2-pyridinethiol (4), and 6-methyl-2-pyridinethiol (5), was synthesized. Their photophysical properties were compared with a model complex known to exhibit MMLCT photophysics within the same tridentate motif, [Pt2(4tbpy)2(µ-dppm)][PF6]2 (1) (dppm = bis(diphenylphosphino)methane). The MMLCT energies in 2-5 were significantly lower than in 1 and in similar bidentate systems, as evidenced by red-shifted absorption bands extending past 650 nm and photoluminescence (PL) maxima between 750-790 nm. Femtosecond transient absorption spectroscopy showed that the population and subsequent relaxation of the 3MMLCT excited state in 2-5 are similar to those in 1, with noticeably reduced time constants. The growth of the 3MMLCT excited state in 2-5 was observed with a shortened time constant of ~55 ps, which subsequently relaxes on the timescale of 2-7 ns, atypical for these triplet charge transfer excited states.
{"title":"Enhanced MMLCT Character in Thiol-Bridged Pt(II) Dimers Featuring Tridentate Cyclometalating Ligands","authors":"Sarah Kromer, Liam J Dress, Evgeny O. Danilov, Livia I Cohen, Adrienne Faulkner, Felix N Castellano","doi":"10.1039/d6dt00411c","DOIUrl":"https://doi.org/10.1039/d6dt00411c","url":null,"abstract":"Thiol-pyridine and thiol-quinoline bridging ligands have previously been shown to reduce the metal-metal separation in Pt(II) dimers. Additionally, coordination complexes of the tridentate cyclometalating ligand 4-tolyl-6-phenyl-2,2’-bipyridine (4tpbpy) exhibit enhanced Pt dz<small><sup>2</sup></small> orbital overlap through improved π-stacking of the cyclometalating ligands (CMLs), lengthening the Pt-Pt distance at which metal-metal-to-ligand charge transfer (MMLCT) transitions can be observed. To collectively study these phenomena, a series of molecules using the 4tpbpy CML with thiol-containing bridges: 2-benzothiazolethiol (<strong>2</strong>), 2-quinolinethiol (<strong>3</strong>), 2-pyridinethiol (<strong>4</strong>), and 6-methyl-2-pyridinethiol (<strong>5</strong>), was synthesized. Their photophysical properties were compared with a model complex known to exhibit MMLCT photophysics within the same tridentate motif, [Pt2(4tbpy)<small><sub>2</sub></small>(µ-dppm)][PF<small><sub>6</sub></small>]<small><sub>2</sub></small> (<strong>1</strong>) (dppm = bis(diphenylphosphino)methane). The MMLCT energies in <strong>2-5</strong> were significantly lower than in <strong>1</strong> and in similar bidentate systems, as evidenced by red-shifted absorption bands extending past 650 nm and photoluminescence (PL) maxima between 750-790 nm. Femtosecond transient absorption spectroscopy showed that the population and subsequent relaxation of the <small><sup>3</sup></small>MMLCT excited state in <strong>2-5 </strong>are similar to those in<strong> 1</strong>, with noticeably reduced time constants. The growth of the 3MMLCT excited state in 2-5 was observed with a shortened time constant of ~55 ps, which subsequently relaxes on the timescale of 2-7 ns, atypical for these triplet charge transfer excited states.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"33 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478675","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}
Ilenia Serra, Daniel Schmidt, Pablo Javier Gonzalez, Paul Furtmueller, Christian Obinger, Sabine Van Doorslaer, Inés García-Rubio
Nitrite plays a fundamental role in the environmental nitrogen cycle and various biochemical reactions. Heme proteins such as globins and peroxidases, often participate in nitrite-mediated pathways, sparking interest in the coordination geometry of nitrite to the heme iron. In most cases, nitrite binds the ferric heme iron via the nitrogen atom (N-nitro mode), while for myoglobin and hemoglobin a less common O-nitrito ligation through one oxygen atom was reported. Our previous study on nitrite binding to the heme-containing enzyme chlorite dismutase (Cld) using continuous-wave electron paramagnetic resonance and crystal-field theory, supported by molecular dynamics simulations, suggested the coexistence of both O-nitrito and N-nitro ligation modes. Here, we present an in-depth hyperfine sublevel correlation (HYSCORE) analysis of NO2-ligated ferric horse heart myoglobin, a Clade-II Cld from Cyanothece sp. PCC7425 and a Clade-I Cld from Magnetospirillum sp. 15N-labelled nitrite was used to discriminate the signals ascribed to the nitrogen nucleus of nitrite from the endogenous N nuclei. The O-nitrito and N-nitro modes can be distinguished based on the nitrite nitrogen hyperfine coupling. Moreover, we describe a distinct HYSCORE spectral fingerprint for the O-nitrito binding mode which can be used as direct evidence of the ligation mode without further detailed analysis. Together, these results provide a generally applicable EPR/HYSCORE‑based tool for (bio)inorganic nitrite coordination chemistry of heme systems, enabling more reliable interpretation of nitrite reactivity and mechanism in heme-based catalysts and nitrite-processing enzymes.
