Editorial

http://www.sciencedirect.com/science/article/B6TG0-4JW7X04-9/1/e839ed9a3d5631f25adada92860abac

DNA imaged on a HOPG electrode surface by AFM with controlled potential

Single-molecule AFM imaging of single-stranded and double-stranded DNA molecules self-assembled from solution onto a HOPG electrode surface is reported. The interaction of DNA with the hydrophobic surface induced DNA aggregation, overlapping, intra- and intermolecular interactions. Controlling the electrode potential and using the phase images as a control method, to confirm the correct topographical characterization, offers the possibility to enlarge the capability of AFM imaging of DNA immobilized onto conducting substrates, such as HOPG. The application of a potential of +300 mV (versus AgQRE) to the HOPG enhanced the robustness and stability of the adsorbed DNA molecules, increasing the electrostatic interaction between the positively charged electrode surface and the negatively charged DNA sugar-phosphate backbone.http://www.sciencedirect.com/science/article/B6W72-4D5X9NS-1/1/d1528546598a5fb98abb8331a760556

Reversed-Phase High-Performance Liquid Chromatography with Electrochemical Detection of Anthocyanins

Abstract: Anthocyanins, flavonoid compounds present in grapes and wines, were determined by reverse-phase high-performance liquid chromatography (RP-HPLC) with electrochemical detection (RP-HPLC-ED). The method developed consists of RP-HPLC gradient elution with voltammetric detection using a glassy carbon electrode after separation in an Inertsil ODS-3V analytical column. Good peak resolution was obtained following direct injection of a 50 mL sample of anthocyanins in a mobile phase of pH 2.20. The results show that six different anthocyanins: cyanidin-3-O-glucoside chloride (kuromanin chloride), cyanidin-3,5-di-O-glucoside chloride (cyanin chloride), malvidin-3-O-glucoside chloride (oenin chloride), malvidin-3,5-di-O-glucoside chloride (malvin chloride), delphinidin-3-O-glucoside chloride (myrtillin chloride), and peonidine-3-O-glucoside chloride, all with antioxidant properties, can be separated in a single run by direct injection of solution. The limit of detection (LOD) for these compounds was lower than 0.3 mM. The method can also be applied to the analysis of these compounds in red wines and in skins and pulp extracts of red grapes, since all these antioxidants are electroactive

Electrochemical evaluation of glutathione S-transferase kinetic parameters

Glutathione S-transferases (GSTs), are a family of enzymes belonging to the phase II metabolism that catalyse the formation of thioether conjugates between the endogenous tripeptide glutathione and xenobiotic compounds. The voltammetric behaviour of glutathione (GSH), 1-chloro-2,4-dinitrobenzene (CDNB) and glutathione S-transferase (GST), as well as the catalytic conjugation reaction of GSH to CDNB by GST was investigated at room temperature, T = 298.15 K (25 °C), at pH 6.5, for low concentration of substrates and enzyme, using differential pulse (DP) voltammetry at a glassy carbon electrode. Only GSH can be oxidized; a sensitivity of 0.14 nA/μM and a LOD of 6.4 μM were obtained. The GST kinetic parameter electrochemical evaluation, in relation to its substrates, GSH and CDNB, using reciprocal Michaelis–Menten and Lineweaver–Burk double reciprocal plots, was determined. A value of KM ~ 100 μM was obtained for either GSH or CDNB, and Vmax varied between 40 and 60 μmol/min per mg of GST

Synthesis and electrochemical study of new 3-(hydroxyphenyl)benzo[f]coumarins

New hydroxyl substituted 3-arylbenzo[f]coumarins (compounds 6–10) have been designed and synthesized. Their electrochemical redox mechanisms, and the influence of one or two hydroxyl groups, in different positions on the coumarin scaffold, was investigated by cyclic, differential pulse and square wave voltammetry, at a glassy carbon electrode, at different pHs, and a comparative study was performed. The structural information obtained enabled a better understanding of the structure/electrochemical relationship of hydroxyl substituted 3-arylbenzo[f]coumarins, compounds with important antioxidant properties

Development of an HPLC method with electrochemical detection of femtomoles of 8-oxo-7,8-dihydroguanine and 8-oxo-7,8-dihydro-2'-deoxyguanosine in the presence of uric acid

A selective method based on high performance liquid chromatography with electrochemical detection (HPLC-ECD) was developed to enable simultaneous detection of 8-oxo-7,8-dihydroguanine (8-oxoGua) and 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo), products of DNA oxidative damage, in the presence of uric acid (UA), a strong interferent in their electrochemical detection. The method developed consists of HPLC isocratic elution with amperometric detection on a glassy carbon electrode, enabling a detection limit for 8-oxoGua and 8-oxodGuo lower than 1 nM in standard mixtures. Detection of low concentrations up to 25 nM of 8-oxoGua and 8-oxodGuo in the presence of UA in a 104-fold higher concentration was achieved after one-step solid phase extraction (SPE). The method was tested with urine samples and it was possible to detect and quantify the presence of 8-oxoGua, and to confirm that UA was eliminated after uricase degradation and SPE. The LOD found in urine samples was about 80 nM, a value higher than in standard mixtures, due to the increase of background current in the urine matrix. The results presented here contribute to the development of a methodological approach to simultaneous determination of 8-oxoGua and 8-oxodGuo in urine samples.http://www.sciencedirect.com/science/article/B6THP-4BG45K9-1/1/203c0cf340998db82825488fecf36e4

