Degradation of hydroxychloroquine by electrochemical advanced oxidation processes.

In this work, the degradation of hydroxychloroquine (HCQ) drug in aqueous solution by electrochemical advanced oxidation processes including electrochemical oxidation (EO) using boron doped diamond (BDD) and its combination with UV irradiation (photo-assisted electrochemical oxidation, PEO) and sonication (sono-assisted electrochemical oxidation, SEO) was investigated. EO using BDD anode achieved the complete depletion of HCQ from aqueous solutions in regardless of HCQ concentration, current density, and initial pH value. The decay of HCQ was more rapid than total organic carbon (TOC) indicating that the degradation of HCQ by EO using BDD anode involves successive steps leading to the formation of organic intermediates that end to mineralize. Furthermore, the results demonstrated the release chloride (Cl-) ions at the first stages of HCQ degradation. In addition, the organic nitrogen was converted mainly into NO3 - and NH4 + and small amounts of volatile nitrogen species (NH3 and NOx). Chromatography analysis confirmed the formation of 7-chloro-4-quinolinamine (CQLA), oxamic and oxalic acids as intermediates of HCQ degradation by EO using BDD anode. The combination of EO with UV irradiation or sonication enhances the kinetics and the efficacy of HCQ oxidation. PEO requires the lowest energy consumption (EC) of 63 kWh/m3 showing its cost-effectiveness. PEO has the potential to be an excellent alternative method for the treatment of wastewaters contaminated with HCQ drug and its derivatives.

Antitumoral Potency by Immunomodulation of Chloroform Extract from Leaves of Nitraria retusa, Tunisian Medicinal Plant, via its Major Compounds ß-sitosterol and Palmitic Acid in BALB/c Mice Bearing Induced Tumor.

This study evaluated the antitumoral effect of Chloroform extract from Nitraria retusa leaves, via its major compounds ß-sitosterols and palmitic acid. BALB/c mice were subcutaneously inoculated with B16-F10 cells, then treated intra-peritoneally after 7 days with the chloroform extract for 21 days. They were then euthanized, and the tumors were weighed. Lung parenchyma was analyzed. Lymphocyte and macrophages proliferation, cytotoxic T lymphocyte (CTL) activities were evaluated using the MTT assay. Macrophage phagocytosis was evaluated by measuring the lysosomal activity and nitric oxide production. Antioxidant activity was studied by cellular antioxidant activity on macrophage and splenocytes and by lipid peroxidation inhibitory activity in liver cells, kidney, and serum. ß-sitosterols and palmitic acid, major compounds of chloroform extract, impeded remarkably the expansion of the transplantable tumor, protected the lung parenchyma, and increased splenocytes proliferation and both CTL activities in tumor-bearing mice. ß-sitosterols and palmitic acid were also seen to have enhanced lysosomal activity of host macrophages and antioxidant cellular activity. Also, they showed an inhibitory effect of lipid peroxidation. Our results suggest that antitumoral effect of ß-sitosterols and palmitic acid from chloroform extract is related with its immunomodulatory activity, and opens the way for a nutrition application and coprocessing phytotherapy against cancer.

Reversal of resistance in bacteria underlies synergistic effect of essential oils with conventional antibiotics.

