Journal of Inorganic Biochemistry最新文献

{"title":"Synthesis, anticancer activity, and mechanistic investigations of aryl-alkyl diorganotin arylformylhydrazone complexes","authors":"Wujiu Jiang ,&nbsp;Qing Luo ,&nbsp;Wei Huang ,&nbsp;Yuxing Tan ,&nbsp;Yiyuan Peng","doi":"10.1016/j.jinorgbio.2024.112756","DOIUrl":"10.1016/j.jinorgbio.2024.112756","url":null,"abstract":"<div><div>Diorganotin acylhydrazone complexes with mitochondrial targeting demonstrate significant potential as replacements for platinum-based complexes due to their potent anticancer properties. Twelve methylphenyltin arylformylhydrazone complexes have been synthesized by microwave “one-pot” reaction. The complexes have been characterized by FT-IR, multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn), TGA, and HRMS. Crystal structures were determined for <strong>10</strong> out of the <strong>12</strong> complexes under study. Structures <strong>1</strong> through <strong>8</strong>, <strong>10</strong> and <strong>12</strong> possessed a central symmetric structure of a di-nuclear Sn₂O₂ tetrahedral ring. All complexes were tested for their inhibitory activity against human cell lines NCI-H460, MCF-7, and HepG2. Complex <strong>8</strong> exhibited the most effective inhibitory effect on HepG2 cells, with an IC₅₀ value of 1.34 ± 0.04 μM. Preliminary studies on the anticancer mechanism suggest that complex <strong>8</strong> induces apoptosis in HepG2 cells <em>via</em> the mitochondrial pathway, accompanied by G2/M phase cell cycle arrest.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112756"},"PeriodicalIF":3.8,"publicationDate":"2024-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398991","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":"Ruthenium complexes with abiraterone acetate as antiproliferative agents","authors":"Anastasia A. Antonets ,&nbsp;Ekaterina V. Spitsyna ,&nbsp;Vladimir Yu. Tyurin ,&nbsp;Dmitrii M. Mazur ,&nbsp;Dmitry S. Yakovlev ,&nbsp;Denis A. Babkov ,&nbsp;Mariya S. Pshenichnikova ,&nbsp;Alexander A. Spasov ,&nbsp;Elena R. Milaeva ,&nbsp;Alexey A. Nazarov","doi":"10.1016/j.jinorgbio.2024.112754","DOIUrl":"10.1016/j.jinorgbio.2024.112754","url":null,"abstract":"<div><div>This study is dedicated to the development of multimodal anticancer agents. We have obtained ruthenium complexes conjugated with the steroid-type antitumor drug abiraterone acetate in order to take advantage of the dual antitumor properties of both ruthenium and abiraterone. The compounds exhibit good antiproliferative activity against cancer cells, with selectivity over primary fibroblasts. Real-time cell analysis revealed that compound dichlorido(η⁶<span><span>6</span></span>-p-cymene)(abiraterone acetate)ruthenium(II) had pronounced antiproliferation activity compared to abiraterone acetate. Flow cytometric studies on the mechanism of cell death have revealed that the most active compound induces apoptosis more effectively than abiraterone acetate. Our findings demonstrate the potential of this novel dual-action compound as promising candidates for further development as anticancer agents.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112754"},"PeriodicalIF":3.8,"publicationDate":"2024-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142387007","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":"Antibacterial profile and antiproliferative activities over human tumor cells of new silver(I) complexes containing two distinct trifluoromethyl uracil isomers","authors":"Gabriele de Menezes Pereira ,&nbsp;Julia H. Bormio Nunes ,&nbsp;Vinicius Souza Macedo ,&nbsp;Douglas Henrique Pereira ,&nbsp;Kaio Eduardo Buglio ,&nbsp;Daniele D. Affonso ,&nbsp;Ana Lucia T.G. Ruiz ,&nbsp;João Ernesto de Carvalho ,&nbsp;Silmara Cristina L. Frajácomo ,&nbsp;Wilton R. Lustri ,&nbsp;Carmen Silvia Passos Lima ,&nbsp;Fernando R.G. Bergamini ,&nbsp;Alexandre Cuin ,&nbsp;Norberto Masciocchi ,&nbsp;Pedro Paulo Corbi","doi":"10.1016/j.jinorgbio.2024.112752","DOIUrl":"10.1016/j.jinorgbio.2024.112752","url":null,"abstract":"<div><div>New silver(I) complexes of 5-(trifluoromethyl)uracil (5TFMU) and 6-(trifluoromethyl)uracil (6TFMU) isomers were synthesized, characterized, and evaluated as antibacterial and antiproliferative agents. Based on elemental and thermogravimetric analyses, the Ag-5TFMU