{"title":"A review on coordination and biological properties of selenosemicarbazone.","authors":"Vins Daniel, Vipin Singh, Prabal Gupta, Anandaram Sreekanth","doi":"10.1016/j.jinorgbio.2025.113020","DOIUrl":"10.1016/j.jinorgbio.2025.113020","url":null,"abstract":"<p><p>The review highlights the synthesis, coordination behavior, and extensive biological activities of selenosemicarbazones and their metal complexes. Over 110 selenosemicarbazone ligands coordinated with metals such as Cu, Ni, Zn, Pt, and Pd are discussed, showcasing significant structural diversity. These compounds uniquely combine the pharmacophoric semicarbazone moiety with selenium, a redox-active trace element, resulting in enhanced stability, reactivity, and biological performance. Coordinated metal complexes demonstrate potent antibacterial, anticancer, antioxidant, and antiparasitic activities. Mechanistic insights include reactive oxygen species (ROS) generation, metalloenzyme inhibition, and DNA binding. Recent developments in structure-activity relationships and therapeutic targeting are emphasized.</p>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"272 ","pages":"113020"},"PeriodicalIF":3.2,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144803148","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}
Seth A. Wiley, Isaac J. Spackman , Carolyn E. Lubner
{"title":"Differential ligation alters electronic state and coupling signals of iron-sulfur clusters in flavin-based electron bifurcation","authors":"Seth A. Wiley, Isaac J. Spackman , Carolyn E. Lubner","doi":"10.1016/j.jinorgbio.2025.113051","DOIUrl":"10.1016/j.jinorgbio.2025.113051","url":null,"abstract":"<div><div>Flavin-based electron bifurcation (FBEB) is employed by microorganisms for controlling pools of redox equivalents by reversibly splitting electron pairs into high- and low-energy levels from an initial midpoint potential. Our ability to harness this phenomenon is crucial for biocatalytic design which is limited by our understanding of energy coupling in the bifurcation system. In <em>Pyrococcus furiosus</em>, FBEB is carried out by the NADH-dependent ferredoxin:NADP<sup>+</sup>-oxidoreductase (NfnSL), coupling the uphill reduction of ferredoxin in NfnL to the downhill reduction of NAD<sup>+</sup> in NfnS from oxidation of NADPH. Flanking the bifurcating flavin are two site-differentiated iron‑sulfur clusters; the nearest is a glutamate-ligated [4Fe—4S] cluster in NfnL. Recent biochemical experiments substituting the native glutamate with cysteine led to loss of coupling between the uphill and downhill pathways, in contrast to the tight thermodynamic coupling in the native system. To understand how this decoupling is biochemically manifested by the cysteine-substituted [4Fe—4S] in NfnL, we employed electron paramagnetic resonance (EPR) spectroscopy to identify changes in electronic architecture and square wave voltammetry (SWV) to probe thermodynamic shifts produced by the substitution. We observed notable <em>g</em>-value shifts in the EPR for the cysteine-substituted iron‑sulfur cluster in addition to significant downward shifts in the redox potential, as well as the disappearance of several low-field signals observed in the native NfnSL complex. These results suggest the site-differentiated glutamate residue facilitates higher spin states in the [4Fe<img>4S] cluster to bridge energetic gaps in electron transfer to the bifurcating flavin in the native complex, preventing unwanted short-circuiting seen in the cysteine-substituted complex.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"274 ","pages":"Article 113051"},"PeriodicalIF":3.2,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145007505","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}
José Ortega-Campos , Mercedes Fernández , Santiago Rostán , Ana Liempi , Ulrike Kemmerling , Leopoldo Suescun , Juan Diego Maya , Claudio Olea-Azar , Lucía Otero
{"title":"1,10-phenanthroline enhances the antiparasitic activity and selectivity of Cu(II) and Zn(II) metal complexes with coumarin-thiosemicarbazone hybrid ligands","authors":"José Ortega-Campos , Mercedes Fernández , Santiago Rostán , Ana Liempi , Ulrike Kemmerling , Leopoldo Suescun , Juan Diego Maya , Claudio Olea-Azar , Lucía Otero","doi":"10.1016/j.jinorgbio.2025.113050","DOIUrl":"10.1016/j.jinorgbio.2025.113050","url":null,"abstract":"<div><div>Chagas disease, caused by <em>Trypanosoma cruzi</em>, remains a major public health concern with limited therapeutic options and significant toxicity associated with current treatments. In this work, eight novel heteroleptic complexes of the type [M(L)(phen)], where M = Cu(II) or Zn(II), L = coumarin-thiosemicarbazone hybrid ligands, and phen = 