The pervasive of bacterial resistance earnestly threaten the prevention and the treatment of infectious diseases. Therefore, scientific communities take precedence over development of new antimicrobial agents. The aim of the study was to determine antimicrobial potency of three North-African essential oils Pituranthos chloranthus, Teucruim ramosissimum and Pistacia lentiscus individually, and in combination with antibiotics, to inhibit the growth of highly resistant clinical pathogen. Bacteria clinically isolated from patients, subsequently, challenged to a panel of drugs to determine the antibiotic-resistance profiles. Drugs displaying clinically irrelevant CMI were subjected to further studies in order to rescue antibiotic actions. Singular activity of essential oils and activity when combined with an antibiotic was hence elucidated. The results obtained highlighted the occurrence of strong antibacterial potential of essential oils when administrated alone. In the interactive experiment essential oils were found highly effective in reducing the resistance of Methicillin-resistant Staphylococcus aureus to amoxicillin, tetracycline, piperacillin, ofloxacin and oxacillin and resistance of Acinetobacter baumannii to amoxicillin and to ofloxacin in interactive manner. Furthermore, the results proved synergism among essential oils and both antibiotics ofloxacin and novobiocin against the Extended-Spectrum Beta-Lactamase producing E. coli (ESBL). Time kill kinetics was performed with a combination of sub-inhibitory concentrations to confirm the efficiency and killing rate of the combination over time. Further, the hypothetical toxicity of essential oils against human keratinocytes HaCat and murine spleenocytes were examined. The chemical composition of essential oils was assessed by GC/MS analysis and the major constituents found were sabinene, limonene, terpinen-4-ol, and ß-eudesmol.

Immunomodulatory and cellular antioxidant activities of pure compounds from Teucrium ramosissimum Desf.

Evaluation of the immunomodulatory activity of plant compounds is an interesting and growing area of research. Teucrium ramosissimum Desf. is a native and endemic medicinal plant from the South of Tunisia traditionally used for the treatment of many diseases. The anti-inflammatory activity of apigenin-7-glucoside, genkwanin, and naringenin isolated from T. ramosissimum were assayed. The phagocytic activities of macrophage and lymphocyte proliferation were investigated in the absence and presence of mitogens (lipopolysaccharide [LPS] or lectin). Depending on the concentrations, the compounds affect macrophage functions by modulating their lysosomal enzyme activity and nitric oxide (NO) release. The tested compounds enhance significantly splenocyte proliferation, either with or without mitogen stimulation. In studies to assess any potential effects of apigenin-7-glucoside, genkwanin, and naringenin on innate immunity, the results showed that these compounds significantly enhanced the killing activity of natural killer (NK) cells and cytotoxic activity of the T lymphocyte (CTL) isolated from splenocytes. These results suggest that T. ramosissimum compounds such as apigenin-7-glucoside, genkwanin, and naringenin may be potentially useful for modulating immune cell functions in physiological and pathological conditions.

The contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using diamond anodes.

In this work, the contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using boron-doped diamond (BDD) anodes was investigated in different electrolytes. A complete mineralization of cyanuric acid was obtained in NaCl; however lower degrees of mineralization of 70% and 40% were obtained in Na2SO4 and NaClO4, respectively. This can be explained by the nature of the oxidants electrogenerated in each electrolyte. It is clear that the contribution of active chlorine (Cl2, HClO, ClO(-)) electrogenerated from oxidation of chlorides on BDD is much more important in the electrolytic degradation of cyanuric acid than the persulfate and hydroxyl radicals produced by electro-oxidation of sulfate and water on BDD anodes. This could be explained by the high affinity of active chlorine towards nitrogen compounds. No organic intermediates were detected during the electrolytic degradation of cyanuric acid in any the electrolytes, which can be explained by their immediate depletion by hydroxyl radicals produced on the BDD surface. Nitrates and ammonium were the final products of electrolytic degradation of cyanuric acid on BDD anodes in all electrolytes. In addition, small amounts of chloramines were formed in the chloride medium. Low current density (≤10mA/cm(2)) and neutral medium (pH in the range 6-9) should be used for high efficiency electrolytic degradation and negligible formation of hazardous chlorate and perchlorate.

Antitumoral potency of methanolic extract from Nitraria retusa leaves via its immunomodulatory effect.

