Lidia Zapała , Ewa Ciszkowicz , Małgorzata Kosińska-Pezda , Urszula Maciołek , Anna E. Kozioł , Anna Miłoś , Elżbieta Woźnicka , Aleksandra Bocian , Wojciech Zapała , Katarzyna Rydel-Ciszek , Maria Grazia Perrone
{"title":"Novel silver(I) complexes with fenamates: Insights into synthesis, spectral characterization, and bioactivity","authors":"Lidia Zapała , Ewa Ciszkowicz , Małgorzata Kosińska-Pezda , Urszula Maciołek , Anna E. Kozioł , Anna Miłoś , Elżbieta Woźnicka , Aleksandra Bocian , Wojciech Zapała , Katarzyna Rydel-Ciszek , Maria Grazia Perrone","doi":"10.1016/j.jinorgbio.2025.112846","DOIUrl":"10.1016/j.jinorgbio.2025.112846","url":null,"abstract":"<div><div>Six new Ag(I) ions complexes with <em>N</em>-phenylanthranilic, mefenamic, and niflumic acids have been synthesized. Three of them are binary complexes with the [Ag(L)] formula (where L represents <em>N-</em>phenylanthranilate (nfa), mefenamate (mfa), or niflumate (nif) ions), and the other three complexes are ternary with the formula [Ag(L)(phen)<sub>2</sub>]⋅nH<sub>2</sub>O (where phen - 1,10-phenanthroline). The complexes were characterized by elemental analysis, differential scanning calorimetry (DSC), X-ray fluorescence, powder X-ray diffraction, and single-crystal X-ray structure analysis. <strong>Additionally,</strong> techniques such as ESI-MS spectrometry, <sup>1</sup>H NMR, UV–Vis, and FTIR spectroscopy were employed. The X-ray crystallography showed that in the solid [Ag(nif)] complex, the cation showed an unusual structure with coordination number 5, i.e. AgO<sub>3</sub>NC. The silver cation interacts with three niflumate anions, forming a two-dimensional coordination polymer. Complexes have potential antibacterial efficacy with varied minimum inhibitory concentration values (MIC) between 45.96 and 800 μM against multidrug-resistant <em>Pseudomonas aeruginosa</em>. Antibacterial combination therapy of Ag(I) complexes with chloramphenicol (CHL) and kanamycin (KAN) showed a very strong synergistic impact against <em>P. aeruginosa</em> with no cytotoxic effect on normal human fibroblasts. Complexes [Ag(nif)] and [Ag(nfa)] inhibit protein denaturation, bind to BSA via <strong>static quenching</strong> (k<sub>q</sub> = 0.65–1.08 × 10<sup>13</sup> M<sup>−1</sup> s<sup>−1</sup>). Furthermore, the formation of these complexes enhances the penetration of the drug across <strong>human membrane monolayers</strong>, which could improve bioavailability and therapeutic potential. The [Ag(nif)] complex demonstrates significant potential for topical dermal application due to its antimicrobial and anti-inflammatory properties. Notably, among all complexes evaluated, it displays the lowest BA/AB ratio (5.41), facilitating the most efficient transdermal permeation.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"266 ","pages":"Article 112846"},"PeriodicalIF":3.8,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143386446","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}
Chongyang Wu , Yanni Shan , Jingming Luo , Xudong Fan , Ren Zheng , Suhang Guo , Xinjun Cai
{"title":"Silver(I) complexes containing bioactive salicylic acid derivatives: Synthesis, characterization, antibacterial activity, and their underlying mechanism","authors":"Chongyang Wu , Yanni Shan , Jingming Luo , Xudong Fan , Ren Zheng , Suhang Guo , Xinjun Cai","doi":"10.1016/j.jinorgbio.2025.112845","DOIUrl":"10.1016/j.jinorgbio.2025.112845","url":null,"abstract":"<div><div>Recognizing that silver-metallodrugs are a potential source of novel anti-infective therapeutic agents, this work adopts the complexation of biologically active salicylic acid derivatives with inherently antibacterial silver(I) ions as a strategy for developing new antibacterial agents. The synthesized silver(I) complexes were characterized by elemental analysis, spectroscopy, and X-ray diffraction analysis. The crystallographic results indicate that the silver(I) ion in complexes [Ag(imH)<sub>2</sub>](SalH) (<strong>1</strong>) and [Ag(imH)<sub>2</sub>](DiSalH)·H<sub>2</sub>O (<strong>2</strong>) only coordinates with the imidazole nitrogen atom, while the 4-aminosalicylic acid in complex [Ag(imH)<sub>2</sub>(AmSalH)]·H<sub>2</sub>O (<strong>3</strong>) additionally coordinate with the silver(I) ion through the amino nitrogen atom. Salicylic acid molecules play an important role in