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Sample records for mustard allyl isothiocyanate

  1. No metabolic effects of mustard allyl-isothiocyanate compared with placebo in men

    NARCIS (Netherlands)

    Langeveld, Mirjam; Tan, Chong Yew; Soeters, Maarten R.; Virtue, Samuel; Watson, Laura Pe; Murgatroyd, Peter R.; Ambler, Graeme K.; Vidal-Puig, Santiago; Chatterjee, Krishna V.; Vidal-Puig, Antonio

    2017-01-01

    Background: Induction of nonshivering thermogenesis can be used to influence energy balance to prevent or even treat obesity. The pungent component of mustard, allyl-isothiocyanate (AITC), activates the extreme cold receptor transient receptor potential channel, subfamily A, member 1 and may thus

  2. Inhibition of bladder cancer cell proliferation by allyl isothiocyanate (mustard essential oil)

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    Sávio, André Luiz Ventura, E-mail: savio.alv@gmail.com [UNESP – Universidade Estadual Paulista, Faculdade de Medicina de Botucatu, Departamento de Patologia, Botucatu, SP (Brazil); Nicioli da Silva, Glenda [UFOP – Universidade Federal de Ouro Preto, Escola de Farmácia, Departamento de Análises Clínicas, Ouro Preto, MG (Brazil); Salvadori, Daisy Maria Fávero [UNESP – Universidade Estadual Paulista, Faculdade de Medicina de Botucatu, Departamento de Patologia, Botucatu, SP (Brazil)

    2015-01-15

    Highlights: • AITC inhibits mutant and wild-type TP53 cell proliferation. • Morphological changes and cells debris were observed after AITC treatment in both cells. • BAX and BCL2 expression modulation was observed in wild-type TP53 cells. • BCL2, BAX and ANLN increased and S100P decreased expression was detected in mutated TP53 cells. • AITC effects in gene modulation are dependent TP53 gene status. - Abstract: Natural compounds hold great promise for combating antibiotic resistance, the failure to control some diseases, the emergence of new diseases and the toxicity of some contemporary medical products. Allyl isothiocyanate (AITC), which is abundant in cruciferous vegetables and mustard seeds and is commonly referred to as mustard essential oil, exhibits promising antineoplastic activity against bladder cancer, although its mechanism of action is not fully understood. Therefore, the aim of this study was to investigate the effects of AITC activity on bladder cancer cell lines carrying a wild type (wt; RT4) or mutated (T24) TP53 gene. Morphological changes, cell cycle kinetics and CDK1, SMAD4, BAX, BCL2, ANLN and S100P gene expression were evaluated. In both cell lines, treatment with AITC inhibited cell proliferation (at 62.5, 72.5, 82.5 and 92.5 μM AITC) and induced morphological changes, including scattered and elongated cells and cellular debris. Gene expression profiles revealed increased S100P and BAX and decreased BCL2 expression in RT4 cells following AITC treatment. T24 cells displayed increased BCL2, BAX and ANLN and decreased S100P expression. No changes in SMAD4 and CDK1 expression were observed in either cell line. In conclusion, AITC inhibits cell proliferation independent of TP53 status. However, the mechanism of action of AITC differed in the two cell lines; in RT4 cells, it mainly acted via the classical BAX/BCL2 pathway, while in T24 cells, AITC modulated the activities of ANLN (related to cytokinesis) and S100P. These data confirm

  3. Inhibition of bladder cancer cell proliferation by allyl isothiocyanate (mustard essential oil)

    International Nuclear Information System (INIS)

    Sávio, André Luiz Ventura; Nicioli da Silva, Glenda; Salvadori, Daisy Maria Fávero

    2015-01-01

    Highlights: • AITC inhibits mutant and wild-type TP53 cell proliferation. • Morphological changes and cells debris were observed after AITC treatment in both cells. • BAX and BCL2 expression modulation was observed in wild-type TP53 cells. • BCL2, BAX and ANLN increased and S100P decreased expression was detected in mutated TP53 cells. • AITC effects in gene modulation are dependent TP53 gene status. - Abstract: Natural compounds hold great promise for combating antibiotic resistance, the failure to control some diseases, the emergence of new diseases and the toxicity of some contemporary medical products. Allyl isothiocyanate (AITC), which is abundant in cruciferous vegetables and mustard seeds and is commonly referred to as mustard essential oil, exhibits promising antineoplastic activity against bladder cancer, although its mechanism of action is not fully understood. Therefore, the aim of this study was to investigate the effects of AITC activity on bladder cancer cell lines carrying a wild type (wt; RT4) or mutated (T24) TP53 gene. Morphological changes, cell cycle kinetics and CDK1, SMAD4, BAX, BCL2, ANLN and S100P gene expression were evaluated. In both cell lines, treatment with AITC inhibited cell proliferation (at 62.5, 72.5, 82.5 and 92.5 μM AITC) and induced morphological changes, including scattered and elongated cells and cellular debris. Gene expression profiles revealed increased S100P and BAX and decreased BCL2 expression in RT4 cells following AITC treatment. T24 cells displayed increased BCL2, BAX and ANLN and decreased S100P expression. No changes in SMAD4 and CDK1 expression were observed in either cell line. In conclusion, AITC inhibits cell proliferation independent of TP53 status. However, the mechanism of action of AITC differed in the two cell lines; in RT4 cells, it mainly acted via the classical BAX/BCL2 pathway, while in T24 cells, AITC modulated the activities of ANLN (related to cytokinesis) and S100P. These data confirm

  4. Inhibition of Listeria monocytogenes on cooked cured chicken breasts by acidified coating containing allyl isothiocyanate or deodorized Oriental mustard extract.

