Glassy carbon electrodes (GCE) modified by a bilayer of phospholipids (BLM) have been used to monitor the passage of redox probes and ferrocene-labelled peptides across lipid membranes of an anionic (DOPG) or a zwitterionic (globally neutral DPhPC) phospholipid. The gel-phase neutral DPhPC showed a strong association with neutral probes like ferrocene methanol but expelled positively or negatively charged species, as observed on cyclic voltammograms. Anionic DOPG underwent a strong electrostatic interaction with the positively charged hexaamine ruthenium(III) complex, leading to aggregates that caused swelling and destructuration of the BLM. With positively charged ferrocene-tagged peptides, DOPG-modified GCE allowed the observation of cyclic voltammograms exhibiting both a potential shift with respect to bare GCE and increased peak intensity, accounting for the slow but favored partition of the peptides between the BLM and the solution.

Numerous methods have been developed for determination of antioxidant (AO) activity in vitro, but only several spectrophotometrical assays are frequently applied. Among them, probably the most simple is FRAP assay, based on the reduction of Fe(III) to Fe(II) by antioxidants. In this work the applicability of that reaction for the development of electrochemical method for AO activity determination was examined. The two common electrochemical techniques: direct current polarography and cyclic voltammetry on platinum working electrode were used. The developed fast, simple and without a need for the calibration against standard (such as Trolox or gallic acid) electrochemical methods were applied to determination of the AO activity of ten natural antioxidants. The AO activities determined by two developed methods and three frequently applied spectrophotometric assays (ABTS, DPPH and FRAP) correlated well. All the obtained correlation coefficients (R) were above 0.9. The cyclic voltammetric method fulfills green chemistry principles.

In this paper, the synthesis of fourteen alkylamino and arylamino derivatives of sesquiterpene quinone avarone and its model compound tert-butylquinone is described. Branched, cyclic, allylic and benzylic alkylamino/arylamino groups were introduced into the quinone moiety. For all the obtained derivatives, their biological activity and redox properties were studied. The cytotoxic activity of the synthesized derivatives towards multidrug resistant (MDR) human non-small cell lung carcinoma NCI-H460/R cells, their sensitive counterpart NCI-H460 and human normal keratinocytes (HaCaT) was investigated. The antimicrobial activity towards Gram-positive and Gram-negative bacteria, and fungal cultures was determined. Some of the synthesized derivatives showed selectivity for cancer cells, including MDR cells. Regarding their cell death induction potential, the most promising compounds were allylamino derivatives, preferentially triggering apoptosis, with high selectivity for cancer cells, including MDR cells. Several compounds showed promising antimicrobial activity, comparable to those of commercial antibiotic and antimycotic agents.

In this work, synthesis of alkylamino and aralkylamino derivatives of sesquiterpene quinone avarone and its model compound tert-butylquinone was described. For all obtained derivatives biological activity was studied. Cytotoxic activity of the synthesized derivatives towards multidrug resistant MDR human non-small cell lung carcinoma NCI-H460/R cells, their sensitive counterpart NCI-H460 and human normal keratinocytes (HaCaT) as well as detection of cell death superoxide anion generation were investigated. Antimicrobial activity towards Gram positive and Gram negative bacteria and fungal cultures was determined. The results showed that strong cytotoxic activity toward cancer cells was improved with simple avarone mimetics. Some derivatives were selective towards MDR cancer cells. The most active derivatives induced apoptosis in both cancer cell lines, but not in normal cells. Superoxide production was induced by 2,6-disubstituted compounds in MDR cancer cells and not by less active 2,5-disubstituted compounds and was accompanied by the collapse of the mitochondrial transmembrane potential. Two tert-butylquinone derivatives were particularly selective towards MDR cancer cells. Some tert-butylquinone derivatives exhibited a strong antimicrobial activity.

A series of eighteen derivatives of marine sesquiterpene quinone avarone and its model system tert -butylquinone with amino acids has been synthesized by nucleophilic addition of amino acids to the quinones. In vitro cytotoxic activity toward human cancer cell lines (HeLa, A549, Fem-X, K562, MDA-MB-453) and normal MRC-5 cell line was determined. Several compounds showed very strong inhibitory activity with IC 50 values less than 10 μM. Avarone derivatives were more active than the corresponding tert -butylquinone derivatives. The results of the cytofluorimetric analysis of cell cycle of HeLa cells showed that apoptosis might be one of possible mechanism of action of these compounds in cancer cells. In order to examine the influence of caspases on cell death, the apoptotic mechanisms induced by the tested compounds were determined using specific caspases 3, 8 and 9 inhibitors. For all compounds antibacterial activities against six strains of Gram-positive and four strains of Gram-negative bacteria were determined, as well as antifungal activity against three fungal species.

Benzyl alcohol, a potent anesthetic and bacteriostatic, can be efficiently glucosylated by α-glucosidase from Saccharomyces cerevisiae to produce benzyl alcohol α-glucoside with a 75% yield. However, while studying the transglucosylation reaction conditions, it was found out that benzyl alcohol is a non-competitive inhibitor of α-glucosidase's hydrolytic activity (Ki=18mM, toward maltose). Due to its interesting ability to be glycosylated by the enzyme and to inhibit its hydrolytic activity, we proposed a plausible mechanism for the phenolic α-glucosydase inhibitor's binding, since the mechanism of inhibition has not yet been elucidated.