and Ag-6TFMU species are formulated as AgC₅H₂F₃N₂O₂ and Ag₂C₅HF₃N₂O₂, respectively. Infrared and ¹³C solid-state nuclear magnetic resonance spectroscopies suggest coordination of the trifluoromethyluracil isomers to silver by both nitrogen and oxygen atoms. Confirmation of their structure and connectivity was achieved, in the absence of single crystals of suitable quality, by state-of-the-art structural powder diffraction methods. In Ag-5TFMU, the organic ligand is tridentate and two distinct metal coordination environments are found (linear AgN₂ as well as <em>C</em>_<em>2v</em> AgO₄ geometries), whereas Ag-6TFMU contains a complex polymeric structure with tetradentate dianionic 6TFMU moieties and <em>five</em> distinct AgX₂ (X = N, O) fragments, further stabilized by ancillary (longer) Ag^…O contacts. These species presented modest activity over Gram-positive and Gram-negative bacterial strains, whereas Ag-6TFMU was active over a set of tumor cells, with the best activity over prostate (PC-3) and kidney cell lines and selectivity indices of 4.6 and 1.3, respectively. On the other hand, Ag-5TFMU was active over all considered tumor cells except MCF-7 (breast cancer). The best activity was found for PC-3 cells, but no selectivity was observed. The Ag-5TFMU and Ag-6TFMU species also reduced the proliferation of tongue squamous cell carcinoma cell lines SCC − 4 and SCC-15. Preliminary biophysical assays by circular dichroism suggest that the Ag-5TFMU complex interacts with DNA by intercalation, an effect not seen in Ag-6TFMU.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112752"},"PeriodicalIF":3.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374875","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":"Synthesis, structures, and cytotoxicity insights of organotin(IV) complexes with thiazole-appended pincer ligand","authors":"Tushar S. Basu Baul ,&nbsp;Swmkwr Brahma ,&nbsp;Rupen Tamang ,&nbsp;Andrew Duthie ,&nbsp;Biplob Koch ,&nbsp;Sean Parkin","doi":"10.1016/j.jinorgbio.2024.112750","DOIUrl":"10.1016/j.jinorgbio.2024.112750","url":null,"abstract":"<div><div>Diorganotin complexes of the compositions [Me₂Sn(L)] (<strong>1</strong>), [<em>n</em>-Bu₂Sn(L)] (<strong>2</strong>), [Ph₂Sn(L)]⋅C₆H₆ (<strong>3</strong>), [Bz₂Sn(L)]⋅C₆H₆ (<strong>4</strong>) and [<em>n</em>-Oct₂Sn(L)] (<strong>5</strong>) were synthesized by reacting R₂SnO (R = Me, <em>n</em>-Bu, Ph, Bz or <em>n</em>-Oct) with the <em>N</em>^<em>2</em>,<em>N</em>^<em>6</em>-di(thiazol-2-yl)pyridine-2,6-dicarboxamide (H₂L, where H₂ denotes the two acidic protons) in refluxing toluene. Additionally, the mono-<em>n</em>-butyltin complex [<em>n</em>-BuSn(HL)Cl₂]·H₂O (<strong>6</strong>) was synthesized from <em>n</em>-BuSnCl₃ and H₂L in acetonitrile. Compounds were characterized by FT-IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy, while their solid-state structures were examined using single-crystal X-ray diffraction studies. In diorganotin compounds <strong>1</strong>–<strong>5</strong>, the dianionic tridentate ligands (N_py, N⁻, N⁻) act as κ-<em>N</em>^<em>3</em> chelators. In <strong>6</strong>, the L moiety (O, N_py, N⁻) acts as a κ-<em>ON</em>^<em>2</em> tridentate chelator, with involvement of one of the carboxamide oxygen atoms. The coordination polyhedron around the Sn(IV) ion is completed either by two axial Sn-R ligands in compounds <strong>1</strong>–<strong>5</strong> or by <em>n</em>-Bu and Cl ligands in compound <strong>6</strong>, giving rise to distorted trigonal bipyramid or octahedral structures, respectively. The tin NMR results show that the penta-coordinated structures of compounds <strong>1</strong>–<strong>5</strong> and the hexacoordinated structure of compound <strong>6</strong>, observed in the solid-state, are retained in solution. The <em>in vitro</em> antitumor activities of <strong>1</strong>–<strong>5</strong> were tested on T-47D breast cancer cells. Of these, diphenyltin compound <strong>3</strong> showed the highest anti-proliferative effect, with an IC₅₀ of 10 ± 1.60 μM. Compound <strong>3</strong> exhibited selective toxicity, potentially inducing apoptosis via reactive oxygen species generation and nuclear changes, indicating promise as a breast cancer treatment. This study is the first to explore thiazole-appended organotin compounds for cytotoxicity.