the construction of the three-dimensional network structure through weak interactions. In addition, thermogravimetric analysis, stability, and silver(I) ion release experiments indicate that these complexes have good stability and slow ion release rates. Cell toxicity and antibacterial tests were conducted on selected cell lines and microorganisms using complexes <strong>1–3</strong>, and compared with silver(I) salts, organic ligands, and antibiotic. All complexes exhibit better biocompatibility and certain anti-tumor selectivity than silver(I) salts. From the perspective of microbial toxicity, complexes <strong>1–3</strong> all have significant inhibitory effects on three bacteria strains, with complex <strong>1</strong> having the strongest antibacterial activity, exhibiting 4–6 times higher activity against certain strains than AgNO<sub>3</sub> and chloramphenicol. Mechanism studies have shown that cell wall perforation and imbalance of intracellular ROS levels may be possible reasons for silver(I) complexes induced bacterial cell death. The biofilm removal experiment further proves the potential use of silver(I) complexes <strong>1–3</strong> in the treatment of bacterial infections.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"266 ","pages":"Article 112845"},"PeriodicalIF":3.8,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143372856","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}
Tapiwa Chiura, Minh N. Pham, Dana A. Baum, Piotr J. Mak
{"title":"Interactions between heme and G-quadruplex DNA involve the oxygen of guanine","authors":"Tapiwa Chiura, Minh N. Pham, Dana A. Baum, Piotr J. Mak","doi":"10.1016/j.jinorgbio.2025.112843","DOIUrl":"10.1016/j.jinorgbio.2025.112843","url":null,"abstract":"<div><div>Guanine quadruplexes are non-canonical DNA structures with various functions including transcription and translation regulation and telomere protection. These structures are known to bind the heme prosthetic group, resulting in heme-bound G-quadruplexes (heme-G4) that exhibit enhanced peroxidase activity and act as promising biocatalysts. The structure of the heme-G4, specifically how the DNA scaffold interacts with the heme iron, is key in understanding the catalytic mechanism of these DNAzymes. In heme proteins, the nature of a heme axial ligand plays an essential role in manipulating the inherent reactivity of the heme prosthetic group. Several proposals regarding the heme axial ligand in the heme-G4 complexes have been previously presented, including nitrogen or oxygen atoms of the guanine base or a water molecule sandwiched between the heme macrocycle and the DNA quadruplex. Despite numerous studies, no convincing experimental evidence has yet been provided as to the nature of the key proximal ligand. In this work, we present extensive electronic absorption and resonance Raman spectroscopic studies of ferric and ferrous heme-G4 complexes, including their ligated forms. Our studies provide experimental evidence that the oxygen atom of the guanine base acts as an axial ligand supported by detection of the <em>ν</em>(Fe-O<sub>G</sub>) stretching mode at 563 cm<sup>−1</sup> in the spectra of ferric heme-G4. These results provide structural data that can help understand the mechanistic principles behind the observed enhanced peroxidase activity of heme-G4 quadruplexes and aid in design of advanced biocatalysts.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"266 ","pages":"Article 112843"},"PeriodicalIF":3.8,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143350533","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":"Corrigendum to “New insights into the O2-sensing mechanism of FixL and other gas sensing heme proteins” [Journal of Inorganic Biochemistry 259 (2024) 112642]","authors":"Mark F. Reynolds","doi":"10.1016/j.jinorgbio.2024.112746","DOIUrl":"10.1016/j.jinorgbio.2024.112746","url":null,"abstract":"","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"263 ","pages":"Article 112746"},"PeriodicalIF":3.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142338548","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}
Charles R.M. Soukup , Rebekah N. Duffin , Kirralee J. Burke , Laurence Meagher , Philip C. Andrews
