Imine resveratrol analogs (IRAs): The strong antioxidant that can protect lymphocytes from oxidative damage.

Imine resveratrol analogs (IRAs) are promising new agents that can have higher positive effects and, simultaneously, lower negative properties than resveratrol. In this study, three imine hydroxy derivatives (2-((4-hydroxyphenylimino) methyl) phenol [IRA1], 3-((4-hydroxyphenylimino) methyl) phenol [IRA2], and 4-((4-hydroxyphenylimino) methyl) phenol [IRA3]) were prepared and tested in several biological assays. They performed superior to resveratrol in several antioxidant and biological assays, showing high antioxidant capacity and low genotoxicity. Ferric reducing antioxidant power assay (FRAP) and hydroxyl radicals scavenging assay revealed good Fe3+ to Fe2+ reduction and strong inhibition of hydroxyl radical formation, respectively. High dosage (1 mmol/dm3 ) of IRA2 and IRA3 did not cause genotoxicity in human lymphocytes. Moreover, lymphocytes pretreated with all three IRAs accumulated only very few DNA breaks induced by H2 O2 than lymphocytes pretreated with resveratrol. Additionally, the number of detected DNA breaks appearing after removal of damaged DNA bases, 8-oxo-7,8-dihydroguanine (8-oxoG), did not dramatically increase in lymphocytes treated with IRA2. Thus, we concluded that IRAs, especially IRA2, are strong antioxidants with the ability to protect lymphocytes from oxidative damage.

Photo-Reduction of CO2 by VIS Light on Polythiophene-ZSM-5 Zeolite Hybrid Photo-Catalyst.

A new hybrid photo-catalyst based on ZSM-5 zeolite suitable for reduction of carbon dioxide was synthesized. The photo-catalyst was prepared by oxidative polymerization of thiophene with FeCl3 in the presence of ZSM-5 with participation of ultrasound. The synthesized photo-catalyst strongly absorbs light radiation up to approx. 650 nm, with the absorption edge in the NIR region. Reactive radicals were generated by VIS light irradiation in an aqueous suspension consisting of the photo-catalyst with CO2. Formic acid and acetic acid were generated as the main products of the CO2 reduction. EPR spin trapping technique was applied to identify the reactive radical intermediates. In this work, the mechanism of product formation is also discussed.

Synthesis and Free Radical Scavenging Activity of New Hydroxybenzylidene Hydrazines.

Hydroxybenzylidene hydrazines exhibit a wide spectrum of biological activities. Here, we report synthesis and free radical scavenging activity of nine new N-(hydroxybenzylidene)-N'-[2,6-dinitro-4-(trifluoromethyl)]phenylhydrazines. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR, 19F-NMR, IR spectroscopy, LC-MS, and elemental analysis. The prepared compounds were tested for their activity to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH), galvinoxyl radical (GOR), and 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) radicals. The free radical scavenging activity expressed as SC50 values of these compounds varied in a wide range, from a strong to no radical scavenging effect. The most effective radical scavengers were hydroxybenzylidene hydrazines containing three hydroxyl groups in the benzylidene part of their molecules. The prepared compounds were also tested for their activity to inhibit photosynthetic electron transport in spinach chloroplasts. IC50 values of these compounds varied in wide range, from an intermediate to no inhibitory effect.

The Scavenging of DPPH, Galvinoxyl and ABTS Radicals by Imine Analogs of Resveratrol.

Resveratrol (3,5,4'-trihydroxystilbene) is a phytoalexin produced by plants. Resveratrol is known for its anti-cancer, antiviral and antioxidant properties. We prepared imine analogs of resveratrol ((hydroxyphenyliminomethyl)phenols) and tested their antioxidant activity. All prepared resveratrol analogs were able to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH), galvinoxyl radical (GOR) and 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) radicals. The antioxidant activity efficiency correlated with the number and position of hydroxyl groups. The most effective antioxidants were resveratrol analogs containing three hydroxyl groups in the benzylidene part of their molecules. These results provide new insights into the relationship between the chemical structure and biological activity of resveratrol analogs.

Synthesis and Herbicidal Activity of New Hydrazide and Hydrazonoyl Derivatives.

