Remediation of benzo[a]pyrene contaminated soils by moderate chemical oxidation coupled with microbial degradation.

Chemical oxidation is a promising technology for the remediation of organics-contaminated soils. However, residual oxidants and transformation products have adverse effects on microbial activities. This work aimed at moderate chemical oxidation coupled with microbial degradation (MOMD) for the removal of benzo[a]pyrene (BaP) by optimizing the type and dosage of oxidants. Potassium permanganate (KMnO4), Fe2+ + sodium persulfate (Fe2+ + PS), Fenton's reagent (Fe2+ + H2O2), and hydrogen peroxide (H2O2) were compared for BaP removal from loam clay and sandy soils. Overall, the removal efficiency of BaP by a moderate dose of oxidant coupled indigenous microorganism was slightly lower than that by a high dose of relevant oxidant. The contributions of microbial degradation to the total removal of BaP varied for different oxidants and soils. The removal efficiency of BaP from loam clay sandy soil by a moderate dose of KMnO4 (25 mmol/L) was 94.3 ± 1.1 % and 92.5 ± 1.8 %, respectively, which were both relatively higher than those under other conditions. The indirect carbon footprint yielded by the moderate dose of oxidants was 39.2-72.8 % less than that by the complete oxidation. A moderate dose of oxidants also reduced disturbances to soil pH and OC. The microbial communities after MOMD treatment were dominated by Burkholderiaceae, Enterobacteriaceae, Alicyclobacillaceae, and Oxalobacteraceae. These dominant microorganisms promoted the removal of BaP through the expression of polycyclic aromatic hydrocarbon-ring hydroxylated dioxygenase gene. Compared with complete chemical oxidation, MOMD is also a promising technique with the utilization of indigenous microorganism for remediating BaP-contaminated soils.

Recent progress on in-situ chemical oxidation for the remediation of petroleum contaminated soil and groundwater.

Accidental oil leaks and spills can often result in severe soil and groundwater pollution. In situ chemical oxidation (ISCO) is a powerful and efficient remediation technology. In this review, the applications and recent advances of three commonly applied in-situ oxidants (hydrogen peroxide, persulfate, and permanganate), and the gap in remediation efficiency between lab-scale and field-scale applications is critically assessed. Feasible improvements for these measures, especially solutions for the 'rebound effect', are discussed. The removal efficiencies reported in 108 research articles related to petroleum-contaminated soil and groundwater were analyzed. The average remediation efficiency of groundwater (82.7%) by the three oxidants was higher than that of soil (65.8%). A number of factors, including non-aqueous phase liquids, adsorption effect, the aging process of contaminants, low-permeability zones, and vapor migration resulted in a decrease in the remediation efficiency and caused the residual contaminants to rebound from 19.1% of the original content to 57.7%. However, the average remediation efficiency of ISCO can be increased from 40.9% to 75.5% when combined with other techniques. In the future, improving the utilization efficiency of reactive species and enhancing the contact efficiency between oxidants and petroleum contaminants will be worthy of attention. Multi-technical combinations, such as the ISCO coupled with phase-transfer, viscosity control, controlled release or natural attenuation, can be effective methods to solve the rebound problem.

A Ferrofluid with Surface Modified Nanoparticles for Magnetic Hyperthermia and High ROS Production.

A ferrofluid with 1,2-Benzenediol-coated iron oxide nanoparticles was synthesized and physicochemically analyzed. This colloidal system was prepared following the typical co-precipitation method, and superparamagnetic nanoparticles of 13.5 nm average diameter, 34 emu/g of magnetic saturation, and 285 K of blocking temperature were obtained. Additionally, the zeta potential showed a suitable colloidal stability for cancer therapy assays and the magneto-calorimetric trails determined a high power absorption density. In addition, the oxidative capability of the ferrofluid was corroborated by performing the Fenton reaction with methylene blue (MB) dissolved in water, where the ferrofluid was suitable for producing reactive oxygen species (ROS), and surprisingly a strong degradation of MB was also observed when it was combined with H2O2. The intracellular ROS production was qualitatively corroborated using the HT-29 human cell line, by detecting the fluorescent rise induced in 2,7-dichlorofluorescein diacetate. In other experiments, cell metabolic activity was measured, and no toxicity was observed, even with concentrations of up to 4 mg/mL of magnetic nanoparticles (MNPs). When the cells were treated with magnetic hyperthermia, 80% of cells were dead at 43 °C using 3 mg/mL of MNPs and applying a magnetic field of 530 kHz with 20 kA/m amplitude.