{"title":"The antibacterial activity and selectivity of bismuth(III) tris(8-hydroxyquinolinates)","authors":"Charles R.M. Soukup , Rebekah N. Duffin , Kirralee J. Burke , Laurence Meagher , Philip C. Andrews","doi":"10.1016/j.jinorgbio.2025.112836","DOIUrl":"10.1016/j.jinorgbio.2025.112836","url":null,"abstract":"<div><div>The series of bismuth(III) <em>tris</em>(8-hydroxyquinolinates); [Bi(Q\")<sub>3</sub>] (<strong>1</strong>)<strong>,</strong> [Bi(Q'Cl)<sub>3</sub>] (<strong>2</strong>)<strong>,</strong> [Bi(QCl<sub>2</sub>)<sub>3</sub>] (<strong>3</strong>)<strong>,</strong> [Bi(QBr<sub>2</sub>)<sub>3</sub>] (<strong>4</strong>)<strong>,</strong> and [Bi(QI<sub>2</sub>)<sub>3</sub>] (<strong>5</strong>) (where Q\"-<em>H</em> = C<sub>9</sub>H<sub>7</sub>NO; Q'Cl-<em>H</em> = C<sub>9</sub>H<sub>6</sub>NOCl, QCl<sub>2</sub>-<em>H</em> = C<sub>9</sub>H<sub>5</sub>NOCl<sub>2</sub>; QBr<sub>2</sub>-<em>H</em> = C<sub>9</sub>H<sub>5</sub>NOBr<sub>2</sub>; and QI<sub>2</sub>-<em>H</em> = C<sub>9</sub>H<sub>5</sub>NOI<sub>2</sub>) were synthesised, fully characterised, and evaluated for their antibacterial activity towards three Gram-positive bacteria (vancomycin-resistant <em>E. faecalis</em>, <em>S. aureus</em>, methicillin-resistant <em>S. aureus</em>), and four Gram-negative bacteria (<em>A. baumannii</em>, <em>P. aeruginosa</em>, <em>K. pneumoniae</em>, and <em>E. coli</em>) and also their cytotoxicity towards mammalian cells. New crystallographic data on <strong>4</strong> indicates it is dimeric in the solid state through ‘Bi<sub>2</sub>O<sub>2</sub>’ bridging which is consistent with data previously reported for <strong>5</strong>. The five complexes (<strong>1–5)</strong> all exhibited good but variable antibacterial activity and selectivity. Complexes <strong>2</strong> and <strong>5</strong> showed significant activity towards Gram-positive bacteria with MIC (minimum inhibitory concentration) values ranging from 0.78 μM – 3.13 μM and selectivity indices of 6.2 – ≥16.0. For Gram-negative species, complexes <strong>3</strong> and <strong>4</strong> exhibited highly selective activity towards multi-drug resistant strains of <em>A. baumannii</em> with a range of MIC values 0.39–1.56 μM and selectivity indices of 3.14–7.23 respectively. While some of the 8-hydroxyquinolines themselves show reasonable antibacterial activity this is generally enhanced through complexation to bismuth(III).</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"266 ","pages":"Article 112836"},"PeriodicalIF":3.8,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143314190","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hazrat Bilal , Cai-Xiang Zhang , Muhammad Iqbal Choudhary , Sukanya Dej-adisai , Yanghan Liu , Zhen-Feng Chen
{"title":"Copper(II) carboxylate complexes inhibit Staphylococcus aureus biofilm formation by targeting extracellular proteins","authors":"Hazrat Bilal , Cai-Xiang Zhang , Muhammad Iqbal Choudhary , Sukanya Dej-adisai , Yanghan Liu , Zhen-Feng Chen","doi":"10.1016/j.jinorgbio.2025.112835","DOIUrl":"10.1016/j.jinorgbio.2025.112835","url":null,"abstract":"<div><div>Three copper(II) complexes of diphenyl acetic acid (DPAA) pyridine (py), 2,2΄-dipyridylamine (dpa), and 4,7-diphenyl, 1,10-phenanthrline (di-phen), [Cu₂(DPAA)₄(py)<sub>2</sub>] (<strong>Cu-1</strong>), [Cu(DPAA)₂(dpa)] (<strong>Cu-2</strong>), and [Cu₂(DPAA)₄(di-phen)₂] (<strong>Cu-3</strong>) were synthesized and characterized. Their antibacterial activities were evalvated. The minimum inhibitory concentrations (MIC) of these complexes against six tested microbial strains ranged from 1 to 128 μg/mL, and that of vancomycin antibiotic ranged from 0.5 to 2 μg/mL. The bactericidal effects of <strong>Cu-1</strong>, <strong>Cu-2</strong> and <strong>Cu-3</strong> and vancomycin against <em>Staphylococcus aureus</em> (<em>S. aureus</em>) were determined by colony count assay. <strong>Cu-1</strong>, <strong>Cu-2</strong>, and vancomycin showed relatively weaker antibiofilm formation activities; however, <strong>Cu-3</strong> showed enhanced activity against <em>S. aureus</em> proliferation and biofilm formation as confirmed by microscopic analysis. In antibiofilm assays, <strong>Cu-1</strong>, <strong>Cu-2</strong> and <strong>Cu-3</strong> demonstrated high inhibition ability (23–75 %), of mature biofilm formation at concentrations of 5 to 15 μg/mL, and vancomycin at 15 μg/mL inhibited only 47 %. <strong>Cu-3</strong> also effectively killed <em>S. aureus</em> within biofilms at doses up to 2 × MIC μg/mL. Further analysis of extracellular proteins (ECPs) expression revealed, that <strong>Cu-3</strong> had significant potential in suppressing ECPs production. Molecular docking (MD) studies with biofilm associated protein (Bap) and <em>SARS-CoV-2</em> receptors showed high interactions by several bonding types, where <strong>Cu-2</strong> found as potent antiviral agent. Collectively, these findings highlighted the copper complexes potential in antibacterial applications, with <strong>Cu-3</strong> emerging as a potent candidate for <em>S. aureus</em> biofilm inhibition.