1,10-phenanthroline, were synthesized and fully characterized in the solid state and in solution. For comparison, some homoleptic [Cu(HL)₂], [Zn(HL)₂], and [CuCl(HL)] complexes were also prepared. All compounds were evaluated <em>in vitro</em> against <em>Trypanosoma cruzi</em> trypomastigotes. The presence of the phenanthroline co-ligand markedly enhanced trypanocidal activity in both metal series. The [Cu(L)(phen)] complexes showed the highest potency, with submicromolar half-maximal inhibitory concentration values and favourable selectivity indexes. Mechanistic studies revealed that these copper complexes increased intracellular reactive oxygen species and caused mitochondrial membrane depolarization, leading to necrosis as the primary mechanism of parasite death. The redox-active nature of copper likely contributes to this enhanced activity. These findings underscore the relevance of phenanthroline in modulating antiparasitic efficacy and support further development of copper-based complexes bearing this ligand as potential agents for Chagas disease treatment.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"274 ","pages":"Article 113050"},"PeriodicalIF":3.2,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144934012","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}
Micol Zerbini , Pier Lorenzo Solari , Aurelie Jeanson , Diane Jouanneau , Marc Metian , François Oberhaensli , Khalil Sdiri , Gaëlle Creff , Christophe Den Auwer , Maria Rosa Beccia
{"title":"Exploring Americium bioaccumulation in Ascophyllum nodosum seaweed through Europium as a surrogate: A kinetic and speciation study","authors":"Micol Zerbini , Pier Lorenzo Solari , Aurelie Jeanson , Diane Jouanneau , Marc Metian , François Oberhaensli , Khalil Sdiri , Gaëlle Creff , Christophe Den Auwer , Maria Rosa Beccia","doi":"10.1016/j.jinorgbio.2025.113052","DOIUrl":"10.1016/j.jinorgbio.2025.113052","url":null,"abstract":"<div><div>Studies of metallic radionuclides in oceans represent an important field of research. Because of their direct impact on marine ecosystems, they are especially important for assessing environmental health and safety. The high chemical – and radio – toxicity of heavy actinide elements makes them a particular threat to organisms, regardless of isotopy. Among these, americium is well known for its strong biosorption potential and combined chemo – radiotoxic effects. This study investigates the bioaccumulation of <sup>241</sup>Am and of <sup>153</sup>Eu (stable) and <sup>152</sup>Eu as its chemical surrogate, in the brown macroalga <em>Ascophyllum nodosum</em>. Environmental analogies between <sup>152</sup>Eu and <sup>241</sup>Am are discussed, validating Europium as a reliable homolog in this system. Biokinetic accumulation models across trace and ultra-trace concentration levels are reported showing consistent behavior within the data, with a mono-exponential saturation pattern best fitting. Alginate was identified as a primary chelating agent, with speciation studies revealing potential alginate – Europium complexes in algal tissues. These findings highlight the essential role of algal polysaccharides in the uptake of metallic radionuclides and provide an entry into the ecological risk assessment associated with marine ecosystem contamination.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"274 ","pages":"Article 113052"},"PeriodicalIF":3.2,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145046939","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}
Farooq Ahmad , Muhammad Saif Ur Rahman , Tahir Muhmood
{"title":"Praseodymium doped cerium oxide nanozyme as a functional analog of topoisomerase I","authors":"Farooq Ahmad , Muhammad Saif Ur Rahman , Tahir Muhmood","doi":"10.1016/j.jinorgbio.2025.113048","DOIUrl":"10.1016/j.jinorgbio.2025.113048","url":null,"abstract":"<div><div>Topoisomerases are essential hydrolases that facilitate the topological rearrangement of DNA by cleaving nucleic acid strands. Specifically, topoisomerase I (TOPO I) enhances DNA transcription by introducing single-strand breaks in the DNA double helix, relaxing supercoiled DNA, and catalyzing the subsequent re-ligation of the cleavage sites. However, the intricate catalytic mechanism of TOPO I has posed significant challenges for developing effective enzymatic mimics. Here, we demonstrate that praseodymium-doped cerium oxide nanoparticles (CeO₂:Pr<sup>3+</sup>) exhibit the TOPO I-like catalytic activity, mediating the topological rearrangement of supercoiled DNA. CeO₂:Pr<sup>3+</sup> nanoparticles act as functional analog of TOPO I enzyme, catalyzing the transition of plasmid DNA from a supercoiled to a nicked open circular configuration compared to undoped CeO₂ nanoparticles. Mechanistic studies revealed that Pr<sup>3+</sup> doping enhances Ce(III) activity by replacing Ce-bound hydroxide, a weak nucleophile, thereby facilitating phosphodiester bond cleavage. This modification improves substrate turnover rates and higher catalytic efficiency at low substrate concentrations. These findings underscore the potential of Pr<sup>3+</sup> doping to advance the design of enzyme with similar functional activity for industrial and laboratory applications requiring efficient nucleic acid manipulation.