{"title":"Nitrite Binding Modes in Ferric Heme Proteins probed by HYSCORE Spectroscopy","authors":"Ilenia Serra, Daniel Schmidt, Pablo Javier Gonzalez, Paul Furtmueller, Christian Obinger, Sabine Van Doorslaer, Inés García-Rubio","doi":"10.1039/d6dt00171h","DOIUrl":"https://doi.org/10.1039/d6dt00171h","url":null,"abstract":"Nitrite plays a fundamental role in the environmental nitrogen cycle and various biochemical reactions. Heme proteins such as globins and peroxidases, often participate in nitrite-mediated pathways, sparking interest in the coordination geometry of nitrite to the heme iron. In most cases, nitrite binds the ferric heme iron via the nitrogen atom (N-nitro mode), while for myoglobin and hemoglobin a less common O-nitrito ligation through one oxygen atom was reported. Our previous study on nitrite binding to the heme-containing enzyme chlorite dismutase (Cld) using continuous-wave electron paramagnetic resonance and crystal-field theory, supported by molecular dynamics simulations, suggested the coexistence of both O-nitrito and N-nitro ligation modes. Here, we present an in-depth hyperfine sublevel correlation (HYSCORE) analysis of NO2-ligated ferric horse heart myoglobin, a Clade-II Cld from Cyanothece sp. PCC7425 and a Clade-I Cld from Magnetospirillum sp. 15N-labelled nitrite was used to discriminate the signals ascribed to the nitrogen nucleus of nitrite from the endogenous N nuclei. The O-nitrito and N-nitro modes can be distinguished based on the nitrite nitrogen hyperfine coupling. Moreover, we describe a distinct HYSCORE spectral fingerprint for the O-nitrito binding mode which can be used as direct evidence of the ligation mode without further detailed analysis. Together, these results provide a generally applicable EPR/HYSCORE‑based tool for (bio)inorganic nitrite coordination chemistry of heme systems, enabling more reliable interpretation of nitrite reactivity and mechanism in heme-based catalysts and nitrite-processing enzymes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471113","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}
Burak Kıvrak, Hasan Akyildiz, Oğuzhan Akgöl, Muharrem Karaaslan, Mustafa Akyol
The development of lightweight materials with high microwave absorption efficiency is critical for advanced stealth and electromagnetic interference applications. Hybrid composites that integrate dielectric and magnetic components offer enhanced attenuation by leveraging multiple loss mechanisms. To explore this potential, we decorated MoS2 particles with magnetic Co nanoparticles (Co content ranging from 5–20 wt.%) and systematically investigated their microwave absorption properties over the 2–18 GHz frequency range. The individual materials and hybrid structures were synthesized using a multi-step strategy involving solution-based methods such as hydrothermal synthesis, chemical reduction of reactants, and sonication. Structural, morphological, compositional, and magnetic analyses collectively confirmed the successful incorporation and uniform dispersion of Co within the nanosheets of MoS2 host. Meanwhile, the microwave absorption properties revealed a strong dependence on Co content. Notably, the nanocomposite containing 15 wt.% Co exhibited superior performance, achieving a minimum reflection loss of −17.17 dB at 13.84 GHz and an ultra-broad effective absorption bandwidth of 7.51 GHz. This performance is attributed to synergy between the dielectric, magnetic, and morphologically derived mechanisms. Further, the hybrid design enables tunable interactions with incident waves, facilitating broad frequency coverage and enhanced attenuation. Overall, this work demonstrates the effectiveness of MoS2–Co nanocomposites and their compatibility with advanced stealth and microwave absorption applications in this frequency range.