BACKGROUND: The purpose of this study was to assess the antitumoral effect of the methanol extract (MeOH) from Nitraria retusa leaves and to investigate its immunomodulatory activity that mediated the prevention of tumor progression in tumor-bearing mice. METHODS: Balb/c mice weighing 18-20 g were subcutaneously implanted with B16-F10 cells then injected intra-peritoneally, 7 days later with (200 mg/kg bw) of MeOH extract, for 21 days. After euthanization on day 21, the tumors were weighed. Lymphocyte proliferation, cytotoxic T lymphocyte (CTL) and NK activity were evaluated using the MTT assay. Macrophage phagocytosis was studied by measuring their lysosomal activity and nitric oxide production. RESULTS: The methanol extract inhibited significantly the growth of the implanted tumor, and increased remarkably splenocyte proliferation as well as NK and CTL activities, in tumor-bearing mice. It also promoted lysosomal activity of treated animal macrophages. CONCLUSION: Our findings suggest that antitumoral effect of MeOH extract is related with to immunomodulatory activity.

INTRODUCTION: Le but de cette étude est d'évaluer l'effet antitumoral de l'extrait méthanolique (MeOH) issue des feuilles de N. retusa via son potentiel immunomodulateur et sa capacité à prévenir la progression tumoral chez des souris porteuses de tumeurs. MÉTHODES: Pour cette étude, nous avons implanté par voie sous-cutanée, chez des souris Balb/c de 18 à 20 g, des cellules B16-F10. Après apparition de la tumeur, au bout de 7jours de l'injection de B16-F10, nous avons entamé un traitement par injection intrapéritonéale de 200 mg/kg de poids corporel, d'extrait MeOH, et ce durant 21 jours. Les animaux sont euthanasiés au 21ème jour, et les tumeurs sont pesées. La prolifération des splénocytes et des lymphocytes T cytotoxiques (CTL) à été évalué à l'aide du test au MTT. L'évaluation de l'activité NK à également été effectuée à l'aide du par le même test. Dans un second volet, nous avons étudié l'activité phagocytaire des macrophages en évaluant leur activité lysosomale et la production d'oxyde nitrique. RÉSULTATS: L'extrait MeOH révèle, un fort potentiel inhibiteur de la croissance de la tumeur transplantée, une augmentation de façon remarquable de la prolifération des splénocytes ainsi qu'une forte induction des activités NK et CTL chez des souris porteuses de tumeurs. Aussi l'extrait a considérablement induit l'activité phagocytaire des macrophages en augmentant leur activité lysosomale ainsi que la production de monoxide d'azote, par ces cellules. CONCLUSION: Nos résultats suggèrent fortement que l'effet antitumoral de l'extrait méthanolique passe par son potentiel immunomodulatrice.

Evaluation of the antimutagenic, antigenotoxic, and antioxidant activities of Eriobotrya japonica leaves.

CONTEXT: The leaves of Eriobotrya japonica (Thunb.) Lindl. (Rosaceae) are used in traditional medicine to treat inflammatory diseases. However, information about the antigenotoxic and antioxidant properties of its leaves remains to be elucidated. OBJECTIVE: The objective of this work was to evaluate the mutagenic/antimutagenic, genotoxic/antigenotoxic, and antioxidant potentials of aqueous and total oligomers flavonoid (TOF) extracts from E. japonica. MATERIALS AND METHODS: The mutagenic/antimutagenic and genotoxic/antigenotoxic potentials of extracts (50, 250, and 500 µg/plate) were evaluated, respectively, by the Ames test with 48 h incubation and the SOS chromotest test with 2 h incubation. The antioxidant capacity of these extracts (ranging from 50 to 700 µg/mL) was tested using xanthine/xanthine oxidase and the deoxyribose assays. RESULTS: Eriobotrya japonica extracts showed neither mutagenic nor genotoxic effect. The highest protective effect against methyl methanesulfonate and 2-aminoanthracene was obtained in the presence of aqueous extract, with IC50 values of 80 and 140 µg/plate, respectively, against S. typhimurium TA104. Moreover, this extract (500 µg/plate) was also able to reduce significantly the genotoxicity induced by nitrofurantoin and aflatoxin B1 with IC50 values of 140 and 240 µg/assay, respectively. Likewise, aqueous and TOF extracts inhibited xanthine oxidase and superoxide anion formation with IC50 values ranging from 45 to 95 and from 70 to 90 µg/mL, respectively. However, TOF extract is more efficient in inhibiting hydroxyl radical and chelating iron ion with IC50 values of 140 and 400 µg/mL, respectively, when compared with the aqueous extract. CONCLUSION: Eriobotrya japonica prevents the genotoxicity of some carcinogenic substances probably thanks to its antioxidant capacities.

