Curcumin Electrochemistry-Antioxidant Activity Assessment, Voltammetric Behavior and Quantitative Determination, Applications as Electrode Modifier.

Curcumin (CU) is a polyphenolic compound extracted from turmeric, a well-known dietary spice. Since it has been shown that CU exerts beneficial effects on human health, interest has increased in its use but also in its analysis in different matrices. CU has an antioxidant character and is electroactive due to the presence of phenolic groups in its molecule. This paper reviews the data reported in the literature regarding the use of electrochemical techniques for the assessment of CU antioxidant activity and the investigation of the voltammetric behavior at different electrodes of free or loaded CU on various carriers. The performance characteristics and the analytical applications of the electrochemical methods developed for CU analysis are compared and critically discussed. Examples of voltammetric investigations of CU interaction with different metallic ions or of CU or CU complexes with DNA as well as the CU applications as electrode modifiers for the enhanced detection of various chemical species are also shown.

State of the Art on Developments of (Bio)Sensors and Analytical Methods for Rifamycin Antibiotics Determination.

This review summarizes the literature data reported from 2000 up to the present on the development of various electrochemical (voltammetric, amperometric, potentiometric and photoelectrochemical), optical (UV-Vis and IR) and luminescence (chemiluminescence and fluorescence) methods and the corresponding sensors for rifamycin antibiotics analysis. The discussion is focused mainly on the foremost compound of this class of macrocyclic drugs, namely rifampicin (RIF), which is a first-line antituberculosis agent derived from rifampicin SV (RSV). RIF and RSV also have excellent therapeutic action in the treatment of other bacterial infectious diseases. Due to the side-effects (e.g., prevalence of drug-resistant bacteria, hepatotoxicity) of long-term RIF intake, drug monitoring in patients is of real importance in establishing the optimum RIF dose, and therefore, reliable, rapid and simple methods of analysis are required. Based on the studies published on this topic in the last two decades, the sensing principles, some examples of sensors preparation procedures, as well as the performance characteristics (linear range, limits of detection and quantification) of analytical methods for RIF determination, are compared and correlated, critically emphasizing their benefits and limitations. Examples of spectrometric and electrochemical investigations of RIF interaction with biologically important molecules are also presented.

Past and Present of Electrochemical Sensors and Methods for Amphenicol Antibiotic Analysis.

Amphenicols are broad-spectrum antibiotics. Despite their benefits, they also present toxic effects and therefore their presence in animal-derived food was regulated. Various analytical methods have been reported for their trace analysis in food and environmental samples, as well as in the quality control of pharmaceuticals. Among these methods, the electrochemical ones are simpler, more rapid and cost-effective. The working electrode is the core of any electroanalytical method because the selectivity and sensitivity of the determination depend on its surface activity. Therefore, this review offers a comprehensive overview of the electrochemical sensors and methods along with their performance characteristics for chloramphenicol, thiamphenicol and florfenicol detection, with a focus on those reported in the last five years. Electrode modification procedures and analytical applications of the recently described devices for amphenicol electroanalysis in various matrices (pharmaceuticals, environmental, foods), together with the sample preparation methods were discussed. Therefore, the information and the concepts contained in this review can be a starting point for future new findings in the field of amphenicol electrochemical detection.

Insights into Structure and Biological Activity of Copper(II) and Zinc(II) Complexes with Triazolopyrimidine Ligands.

In an attempt to increase the biological activity of the 1,2,4-triazolo[1,5-a]pyrimidine scaffold through complexation with essential metal ions, the complexes trans-[Cu(mptp)2Cl2] (1), [Zn(mptp)Cl2(DMSO)] (2) (mptp: 5-methyl-7-phenyl-1,2,4-triazolo[1,5-a]pyrimidine), [Cu2(dmtp)4Cl4]·2H2O (3) and [Zn(dmtp)2Cl2] (4) (dmtp: 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine), were synthesized and characterized as new antiproliferative and antimicrobial species. Both complexes (1) and (2) crystallize in the P21/n monoclinic space group, with the tetrahedral surroundings generating a square-planar stereochemistry in the Cu(II) complex and a tetrahedral stereochemistry in the Zn(II) species. The mononuclear units are interconnected in a supramolecular network through π-π interactions between the pyrimidine moiety and the phenyl ring in (1) while supramolecular chains resulting from C-H∙∙∙π interactions were observed in (2). All complexes exhibit an antiproliferative effect against B16 tumor cells and improved antibacterial and antifungal activities compared to the free ligands. Complex (3) displays the best antimicrobial activity against all four tested strains, both in the planktonic and biofilm-embedded states, which can be correlated to its stronger DNA-binding and nuclease-activity traits.

