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Goethite promoted biodegradation of 2,4-dinitrophenol under nitrate reduction condition.

Iron oxide may interact with other pollutants in the aquatic environments and further influence their toxicity, transport and fate. The current study was conducted to investigate the biodegradation of 2,4-dinitrophenol (2,4-DNP) in the presence of iron oxide of goethite under anoxic condition using nitrate as the electron acceptor. Experiment results showed that the degradation rate of 2,4-DNP was improved by goethite. High performance liquid chromatography-mass spectra analysis results showed that goethite promoted degradation and transformation of 2,4-diaminophenol and 2-amino-4-nitrophenol (2-nitro-4-aminophenol). Microbial community analysis results showed that the abundance of Actinobacteria, which have the potential ability to degrade PAHs, was increased when goethite was available. This might partially explain the higher degradation of 2,4-DNP. Furthermore, another bacterium of Desulfotomaculum reducens which could reduce soluble Fe(III) and nitrate was also increased. Results further confirmed that nanomaterials in the aquatic environment will influence the microbial community and further change the transformation process of toxic pollutants.

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Investigation of the early-response genes in chemical-induced renal carcinogenicity for the prediction of chemical carcinogenicity in rats.

This study was designed to identify early-response genes of chemical-induced renal carcinogenicity for the prediction of chemical carcinogenicity in rats. We conducted a 28-day repeated-dose test in male Crl:CD (SD) rats with 12 carcinogens and 10 non-carcinogens as the training dataset, and five carcinogens and five non-carcinogens as the validation dataset. Renal gene expression profiles were analyzed by using a microarray. Fifteen candidate genes were selected from the gene expression profiles of the training dataset as genes that showed specific expression in response to carcinogens. To assess the prediction performance of the candidate genes for renal carcinogenicity, a prediction formula was developed on the basis of the gene expression data. When this formula was applied to the training dataset to check its predictive performance, all of the carcinogens and non-carcinogens were predicted correctly; the prediction formula was then applied to the validation dataset, and five carcinogens and four non-carcinogens were correctly predicted. However, 4-Hydroxy-m-phenylenediammonium dichloride (AMIDOL), a known non-renal carcinogen, was judged as positive. Therefore, the accuracy of the prediction formula for renal carcinogenicity was 100% for the training dataset and 90% for the validation dataset. Among the predictive genes, Hamp and Ranbp1 are known to be important for cell growth and cell cycle regulation, which are important events in carcinogenesis. Given our current limited knowledge of the genes responsible for renal carcinogenesis, the identification of candidate genes of chemical-induced renal carcinogenicity by use of this gene expression-based prediction method represents a promising advance in renal carcinogen identification.

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A Combined 28-Day Oral Toxicity Study of HFPO-Amidol (CASRN 75888-49-2) With Reproductive/Developmental Toxicity Screening Test in Wistar Han Rats.

HFPO-Amidol (CAS # 75888-49-2) is a new hexafluoropropylene oxide (HFPO)-based intermediate developed as an alternative to longer chain perfluorinated compounds. The repeated-dose toxicity of this material was evaluated in an Organization for Economic Cooperation and Development 422-compliant, 28-day oral exposure study with a concurrent reproductive/developmental toxicity screening test. Wistar rats received doses of 0, 30, 300, or 1000 mg/kg/d by oral gavage. Statistically significant changes in body weight gain of 1000 mg/kg/d females during the postcoitum period were possibly related to treatment but were considered not adverse, given the slight nature of the changes. The lower food consumption of 300 mg/kg/d females during the postcoitum and lactation period was not considered treatment related given the absence of a time- and dose-related trend and because food intake was generally similar to control levels after allowance for body weights. Statistically significant changes in motor activity (total movements and total ambulations) were noted in 1000 mg/kg/d main male and female rats. The changes observed in female rats were considered not treatment related in the absence of a dose-response trend. The higher motor activity of high-dose males was primarily apparent within the first 10 minutes of the 60-minute measurement period and was suggestive of temporary hyperreactivity to a new environment/stimulus. This increased peak motor activity remained present although at an apparent lower magnitude when measured 13 days after withdrawal of treatment. Because the possible toxicological relevance of the temporarily increased motor activity observed in 1000 mg/kg/d males could not be excluded, these changes were considered possibly adverse in nature. No treatment-related or toxicologically relevant effects were noted on the other parental, reproductive, and developmental parameters investigated in this study. The parental systemic no observed adverse effect level (NOAEL) for this study is 300 mg/kg/d (based on increased motor activity in males), while the reproductive and developmental NOAEL is 1000 mg/kg/d.

