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The three new dioxo-tetraazamacrocyclic ligands with a fused, very rigid bispidine (3,7-diazabicyclo[3.3.1]nonane) group connecting the two tertiary amine donors, and ethyl, propyl, or benzene groups connecting the two amide donors are highly preorganized and lead to very stable, uncharged Cu(II) complexes. Solution spectroscopy and solid state structures indicate that these are square pyramidal with a solvent molecule occupying the apical position. Cyclic voltammetry defines a reversible Cu(III/II) couple and a strongly negative irreversible Cu(II/I) couple (ca. -2 V vs Fc/Fc(+)), indicating that the Cu(II) complexes are very stable in solution. This is supported by superoxide dismutase (SOD) and human serum challenge experiments as well as the biodistribution, which all show that the benzene-based ligand has the highest in vitro and in vivo stability and that this was expected on the basis of the macrocycle ring size and shape and the highest degree of preorganization. This ligand is easy to functionalize for a possible coupling to biological vector molecules and/or fluorescence markers for PET (positron emission tomography) and multimodal imaging (i.e., PET and optical imaging).
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http://dx.doi.org/10.1021/ic500476u | DOI Listing |
Chemistry
September 2025
IISER Tirupati: Indian Institute of Science Education and Research Tirupati, Tirupati, 517619, INDIA.
Nitric oxide (NO) is one of the crucial biological signaling molecules, yet achieving its selective and spatiotemporal detection in in-situ/invitro or biological systems at specific pH remains a significant challenge. Hence, a probe capable of directly detecting NO would be immensely valuable in understanding its reactivity and biological functions. Here, to develop a Cu(II)-based probe for selective NO detection, we synthesized a Cu(II)-complex (1) using a N3-tridentate ligand having a pendant dansyl fluorophore (L) and evaluated it's NO reactivity under varying pH conditions.
View Article and Find Full Text PDFOrg Lett
September 2025
School of Chemical Sciences, National Institute of Science Education and Research, An OCC of Homi Bhabha National Institute, Bhubaneswar 752050, India.
Selective reduction of heteroaromatic compounds to partially hydrogenated, dearomatized molecules is a tantalizing task. A well-defined, air stable, and pyridine-based Cu(II) NNN pincer complex is developed, which catalyzes selective 1,2-reduction of quinolines. The unstable 1,2-hydrogenated quinolines are transformed into the corresponding amides and isolated in good yields.
View Article and Find Full Text PDFJ Inorg Biochem
September 2025
Área Química Inorgánica, Facultad de Química, Universidad de la República, Montevideo, Uruguay. Electronic address:
Chagas disease, caused by Trypanosoma cruzi, 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.
View Article and Find Full Text PDFOrg Lett
September 2025
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, China.
Cyclization of -dibromo tetrapyrrolic Ni complex with KS, NaSe, and NaTe gave Ni 5-sulfacorrole, Ni 5-selenacorrole, and Ni 5-telluracorrole, respectively, as the first example of 5-heterocorrole. The corresponding Cu 5-heterocorroles were similarly synthesized from Cu complex , while Ni 5-oxacorrole was synthesized by reaction of with Ni(cod) and 2,2'-bipyridine and subsequent oxygen-insertion reaction of molecular oxygen, and Cu 5-oxacorrole was obtained from reaction of with Cu thiophene-2-carboxylate (CuTC) and tetrabutylammonium hydroxide. Moderate aromatic characters of the Ni 5-heterocorroles are evinced by the H NMR chemical shifts, the absorption spectra, and DFT calculations.
View Article and Find Full Text PDFRSC Adv
August 2025
Department of Chemistry, University of California, Davis One Shields Avenue Davis CA 95616 USA
Imbalances in cellular copper are increasingly implicated in metabolic disorders. Food-derived peptides are gaining attention for their ability to alleviate metabolic disease symptoms with little to no toxicity. In this work, we enriched copper-binding peptides from enzymatic digestions of rice bran protein hydrolysates Cu(ii)-based immobilized-metal affinity-based separations, identified the sequences by mass spectrometry, and performed physicochemical and sequence analysis of the enriched peptides.
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