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112750"},"PeriodicalIF":3.8,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142387008","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":"Non-peripheral octasubstituted zinc(II) phthalocyanines bearing pyridinepropoxy substituents – Antibacterial, anticancer photodynamic and sonodynamic activity","authors":"Marcin Wysocki ,&nbsp;Daniel Ziental ,&nbsp;Zekeriya Biyiklioglu ,&nbsp;Malgorzata Jozkowiak ,&nbsp;Hüseyin Baş ,&nbsp;Jolanta Dlugaszewska ,&nbsp;Hanna Piotrowska-Kempisty ,&nbsp;Emre Güzel ,&nbsp;Lukasz Sobotta","doi":"10.1016/j.jinorgbio.2024.112751","DOIUrl":"10.1016/j.jinorgbio.2024.112751","url":null,"abstract":"<div><div>The novel non-peripheral octa-substituted zinc(II) phthalocyanines with 3- and 4-pyridinepropoxy substituents were synthesized via cyclization of substituted phthalonitriles and further characterized. Their photodynamic and sonodynamic activity were then assessed toward bacteria and cancer cells. Additionally, inhibition activity against common human enzymes was evaluated. The singlet oxygen generation (with 1,3-diphenylisobenzofuran – DPBF as an unspecific chemical quencher of singlet oxygen) were measured under light irradiation, whereas under ultrasounds (1 MHz, 3 W) the stability of DPBF in the presence of sensitizer was evaluated. Both phthalocyanines revealed high photostability in DMSO and moderate in DMF, whereas the sonostability in DMF was moderate. Calculated light-induced singlet oxygen generation quantum yields were similar for both compounds and oscillated around 0.33 in DMF and 0.67 in DMSO. Sonodynamic manner revealed moderately high DPBF decomposition upon 1 MHz. Significant bacterial reduction was noted in both photodynamic and sonodynamic manner, reaching &gt;3 log reduction against MRSA and <em>S. epidermidis</em>. Both compounds showed ca. 50 % viability reduction toward hypopharyngeal tumor (FaDu). Moreover, up to 60 % viability reduction was observed in squamous cell carcinoma (SCC-25). In summary, this molecular building of the efficient phthalocyanine-based sensitizer is a potential therapeutic for photodynamic and sonodynamic applications.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112751"},"PeriodicalIF":3.8,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142378936","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}

{"title":"Structure, properties, and decomposition in biological systems of a new nitrosyl iron complex with 2-methoxythiophenolyls, promising for the treatment of cardiovascular diseases","authors":"Оlesya V. Pokidova ,&nbsp;Veronika O. Novikova ,&nbsp;Nina S. Emel’yanova ,&nbsp;Ludmila M. Mazina ,&nbsp;Alina S. Konyukhova ,&nbsp;Alexander V. Kulikov ,&nbsp;Gennadii V. Shilov ,&nbsp;Nikolai S. Ovanesyan ,&nbsp;Tatyana S. Stupina ,&nbsp;Natalia A. Sanina","doi":"10.1016/j.jinorgbio.2024.112747","DOIUrl":"10.1016/j.jinorgbio.2024.112747","url":null,"abstract":"<div><div>A new promising binuclear tetranitrosyl iron complex with 2-methoxythiophenolyl of the composition [Fe₂(C₇H₇OS)₂(NO)₄] (complex <strong>1</strong>), which acts on the therapeutic targets of cardiovascular diseases, guanylate and adenylate cyclase, has been synthesized. X-ray diffraction data show the presence of two isoforms of complex <strong>1</strong>; according to quantum chemical calculations, the structure of only the <em>trans</em> isomer is stable in solutions.</div><div>The processes of transformation of complex <strong>1</strong> in DMSO, in aqueous solutions, as well as in the presence of bovine serum albumin, reduced glutathione, and mucin were studied. DMSO promotes the decomposition of the original complex <strong>1</strong> into mononuclear products. In biological systems, the mechanisms of decomposition of the complex <strong>1</strong> differ from aqueous solutions. In albumin solution, a gradual formation of a high-molecular-weight dinitrosyl complex is observed, obtained by coordinating the [Fe(NO)₂]⁺ fragment with the amino acid groups of the protein. In the presence of mucin, an EPR signal from stable mononitrosyl products is observed. The introduction of glutathione into the system of the complex <strong>1</strong> leads to the replacement of one initial thioligand with glutathione. In the model systems under study, a more efficient and prolonged generation of NO groups is observed compared to a buffer solution.