Evaluation of the Therapeutic Effects of the Hydroethanolic Extract of Portulaca oleracea on Surgical-Induced Peritoneal Adhesion.

OBJECTIVE: Peritoneal adhesion (PA) is an abnormal connective tissue that usually occurs between tissues adjacent to damaged organs during processes such as surgery. In this study, the anti-inflammatory and antioxidant effects of Portulaca oleracea (PO) were investigated against postoperative-induced peritoneal adhesion. METHODS: Thirty healthy male Wistar rats (220 ± 20 g, 6-8 weeks) were randomly divided into four groups: (1) normal, (2) control (induced peritoneal adhesion), and (3) and (4) PO extracts (induced peritoneal adhesion and received 100 or 300 mg/kg/day of PO extract for seven days). Finally, macroscopic and microscopic examinations were performed using different scoring systems and immunoassays in the peritoneal lavage fluid. RESULTS: We found that the levels of adhesion scores and interleukin- (IL-) 1ß, IL-6, IL-10, tumour necrosis factor- (TNF-) α, transforming growth factor- (TGF-) ß 1, vascular endothelial growth factor (VEGF), and malondialdehyde (MDA) were increased in the control group. However, PO extract (100 and 300 mg/kg) notably reduced inflammatory (IL-1ß, IL-6, and TNF-α), fibrosis (TGF-ß 1), angiogenesis (VEGF), and oxidative (MDA) factors, while increased anti-inflammatory cytokine IL-10, antioxidant factor glutathione (GSH), compared to the control group. CONCLUSION: Oral administration of PO improved postoperational-induced PA by alleviating the oxidative factors, fibrosis, inflammatory cytokines, angiogenesis biomarkers, and stimulating antioxidative factors. Hence, PO can be considered a potential herbal medicine to manage postoperative PA. However, further clinical studies are required to approve the effectiveness of PO.

Amelioration of Pterostilbene Antiproliferative, Proapoptotic, and Oxidant Potentials in Human Breast Cancer MCF7 Cells Using Zein Nanocomposites.

PURPOSE: This study aimed to explain the influence of zein nanosphere (ZN NS) formulation on the pharmacotherapeutic profile of PTS in MCF7 cells. METHODS: Liquid-liquid phase separation was used to formulate PTS-ZN NSs. The formulations developed were evaluated for particle-size analysis, encapsulation efficiency, and in vitro diffusion. Also, assays of cytotoxicity, uptake, cell-cycle progression, annexin V, apoptotic gene mRNA expression and biochemical assays were carried out. RESULTS: The PTS-ZN NS formulation selected showed 104.5±6.2 nm, 33.4±1.8 mV, 95.1%±3.6%, and 89.1%±2.65% average particle size, zeta-potential, encapsulation efficiency and in vitro diffusion, respectively. With MCF7 cells, IC50 was reduced approximately 15-fold, with increased cellular uptake, accumulation in the G2/M phase, increased percentage of cells in the pre-G1 phase, amelioration of early and late apoptosis, raised mRNA expression of CASP3 and CASP7, lower expression of cyclin-CDK1, and enhanced oxidant potential through decreased glutathione reductase (GR) activity, and enhanced reactive oxygen-species generation and lipid-peroxidation products. CONCLUSION: PTS-ZN NSs indicated enhanced antiproliferative, proapoptotic, and oxidant potential toward MCF7 cells compared to free PTS. Ameliorated results of nanosized carriers, cellular uptake, and sustained diffusion may contribute to these outcomes.

Study on a novel spherical polysaccharide from Fructus Mori with good antioxidant activity.