Our investigation of the catalytic properties of Saccharomyces cerevisiae α-glucosidase (AGL) using hydroxybenzyl alcohol (HBA) isomers as transglucosylation substrates and their glucosides in hydrolytic reactions demonstrated interesting findings pertaining to the aglycon specificity of this important enzyme. AGL specificity increased from the para(p)- to the ortho(o)-HBA isomer in transglucosylation, whereas such AGL aglycon specificity was not seen in hydrolysis, thus indicating that the second step of the reaction (i.e., binding of the glucosyl acceptor) is rate-determining. To study the influence of substitution pattern on AGL kinetics, we compared AGL specificity, inferred from kinetic constants, for HBA isomers and other aglycon substrates. The demonstrated inhibitory effects of HBA isomers and their corresponding glucosides on AGL-catalyzed hydrolysis of p-nitrophenyl α-glucoside (PNPG) suggest that HBA glucosides act as competitive, whereas HBA isomers are noncompetitive, inhibitors. As such, we postulate that aromatic moieties cannot bind to an active site unless an enzyme-glucosyl complex has already formed, but they can interact with other regions of the enzyme molecule resulting in inhibition.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Cyclic voltammetry and ultramicroelectrodes were used to investigate the kinetic aspects of the electrochemical bromination of 3,4,6-tri-O-acetyl-d-glucal (1) in acetonitrile (AN), dichloromethane (DCM), and dimethylsulfoxide (DMSO). Qualitative and quantitative results, determined notably from the kinetic parameter [glucal]/v representing the competition between glucal concentration and time, clearly showed that glucal bromination depended on the nature of both the solvent and the in situ electrogenerated reactive brominated species (Br2 or Br3−) obtained from the oxidation of a bromide salt. It was especially shown that Br2 reacted more rapidly than Br3− towards (1). On the other hand, the reactivity of both brominated species appeared to follow the solvent polarity order since the highest reactivity was obtained in DMSO whereas the lowest one was found in DCM.

The one-pot synthesis of seven new (2-alkylthiobenzoyl)ferrocenes has been achieved by Friedel–Crafts acylation of ferrocene with acid chlorides generated in situ from the corresponding carboxylic acids and phosphorous trichloride. The obtained compounds were characterized by spectroscopic data (UV, IR, 1H and 13C NMR), whereas their electrochemical properties have been investigated by cyclic voltammetry. The single-crystal X-ray structure determinations for three of them are also reported. Each of the three derivatives exhibits the intramolecular C–H…O interaction which involves the donor from the cyclopentadienyl (Cp) ring and the carbonyl oxygen as acceptor. This interaction favors the coplanar arrangement of the two moieties. The angles between the vectors coinciding the C–O bonds and the corresponding Cp planes are all below 6.4°. Conventional hydrogen bonds do not exist in any of the three crystal structures but some weak intermolecular interactions of the C–H…O, C–H…S and C–H…π types have been found and analyzed in detail. Different geometrical parameters for these crystal structures as well as for 22 similar ones extracted from Cambridge Structural Database (CSD) have been compared and analyzed.

Bromination of glycals with tribromides formed in situ from bromine and different bromide salts in dichloromethane (DCM) or acetonitrile (AN) was found to give predominantly the products of anti addition of bromine from the C-6 side in high yields. The same selectivity, which was much higher compared to bromination with bromine alone, was achieved in bromination of these substrates by anodic generation of bromine from the same salts.

Our previous experiences with incorporation of polyoxometalates (POMs) ill different substrates have been very successful, because new nanocomposites with better conductive, catalytical and biochemical characteristics have been obtained. The results of intercalation of different mass% of ammonium decavanadate (ADV) in Al-pillared interlayered clays (Al-PILCs) are presented.The Al-PILCs were prepared using natural raw material, bentonite, containing a high percentage of montmorillonite (MM). Synthesis of ADV has been described in a previous paper. The structure of ADV hexahydrate was determined at low temperature, 100 K. A kappa refinement was performed to estimate the atomic charges.A sol-gel procedure was applied to obtain Al-PILCs composite intercalated with ADV hexahydrate (from 2 to 5 mass% of ADV). Structure and morphological properties of the new material, a nanocomposite of Al-PILCs-ADV, were investigated by X-ray powder diffraction (XRPD) and atomic force microscopy (AFM). To understand better how ADV is incorporated in the MM substrate, specific surface areas, pore structures and pore distributions were determined.Electrical and dielectric properties of the new materials were investigated by thermally stimulated depolarization currents (TSDCs) and broadband dielectric relaxation spectroscopy (DRS). The electrical conductivity of the nanocomposite was found to increase, in relation to MM, by intercalating with a small amount of ADV. (C) 2008 Published by Elsevier Ltd.

We have investigated the electrochemical oxidation of a number natural phenolics (salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, protocatechuic acid, o-coumaric acid, m-coumaric acid, p-coumaric acid, caffeic acid, quercetin and rutin) using cyclic voltammetry. The antioxidant properties of these compounds were also studied. A structural analysis of the tested phenolics suggests that multiple OH substitution and conjugation are important determinants of the free radical scavenging activity and electrochemical behavior. Compounds with low oxidation potentials (Epa lower than 0.45) showed antioxidant activity, whereas compounds with high Epa values (>0.45) act as prooxidants.