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"273 ","pages":"Article 113048"},"PeriodicalIF":3.2,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144919676","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}
Magdalena Malik , Tomasz Mazur , Marta Gordel-Wójcik , Anna Świtlicka , Anna Duda-Madej , Alina Bieńko
{"title":"Linking structure to activity in Ni(II) complexes with {NiN₂O₄} geometry via spectroscopic analysis","authors":"Magdalena Malik , Tomasz Mazur , Marta Gordel-Wójcik , Anna Świtlicka , Anna Duda-Madej , Alina Bieńko","doi":"10.1016/j.jinorgbio.2025.113047","DOIUrl":"10.1016/j.jinorgbio.2025.113047","url":null,"abstract":"<div><div>This study presents the synthesis, structural characterization, and biological evaluation of three nickel(II) complexes containing bioactive ligands: two bidentate pyridyl alcohols (2-pymetH and 2-pyetH) and a mixed-ligand system with memantine and acetylacetone. Single-crystal X-ray diffraction revealed that all complexes adopt a distorted octahedral geometry with a {NiN₂O₄} coordination core, differing in ligand orientation, symmetry, and supramolecular packing. Complementary spectroscopic techniques, including FT-IR, Raman, and UV–Vis, confirmed successful ligand coordination and complex integrity. Fluorescence studies indicated comparable photophysical properties among the complexes, with emission lifetimes of approximately 8 ns. Thermal and solution stability studies demonstrated greater structural robustness for the monoligand complexes (<strong>1</strong> and <strong>2</strong>), whereas partial ligand dissociation was observed in the mixed-ligand complex <strong>3</strong>. Antimicrobial testing revealed that complex <strong>3</strong> exhibited enhanced activity against resistant Gram-negative bacteria (including <em>A. baumannii</em>, <em>S. maltophilia</em>), while complexes <strong>1</strong> and <strong>2</strong> demonstrated notable antifungal activity against <em>Candida albicans</em> (MIC<sub>50</sub> = 64 μg/ml). These findings underscore the importance of ligand identity, coordination geometry, and complex stability on the biological and photophysical performance of Ni(II) complexes. Collectively, the findings support the potential of these systems as scaffolds for development of novel Ni-based antimicrobial agents.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"274 ","pages":"Article 113047"},"PeriodicalIF":3.2,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144933925","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}
Guan-Dong Zhang , Wei Hao , Zheng-Hong Yu , Hong-Ke Liu , Zhi Su
{"title":"COX-2 targeting Ru-arene complexes from metal-ligand synergistic enhancement strategy for breast cancer therapy","authors":"Guan-Dong Zhang , Wei Hao , Zheng-Hong Yu , Hong-Ke Liu , Zhi Su","doi":"10.1016/j.jinorgbio.2025.113044","DOIUrl":"10.1016/j.jinorgbio.2025.113044","url":null,"abstract":"<div><div>Triple-negative breast cancer (TNBC) has been a significant therapeutic challenge, due to its aggressive and metastatic characteristics. Cyclooxygenase-2 (COX-2), which is frequently overexpressed in TNBC and implicated in tumor progression, is considered as a potent therapeutic target. In this study, we reported a novel Ru-arene complex, <strong>Ru-tol</strong>, utilizing a metal-ligand synergistic enhancement (MLSE) strategy. Toxic <strong>Ru-tol</strong> was synthesized from the non-toxic precursors aryl ruthenium azide and tolfenamic acid. Complex <strong>Ru-tol</strong> not only owned the enhanced antiproliferative performance, but also preserved the COX-2 inhibitory activity of tolfenamic acid. <strong>Ru-tol</strong> could induce the generation of intracellular reactive oxygen species (ROS), leading to the mitochondrial and nuclear damages, which ultimately results in the apoptotic and autophagic cell death. Moreover, <strong>Ru-tol</strong> significantly downregulated the expression of COX-2, matrix metalloproteinases (MMP)-2 and MMP-9, and effectively suppressed the cell migration and invasion. <strong>Ru-tol</strong> demonstrated supeior penetration capacity and antiproliferative efficacy in 3D multicellular tumor spheroids (MCTS), suggesting the potent clinical applications. This work not only demonstrated the efficiency of MLSE strategy for the development of novel anti-cancer metal-based drugs, but also presented a promising target for the TNBC treatment.