A novel polysaccharide (MFP1P) was isolated from Fructus Mori, followed by purification via DEAE-52 cellulose and 27 % ethanol fraction. The MFP1P had the molecular weight of 56.78 kDa and the total sugar content of 93.32±0.54 %. And the MFP1P is mainly composed of glucose, galactose, galacturonic acid and mannose with molar ratio of 66.62 %, 13.94 %, 18.24 % and 1.20 %, respectively. MFP1P was mainly composed of →3)-α-D-Gal (1→, ß-D-Man-(1→ and →6)-α-D-Glc (1→ glycosidic bond and showed a spherical chain conformation with uniform distribution in solution. The MFP1P exhibited great antioxidant activity with oxygen-free radical absorption capacity (ORAC) values of 291.63±6.81 µmol TE/g and MDA IC50 of 0.289±0.022 mg/mL.

An Oculus to Profile and Probe Target Engagement In Vivo: How T-REX Was Born and Its Evolution into G-REX.

Here we provide a personal account of innovation and design principles underpinning a method to interrogate precision electrophile signaling that has come to be known as "REX technologies". This Account is framed in the context of trying to improve methods of target mining and understanding of individual target-ligand engagement by a specific natural electrophile and the ramifications of this labeling event in cells and organisms. We start by explaining from a practical standpoint why gleaning such understanding is critical: we are constantly assailed by a battery of electrophilic molecules that exist as a consequence of diet, food preparation, ineluctable endogenous metabolic processes, and potentially disease. The resulting molecules, which are detectable in the body, appear to be able to modify function of specific proteins. Aside from potentially being biologically relevant in their own right, these labeling events are essentially identical to protein-covalent drug interactions. Thus, on what proteins and even in what ways a covalent drug will work can be understood through the eyes of natural electrophiles; extending this logic leads to the postulate that target identification of specific electrophiles can inform on drug design. However, when we entered this field, there was no way to interrogate how a specific labeling event impacted a specific protein in an unperturbed cell. Methods to evaluate stoichiometry of labeling, and even chemospecificity of a specific phenotype were limited. There were further no generally accepted ways to study electrophile signaling that did not hugely disturb physiology.We developed T-REX, a method to study single-protein-specific electrophile engagement, to interrogate how single-protein electrophile labeling shapes pathway flux. Using T-REX, we discovered that labeling of several proteins by a specific electrophile, even at low occupancy, leads to biologically relevant signaling outputs. Further experimentation using T-REX showed that in some instances, single-protein isoforms were electrophile responsive against other isoforms, such as Akt3. Selective electrophile-labeling of Akt3 elicited inhibition of Akt-pathway flux in cells and in zebrafish embryos. Using these data, we rationally designed a molecule to selectively target Akt3. This was a fusion of the naturally derived electrophile and an isoform-nonspecific, reversible Akt inhibitor in phase-II trials, MK-2206. The resulting molecule was a selective inhibitor of Akt3 and was shown to fare better than MK-2206 in breast cancer xenograft mouse models. Recently, we have also developed a means to screen electrophile sensors that is unbiased and uses a precise burst of electrophiles. Using this method, dubbed G-REX, in conjunction with T-REX, we discovered new DNA-damage response upregulation pathways orchestrated by simple natural electrophiles. We thus emphasize how deriving a quantitative understanding of electrophile signaling that is linked to thorough and precise mechanistic studies can open doors to numerous medicinally and biologically relevant insights, from gleaning better understanding of target engagement and target mining to rational design of targeted covalent medicines.

Anticancer Effects and Mechanisms of Action of Plumbagin: Review of Research Advances.

Plumbagin (PLB), a natural naphthoquinone constituent isolated from the roots of the medicinal plant Plumbago zeylanica L., exhibited anticancer activity against a variety of cancer cell lines including breast cancer, hepatoma, leukemia, melanoma, prostate cancer, brain tumor, tongue squamous cell carcinoma, esophageal cancer, oral squamous cell carcinoma, lung cancer, kidney adenocarcinoma, cholangiocarcinoma, gastric cancer, lymphocyte carcinoma, osteosarcoma, and canine cancer. PLB played anticancer activity via many molecular mechanisms, such as targeting apoptosis, autophagy pathway, cell cycle arrest, antiangiogenesis pathway, anti-invasion, and antimetastasis pathway. Among these signaling pathways, the key regulatory genes regulated by PLB were NF-kß, STAT3, and AKT. PLB also acted as a potent inducer of reactive oxygen species (ROS), suppressor of cellular glutathione, and novel proteasome inhibitor, causing DNA double-strand break by oxidative DNA base damage. This review comprehensively summarizes the anticancer activity and mechanism of PLB.