Efficient degradation of chloroquine drug by electro-Fenton oxidation: Effects of operating conditions and degradation mechanism.

In this work, the degradation of chloroquine (CLQ), an antiviral and antimalarial drug, using electro-Fenton oxidation was investigated. Due to the importance of hydrogen peroxide (H2O2) generation during electro-Fenton oxidation, effects of pH, current density, molecular oxygen (O2) flow rate, and anode material on H2O2 generation were evaluated. H2O2 generation was enhanced by increasing the current density up to 60 mA/cm2 and the O2 flow rate up to 80 mL/min at pH 3.0 and using carbon felt cathode and boron-doped diamond (BDD) anode. Electro-Fenton-BDD oxidation achieved the total CLQ depletion and 92% total organic carbon (TOC) removal. Electro-Fenton-BDD oxidation was more effective than electro-Fenton-Pt and anodic oxidation using Pt and BDD anodes. The efficiency of CLQ depletion by electro-Fenton-BDD oxidation raises by increasing the current density and Fe2+ dose; however it drops with the increase of pH and CLQ concentration. CLQ depletion follows a pseudo-first order kinetics in all the experiments. The identification of CLQ degradation intermediates by chromatography methods confirms the formation of 7-chloro-4-quinolinamine, oxamic, and oxalic acids. Quantitative amounts of chlorides, nitrates, and ammonium ions are released during electro-Fenton oxidation of CLQ. The high efficiency of electro-Fenton oxidation derives from the generation of hydroxyl radicals from the catalytic decomposition of H2O2 by Fe2+ in solution, and the electrogeneration of hydroxyl and sulfates radicals and other strong oxidants (persulfates) from the oxidation of the electrolyte at the surface BDD anode. Electro-Fenton oxidation has the potential to be an alternative method for treating wastewaters contaminated with CLQ and its derivatives.

Electrochemical Oxidation/Disinfection of Urine Wastewaters with Different Anode Materials.

In the present work, electrochemical technology was used simultaneously for the deactivation of microorganisms and the destruction of micro-pollutants contained in synthetic urine wastewaters. Microorganisms (E. coli) were added to synthetic urine wastewaters to mimic secondary treated sewage wastewaters. Different anode materials were employed including boron-doped diamond (BDD), dimensionally stable anode (DSA: IrO2 and RuO2) and platinum (Pt). The results showed that for the different anode materials, a complete deactivation of E. coli microorganisms at low applied electric charge (1.34 Ah dm-3) was obtained. The complete deactivation of microorganisms in wastewater seems to be directly related to active chlorine and oxygen species electrochemically produced at the surface of the anode material. Complete depletion of COD and TOC can be attained during electrolyses with BDD anode after the consumption of specific electric charges of 4.0 and 8.0 Ah dm-3, respectively. Higher specific electric charges (>25 Ah dm-3) were consumed to removal completely COD and about 75% of TOC during electrolyses with DSA anodes (IrO2 and RuO2). However, the electrolysis using Pt anode can partially remove and even after the consumption of high specific electric charges (>40 Ah dm-3) COD and TOC did not exceed 50 and 25%, respectively. Active chlorine species including hypochlorite ions and chloramines formed during electrolysis contribute not only to deactivate microorganisms but also to degrade organics compounds. High conversion yields of organic nitrogen into nitrates and ammonium were achieved during electrolysis BDD and DSA anodes. The results have confirmed that BDD anode is more efficient than with IrO2, RuO2 and Pt electrodes in terms of COD and TOC removals. However, higher amounts of perchlorates were measured at the end of the electrolysis using BDD anode.