</div><div>The obtained data on the influence of the environment on the properties of the complex <strong>1</strong> in combination with a study of their effect on enzymes allow us to recommend it for further study as a potential drug with vasodilator, antianginal, and hypotensive properties.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112747"},"PeriodicalIF":3.8,"publicationDate":"2024-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374877","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":"Uridine triphosphate hybrid catalyst for carbon‑carbon bond formation reactions with enhanced enantioselectivity by mercury(II) ions","authors":"Li Liu,&nbsp;Xingchen Dong,&nbsp;Weijun Qin,&nbsp;Yashao Chen,&nbsp;Changhao Wang","doi":"10.1016/j.jinorgbio.2024.112748","DOIUrl":"10.1016/j.jinorgbio.2024.112748","url":null,"abstract":"<div><div>DNA hybrid catalysts are constructed by embedding active metal species into the chiral scaffolds of DNA, which have been successfully applied to some important aqueous-phase enantioselective transformations. Owing to simple components and inherent chirality, nucleotide hybrid catalysts are emerging in response to soving the unclear locations of catalytic centers and the plausible catalytic mechanisms in DNA-based asymmetric catalysis. However, the tertiary structure of nucleotides lacks tunability, severely impeding further design of nucleotide hybrid catalysts for potential applications. To this end, a design strategy for tunable nucleotide hybrid catalysts is put forward by introducing metal-mediated base pairs. Herein, we found that the formation of uracil‑mercury(II)-uracil (U-Hg²⁺-U) base pairs could enhance the enantioselectivity in uracil-containing nucleotide-based asymmetric reactions. Compared with uracil triphosphate (UTP) complexing with Cu²⁺ ions (UTP∙Cu²⁺), the presence of Hg²⁺ ions gave rise to an increased enantiomeric excess (ee) of 38 % in Diels-Alder reactions and 22 % ee in Michael reactions. The Hg²⁺-tuning behaviors of UTP hybrid catalyst have been demonstrated to largely depend on nucleotides, Hg²⁺ concentrations, metal cofactors, additives and reaction types. Based on ultraviolet-visible, circular dichroism and nuclear magnetic resonance spectroscopic techniques, the chiral enhancement of Hg²⁺-containing UTP hybrid catalyst is proved to largely depend on the formation of U-Hg²⁺-U base pairs and the plausible cross-linked structure of UTP-Hg²⁺-UTP/Cu²⁺ assembly. This work provides a tunable strategy based on the concept of metal-mediated base pairs, allowing further design of potent oligonucleotide-based catalysts for other enantioselective reactions.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112748"},"PeriodicalIF":3.8,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370597","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":"Pd(II)/1,10-phenanthroline complexes bearing arene ligands: On the role of N- vs O-coordination to tune their cellular activity and binding ability towards DNA and RNA","authors":"Francesca Binacchi ,&nbsp;Damiano Cirri ,&nbsp;Eleonora Bimbi ,&nbsp;Natalia Busto ,&nbsp;Alessandro Pratesi ,&nbsp;Tarita Biver","doi":"10.1016/j.jinorgbio.2024.112749","DOIUrl":"10.1016/j.jinorgbio.2024.112749","url":null,"abstract":"<div><div>Three Pd(II)-based complexes of 1,10-phenanthroline and <em>N</em>- or <em>O</em>-coordinating ligands have been synthesised and tested with different relevant biosubstrates like double-stranded DNA, double and triple helix of RNA, DNA G-quadruplexes of different conformations and bovine serum albumin. Here a correlation between N- vs O-coordinating elements and binding mechanism emerged, where the N-coordinating ligands proved to be the most promising. These outcomes were confirmed also in the cellular experiments. The Pd(II) complex with naphthalene-1,8-diamine is the one that is able to be carried by BSA, to strongly bind nucleic acids, to produce reactive oxygen species (ROS) and to show the best cellular performances (poorly toxic towards healthy cells and highly toxic against the cisplatin-resistant cancer cell line). On the opposite, the complex with benzene-1,2-diolate may be sequestered by BSA, weakly binds nucleic acids, does not produce ROS and shows poor cellular activity. The complex with benzene-1,2-diamine stays in between. Other mechanistic details are discussed which show that the biophysical behaviour is the sum of the contribution of aromaticity, charge and <em>N-</em> or <em>O-</em>coordination.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112749"},"PeriodicalIF":3.8,"publicationDate":"2024-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142374876","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}