Colorants in cheese manufacture: Production, chemistry, interactions, and regulation.

Colored Cheddar cheeses are prepared by adding an aqueous annatto extract (norbixin) to cheese milk; however, a considerable proportion (∼20%) of such colorant is transferred to whey, which can limit the end use applications of whey products. Different geographical regions have adopted various strategies for handling whey derived from colored cheeses production. For example, in the United States, whey products are treated with oxidizing agents such as hydrogen peroxide and benzoyl peroxide to obtain white and colorless spray-dried products; however, chemical bleaching of whey is prohibited in Europe and China. Fundamental studies have focused on understanding the interactions between colorants molecules and various components of cheese. In addition, the selective delivery of colorants to the cheese curd through approaches such as encapsulated norbixin and microcapsules of bixin or use of alternative colorants, including fat-soluble/emulsified versions of annatto or beta-carotene, has been studied. This review provides a critical analysis of pertinent scientific and patent literature pertaining to colorant delivery in cheese and various types of colorant products on the market for cheese manufacture, and also considers interactions between colorant molecules and cheese components; various strategies for elimination of color transfer to whey during cheese manufacture are also discussed.

Serum and milk concentrations of oxidant and anti-oxidant markers in dairy cows affected with bloody milk.

This study was conducted to determine the serum and milk levels of thiobarbturic acid-reac- tive substances (TBARS), nitric oxide (NO), superoxide dismutase (SOD), glutathione peroxi- dase (GSH-Px), vitamin E and selenium, IL-4 and IL-6 in lactating dairy cows affected with bloody milk using commercially available ELISA kits. Milk and whole blood samples were collected from 60 cows affected with bloody milk and 20 apparently healthy cows for control. In the serum, levels of GSH-Px and SOD were significantly (p˂0.05) higher in healthy cows compared to cows affected with bloody milk while the levels of TBARS and NO were significantly (p˂0.05) higher in affected cows. In the milk, levels of SOD, TBARS and NO were significantly (p˂0.05) higher in affected cows. In the serum, levels of vitamin E were significantly (p˂0.05) lower in affected cows compared to healthy cows, while no significant changes were observed in the levels of this vitamin in the milk between healthy and affected cows. In the serum, levels of selenium were significantly (p˂0.05) lower in affected cows while in milk, selenium levels were significantly (p˂0.05) higher in affected cows compared to healthy ones. Levels of IL-4 were significantly (p˂0.05) lower in the serum and milk of affected cows compared to healthy cows while levels of IL-6 were significantly (p˂0.05) higher in both serum and milk of affected cows. Results of this study suggest a possible role of oxidative stress in the pathogenesis of bloody milk in dairy cows.

Redox Interactions of Vitamin C and Iron: Inhibition of the Pro-Oxidant Activity by Deferiprone.

Ascorbic acid (AscH2) is one of the most important vitamins found in the human diet, with many biological functions including antioxidant, chelating, and coenzyme activities. Ascorbic acid is also widely used in a medical practice especially for increasing the iron absorption and as an adjuvant therapeutic in the iron chelation therapy, but its mode of action and implications in the iron metabolism and toxicity are not yet clear. In this study, we used UV-Vis spectrophotometry, NMR spectroscopy, and EPR spin trapping spectroscopy to investigate the antioxidant/pro-oxidant effects of ascorbic acid in reactions involving iron and the iron chelator deferiprone (L1). The experiments were carried out in a weak acidic (pH from 3 to 5) and neutral (pH 7.4) medium. Ascorbic acid exhibits predominantly pro-oxidant activity by reducing Fe3+ to Fe2+, followed by the formation of dehydroascorbic acid. As a result, ascorbic acid accelerates the redox cycle Fe3+ ↔ Fe2+ in the Fenton reaction, which leads to a significant increase in the yield of toxic hydroxyl radicals. The analysis of the experimental data suggests that despite a much lower stability constant of the iron-ascorbate complex compared to the FeL13 complex, ascorbic acid at high concentrations is able to substitute L1 in the FeL13 chelate complex resulting in the formation of mixed L12AscFe complex. This mixed chelate complex is redox stable at neutral pH = 7.4, but decomposes at pH = 4-5 during several minutes at sub-millimolar concentrations of ascorbic acid. The proposed mechanisms play a significant role in understanding the mechanism of action, pharmacological, therapeutic, and toxic effects of the interaction of ascorbic acid, iron, and L1.