    Science.gov (United States)

    Olaimat, Amin N; Holley, Richard A

    2016-08-01

    Ready-to-eat meats are considered foods at high risk to cause life-threatening Listeria monocytogenes infections. This study screened 5 L. monocytogenes strains for their ability to hydrolyze sinigrin (a glucosinolate in Oriental mustard), which formed allyl isothiocyanate (AITC) and reduced L. monocytogenes viability on inoculated vacuum-packed, cooked, cured roast chicken slices at 4 °C. Tests involved incorporation of 25-50 μl/g AITC directly or 100-250 mg/g Oriental mustard extract in 0.5% (w/v) κ-carrageenan/2% (w/v) chitosan-based coatings prepared using 1.5% malic or acetic acid. L. monocytogenes strains hydrolyzed 33.6%-48.4% pure sinigrin in MH broth by 21 d at 25 °C. Acidified κ-carrageenan/chitosan coatings containing 25-50 μl/g AITC or 100-250 mg/g mustard reduced the viability of L. monocytogenes and aerobic bacteria on cooked, cured roast chicken slices by 4.1 to >7.0 log10 CFU/g compared to uncoated chicken stored at 4 °C for 70 d. Coatings containing malic acid were significantly more antimicrobial than those with acetic acid. During storage for 70 d, acidified κ-carrageenan/chitosan coatings containing 25-50 μl/g AITC or 250 mg/g mustard extract reduced lactic acid bacteria (LAB) numbers 3.8 to 5.4 log10 CFU/g on chicken slices compared to uncoated samples. Acidified κ-carrageenan/chitosan-based coatings containing either AITC or Oriental mustard extract at the concentrations tested had the ability to control L. monocytogenes viability and delay growth of potential spoilage bacteria on refrigerated, vacuum-packed cured roast chicken. Copyright © 2016. Published by Elsevier Ltd.

  5. Allyl isothiocyanate induced stress response in Caenorhabditis elegans

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    Saini AkalRachna K

    2011-11-01

    Full Text Available Abstract Background Allyl isothiocyanate (AITC from mustard is cytotoxic; however the mechanism of its toxicity is unknown. We examined the effects of AITC on heat shock protein (HSP 70 expression in Caenorhabditis elegans. We also examined factors affecting the production of AITC from its precursor, sinigrin, a glucosinolate, in ground Brassica juncea cv. Vulcan seed as mustard has some potential as a biopesticide. Findings An assay to determine the concentration of AITC in ground mustard seed was improved to allow the measurement of AITC release in the first minutes after exposure of ground mustard seed to water. Using this assay, we determined that temperatures above 67°C decreased sinigrin conversion to AITC in hydrated ground B. juncea seed. A pH near 6.0 was found to be necessary for AITC release. RT-qPCR revealed no significant change in HSP70A mRNA expression at low concentrations of AITC ( 1.0 μM resulted in a four- to five-fold increase in expression. A HSP70 ELISA showed that AITC toxicity in C. elegans was ameliorated by the presence of ground seed from low sinigrin B. juncea cv. Arrid. Conclusions • AITC induced toxicity in C. elegans, as measured by HSP70 expression. • Conditions required for the conversion of sinigrin to AITC in ground B. juncea seed were determined. • The use of C. elegans as a bioassay to test AITC or mustard biopesticide efficacy is discussed.

  6. Effect of allyl isothiocyanate on developmental toxicity in exposed Xenopus laevis embryos

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    John Russell Williams

    2015-01-01

    Full Text Available The pungent natural compound allyl isothiocyanate isolated from the seeds of Cruciferous (Brassica plants such as mustard is reported to exhibit numerous beneficial health-promoting antimicrobial, antifungal, anticarcinogenic, cardioprotective, and neuroprotective properties. Because it is also reported to damage DNA and is toxic to aquatic organisms, the objective of the present study was to determine whether it possesses teratogenic properties. The frog embryo teratogenesis assay-Xenopus (FETAX was used to determine the following measures of developmental toxicity of the allyl isothiocyanate: (a 96-h LC50, defined as the median concentration causing 50% embryo lethality; (b 96-h EC50, defined as the median concentration causing 50% malformations of the surviving embryos; and (c teratogenic malformation index (TI, equal to 96-h LC50/96-h EC50. The quantitative results and the photographs of embryos before and after exposure suggest that allyl isothiocyanate seems to exhibit moderate teratogenic properties. The results also indicate differences in the toxicity of allyl isothiocyanate toward exposed embryos observed in the present study compared to reported adverse effects of allyl isothiocyanate in fish, rodents, and humans. The significance of the results for food safety and possible approaches to protect against adverse effects of allyl isothiocyanate are discussed.