Three new hydrazide and five new hydrazonoyl derivatives were synthesized. The chemical structures of these compounds were confirmed by 1H-NMR, IR spectroscopy and elemental analysis. The prepared compounds were tested for their activity to inhibit photosynthetic electron transport in spinach chloroplasts and growth of the green algae Chlorella vulgaris. IC50 values of these compounds varied in wide range, from a strong to no inhibitory effect. EPR spectroscopy showed that the active compounds interfered with intermediates Z•/D•, which are localized on the donor side of photosystem II. Fluorescence spectroscopy suggested that the mechanism of inhibitory action of the prepared compounds possibly involves interactions with aromatic amino acids present in photosynthetic proteins.

Effect of Pb2+ ions on photosynthetic apparatus.

Using model lead compounds Pb(NO3)2 and Pb(CH3CHOO)2, the mechanism and the site of action of Pb2+ ions in the photosynthetic apparatus of spinach chloroplasts were studied. Both compounds inhibited photosynthetic electron transport (PET) through photosystem 1 (PS1) and photosystem 2 (PS2), while Pb(NO3)2 was found to be more effective PET inhibitor. Using EPR spectroscopy the following sites of Pb2+ action in the photosynthetic apparatus were determined: the water-splitting complex and the Z•/D• intermediates on the donor side of PS2 and probably also the ferredoxin on the acceptor side of PS1, because cyclic electron flow in chloroplasts was impaired by treatment with Pb2+ ions. Study of chlorophyll fluorescence in suspension of spinach chloroplasts in the presence of Pb2+ ions confirmed their site of action in PS2. Using fluorescence spectroscopy also formation of complexes between Pb2+ and amino acid residues in photosynthetic proteins was confirmed and constants of complex formation among Pb2+ and aromatic amino acids were calculated for both studied lead compounds.

Investigating the spectrum of biological activity of ring-substituted salicylanilides and carbamoylphenylcarbamates.

In this study, a series of twelve ring-substituted salicylanilides and carbamoylphenylcarbamates were prepared and characterized. The compounds were analyzed using RP-HPLC to determine lipophilicity. They were tested for their activity related to the inhibition of photosynthetic electron transport (PET) in spinach (Spinacia oleracea L.) chloroplasts. Moreover, their site of action in the photosynthetic apparatus was determined. Primary in vitro screening of the synthesized compounds was also performed against mycobacterial, bacterial and fungal strains. Several compounds showed biological activity comparable with or higher than the standards 3-(3,4-dichlorophenyl)-1,1-dimethylurea, isoniazid, penicillin G, ciprofloxacin or fluconazole. The most active compounds showed minimal anti-proliferative activity against human cells in culture, indicating they would have low cytotoxicity. For all compounds, the relationships between lipophilicity and the chemical structure are discussed.

Antioxidative effect of some hydroxy substituted aromatic bisimines.

This work deals with antioxidative properties of some derivatives 4,4'-bis(dihydroxybenzylanilidenamino) diphenylmethanes and diphenylethers, which structure is similar to resveratrol. Four derivatives of above-mentioned compounds were synthesized with hydroxyl (OH) groups in various positions. It was found that derivatives with two OH groups in 2 and 5 positions were very good scavengers of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radicals in both methanol and chloroform. On the other hand derivatives with OH groups in positions 2 and 4 did not scavenge DPPH radicals. The calculation of free enthalpies (by quantum chemical method AM1) necessary for the formations of anions or radicals support above mentioned findings because the enthalpies for effective derivatives were lesser, than for ineffective ones. Also, it was found that studied compounds did not scavenge hydroxyl radicals whereas resveratrol did it.

Antimutagenic activity and radical scavenging activity of water infusions and phenolics from ligustrum plants leaves.

