Novel, fast, and reliable electrochemical dsDNA biosensor based on O-terminated pristine nanocrystalline boron-doped diamond electrode for DNA interaction studies.

We present a novel application of a nanocrystalline boron-doped diamond electrode (B-NCDE) for the construction of an electrochemical DNA biosensor based on double-stranded DNA (dsDNA) for various bioanalytical applications. Surface characterization of the transducer surface (prior and after the fabrication of negatively charged O-terminated surface - O-B-NCDE) was performed by scanning electron microscopy (SEM), Raman spectroscopy, and linear sweep voltammetry (LSV) that was further used for the voltammetric determination, scan rate dependence investigation, and repeatability examination of dsDNA electrochemical oxidation at the O-B-NCDE. The fabrication of a dsDNA/O-B-NCDE biosensor via electrostatic adsorption of dsDNA involved a thorough optimization process of deposition potential (Edep), deposition time (tdep), and optimal saturation concentration (cg(satur)) with optimal values of 0.3 V, 3 min, and 10 mg/mL. The bioanalytical applicability of the fabricated dsDNA/O-B-NCDE biosensor was verified by examining the nature of the interaction between dsDNA and five selected DNA intercalators - namely thioridazine hydrochloride (TR), trimipramine maleate (TRIM), levomepromazine maleate (LEV), imipramine hydrochloride (IMI), and prochlorperazine maleate (PER) - where intercalation was proven for all of the five tested compounds. Moreover, the proposed novel bioanalytical test offers the possibility to selectively distinguish between the phenothiazine representatives (TR, LEV, and PER) and representatives of tricyclic antidepressants group (TRIM and IMI).

Kinetics and thermodynamics of limonene ozonolysis.

Using density functional methods, the initial reaction steps of limonene ozonolysis have been investigated with a focus on primary ozonide formation and its decomposition to Criegee intermediates and carbonyl compounds. The ozonide formation is highly exothermic, and the decomposition channels have similar free energies of activation, ΔG(‡), indicating that there is no primary pathway for ozonide decomposition. Assuming that ozonide formation is the rate limiting step, the theoretical rate coefficient, k = 1.6 × 10(-16) molecule(-1) cm(3) s(-1), evaluated at the CCSD(T)/6-31G(d,p)//BHandHLYP/cc-pvdz level and 298.15 K for d-limonene is in good agreement with the experimental value, k(exp) = 3.3 × 10(-16) molecule(-1) cm(3) s(-1). The theoretical Arrhenius expression is also in good agreement with experimental results.