Biological Activity of Triazolopyrimidine Copper(II) Complexes Modulated by an Auxiliary N-N-Chelating Heterocycle Ligands.

Novel complexes of type [Cu(N-N)(dmtp)2(OH2)](ClO4)2·dmtp ((1) N-N: 2,2'-bipyridine; (2) L: 1,10-phenantroline and dmtp: 5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine) were designed in order to obtain biologically active compounds. Complexes were characterized as mononuclear species that crystallized in the space group P-1 of the triclinic system with a square pyramidal geometry around the copper (II). In addition to the antiproliferative effect on murine melanoma B16 cells, complex (1) exhibited low toxicity on normal BJ cells and did not affect membrane integrity. Complex (2) proved to be a more potent antimicrobial in comparison with (1), but both compounds were more active in comparison with dmtp-both against planktonic cells and biofilms. A stronger antimicrobial and antibiofilm effect was noticed against the Gram-positive strains, including methicillin-resistant Staphylococcus aureus (MRSA). Both electron paramagnetic resonance (EPR) and Saccharomyces cerevisiae studies indicated that the complexes were scavengers rather than reactive oxygen species promoters. Their DNA intercalating capacity was evidenced by modifications in both absorption and fluorescence spectra. Furthermore, both complexes exhibited nuclease-like activity, which increased in the presence of hydrogen peroxide.

Disposable Pencil Graphite Electrode for Diosmin Voltammetric Analysis.

Diosmin (DIO) is a naturally occurring flavonoid with multiple beneficial effects on human health. The presence of different hydroxyl groups in diosmin structure enables its electrochemical investigation and quantification. This work presents, for the first time, diosmin voltammetric behavior and quantification on the cost-effective, disposable pencil graphite electrode (PGE). Diosmin oxidation on PGE involves two irreversible steps, generating products with reversible redox behaviors. All electrode processes are pH-dependent and predominantly adsorption-controlled. Differential pulse (DPV) and adsorptive stripping differential pulse (AdSDPV) voltammetric methods have been optimized for diosmin quantification o an H-type PGE, in 0.100 mol/L H2SO4. The linear ranges and limits of detection were for DPV 1.00 × 10-6-1.00 × 10-5 mol/L and 2.76 × 10-7 mol/L DIO for DPV and 1.00 × 10-7-2.50 × 10-6 mol/L and 7.42 × 10-8 mol/L DIO for AdSDPV, respectively. The DPV method was successfully applied for diosmin quantification in dietary supplement tablets. The percentage recovery was 99.87 ± 4.88%.

Voltammetric determination of polyphenolic content as rosmarinic acid equivalent in tea samples using pencil graphite electrodes.

The quasi-reversible, diffusion controlled behavior of rosmarinic acid (RA) on a disposable pencil graphite electrode (PGE) was established by cyclic voltammetry. Using the anodic oxidation peak presented by RA on the PGE a differential pulse voltammetric (DPV) method was developed for the quantitative determination of RA. The linear range was 10(-8) - 10(-5) M RA and the detection and quantification limits were 7.93 × 10(-9) M and 2.64 × 10(-8) M RA, respectively. The applicability of the developed method was tested by recovery studies and by the assessment of the total polyphenolic contents (TPCDPV) of green, white and black Turkish teas, which were found to be 40.74, 30.04 and 23.97 mg rosmarinic acid equivalent/g dry tea, respectively. These results were in good agreement with those obtained by the Folin-Ciocalteu method. The developed method is a sensitive and cheap tool for the rapid and precise evaluation of TPCDPV of tea samples.