Water infusions of Ligustrum delavayanum and Ligustrum vulgare leaves and eight phenolics isolated therefrom have been assayed in vitro on ofloxacin-induced genotoxicity in the unicellular flagellate Euglena gracilis. The tested compounds luteolin, quercetin, luteolin-7-glucoside, luteolin-7-rutinoside, quercetin-3-rutinoside, apigenin-7-rutinoside, tyrosol and esculetin inhibited the mutagenic activity of ofloxacin (43 microM) in E. gracilis. Water infusions from leaves of L. delavayanum and L. vulgare showed higher antimutagenic effect (p(t) < 0.001). The activity of these samples against ofloxacin (86 microM)-induced genotoxicity was lower, but statistically significant (p(t) < 0.05), excluding the water infusion of L. delavayanum leaves (p(t) < 0.01). Efficacy of quercetin, luteolin-7-rutinoside, apigenin-7-rutinoside was insignificant. The antimutagenic effect of most phenolics we studied could be clearly ascribed to their DPPH scavenging activity, substitution patterns and lipophilicity.

The structure of DNA-DOPC aggregates formed in presence of calcium and magnesium ions: a small-angle synchrotron X-ray diffraction study.

The structure of aggregates formed due to DNA interaction with dioleoylphosphatidylcholine (DOPC) vesicles in presence of Ca(2+) and Mg(2+) cations was investigated using synchrotron small-angle X-ray diffraction. For DOPC/DNA=1:1 mol/base and in the range of concentration of the cation(2+) 0-76.5 mM, the diffractograms show the coexistence of two lamellar phases: L(x) phase with repeat distance d(Lx) approximately 8.26-7.39 nm identified as a phase where the DNA strands are intercalated in water layers between adjacent lipid bilayers, and L(DOPC) phase with repeat distance d(DOPC) approximately 6.45-5.65 nm identified as a phase of partially dehydrated DOPC bilayers without any divalent cations and DNA strands. The coexistence of these phases was investigated as a function of DOPC/DNA molar ratio, length of DNA fragments and temperature. If the amount of lipid increases, the fraction of partially dehydrated L(DOPC) phase is limited, depends on the portion of DNA in the sample and also on the length of DNA fragments. Thermal behaviour of DOPC+DNA+Ca(2+) aggregates was investigated in the range 20-80 degrees C. The transversal thermal expansivities of both phases were evaluated.

Inactivation of bacteria G(+)-S. aureus and G(-)-E. coli by phototoxic polythiophene incorporated in ZSM-5 zeolite.

A new heterogeneous photocatalyst was prepared by oxidative polymerization of the thiophene with ferric chloride in the ZSM-5 zeolite type. The synthesized polythiophene absorbs radiation in the visible range of the electromagnetic spectrum and by illumination with visible light generates reactive oxygen species (ROS) in water medium. During illumination reactive hydroxyl radical was detected by the spin trapping EPR method. Efficiency of the photocatalyst was tested on the killing of Gram-positive bacteria Staphylococcus aureus and Gram negative bacteria Escherichia coli.

Silymarin and its components scavenge phenylglyoxylic ketyl radicals.

The antioxidant properties of silymarin and its flavanolignan components (silybin, silychristin and silydianin) were tested. Silymarin, silychristin and silydianin exhibit relatively good antioxidant effectiveness against phenylglyoxylic ketyl radicals and DPPH. The most effective scavengers of phenylglyoxylic ketyl radicals were silymarin and silychristin whereas silydianin was ca. 5-times less active than the first two compounds whereas silybin was ineffective. The scavenging properties of the studied compounds against DPPH radicals were in the same sequence: silymarin>silychristin>silydianin>silybin.

Free radical scavenging activity of different extracts and some constituents from the leaves of Ligustrum vulgare and L. delavayanum.

The free radical scavenging activity of the water infusions, different organic solvent extracts and some constituents from Ligustrum vulgare and Ligustrum delavayanum leaves was assessed with the aid of DPPH radical. Among the samples screened, water infusions had the strongest free radical scavenging capacity. From the tested compounds scavenging active flavonoid aglycones are present in the most active chloroform fractions from both leaves samples.

Radical scavenging and anti-lipoperoxidative activities of Smallanthus sonchifolius leaf extracts.