Oxyresveratrol Possesses DNA Damaging Activity.

Artocarpus lakoocha Wall. ex Roxb. (family: Moraceae) has been used as a traditional Thai medicine for the treatment of various parasitic diseases. This species has been reported to be the source of phytochemicals, which show potent biological activities. The objective of this study was to investigate the phytochemical profile of the extracts of the heartwood of A. lakoocha and their pro-oxidant activity in vitro. The heartwood was ground, extracted, and then chromatographic and spectroscopic analyses were carried out; oxyresveratrol was identified as the major component in the extracts. The pro-oxidant activity was investigated using DNA-nick, reactive oxygen species and reducing assays. The results showed that oxyresveratrol induced DNA damage dose-dependently in the presence of copper (II) ions. It was also found to generate reactive oxygen species (ROS) in a dose-dependent manner and reduce copper (II) to copper (I). It is concluded that oxyresveratrol is the most abundant stilbenoid in A. lakoocha heartwood. The compound exhibited pro-oxidant activity in the presence of copper (II) ions, which may be associated with its ability to act as an anticancer compound.

Recent Advances in Copper Catalyzed Alcohol Oxidation in Homogeneous Medium.

The development of sustainable processes and products through innovative catalytic materials and procedures that allow a better use of resources is undoubtedly one of the most significant issues facing researchers nowadays. Environmental and economically advanced catalytic processes for selective oxidation of alcohols are currently focused on designing new catalysts able to activate green oxidants (dioxygen or peroxides) and applying unconventional conditions of sustainable significance, like the use of microwave irradiation as an alternative energy source. This short review aims to provide an overview of the recently (2015-2020) discovered homogeneous aerobic and peroxidative oxidations of primary and secondary alcohols catalyzed by copper complexes, highlighting new catalysts with potential application in sustainable organic synthesis, with significance in academia and industry.

Synergistic effects of combining ozonation, ceramic membrane filtration and biologically active carbon filtration for wastewater reclamation.

In this study, we proposed to apply an integrated process which is comprised of in situ ozonation, ceramic membrane filtration (CMF) and biologically active carbon (BAC) filtration to wastewater reclamation for indirect potable reuse purpose. A pilot-scale (20 m3/d) experiment had been run for ten months to validate the prospect of the process in terms of treatment performance and operational stability. Results showed that the in situ O3 + CMF + BAC process performed well in pollutant removal, with chemical oxygen demand, ammonia, nitrate nitrogen, total phosphorus and turbidity levels in the treated water being 5.1 ±â€¯0.9, 0.05 ±â€¯0.01, 10.5 ±â€¯0.8, <0.06 mg/L, and <0.10 NTU, respectively. Most detected trace organic compounds were degraded by>96%. This study demonstrated that synergistic effects existed in the in situ O3 + CMF + BAC process. Compared to pre-ozonation, in situ ozonation in the membrane tank was more effective in controlling membrane fouling (maintaining operational stability) and in degrading organic pollutants, which could be attributed to the higher residual ozone concentration in the tank. Because of the removal of particulate matter by CMF, water head loss of the BAC filter increased slowly and prolonged the backwashing interval to 30 days. BAC filtration was also effective in removing ammonia and N-nitrosodimethylamine from the ozonated water.

A novel gold nanocluster-based fluorometric biosensor for measuring prooxidant activity with a large Stokes shift.

A chicken egg white protein-protected gold nanocluster (CEW-AuNC) based fluorogenic biosensor, where protein was used as both reducing and protecting agent, was developed to determine the Cu(II)-induced prooxidant activity of natural antioxidants abundant in food and biological samples. Gold nanoclusters, prepared using egg white proteins, exhibited strong fluorescence. The prooxidant activity of the tested antioxidants was indirectly measured by their reducing action on Cu(II) to Cu(I), and the reduced cuprous ion was bound to the thiol groups in the CEW-AuNC structure, causing a decrease in fluorescence intensity. Epicatechin, catechin, epigallocatechin gallate, morin, rutin, quercetin, gallic, chlorogenic, and rosmarinic acids, glutathione, cysteine, N-acetyl cysteine, bilirubin, resveratrol, and α-tocopherol were studied as natural antioxidants. A fluorometric method showing a large Stokes shift with excitation/emission maxima at 360∕640 nm was developed to sensitively measure the decrease in the fluorescence of CEW-AuNC associated with the binding of copper(I) to the protein structure. Total prooxidant activities of the binary, ternary, and quaternary synthetic mixtures and of some food and synthetic serum samples were determined. The biosensor response was statistically compared to that of its spectrophotometric counterpart. This method can be used for the control of the oxidative stability of foods with a prolonged shelf life.