Ethyl lactate as a greener alternative to acetonitrile in RPLC: a realistic appraisal.

Appropriate substitution of acetonitrile (ACN) in mobile phases for reversed-phase liquid chromatography (RPLC) by low toxicity, ecologically friendly alternative solvents emerges as a greener approach in separation sciences. Ethyl lactate is considered as a green solvent in organic synthesis, industrial extraction processes and many other applicative fields. Its ability to substitute ACN in mobile phases for RPLC applications was barely investigated. The feasibility of such a replacement was tested for the separation of the mixture of 16 polycyclic aromatic hydrocarbons listed by the Environmental Protection Agency. The analytical approach was found to be achievable, with some compromises in terms of elution order, peak efficiency and UV detectability. Thermodynamic aspects of the chromatographic process were also comparatively assessed. Correlations between the elution order and some molecular descriptors were also discussed.

N,N-dimethylbiguanide complexes displaying low cytotoxicity as potential large spectrum antimicrobial agents.

The new complexes M(DMBG)(2)(ClO(4))(2) (M:Mn, Ni, Cu and Zn; DMBG: N,N-dimethylbiguanide) have been synthesized and characterized by IR, EPR, (1)H NMR, (13)C NMR as well as electronic spectroscopy data. Complex [Ni(DMBG)(2)](ClO(4))(2).2DMF (DMF: N,N-dimethylformamide) crystallizes in the monoclinic P2(1)/c space group while [Cu(DMBG)(2)](ClO(4))(2) adopt monoclinic P21/c space group as X-ray single crystal data indicate. The redox behavior of complexes was investigated by cyclic voltammetry. The metal-free N,N-dimethylbiguanide and complexes exhibit specific anti-infective properties as demonstrated the low MIC values, a large antimicrobial spectrum and also inhibit the ability of Pseudomonas aeruginosa and Staphylococcus aureus strains to colonize the inert surfaces. The complexes exhibit also a low cytotoxicity levels on HeLa cells.

Prospects for new antimicrobials based on N,N-dimethylbiguanide complexes as effective agents on both planktonic and adhered microbial strains.

Metal-free N,N-dimethylbiguanidium acetate and novel complexes M(DMBG)(2)(CH(3)COO)(2).nH(2)O (M: Mn(II), Ni(II), Cu(II) and Zn(II)) were screened for their antimicrobial properties against Gram-positive (Bacillus subtilis, Listeria monocytogenes, Staphylococcus aureus), Gram-negative (Klebsiella pneumoniae, Escherichia coli, Pseudomonas aeruginosa) bacteria and fungal (Candida albicans) strains. The ability of compounds to inhibit the microbial adherence ability to the inert substratum as well as their cytotoxicity was also assessed. Our results are demonstrating that some of the tested compounds are exhibiting potent antimicrobial activity accompanied by low cytotoxicity on HeLa cells. The complexes were characterized using microanalytical, IR, EPR, (1)H NMR as well as UV-vis methods. The redox behaviour of complexes was investigated by cyclic voltammetry. The new derivative (HDMBG)(CH(3)COO) crystallizes in the monoclinic P2(1)/n space group as X-ray single-crystal data indicate.

Differential pulse cathodic stripping voltammetric determination of selenium in pharmaceutical products.

The aim of this paper is to determine selenium from pharmaceutical products by differential pulse cathodic stripping voltammetry. Firstly, were established the optimum parameters for voltammetric determination of selenium (electrolyte, deposition time, pulse duration, pulse amplitude, etc.) and secondly, the content of selenium was determined in five pharmaceutical products. The drug samples were treated with a mixture of 6 ml HNO(3) and 1 ml H(2)O(2) in the microwave oven. Due to the matrix effects the method of addition is preferred. The peak potential is -0.545 V vs. Ag/AgCl, and the calibration curve is linear up to 0.125 ng/ml, but selenium was determined from pharmaceutical products used the calibration curve in the range 8-64 ng/ml, due to the concentration of selenium in these tablets.