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"273 ","pages":"Article 113044"},"PeriodicalIF":3.2,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144908489","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-mediated base pairs of 5-fluorouracil with other pyrimidine bases and a phenanthroline derivative","authors":"Florian Mai, Jens Müller","doi":"10.1016/j.jinorgbio.2025.113045","DOIUrl":"10.1016/j.jinorgbio.2025.113045","url":null,"abstract":"<div><div>The ability of 5-fluorouracil (F) to form metal-mediated hetero base pairs in DNA duplexes was evaluated applying the metal ions Hg(II) and Ag(I) as well as the pyrimidine residues thymine (T) and cytosine (C) and the nucleo-base surrogate 1<em>H</em>-imidazo[4,5-<em>f</em>][1,10]phenanthroline (P) as complementary nucleobases. A particular focus was placed on the question how the stabilizing effect of metal-mediated hetero base pair formation relates to that of the respective homo base pairs. Interestingly, no general correlation was observed. While F–M<sup><em>n</em>+</sup>–T pairs exert an average stabilization compared to the homo base pairs, the stability of duplexes containing an F–M<sup><em>n</em>+</sup>–C pair is governed by C in the case of Hg(II) and by F in the case of Ag(I). A strong sequence-dependence of the stabilizing effect was found when F pairs with P. Here, the formation of F–Ag(I)–P and P–Hg(II)–F pairs within an identical sequence context is particularly stabilizing, whereas F–Hg(II)–P and P–Ag(I)–F pairs are much less stabilizing. Apparently, the size ratio of the nucleobases involved in the metal-mediated base pair plays an important role, too. The results of this study are important for the DNA sequence design of duplexes with tailor-suited metal-mediated base pairs.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"273 ","pages":"Article 113045"},"PeriodicalIF":3.2,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144908487","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}
Dhruv C. Rathod , Negin Sadat Babaiha , Elena Kullmann , Martin Hofmann-Apitius , Diana Imhof
{"title":"Knowledge graph-driven curation of heme-TLR4 interactions in inflammatory pathways","authors":"Dhruv C. Rathod , Negin Sadat Babaiha , Elena Kullmann , Martin Hofmann-Apitius , Diana Imhof","doi":"10.1016/j.jinorgbio.2025.113040","DOIUrl":"10.1016/j.jinorgbio.2025.113040","url":null,"abstract":"<div><div>Heme, a vital iron-containing molecule, serves fundamental roles in oxygen transport and electron transfer but also acts as an extracellular signaling entity, significantly influencing inflammatory responses. Elevated levels of labile heme resulting from hemolytic events or therapeutic treatments may activate inflammatory signaling pathways, particularly through the Toll-like receptor 4 (TLR4). In this study, we systematically expanded the previously developed Heme Knowledge Graph (HemeKG) to comprehensively incorporate recent findings regarding heme-TLR4 interactions. By employing rigorous literature curation and validation using Biological Expression Language (BEL) standards and the e:BEL Python package, we successfully integrated newly identified molecular entities, notably activator protein 1 (AP-1), interleukin-12 (IL-12), cluster of differentiation 80 (CD80), cluster of differentiation 86 (CD86), and chemokine (C-X-C motif) ligand 1 (CXCL1), into the existing HemeKG framework. Pathway enrichment analysis across Kyoto Encyclopedia of Genes and Genomes (KEGG), Reactome, and WikiPathways databases robustly supported these integrations, consistently identifying significant enrichment of the TLR4 signaling cascade. The updated HemeKG thus provides an integrated and predictive platform, enhancing our understanding of the complex interactions between heme-driven inflammatory pathways and metabolic dysregulation.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"273 ","pages":"Article 113040"},"PeriodicalIF":3.2,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144902738","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":"Special Issue ISMEC 2023: 51st International symposium of metal complexes","authors":"Mauro Formica, Vieri Fusi","doi":"10.1016/j.jinorgbio.2025.113043","DOIUrl":"10.1016/j.jinorgbio.2025.113043","url":null,"abstract":"","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"273 ","pages":"Article 113043"},"PeriodicalIF":3.2,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144938144","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}