Sorbus domestica Leaf Extracts and Their Activity Markers: Antioxidant Potential and Synergy Effects in Scavenging Assays of Multiple Oxidants.

Sorbus domestica leaves are a traditionally used herbal medicine recommended for the treatment of oxidative stress-related diseases. Dry leaf extracts (standardized by LC-MS/MS and LC-PDA) and nine model activity markers (polyphenols), were tested in scavenging assays towards six in vivo-relevant oxidants (O2•-, OH•, NO•, H2O2, ONOO-, HClO). Ascorbic acid (AA) and Trolox (TX) were used as positive standards. The most active extracts were the diethyl ether and ethyl acetate fractions with activities in the range of 3.61-20.03 µmol AA equivalents/mg, depending on the assay. Among the model compounds, flavonoids were especially effective in OH• scavenging, while flavan-3-ols were superior in O2•- quenching. The most active constituents were quercetin, (-)-epicatechin, procyanidins B2 and C1 (3.94-24.16 µmol AA/mg), but considering their content in the extracts, isoquercitrin, (-)-epicatechin and chlorogenic acid were indicated as having the greatest influence on extract activity. The analysis of the synergistic effects between those three compounds in an O2•- scavenging assay demonstrated that the combination of chlorogenic acid and isoquercitrin exerts the greatest influence. The results indicate that the extracts possess a strong and broad spectrum of antioxidant capacity and that their complex composition plays a key role, with various constituents acting complementarily and synergistically.

Exploring the possibility of predicting long-term oxidative stability in prototype skincare formulations using various lipid oxidation initiators.

OBJECTIVE: The purpose of this study was to identify an effective lipid oxidation initiator which could predict, within 1 month, the long-term oxidative stability of a prototype skincare formulation. The main purpose was to find a potential initiator not to assess oxidation stability of the formulations. METHODS: Four initiators (below) were examined in three steps: Reaction kinetics using a Clark electrode (Oxygraph); Effect of adding an initiator on the product's physical and oxidative stability in prototype skincare formulations by visual observation, peroxide value and headspace GC-MS determination of volatile oxidation products; and Ability to differentiate unstable vs. stable prototype creams by initiator addition. The four initiators explored were: FeCl2 /H2 O2 , FeCl3 /ascorbic acid, 2,2'-Azobis(2,4-dimethylvaleronitrile) (AMVN) and 2,2'-Azobis(2-methylpropionamidine) dihydrochloride (AAPH) RESULTS: In Oxygraph, the initiator systems FeCl2 /H2 O2 and FeCl3 /ascorbic acid were good accelerators of oxygen consumption. The addition of FeCl2 /H2 O2 to prototype formulations did not affect the physical stability. However, the addition of FeCl3 /ascorbic acid to prototype formulations resulted in phase separation and FeCl3 /ascorbic acid was therefore deemed unusable. Moreover, the addition of AAPH or AMVN resulted in an increased and decreased viscosity respectively. In the oxidation stability study, peroxide value increased significantly when AMVN was added. However, the peroxide value remained low for the other initiators and the control (no initiator). The secondary volatile oxidation product, butanal, increased most with the FeCl2 /H2 O2 addition. Three out of the four initiators did not have the ability to rank the stable and unstable formulations in accordance with the result obtained for volatile oxidation products after 42 days of storage at 20°C of formulations without initiator. Only, FeCl2 /H2 O2 was able to rank the formulations in accordance with the oxidative stability observed for volatile oxidation products after 42 days of storage. CONCLUSION: FeCl2 /H2 O2 showed potential as an initiator to predict the oxidative stability of skincare formulations, but more studies are needed to confirm the result in a broader range of products over a longer time.