Enhancing the performance of electro-peroxone by incorporation of UV irradiation and BDD anodes.

In this work, the treatment of 4-nitrophenol (NP) in water by ozonation, electrolysis, electro-peroxone (EP), and photo-electro-peroxone (PEP) processes was investigated. PEP process is based on the combination of ozonation, UV irradiation, and electrolysis using a carbon felt cathode and a boron-doped diamond (BDD) anode. In this process, H2O2 is electrochemically generated from reduction of O2 in the ozone generator effluent at a carbon felt cathode. The in situ generated H2O2 is simultaneously decomposed by UV-photolysis and by reaction with O3 to form HO• radicals that can rapidly and non-selectively oxidize organic pollutants. The results showed that PEP is the most efficient process for a rapid NP degradation in water than the other individual and combined methods. In addition, PEP process was able to completely remove total organic carbon (TOC) from NP solution after consumption of 4.1 kWh/kg TOC removed. Hydroquinone, 1,2,4-trihydroxybenzene, oxalic and maleic acids were identified as the main intermediates of NP degradation. The addition of iron to NP solution did not significantly affect the efficiency of PEP process. The results demonstrated that the incorporation of BDD anodes and UV light in PEP process can significantly enhance the kinetics and minimize energy requirements.

Mechanism and kinetics of electrochemical degradation of uric acid using conductive-diamond anodes.

Uric acid (UA) is one of the principal effluents of urine wastewaters, widely used in agriculture as fertilizer, which is potentially dangerous and biorefractory. Hence, the degradation of UA (2,6,8-trihydroxy purine) in aqueous solution of pH 3.0 has been studied by conductive-diamond electrochemical oxidation. Hydroxyl radicals formed from water oxidation at the surface of boron-doped diamond anodes were the main oxidizing agents. Effects of current density and supporting electrolyte on the degradation rate and process efficiency are assessed. Results show that the increase of current density from 20 to 60 mA cm(-2) leads to a decrease in the efficiency of the electrochemical process. In addition, the best degradation occurred in the presence of NaCl as conductive electrolyte. Interestingly, an almost total mineralization of 50 ppm UA was obtained when anodic oxidation was performed at low current densities (20 mA cm(-2)) and in the presence of NaCl. This result confirmed that the electrolysis using diamond anodes is a very interesting technology for the treatment of UA. The identification of UA transformation products was performed by high-performance liquid chromatography (HPLC). HPLC analysis of treated solutions revealed that oxalic acid and urea were the two intermediates found. Oxalic acid was the most persistent product. Based on detected intermediates and bibliographic research, a mechanism of UA mineralization by anodic oxidation has been proposed. Ionic chromatography analysis confirmed the release of [Formula: see text] and [Formula: see text] ions during UA mineralization.

Investigation of immunomodulatory and anti-inflammatory effects of eriodictyol through its cellular anti-oxidant activity.

Many studies have been performed to assess the potential utility of natural products as immunomodulatory agents to enhance host responses against infection or to ameliorate immune-based pathologies. To determine whether eriodictyol has immunomodulatory effects and clarify which types of immune effector cells are stimulated in vitro, we investigated the stimulatory effect of eriodictyol on spleen cells isolated from BALB/c mice. Eriodictyol significantly stimulated splenocyte proliferation. However, only B lymphocytes (not T lymphocytes) could be stimulated by eriodictyol in a dose-related manner. Studies assessing potential effect of eriodictyol on innate immunity reported that eriodictyol enhanced significantly the killing activity of natural killer (NK) cells, T lymphocytes, and macrophages. We also demonstrated that eriodictyol inhibited nitric oxide (NO) production and lysosomal enzyme activity in murine peritoneal macrophages cultured ex-vivo, suggesting a potential anti-inflammatory effect in situ. Eriodictyol revealed also a cellular anti-oxidant activity in splenocytes and macrophages. Furthermore, eriodictyol increased catalase activity in spleen cells. From this data, it can be concluded that eriodictyol exhibited an immunomodulatory effect that could be ascribed in part to a cytoprotective effect related to its anti-oxidant activity.