{"title":"Broadband Microwave Absorption in MoS2–Co Nanocomposites by the Synergy of Dielectric and Magnetic Losses","authors":"Burak Kıvrak, Hasan Akyildiz, Oğuzhan Akgöl, Muharrem Karaaslan, Mustafa Akyol","doi":"10.1039/d6dt00271d","DOIUrl":"https://doi.org/10.1039/d6dt00271d","url":null,"abstract":"The development of lightweight materials with high microwave absorption efficiency is critical for advanced stealth and electromagnetic interference applications. Hybrid composites that integrate dielectric and magnetic components offer enhanced attenuation by leveraging multiple loss mechanisms. To explore this potential, we decorated MoS<small><sub>2</sub></small> particles with magnetic Co nanoparticles (Co content ranging from 5–20 wt.%) and systematically investigated their microwave absorption properties over the 2–18 GHz frequency range. The individual materials and hybrid structures were synthesized using a multi-step strategy involving solution-based methods such as hydrothermal synthesis, chemical reduction of reactants, and sonication. Structural, morphological, compositional, and magnetic analyses collectively confirmed the successful incorporation and uniform dispersion of Co within the nanosheets of MoS2<small><sub></sub></small> host. Meanwhile, the microwave absorption properties revealed a strong dependence on Co content. Notably, the nanocomposite containing 15 wt.% Co exhibited superior performance, achieving a minimum reflection loss of −17.17 dB at 13.84 GHz and an ultra-broad effective absorption bandwidth of 7.51 GHz. This performance is attributed to synergy between the dielectric, magnetic, and morphologically derived mechanisms. Further, the hybrid design enables tunable interactions with incident waves, facilitating broad frequency coverage and enhanced attenuation. Overall, this work demonstrates the effectiveness of MoS2<small><sub></sub></small>–Co nanocomposites and their compatibility with advanced stealth and microwave absorption applications in this frequency range.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"51 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489420","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}
Gabriela Kuzderova, Róbert Gyepes, Alan Liška, Jana Havlickova, Maria Vilkova, Simona Zilakova, Martin Kello, Tomas Pagac, Petra Olejníková, Eva Petrovova, Henrieta Matajová, Maria Kozurkova, Danica Sabolová, Michaela Rendošová, Zuzana Vargova, Ľudmila Balážová
N-methyl and N-glycyl glycine derivatives - namely (trimethylammonium)acetate (N,N,N-trimethylglycine, betaine, Bet), N,N-dimethylglycine (Dmg), N-methylglycine (sarcosine, Sar), and glycylglycylglycine (GlyGlyGly) - as naturally occurring glycine metabolites, were employed as stabilizing ligands for silver(I) ions, leading to the formation of water-soluble polymeric coordination compounds: {[Ag(HSar)(NO₃)]}ₙ (AgSar), {[Ag(HDmg)(NO₃)]}ₙ (AgDmg), {[Ag₃(HBet)₂(NO₃)₃]}ₙ (AgBet), and [Ag(HGlyGlyGly)(NO₃)] (AgGlyGlyGly). The composition and structures of the resulting complexes were unambiguously confirmed using attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), elemental analysis, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction (SC-XRD). Speciation and stability studies in relevant test and growth media were conducted using a novel multi-technique approach combining potentiometric titrations, electrochemical measurements, 1H NMR and UV-Vis spectroscopy and were additionally supported by theoretical calculations. From a biological evaluation standpoint, all complexes demonstrated significantly enhanced antistaphylococcal activity (including S. aureus L12) compared to silver(I) nitrate (AgNO₃), with AgBet and AgGlyGlyGly exhibiting approximately 10-fold, and AgSar and AgDmg approximately 5-fold, increased efficacy. Moreover, AgBet and AgGlyGlyGly were nearly twice as active as silver(I) sulfadiazine (AgSD), a clinically used but poorly water-soluble antimicrobial agent. Remarkably, AgBet and AgGlyGlyGly also showed unusual potent antifungal activity, being 10- to 100-fold more effective than both AgNO₃ and AgSD against Rhizopus oryzae, the causative agent of mucormycosis. In cytotoxicity assays, AgSar exhibited the greatest selectivity and sensitivity, being over three times higher than cisplatin (cisPt), against the human breast adenocarcinoma cell line MDA-MB-231. New approaches from the perspectives of structure–activity relationships and bioavailability of the novel silver(I) complexes were explored through human serum albumin (HSA) binding studies and molecular docking calculations, as well as experimental and computational evaluations of lipophilicity and additional Lipinski parameters. Furthermore, the silver(I) complexes action mechanism was assessed via β-galactosidase inhibition and PCR amplification inhibition in E. coli, intracellular reactive oxygen species (ROS) production, and their effects on cell cycle progression and binding to ctDNA.