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"266 ","pages":"Article 112835"},"PeriodicalIF":3.8,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143356051","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":"Jim Kincaid and heme proteins: The Princeton years and beyond","authors":"Thomas G. Spiro","doi":"10.1016/j.jinorgbio.2025.112834","DOIUrl":"10.1016/j.jinorgbio.2025.112834","url":null,"abstract":"<div><div>This article is a personal chronical of Jim Kincaid's scientific career from his postdoctoral years in my laboratory at Princeton, to his final years in his lab at Marquette. He devoted himself to the study of heme proteins, using Raman spectroscopy as a probe of structure and function, producing many notable advances in our understanding of these key biological molecules. Along the way, Jim supported and encouraged many aspiring scientists. Reminiscences from his students and colleagues affirm his enthusiasm for science and for friendship, his generosity of time and attention, his puckish sense of humor, his unfailing kindness and his concern for the well-being of those around him, to the very end of his life. I was fortunate to have him as a student, collaborator, and life-long friend.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"266 ","pages":"Article 112834"},"PeriodicalIF":3.8,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143073367","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":"Two multifunctional zero-dimensional Gd(III) complexes: magnetocaloric effect and anticancer mechanisms for lung cancer","authors":"Shouying Cao, Yaqing Xie, Xiaotong Lu, Zijie Zhao, Feiya Zhou, Jie Wang, Lili Liang","doi":"10.1016/j.jinorgbio.2025.112832","DOIUrl":"10.1016/j.jinorgbio.2025.112832","url":null,"abstract":"<div><div>Two Gd(III) complexes [GdL(H<sub>2</sub>O)(NO<sub>3</sub>)<sub>2</sub>(CH<sub>3</sub>OH)<sub>0.75</sub>(CH<sub>3</sub>CH<sub>2</sub>OH)<sub>0.25</sub>] (<strong>Gd1</strong>) and [Gd<sub>2</sub>(OOCCH<sub>3</sub>)<sub>2</sub>L<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub>]•2(H<sub>2</sub>O) (<strong>Gd2</strong>) (HL = 2-pyridylcarboxaldehyde isonicotinoylhydrazone) were synthesized with a Schiff base ligand. Crystallographic study reveals both <strong>Gd1</strong> and <strong>Gd2</strong> have a zero-dimensional mononuclear or binuclear structure. Magnetic investigations demonstrate that <strong>Gd1</strong> and <strong>Gd2</strong> exhibit potential magnetocaloric effects due to Gd(III) ions, which provide negligible magnetic anisotropy, and possess low-lying excited spin states. The antiproliferative activity of <strong>Gd1</strong> and <strong>Gd2</strong> to three tumor cell lines was conducted and the results showed <strong>Gd1</strong> and <strong>Gd2</strong> showed more pronounced antiproliferative activity to A549 cells better than cisplatin. The administration of <strong>Gd1</strong> and <strong>Gd2</strong> led to an increase in apoptosis among A549 cells in a concentration-dependent manner, along with a corresponding rise in the levels of reactive oxygen species (ROS) within the cells. Besides, <strong>Gd1</strong> and <strong>Gd2</strong> were able to significantly inhibit tumor cell migration. Cell cycle assay in A549 cells revealed that cell cycle was arrested of G0/G1 phase. Western blotting analysis showed that <strong>Gd1</strong> and <strong>Gd2</strong> complexes could promote apoptosis in A549 cells by modulating the expression of Bcl-2 and Bax proteins.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"265 ","pages":"Article 112832"},"PeriodicalIF":3.8,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057437","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}