Treatment of synthetic urine by electrochemical oxidation using conductive-diamond anodes.

In this work, the electrochemical oxidation of synthetic urine by anodic oxidation using boron-doped diamond as anode and stainless steel as cathode was investigated. Results show that complete depletion of chemical oxygen demand (COD) and total organic carbon (TOC) can be attained regardless of the current density applied in the range 20-100 mA cm(-2). Oxalic and oxamic acids, and, in lower concentrations, creatol and guanidine were identified as the main intermediates. Chloride ions play a very important role as mediators and contribute not only to obtain a high efficiency in the removal of the organics but also to obtain an efficient removal of nitrogen by the transformation of the various raw nitrogen species into gaseous nitrogen through chloramine formation. The main drawback of the technology is the formation of chlorates and perchlorates as final chlorine products. The increase of current density from 20 to 60 mA cm(-2) led to an increase in the rate of COD and TOC removals although the process becomes less efficient in terms of energy consumption (removals of COD and TOC after applying 18 Ah dm(-3) were 93.94 and 94.94 %, respectively, at 20 mA cm(-2) and 89.17 and 86.72 %, respectively, at 60 mA cm(-2)). The most efficient conditions are low current densities and high temperature reaching total mineralization at an applied charge as low as 20 kAh m(-3). This result confirmed that the electrolysis using diamond anodes is a very interesting technology for the treatment of urine.

Evaluation of an eventual ecotoxicity induced by textile effluents using a battery of biotests.

Textile industry is considered as one of the important factors of the economic growth in Tunisia. However, this prominent role has certainly some drawbacks mainly represented by the huge amounts of textile wastewaters generated that become a real menace to nature. Many previous studies showed the purifying potential of some activated sludge and bacteria (Pseudomonas putida) to decolourize textile effluents. However, in many cases, decolourization of wastewaters is not necessary associated with detoxification, generating a real risk for the ecosystem in general. We evaluated in this work the induced toxicity of a textile effluent before and after its treatment with activated sludge followed by P. putida, using a battery of biotests. This study proved the detoxifying power of the activated sludge according to most of ecotoxicity tests. The treatment with P. putida did not improve the quality of the effluent; on the contrary, it could increase its toxicity. Daphnia magna and Raphidocelis subcapitata appear to be the most sensitive organisms in assessing eventual toxicity caused by this kind of wastewaters.

Anodic oxidation of o-nitrophenol on BDD electrode: variable effects and mechanisms of degradation.

The electrochemical oxidation of pesticide, o-nitrophenol (ONP) as one kind of pesticide that is potentially dangerous and biorefractory, was studied by galvanostatic electrolysis using boron-doped diamond (BDD) as anode. The influence of several operating parameters, such as applied current density, supporting electrolyte, and initial pH value, was investigated. The best degradation occurred in the presence of Na2SO4 (0.05 M) as conductive electrolyte. After 8h, nearly complete degradation of o-nitrophenol was achieved (92%) using BDD electrodes at pH 3 and at current density equals 60 mA cm(-2). The decay kinetics of o-nitrophenol follows a pseudo-first-order reaction. Aromatic intermediates such as catechol, resorcinol, 1,2,4-trihydroxybenzene, hydroquinone and benzoquinone and carboxylic acids such as maleic glycolic, malonic, glyoxilic and oxalic, have been identified and followed during the ONP treatment by chromatographic techniques. From these anodic oxidation by-products, a plausible reaction sequence for ONP mineralization on BDD anodes is proposed.