OBJECTIF: Le but de cette étude était d'identifier un initiateur efficace de l'oxydation des lipides qui pourrait prédire, dans un délai d'1 mois, la stabilité oxydative à long terme d'une formulation prototype de soins pour la peau. Le principal objectif était de trouver un initiateur potentiel et non pas d'évaluer la stabilité à l'oxydation des formulations. MÉTHODES: Quatre initiateurs (ci-dessous) ont été évalués au cours de trois étapes: Cinétique de réaction à l'aide d'une électrode de Clark (Oxygraphe); Effet de l'addition d'un initiateur sur la stabilité physique et oxydative du produit dans des prototypes de formulations par observation visuelle de l'indice de peroxyde et détermination des produits d'oxydation volatiles par GC-MS - espace de tête; et Capacité à différencier les prototypes de crèmes instables des prototypes de crèmes stables par addition d'un initiateur. Les quatre initiateurs étudiés étaient : FeCl2 /H2 O2 , FeCl3 /acide ascorbique, 2,2'-azobis (2,4-diméthylvaléronitrile) (AMVN) et 2,2'-azobis (2-méthylpropionamidine), dichlorhydrate (AAPH) RÉSULTATS: Dans l'oxygraphe, les systèmes initiateurs FeCl2 /H2 O2 et FeCl3 /acide ascorbique étaient de bons accélérateurs de la consommation en oxygène. L'addition de FeCl2 /H2 O2 aux prototypes de formulations n'a pas eu d'impact sur la stabilité physique. Cependant, l'addition de FeCl3 /acide ascorbique aux prototypes de formulations a entraîné une séparation des phases et le système FeCl3 /acide ascorbique a donc été jugé inutilisable. De plus, l'addition d'AAPH ou d'AMVN a entraîné une augmentation et une diminution de la viscosité, respectivement. Dans l'étude de stabilité oxydative, l'indice de peroxyde a significativement augmenté lorsque l'AMVN a été ajouté. Cependant, l'indice de peroxyde est resté faible pour les autres initiateurs et le témoin (sans initiateur). L'augmentation la plus importante du produit d'oxydation volatile secondaire, le butanal, a été observée avec l'addition de FeCl2 /H2 O2 . Trois des quatre initiateurs n'ont pas permis de classer les formulations stables et instables d'après le résultat obtenu pour les produits d'oxydation volatiles après 42 jours de conservation à 20 °C des formulations sans initiateur. Seul FeCl2 /H2 O2 a été en mesure de classer les formulations conformément à la stabilité oxydative observée pour les produits d'oxydation volatiles après 42 jours de conservation. CONCLUSION: FeCl2 /H2 O2 a montré un potentiel comme initiateur pour prédire la stabilité oxydative de formulations de soins pour la peau, mais des études supplémentaires sont nécessaires pour confirmer le résultat sur une plus large gamme de produits et sur une plus longue période.

Targeting glutathione S-transferase P and its interactome with selenium compounds in cancer therapy.

The glutathione (GSH) S-transferase family of detoxification and signalling proteins represents a major hub for the metabolism of Selenium-derived compounds. At the same time, these compounds can be used to modulate the expression and multiple activities of GSTs and other glutathione-dependent genes, that are important aspects in both the chemoprevention and therapy of drug-resistant cancers. In this context, the isoform GSTP-1 (GSTP) appears to play a fundamental role. Besides promoting GSH-dependent detoxification of cellular electrophiles, GSTP physically interacts with a number of small molecules and cellular proteins producing regulatory effects across the main signal transduction and transcription pathways (identified as the "regulatory interactome of GSTP"). An emerging molecular mechanism behind such regulatory function is the activity of GSTP as a redox chaperonine responsible for the selective glutathionylation of protein Cys residues in the different subcellular compartments. The redox-sensitive transcription factor Nrf2 was recently identified as one of the regulatory nodes of this interactome at the interface between inflammation, adaptive stress response, and cell death pathways. The influence of Nrf2 in the stress response to cellular electrophiles and its regulatory interaction with GSTP are discussed in this review suggesting the hypothesis that this interaction may represent the actual pharmacological target of Se compounds with thiol peroxidase activity. These points are critically evaluated with a view to further development of these compounds in cancer prevention and the chemotherapy of drug-resistant tumours.