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Determination of the in vivo NAD:NADH ratio in Saccharomyces cerevisiae under anaerobic conditions, using alcohol dehydrogenase as sensor reaction.

With the current quantitative metabolomics techniques, only whole-cell concentrations of NAD and NADH can be quantified. These measurements cannot provide information on the in vivo redox state of the cells, which is determined by the ratio of the free forms only. In this work we quantified free NAD:NADH ratios in yeast under anaerobic conditions, using alcohol dehydrogenase (ADH) and the lumped reaction of glyceraldehyde-3-phosphate dehydrogenase and 3-phosphoglycerate kinase as sensor reactions. We showed that, with an alternative accurate acetaldehyde determination method, based on rapid sampling, instantaneous derivatization with 2,4 diaminophenol hydrazine (DNPH) and quantification with HPLC, the ADH-catalysed oxidation of ethanol to acetaldehyde can be applied as a relatively fast and simple sensor reaction to quantify the free NAD:NADH ratio under anaerobic conditions. We evaluated the applicability of ADH as a sensor reaction in the yeast Saccharomyces cerevisiae, grown in anaerobic glucose-limited chemostats under steady-state and dynamic conditions. The results found in this study showed that the cytosolic redox status (NAD:NADH ratio) of yeast is at least one order of magnitude lower, and is thus much more reduced, under anaerobic conditions compared to aerobic glucose-limited steady-state conditions. The more reduced state of the cytosol under anaerobic conditions has major implications for (central) metabolism. Accurate determination of the free NAD:NADH ratio is therefore of importance for the unravelling of in vivo enzyme kinetics and to judge accurately the thermodynamic reversibility of each redox reaction.

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[Simultaneous determination of six components in hair dyes by ultra performance liquid chromatography-tandem mass spectrometry].

A sensitive method was developed for the simultaneous determination of six components which included 4, 4'-diaminodiphenylamine sulfate hydrate and 2,4-diaminophenol sulfate, etc. in hair dyes by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). After extracted by water through ultrasonic extraction, the samples were analyzed by UPLC-MS/MS. The separation was performed on a Waters BEH-C18 column (100 mmx 2.1 mm, 1.7 microm) with gradient elution of 10 mmol/L ammonium acetate and acetonitrile. The electrospray ionization (ESI) source in positive ion mode was used for the analysis of the six components in the multiple reaction monitoring (MRM) mode. The results showed good linear relationships with all the correlation coefficients (R2) more than 0.99. The limits of detection (LODs, S/N=3) for the six components were in the range of 0.26-4.6 mg/kg. The average recoveries of the six components in the spiked samples were in the range of 83.0%-92.2% with the relative standard deviations (RSDs, n=6) of 5.4%-11.2%. The precision, accuracy, mean recoveries and the matrix effects satisfied the requirements of cosmetic sample measurement. The proposed method has been applied to the determination of six dyes in actual samples. This method is simple, accurate and effective for the simultaneous determination of the six components in hair dyes.

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A novel Schiff-base as a Cu(II) ion fluorescent sensor in aqueous solution.

A new fluorescent Cu(II) sensor (L) obtained from the Schiff base of 5,5'-methylene-bis-salicylaldehyde with amidol (2,4-diaminophenol) was synthesized and characterized by FT-IR, MS, (1)H NMR, (13)C NMR techniques. In the presence of pH 6.5 (KHPO4-Na2HPO4) buffer solutions, copper reacted with L to form a stable 2:1 complex. Fluorescence spectroscopic study showed that Schiff base is highly sensitive towards Cu(II) over other metal ions (K(+), Na(+), Al(3+), Ni(2+), Co(2+), Fe(3+), Zn(2+), Pb(2+)) in DMSO/H2O (30%, v/v). The sensor L was successfully applied to the determination of copper in standard reference material. The structural properties and molecular orbitals of the complex formed between L and Cu(2+) ions were also investigated using quantum chemical computations.

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Direct and indirect single electron transfer (SET)-photochemical approaches for the preparation of novel phthalimide and naphthalimide-based lariat-type crown ethers.