Radical scavenging and anti-lipoperoxidative effects of two organic fractions and two aqueous extracts from the leaves of a neglected Andean crop-yacon (Smallanthus sonchifolius Poepp. & Endl., Asteraceae) were determined using various in vitro models. The extracts' total phenolic content was 10.7-24.6%. They exhibited DPPH (IC50 16.14-33.39 microg/mL) and HO* scavenging activities (4.49-6.51 mg/mL). The extracts did not scavenge phenylglyoxylic ketyl radicals, but they retarded their formation. In the xanthine/xanthine oxidase superoxide radical generating system, the extracts' activities were 26.10-37.67 superoxide dismutase equivalents/mg. As one of the extracts displayed xanthine oxidase inhibitory activity, the effect of the extracts on a nonenzymatically generated superoxide was determined (IC50 7.36-21.01 microg/mL). The extracts inhibited t-butyl hydroperoxide-induced lipoperoxidation of microsomal and mitochondrial membranes (IC50 22.15-465.3 microg/mL). These results make yacon leaves a good candidate for use as a food supplement in the prevention of chronic diseases involving oxidative stress.

Clay mineral particles as effficient carriers of methylene blue used for antimicrobial treatment.

There is a strong demand to identify new strategies for disinfection and treatment of human, animal, and plant pathogens. The presented work shows the potential of clay minerals to contribute to the development of novel disinfection materials. Enhanced antimicrobial effect of a photoactive organic dye, methylene blue (MB), in the colloids of clay mineral was observed. Singlet oxygen (1O2) formed upon visible light irradiation was detected directly using luminescence measurements atthe near-infrared region and by spin-trapping method. While MB adsorbed on clay colloid particles lost the ability to produce 1O2 due to molecular aggregation, surprisingly, the antimicrobial activity was significantly enhanced. Under visible light irradiation, MB/clay minerals dispersions prevented the sporulation of A. niger and Penicillium sp. and inhibited the growth of C. albicans by an additional 6-15% when compared with MB solution. In the experiments with E. coli, the efficiency of MB was increased by the reduction of surviving cells by 27 and 33%. S. aureus proved to be the most susceptible to MB/clay dispersions. Only less than 20% cells survived with respect to the control experiment at the low MB concentration (1.1 x 10(-6) mol dm(-3)). The contradiction between the significant antimicrobial properties of MB in clay colloidal systems and low 1O2 formation can be explained in terms of the photosensitization mechanism. The role of clay particles is most likely to promote the contact between microorganism cells and photoactive MB. Although the dye directly bound to the clay surface exhibits significantly reduced photoactivity, the presence of clay mediates the delivery of dye molecules on the surface or inside cells. The results indicate new perspectives of potential implementations of clay minerals as parts of complex disinfection materials for industrial applications or in understanding similar processes in nature.

Excess copper predisposes photosystem II to photoinhibition in vivo by outcompeting iron and causing decrease in leaf chlorophyll.

Photoinhibition of photosystem II was studied in vivo with bean (Phaseolus vulgaris) plants grown in the presence of 0.3 (control), 4, or 15 microM Cu(2+). Although photoinhibition, measured in the presence of lincomycin to block concurrent recovery, is faster in leaves of Cu(2+)-treated plants than in control leaves, thylakoids isolated from Cu-treated plants did not show high sensitivity to photoinhibition. Direct effects of excess Cu(2+) on chloroplast metabolism are actually unlikely, because the Cu concentration of chloroplasts of Cu-treated plants was lower than that of their leaves. Excess Cu in the growth medium did not cause severe oxidative stress, collapse of antioxidative defenses, or loss of photoprotection. Thus, these hypothetical effects can be eliminated as causes for Cu-enhanced photoinhibition in intact leaves. However, Cu treatment lowered the leaf chlorophyll (Chl) concentration and reduced the thylakoid membrane network. The loss of Chl and sensitivity to photoinhibition could be overcome by adding excess Fe together with excess Cu to the growth medium. The addition of Fe lowered the Cu(2+) concentration of the leaves, suggesting that Cu outcompetes Fe in Fe uptake. We suggest that the reduction of leaf Chl concentration, caused by the Cu-induced iron deficiency, causes the high photosensitivity of photosystem II in Cu(2+)-treated plants. A causal relationship between the susceptibility to photoinhibition and the leaf optical density was established in several plant species. Plant species adapted to high-light habitats apparently benefit from thick leaves because the rate of photoinhibition is directly proportional to light intensity, but photosynthesis becomes saturated by moderate light.