Iridium(III) Complexes of Bifunctional 2-(2-Pyridyl)imidazole Ligands: Electrochemiluminescent Emitters in Aqueous Media.

A series of electrochemiluminescent (ECL) iridium(III) complexes with the general formula [Ir(CN)(pim)] (where CN = cyclometalating ligands 2-phenylpyridinato (ppy) or 2-(2,4-difluorophenyl)pyridinato (dFppy), and pim = 2-(2-pyridyl)imidazole) have been synthesized. In each case, the 2-(2-pyridyl)imidazole ancillary ligand has been modified to facilitate bioconjugation and ECL label development. All complexes exhibit blue-shifted optical and electro-generated phosphorescence relative to the archetypal complex [Ir(ppy)(bpy)] (bpy = 2,2'-bipyridine).

Construction of a Highly Sensitive Thiol-Reactive AIEgen-Peptide Conjugate for Monitoring Protein Unfolding and Aggregation in Cells.

Impairment of the protein quality control network leads to the accumulation of unfolded and aggregated proteins. Direct detection of unfolded protein accumulation in the cells may provide the possibility for early diagnosis of neurodegenerative diseases. Here a new platform based on a peptide-conjugated thiol-reactive aggregation-induced emission fluorogen (AIEgen), named MI-BTD-P (or D1), for labeling and tracking unfolded proteins in cells is reported.

Near-Infrared Electrochemiluminescence from Bistridentate Ruthenium(II) Di(quinoline-8-yl)pyridine Complexes in Aqueous Media.

We report the synthesis, photophysics, electrochemistry and electrochemiluminescence (ECL) of two dqp (dqp=2,6-di(quinoline-8-yl)pyridine) based ruthenium(II) complexes, bearing either a n-butyl ester (1) or the corresponding carboxylic acid functionality (2). The complexes were prepared from [Ru(dqp)(MeCN) ][PF ] by reaction with the dqp precursor using microwave irradiation. In both cases, photoluminescence spectra present strong MLCT-based red/near-infrared (NIR) emissions centred at about 710 nm.

Site-Specific Description of the Enhanced Recognition Between Electrogenerated Nitrobenzene Anions and Dihomooxacalix[4]arene Bidentate Ureas.

Electron transfer controlled hydrogen bonding was studied for a series of nitrobenzene derivative radical anions, working as large guest anions, and substituted ureas, including dihomooxacalix[4]arene bidentate urea derivatives, in order to estimate binding constants (Kb) for the hydrogen-bonding process. Results showed enhanced Kb values for the interaction with phenyl-substituted bidentate urea, which is significantly larger than for the remaining compounds, e.g.

Electrochemical and theoretical analysis of the reactivity of shikonin derivatives: dissociative electron transfer in esterified compounds.

An electrochemical and theoretical analysis of a series of shikonin derivatives in aprotic media is presented. Results showed that the first electrochemical reduction signal is a reversible monoelectronic transfer, generating a stable semiquinone intermediate; the corresponding E(I)⁰ values were correlated with calculated values of electroaccepting power (ω(+)) and adiabatic electron affinities (A(Ad)), obtained with BH and HLYP/6-311++G(2d,2p) and considering the solvent effect, revealing the influence of intramolecular hydrogen bonding and the substituting group at position C-2 in the experimental reduction potential. For the second reduction step, esterified compounds isobutyryl and isovalerylshikonin presented a coupled chemical reaction following dianion formation.

Nature of electrogenerated intermediates in nitro-substituted nor-β-lapachones: the structure of radical species during successive electron transfer in multiredox centers.

Electrochemical, spectroelectrochemical, and theoretical studies of the reduction reactions in nor-β-lapachone derivatives including a nitro redox center showed that reduction of the compounds involves the formation of several radical intermediates, including a biradical dianion resultant from the separate reduction of the quinone and nitro groups in the molecules. Theoretical descriptions of the corresponding Fukui functions f(αα)⁺ and f(ββ)⁺(r) and LUMO densities considering finite differences and frozen core approximations for describing the changes in electron and spin densities of the system allowed us to confirm these results. A description of the potential relationship with the obtained results and biological activity selectivity indexes suggests that both the formation of stable biradical dianion species and the stability of the semiquinone intermediates during further reduction are determining factors in the description of their biological activity.