In this review, we describe direct and indirect photochemical approaches that have been developed for the preparation of phthalimide- and naphthalimide-based, lariat-type crown ethers. The direct route utilizes a strategy in which nitrogen-linked side chains containing polyethoxy-tethered phthalimides and naphthalimides, possessing terminal α-trialkylsilyl groups, are synthesized utilizing concise routes and UV-irradiation to form macrocyclic ring systems. In contrast, the indirect route developed for the synthesis of lariat-type crown ethers employs sequences in which SET-promoted macrocyclization reactions of α-trialkylsilyl-terminated, polyethoxy-tethered phthalimides and naphthalimides are followed by a side chain introduction through substitution reactions at the amidol centers in the macrocyclic ethers. The combined observations made in these investigations demonstrate the unique features of SET-promoted photocyclization reactions that make them well-suited for the use in the synthesis of functionalized crown ethers. In addition, while some limitations exist for the general use of SET-photochemical reactions in large-scale organic synthesis, important characteristics of the photoinduced macrocyclization reactions make them applicable to unique situations in which high temporal and spatial control is required.

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Epidemiological study of fixed drug eruption in Pointe-Noire.

A prospective study was conducted over a 27 month period in order to determine the epidemiological profile of fixed drug eruption (FDE) observed during a dermatological consultation at Pointe-Noire. During the study period 54 out of 9,070 persons consulting (0.6%) suffered from clinically diagnosed FDE. The variables studied were: age, sex, medicine and point of sale. The average age of onset was 30 years. The frequency of onset was higher in males (38 patients) than in females (16 patients). The incriminated medicines were: the sulfamides (48 patients) including Cotrimoxazole (45 patients ) and Sulfadoxine and Pyremethamine (3 patients) Coartem(®) + Doliprane(®) (1 patient), Chloramphenicol(®) (1 patient), Amidol(®) (1 patient), Duocotexin(®) + Paracetamol(®) (1 patient), Surquina(®) (1 patient), Amodiaquine(®) (1 patient). The point of sale was illicit (peddlers, markets) for 44 patients; for 10 patients it was a lawful outlet (pharmacies). This study shows that cotrimoxazole bought at illicit points of sale is the main etiology of FDE in the department, confirming that these medicines are counterfeit. The involvement of dermatologists in the fight against the illicit sale of medicines should be made a priority.

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Application of conductive polymers in biocathode of microbial fuel cells and microbial community.

Four kinds of conductive polymers, polyaniline (PANI) and its co-polymers poly (aniline-co-o-aminophenol) (PANOA), poly (aniline-co-2, 4-diaminophenol) (PANDAP) and poly (aniline-1, 8-diaminonaphthalene) (PANDAN) were applied to modify carbon felts as the aerobic abiotic cathodes and biocathodes in microbial fuel cells (MFC). Compare to unmodified, all the four polymers can significantly improve the power densities for both abiotic cathodes (increased by 300%) and biocathodes (increased by 180%). The co-polymers with different functional groups introduction had further special advantages in MFC performance: PANOA and PANDAP with -OH showed less sensitivity to DO and pH change in cathode; PANDAP and PANDAN with -NH(3) provided better attachment condition for biofilm which endowed them higher power output. With the help of conductive polymer coats, the cathode biofilm became thicker, and according to biodiversity analysis, the predominated phyla changed from β-Proteobacteria (unmodified) to α, γ-Proteobacteria (modified), which may be responsible for the superiority of the modified MFCs.

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Evaluation of therapeutic effects and pharmacokinetics of antibacterial chromogenic agents in a silkworm model of Staphylococcus aureus infection.

The therapeutic effect of dye compounds with antibacterial activity was evaluated in a silkworm model of Staphylococcus aureus infection. Among 13 chromogenic agents that show antibacterial activity against S. aureus (MIC = 0.02 to 19 μg/mL), rifampicin had a therapeutic effect. The ED(50) value in the silkworm model was consistent with that in a murine model. Other 12 dyes did not increase survival of the infected silkworms. We examined the reason for the lack of therapeutic efficacy. Amidol, pyronin G, and safranin were toxic to silkworms, which explained the lack of therapeutic effects. Fuchsin basic and methyl green disappeared quickly from the hemolymph after injection, suggesting that they are not stable in the hemolymph. Although coomassie brilliant blue R250/G250, cresyl blue, and nigrosin showed no toxic effects or instability in the hemolymph, they also did not have a therapeutic effect. The in vitro antibacterial actions of these dyes were inhibited by silkworm plasma or bovine serum albumin and filtration experiments demonstrated that cresyl blue bound to plasma proteins in the silkworm, suggesting that plasma protein binding inhibited the therapeutic efficacy of these four dyes. These findings indicate that drug screening using the silkworm infection model is useful for evaluating toxicity and pharmacokinetics of potential antibiotics.

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