{"title":"Generating globin-like reactivities in [human serum albumin-FeII(heme)] complex through N-donor ligand addition","authors":"Mary Grace I. Galinato ,&nbsp;Christopher Wyant ,&nbsp;Ashley L. Lombardo ,&nbsp;Ethan K. MacIsaac ,&nbsp;Daniella A. Rios-Martinez ,&nbsp;Christopher D. Kimrey ,&nbsp;Alexandra Alfonso Castro","doi":"10.1016/j.jinorgbio.2024.112743","DOIUrl":"10.1016/j.jinorgbio.2024.112743","url":null,"abstract":"<div><div>Human serum albumin (HSA) has a strong binding affinity for heme <em>b</em>, forming a complex in a 1:1 ratio with the co-factor ([HSA-Fe^IIIheme]). This system displays spectroscopic and functional properties comparable to globins when chemical derivatives mimicking them are incorporated into the protein matrix. The aim of this study is to generate globin-like systems using [HSA-Fe^IIIheme] as a protein template and binding N-donor ligands (imidazole, Im; and 1-methylimidazole, 1-MeIm) to construct artificial [HSA-Fe(heme)-(N-donor)] complexes. Their electronic structure and binding thermodynamics are investigated using UV–vis and (synchronous) fluorescence spectroscopies, while ligand-protein interactions are visualized using docking simulations. The imidazole derivatives have a strong affinity for [HSA-Fe^IIIheme] (K ∼ 10⁴–10⁶), where the spontaneous binding of Im and 1-MeIm are dominated by entropic and enthalpic effects, respectively. The reduced form of the [HSA-Fe(heme)-(N-donor)] complexes demonstrate nitrite reductase (NiR) activity similar to that observed in globins, but with significant differences in their rates. [HSA-Fe^IIheme-(1-MeIm)] reduces nitrite ∼4× faster than the Im analogue, and ∼ 30× faster than myoglobin (Mb). The enhanced NiR activity of [HSA-Fe^IIheme-(1-MeIm)] is a cumulative effect of several factors including a slightly expanded and more optimal heme binding pocket, nearby residues as possible proton sources, and a H-bonding interaction between 1-MeIm and residues Arg160 and Lys181 that may have a long-distance influence on the heme π electron density.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112743"},"PeriodicalIF":3.8,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142359426","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":"The application of X-ray fluorescence microscopy and micro-XANES spectroscopy to study neuro-metallomics","authors":"Meg Willans ,&nbsp;Ashley Hollings ,&nbsp;Rhiannon E. Boseley ,&nbsp;Thomas Munyard ,&nbsp;Gaewyn C. Ellison ,&nbsp;Mark J. Hackett","doi":"10.1016/j.jinorgbio.2024.112744","DOIUrl":"10.1016/j.jinorgbio.2024.112744","url":null,"abstract":"<div><div>This early career research highlight provides a review of my own research program over the last decade, a time frame that encompasses my transition from postdoctoral fellowships to independent researcher. As an analytical chemist and applied spectroscopist, the central theme of my research program over this time has been protocol development at synchrotron facilities, with the main objective to investigate brain metal homeostasis during both brain health and brain disease. I will begin my review with an overview of brain metal homeostasis, before introducing analytical challenges associated with its study. I will then provide a brief summary of the two main X-ray techniques I have used to study brain metal homeostasis, X-ray fluorescence microscopy (XFM) and X-ray absorption near edge structure spectroscopy (XANES). The review then finishes with a summary of my main research contributions using these two techniques, put in the context of the results from others in the field.</div></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112744"},"PeriodicalIF":3.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142338549","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}