Antioxidant and prooxidant effects of Piptadeniastrum africanum as the possible rationale behind its broad scale application in African ethnomedicine.

ETHNOPHARMACOLOGICAL RELEVANCE: Piptadeniastrum africanum is widely used in treating oxidative stress related diseases. Oxidative stress, defined as the disturbance in the balance between the production of free radicals and antioxidant defenses, is the root cause of many pathophysiological conditions. Based on the dual properties of prooxidants as toxic and beneficial compounds, both prooxidants and antioxidants may be effective in the treatment of these conditions when the right dose is given to the right subject at the right time for the right duration. AIM OF THE STUDY: This study was aimed at investigating the in vitro and ex vivo anti- and pro-oxidative effects of P. africanum. MATERIALS AND METHODS: Total phenolic and flavonoid contents of methanol and aqueous extracts of P. africanum stem back were quantified spectrophotometrically. The methanol extract, ascorbate radicals and reactive oxygen species in brain and liver homogenates of mice treated with the methanol stem bark extract were analyzed by electron paramagnetic resonance (EPR) spectroscopy. Free radical scavenging of DPPH was determined by spectrophotometric and EPR assays. RESULTS: The methanol extract was richer in both phenolic and flavonoid contents compared to the aqueous extracts and also showed better DPPH radical scavenging capacity. The EPR spectroscopy in vitro analysis exhibited high DPPH scavenging capacity before and after UV irradiation (99.5% and 98.76%) at 40 µg/ml extract. The ex vivo EPR spectroscopy studies demonstrated increased levels of ascorbate radicals (•Asc) in liver and brain homogenates of healthy mice treated with P. africanum in comparison with those of the non treated controls (0.6141 ±â€¯0.026 vs 0.1800 ±â€¯0.0073 arb. units for liver homogenates and 0.9605 ±â€¯0.0492 vs 0.3375 ±â€¯0.0062 arb. units for brain homogenates, correspondingly). Considerably, higher levels of reactive oxygen species (ROS) were measured in mice liver and brain homogenates after treatment with P. africanum extract compared to the control group, as well (1.9402 ±â€¯0.1200 vs 0.6699 ±â€¯0.062 arb. units for liver homogenates and 1.7325 ±â€¯01503 vs 0.3167 ±â€¯0.0403 arb.units, respectively). CONCLUSION: Therefore, P. africanum exhibited antioxidant and pro-oxidant properties which may explain its broad spectrum use in a wide variety of ailments.

Realistic expectations for the treatment of FMGP residuals by chemical oxidants.

Methods to remediate soil and groundwater contamination at former manufactured gas plant (FMGP) sites are scarce. The objective of this study was to investigate the ability of two chemical oxidants (persulfate and permanganate) to degrade FMGP residuals in a dynamic system representative of in situ conditions. A series of physical model trials supported by aqueous and slurry batch experiments using impacted sediments collected from a FMGP site were conducted. To explore treatment expectations a screening model constrained by the experimental data was employed. The results from the aqueous experiments showed that dissolved components (except for benzene) were readily degraded by persulfate or permanganate. In the well-mixed slurry systems, when contact with the oxidant was achieved, 95%, 45% and 30% of the initial mass quantified was degraded by permanganate, unactivated persulfate, and alkaline activated persulfate, respectively. In stark contrast, the total mass removed in the physical model trials was negligible for both permanganate and persulfate irrespective of the bleb or lense architecture used. Hence the net benefit of flushing 6 pore volumes of permanganate or persulfate at a concentration of 30 g/L under the physical model operating conditions was minimal. To achieve a substantial degradation of mass within the treatment system (>40%), results from the screening model indicated that the hydraulic resident time would need to be >10 days and the average lumped mass transfer coefficient increased by two orders-of-magnitude. Results from long-term (5 years) simulations showed that the dissolved concentrations of organic compounds are reduced temporarily as a result of the presence of permanganate but then rebound to a profile that is essentially coincident with a no-treatment scenario following exposure to permanganate. Neither a lower velocity nor higher permanganate dosing affected the long-term behavior of the dissolved phase concentrations; however, increasing the mass transfer rate coefficient had an impact. The findings from this investigation indicate that the efficiency of permanganate or persulfate to treat for FMGP residuals is mass transfer limited.