{"title":"Integrating experimental and theoretical approaches to unveil structure–bioactivity relationships in silver(I) N-substituted glycine complexes","authors":"Gabriela Kuzderova, Róbert Gyepes, Alan Liška, Jana Havlickova, Maria Vilkova, Simona Zilakova, Martin Kello, Tomas Pagac, Petra Olejníková, Eva Petrovova, Henrieta Matajová, Maria Kozurkova, Danica Sabolová, Michaela Rendošová, Zuzana Vargova, Ľudmila Balážová","doi":"10.1039/d5dt03032c","DOIUrl":"https://doi.org/10.1039/d5dt03032c","url":null,"abstract":"N-methyl and N-glycyl glycine derivatives - namely (trimethylammonium)acetate (N,N,N-trimethylglycine, betaine, Bet), N,N-dimethylglycine (Dmg), N-methylglycine (sarcosine, Sar), and glycylglycylglycine (GlyGlyGly) - as naturally occurring glycine metabolites, were employed as stabilizing ligands for silver(I) ions, leading to the formation of water-soluble polymeric coordination compounds: {[Ag(HSar)(NO₃)]}ₙ (AgSar), {[Ag(HDmg)(NO₃)]}ₙ (AgDmg), {[Ag₃(HBet)₂(NO₃)₃]}ₙ (AgBet), and [Ag(HGlyGlyGly)(NO₃)] (AgGlyGlyGly). The composition and structures of the resulting complexes were unambiguously confirmed using attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), elemental analysis, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction (SC-XRD). Speciation and stability studies in relevant test and growth media were conducted using a novel multi-technique approach combining potentiometric titrations, electrochemical measurements, 1H NMR and UV-Vis spectroscopy and were additionally supported by theoretical calculations. From a biological evaluation standpoint, all complexes demonstrated significantly enhanced antistaphylococcal activity (including S. aureus L12) compared to silver(I) nitrate (AgNO₃), with AgBet and AgGlyGlyGly exhibiting approximately 10-fold, and AgSar and AgDmg approximately 5-fold, increased efficacy. Moreover, AgBet and AgGlyGlyGly were nearly twice as active as silver(I) sulfadiazine (AgSD), a clinically used but poorly water-soluble antimicrobial agent. Remarkably, AgBet and AgGlyGlyGly also showed unusual potent antifungal activity, being 10- to 100-fold more effective than both AgNO₃ and AgSD against Rhizopus oryzae, the causative agent of mucormycosis. In cytotoxicity assays, AgSar exhibited the greatest selectivity and sensitivity, being over three times higher than cisplatin (cisPt), against the human breast adenocarcinoma cell line MDA-MB-231. New approaches from the perspectives of structure–activity relationships and bioavailability of the novel silver(I) complexes were explored through human serum albumin (HSA) binding studies and molecular docking calculations, as well as experimental and computational evaluations of lipophilicity and additional Lipinski parameters. Furthermore, the silver(I) complexes action mechanism was assessed via β-galactosidase inhibition and PCR amplification inhibition in E. coli, intracellular reactive oxygen species (ROS) production, and their effects on cell cycle progression and binding to ctDNA.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"6 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471112","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}
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