21710-12-3Relevant articles and documents
An interpretation of gated behavior: Kinetic studies of the oxidation and reduction reactions of bis(2,9-dimethyl-1,10-phenanthroline)copper(I/II) in acetonitrile
Koshino, Nobuyoshi,Kuchiyama, Yoshio,Ozaki, Hiroshi,Funahashi, Shigenobu,Takagi, Hideo D.
, p. 3352 - 3360 (1999)
Reduction reactions of Cu(dmp)2 2+(dmp = 2,9-dimethyl-1,10-phenanthroline) by ferrocene (Fe(Cp)2= bis(cyclopentadienyl)iron(II)), decamethylferrocene (Fe(PMCp)2= bis(pentamethylcyclopentadienyl)iron(II)), and Co(bpy)3 2+(bpy = 2,2′-bipyridine) and oxidation reactions of Cu(dmp)2 +by Ni(tacn)2 3+(tacn = 1,4,7-triazacyclononane) and Mn(bpyO2)3 3+(bpyO2= N,N′-dioxo-2,2′-bipyridine) were studied in acetonitrile for the purpose of interpreting the gated behavior involving copper(II) and -(I) species. It was shown that the electron self-exchange rate constants estimated for the Cu(dmp)2 2+/+couple from the oxidation reaction of Cu(dmp)2 +by Ni(tacn)2 3+(5.9 × 102kg mol-1s-1) and Mn(bpyO2)3 3+(2.9 × 104kg mol-1s-1) were consistent with the directly measured value by NMR (5 × 103kg mol-1s-1). In contrast, we obtained the electron self-exchange rate constant of Cu(dmp)2 2+/+as 1.6 kg mol-1s-1from the reduction of Cu(dmp)2 2+by Co(bpy)3 2+. The pseudo-first-order rate constant for the reduction reaction of Cu(dmp)2 2+by Fe(Cp)2was not linear against the concentration of excess amounts of Fe(Cp)2. A detailed analysis of the reaction revealed that the reduction of Cu(dmp)2 2+involved the slow path related to the deformation of Cu(dmp)2 2+(path B in Scheme 1). By using Fe(PMCp)2(the E° value is 500 mV more negative than that of Fe(Cp)2 +/0) as the reductant, the mixing with another pathway involving deformation of Cu(dmp)2 +(path A in Scheme 1) became more evident. The origin of the Gated Behavior is discussed by means of the energy differences between the normal and deformed Cu(II) and Cu(I) species: the difference in the crystal field activation energies corresponding to the formation of pseudo-tetrahedral Cu(II) from tetragonally distorted Cu(II) and the difference in the stabilization energies of the tetrahedral and tetragonal Cu(I) for the activation of Cu(I) species. The reduction reaction of Cu(dmp)2 2+by Fe(PMCp)2confirmed that the mixing of the two pathways takes place by lowering the energy level corresponding to the less favorable conformational change of Cu(I) species.
Spectroelectrochemical sensing based on multimode selectivity simultaneously achievable in a single device: 14. Enhancing sensitivity of a metal complex ion by ligand exchange
Shtoyko, Tanya,Richardson, John N.,Seliskar, Carl J.,Heineman, William R.
, p. 3191 - 3199 (2005)
Enhancement of the sensitivity of a spectroelectrochemical sensor by ligand exchange within the sensing film during spectroelectrochemical modulation is demonstrated in this paper. This concept is illustrated with a sensor for Cu(en)22+, where en = ethylenediamine, in aqueous solution. A ligand exchange reaction increases the difference in the molar absorptivities of the two complex ions involved in spectroelectrochemical modulation, thus giving a larger optical response. The spectroelectrochemical sensor consists of a cation-selective Nafion-SiO2 composite film spin-coated onto an indium tin oxide (ITO) glass optically transparent electrode (OTE). The film was loaded with 2,9-dimethyl-1,10-phenanthroline (neocuproine, or nc) for the ligand exchange reaction. Reduction of Cu(en)2 2+ at the OTE is accompanied by ligand exchange with nc to form Cu(nc)21+, which has a molar absorptivity of 7950 M -1 cm-1 at λmax = 454 nm. Detection within the sensing film using attenuated total reflectance (ATR) at 454 nm during modulation was accomplished by potential cycling between 0.8 and -0.9 V versus Ag/AgCl. The effects of nc concentration in the film and potential scan rate on the absorbance-time profile for spectroelectrochemical modulation were studied. The calibration curve for Cu(en)22+ was linear within the range of 5 × 10-6 M to 1 × 10-3 M.
A highly emissive heteroleptic copper(I) bis(phenanthroline) complex: [Cu(dbp)(dmp)]+ (dbp = 2,9-di-tert-butyl-1,10-phenanthroline; dmp = 2,9- dimethyl-1,10-phenanthroline)
Miller, Mark T.,Gantzel, Peter K.,Karpishin, Timothy B.
, p. 4292 - 4293 (1999)
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A quantitative method for the assessment of homocysteine thiolactonase enzyme activity
Obeid, Nassr J.,Hadwan, Mahmoud Hussein
, (2021/09/14)
This assay elucidates an accurate, simple, and precise protocol to quantify the activity of homocysteine thiolactonase (HTase). To establish HTase activity, the enzyme samples were incubated with a 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer, which contained suitable concentrations of the homocysteine thiolactone as a substrate. To stop the enzyme's reaction, the CUPRAC reagent (Cu(Nc)22+) was added after a suitable incubation time. The reduction of Cu(II)-neocuproine complex (Cu(Nc)22+) to highly coloured Cu(I)-neocuproine complex (Cu(Nc)2+) by the produced homocysteine was quantified spectrophotometrically at 450 nm (CUPRAC method). The increase in the absorbance of the coloured Cu(I)-neocuproine complex (Cu(Nc)2+) was correlated directly to the activity of HTase. ANOVA analysis was utilised to validate the new method against homocysteine thiolactonase activity using the H+ ions liberating method in matched samples. In conclusion, according to the obtained correlation coefficient (0.9995) from the comparison of the current method with the reference method, the current method is effective in assay HTase activity with high reliability.
FerriNaphth: A fluorescent chemodosimeter for redox active metal ions
Jackson, Randy K.,Shi, Yu,Yao, Xudong,Burdette, Shawn C.
, p. 4155 - 4161 (2010/07/04)
FerriNaphth, a fluorescent chemodosimeter for FeIII, has been prepared and characterized. The probe consists of a catechol ligand linked to a naphthalimide fluorophore by an aniline nitrogen linker. Upon exposure to FeIII, the aminocatechol of FerriNaphth is oxidized to the corresponding quinone, which in its imine-one tautomer, is hydrolyzed to liberate a fluorescent aminonaphthalimide derivative. The fluorescence behavior is consistent with oxidation being promoted by metal coordination.