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Due to their extremely low background signal and high sensitivity, the chemiluminescence (CL) probes have received a great attention in various chemical and biological applications. However, the lack of selectivity is still a challenging task. As an innovative topic of research, in this work we developed a domino-like turn-on CL reaction through proximal-imidazole species for the first time. The oxidation reaction of N-(2H-[1,2,4]thiadiazolo[2,3-a]pyridine-2-ylidene)benzamide (1) by hydrogen peroxide found to promoted by a domino-like reaction between proximal imidazole species and the Co-1 complex formation which accompanied by a dramatically turn-on emission. In the way of explaining the possible mechanism, the application of density functional theory (DFT) studies revealed that there are three possible pathways for the reactions between precursor 1 and HOO in the presence of imidazole to produce the oxidized isomers. The strongest interaction found to occur in pathway 3, in which the sulfur atom was oxidized, while there was some repulsion between HOO and 1, due to the effects of two different charges in pathways 1 and 2. To confirm tits applicability, the CL system was successfully applied to highly selective quantification of vitamin B in some real samples. The linear dynamic range was achieved from 0.08 to 34 ng mL and the detection limit was evaluated as 0.028 ng mL. This new method introduced fluorescence selectivity and CL sensitivity in single technique. It was finally anticipated that the CL amplification through proximal-imidazole species possesses a great potential on tuning various color-emissions based on different metal-ligand complex formations studied.
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http://dx.doi.org/10.1016/j.talanta.2025.127902 | DOI Listing |
Talanta
September 2025
Chemistry Department, Faculty of Science, Yadegar-e-Imam Khomeini (RAH) Shahre-Ray Branch, Islamic Azad University, Tehran, Iran.
Due to their extremely low background signal and high sensitivity, the chemiluminescence (CL) probes have received a great attention in various chemical and biological applications. However, the lack of selectivity is still a challenging task. As an innovative topic of research, in this work we developed a domino-like turn-on CL reaction through proximal-imidazole species for the first time.
View Article and Find Full Text PDFDrug Metab Dispos
June 2016
Departments of Pharmaceutical Candidate Optimization (W.L., W.Z., X.L., X.H., R.M.F., J.C.-C., S.Y.C., L.M., M.Z., Y.-Z.S., W.G.H., B.M.J.), Synthesis and Analysis Technology Team (J.E.L.), Virology (M.G.), and Chemistry (O.D.L., V.N., J.G., J.E., Y.H., M.B., L.G.H.), Bristol-Myers Squibb Company, W
Daclatasvir is a first-in-class, potent, and selective inhibitor of the hepatitis C virus nonstructural protein 5A replication complex. In support of nonclinical studies during discovery and exploratory development, liquid chromatography-tandem mass spectrometry and nuclear magnetic resonance were used in connection with synthetic and radiosynthetic approaches to investigate the biotransformation of daclatasvir in vitro and in cynomolgus monkeys, dogs, mice, and rats. The results of these studies indicated that disposition of daclatasvir was accomplished mainly by the release of unchanged daclatasvir into bile and feces and, secondarily, by oxidative metabolism.
View Article and Find Full Text PDFFront Physiol
September 2015
Department of Chemistry, Stanford University Stanford, CA, USA.
The rationale of the study was two-fold: (i) develop a functional synthetic model of the Cytochrome c oxidase (CcO) active site, (ii) use it as a convenient tool to understand or predict the outcome of the reaction of CcO with ligands (physiologically relevant gases and other ligands). At physiological pH and potential, the model catalyzes the 4-electron reduction of oxygen. This model was immobilized on self-assembled-monolayer (SAM) modified electrode.
View Article and Find Full Text PDFInorg Chem
May 2014
Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, P.O. Wits, Johannesburg, 2050 South Africa.
The synthesis of a Co(III) corrole, [10-(2-[[4-(1H-imidazol-1-ylmethyl)benzoyl]amino]phenyl)-5,15-diphenylcorrolato]cobalt(III), DPTC-Co, bearing a tail motif terminating in an imidazole ligand that coordinates Co(III), is described. The corrole therefore places Co(III) in a similar environment to that in aquacobalamin (vitamin B12a, H2OCbl(+)) but with a different equatorial ligand. In coordinating solvents, DPTC-Co is a mixture of five- and six-coordinate species, with a solvent molecule occupying the axial coordination site trans to the proximal imidazole ligand.
View Article and Find Full Text PDFInorg Chem
August 2010
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA.
This paper presents oriented single-crystal Nuclear Resonance Vibrational Spectroscopy (NRVS) data for the six-coordinate (6C) ferrous heme-nitrosyl model complex [(57)Fe(TPP)(MI)(NO)] (1; TPP(2-) = tetraphenylporphyrin dianion; MI = 1-methylimidazole). The availability of these data enables for the first time the detailed simulation of the complete NRVS data, including the porphyrin-based vibrations, of a 6C ferrous heme-nitrosyl, using our quantum chemistry centered normal coordinate analysis (QCC-NCA). Importantly, the Fe-NO stretch is split by interaction with a porphyrin-based vibration into two features, observed at 437 and 472 cm(-1).
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