Graphite–castor oil polyurethane composite electrode surfaces – AFM morphological and electrochemical characterisation

Graphite–castor oil polyurethane composite electrodes with different graphite weight percentages, 30–70% graphite–polyurethane w w−1, were morphologically studied by atomic force microscopy (AFM) and voltammetry. AFM images and r.m.s. roughness measurements demonstrated that the polyurethane roughness decreased with increasing the graphite content, composites of 50% and 60% graphite–polyurethane w w−1 showing the smother electrode surface. The electrochemical characterisation was performed in solutions of K4Fe(CN)6 by cyclic voltammetry and impedance spectroscopy. For compositions of 60% and 70% graphite–polyurethane w w−1, the cyclic voltammetry results showed the K4Fe(CN)6 system reversibility. The charge transfer resistance, determined from the EIS spectra, decreased significantly with increasing the graphite/polyurethane ratio, and the capacitance increased for higher graphite percentages. AFM and voltammetric results enable to conclude that 60% graphite–polyurethane w w−1 was the optimal composition for the preparation of the graphite–polyurethane composite electrodes

Atomic Force Microscopy and Voltammetric Investigation of Quadruplex Formation between a Triazole-Acridine Conjugate and Guanine-Containing Repeat DNA Sequences

The interactions of the Tetrahymena telomeric repeat sequence d(TG4T) and the polyguanylic acid (poly(G)) sequence with the quadruplex-targeting triazole-linked acridine ligand GL15 were investigated using atomic force microscopy (AFM) at a highly oriented pyrolytic graphite and voltammetry at a glassy carbon electrode. GL15 interacted with both sequences, in a time dependent manner, and G-quadruplex formation was detected. AFM showed the adsorption of quadruplexes as small d(TG4T) and poly(G) spherical aggregates and large quadruplex-based poly(G) assemblies, and voltammetry showed the decrease and disappearance of GL15 and guanine oxidation peak currents and appearance of the G-quadruplex oxidation peak. The GL15 molecule strongly stabilized and accelerated G-quadruplex formation in both Na+ and K+ ion-containing solution, although only K+ promoted the formation of perfectly aligned tetra-molecular G-quadruplexes. The small-molecule complex with the d(TG4T) quadruplex is discrete and approximately globular, whereas the G-quadruplex complex with poly(G) is formed at a number of points along the length of the polynucleotide, analogous to beads on a string.Financial support from Fundação para a Ciência e Tecnologia (FCT), Grant SFRH/BPD/92726/2013 (A.-M. Chiorcea-Paquim), Project Grant (A.D.R. Pontinha), projects PTDC/SAU-BMA/118531/2010, PTDC/QEQ-MED/0586/2012, PEst-C/EME /UI0285/2013 and CENTRO-07-0224-FEDER-002001 (MT4MOBI) (co-financed by the European Community Fund FEDER), FEDER funds through the program COMPETE - Programa Operacional Factores de Competitividade is gratefully acknowledged. Work in the S.N. laboratory was supported by Programme Grant No. C129/A4489, from Cancer Research UK, and by the FP6 framework grant “Molecular Cancer Medicine” from the EU. S.S. was a Maplethorpe Fellow of The University of London.Peer reviewe

An Electrochemical Outlook on Tamoxifen Biotransformation: Current and Future Prospects

Tamoxifen is a nonsteroidal antiestrogen that is currently and widely used in the treatment of breast cancer in all of its stages, in adjuvant therapy as a long-term suppressant of tumor recurrence and also as a chemopreventive agent in women that are in high risk of developing this type of estrogen-dependent cancer. From a toxicological and (bio)analytical point of view the knowledge of the metabolic pathways of a drug is found to be extremely important. So, in the present work the most important tamoxifen biotransformation steps were reviewed in the light of recent pharmacological data. This overview also includes the current controversy concerning tamoxifen DNA-damaging (genotoxic) versus non-genotoxic mechanisms. A special focus will be given to the putative application of electrochemical methods as a modern and reliable analytical tool for determination of tamoxifen and its metabolites. Moreover, the potential of DNA electrochemical sensors for detection of structural damage to DNA as a basis for toxicity screening is highlighted. Future prospects looking for the importance of developing new analytical methodologies are also discussed.info:eu-repo/semantics/publishedVersio

Comparison of the voltammetric behavior of metronidazole at a DNA-modified glassy carbon electrode, a mercury thin film electrode and a glassy carbon electrode

The electroanalytical performance at three electrodes: DNA-modified galssy carbon electrode, mercury thin film electrode and glassy carbon electrode, for the study of the electrochemical reduction of metronidazole is compared. All three electrodes showed a similar trend in the reduction mechanism for metronidazole, depenent on pH in the acid and neutral region and independent in alkaline media, although there was a shift in the peak potentials to more negative values when a bare glassy carbon electrode was used compared to the other two. Besides the advantage of using a solid electrode for the reduction of metronidazole, the DNA-modified galssy carbon electrode enables a lower detection limit of 1.0 muM owing to the preconecentration of the drug on the electrode surface, which is not the case for the mercury thin film or bare glassy carbon electrodes