  7. Noxious heat threshold temperature and pronociceptive effects of allyl isothiocyanate (mustard oil) in TRPV1 or TRPA1 gene-deleted mice.

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    Tékus, Valéria; Horváth, Ádám; Hajna, Zsófia; Borbély, Éva; Bölcskei, Kata; Boros, Melinda; Pintér, Erika; Helyes, Zsuzsanna; Pethő, Gábor; Szolcsányi, János

    2016-06-01

    To investigate the roles of TRPV1 and TRPA1 channels in baseline and allyl isothiocyanate (AITC)-evoked nociceptive responses by comparing wild-type and gene-deficient mice. In contrast to conventional methods of thermonociception measuring reflex latencies, we used our novel methods to determine the noxious heat threshold. It was revealed that the heat threshold of the tail measured by an increasing-temperature water bath is significantly higher in TRPV1(-/-), but not TRPA1(-/-), mice compared to respective wild-types. There was no difference between the noxious heat thresholds of the hind paw as measured by an increasing-temperature hot plate in TRPV1(-/-), TRPA1(-/-) and the corresponding wild-type mice. The withdrawal latency of the tail from 0°C water was prolonged in TRPA1(-/-), but not TRPV1(-/-), mice compared to respective wild-types. In wild-type animals, dipping the tail or paw into 1% AITC induced an 8-14°C drop of the noxious heat threshold (heat allodynia) of both the tail and paw, and 40-50% drop of the mechanonociceptive threshold (mechanical allodynia) of the paw measured by dynamic plantar esthesiometry. These AITC-evoked responses were diminished in TRPV1(-/-), but not TRPA1(-/-), mice. Tail withdrawal latency to 1% AITC was significantly prolonged in both gene-deleted strains. Different heat sensors determine the noxious heat threshold in distinct areas: a pivotal role for TRPV1 on the tail is contrasted with no involvement of either TRPV1 or TRPA1 on the hind paw. Noxious heat threshold measurement appears appropriate for preclinical screening of TRP channel ligands as novel analgesics. Copyright © 2016 Elsevier Inc. All rights reserved.

  8. Assessing Natural Isothiocyanate Air Emissions after Field Incorporation of Mustard Cover Crop

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    Trott, Donna M.; LePage, Jane; Hebert, Vincent

    2012-01-01

    A regional air assessment was performed to characterize volatile natural isothiocyanate (NITC) compounds in air during soil incorporation of mustard cover crops in Washington State. Field air sampling and analytical methods were developed specific to three NITCs known to be present in air at appreciable concentrations during/after field incorporation. The maximum observed concentrations in air for the allyl, benzyl, and phenethyl isothiocyanates were respectively 188, 6.1, and 0.7 lg m-3 during mustard incorporation. Based on limited inhalation toxicity information, airborne NITC concentrations did not appear to pose an acute human inhalation exposure concern to field operators and bystanders.

  9. Allyl isothiocyanate enhances shelf life of minimally processed shredded cabbage.

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    Banerjee, Aparajita; Penna, Suprasanna; Variyar, Prasad S

    2015-09-15

    The effect of allyl isothiocyanate (AITC), in combination with low temperature (10°C) storage on post harvest quality of minimally processed shredded cabbage was investigated. An optimum concentration of 0.05μL/mL AITC was found to be effective in maintaining the microbial and sensory quality of the product for a period of 12days. Inhibition of browning was shown to result from a down-regulation (1.4-fold) of phenylalanine ammonia lyase (PAL) gene expression and a consequent decrease in PAL enzyme activity and o-quinone content. In the untreated control samples, PAL activity increased following up-regulation in PAL gene expression that could be linearly correlated with enhanced o-quinone formation and browning. The efficacy of AITC in extending the shelf life of minimally processed shredded cabbage and its role in down-regulation of PAL gene expression resulting in browning inhibition in the product is reported here for the first time. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Allyl isothiocyanate affects the cell cycle of Arabidopsis thaliana

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    Signe Elisabeth Åsberg

    2015-05-01

    Full Text Available Isothiocyanates (ITCs are degradation products of glucosinolates present in members of the Brassicaceae family acting as herbivore repellents and antimicrobial compounds. Recent results indicate that allyl ITC (AITC has a role in defense responses such as glutathione depletion, ROS generation and stomatal closure. In this study we show that exposure to non-lethal concentrations of AITC causes a shift in the cell cycle distribution of Arabidopsis thaliana leading to accumulation of cells in S-phases and a reduced number of cells in non-replicating phases. Furthermore, transcriptional analysis revealed an AITC-induced up-regulation of the gene encoding cyclin-dependent kinase A while several genes encoding mitotic proteins were down-regulated, suggesting an inhibition of mitotic processes. Interestingly, visualization of DNA synthesis indicated that exposure to AITC reduced the rate of DNA replication. Taken together, these results indicate that non-lethal concentrations of AITC induce cells of A. thaliana to enter the cell cycle and accumulate in S-phases, presumably as a part of a defensive response. Thus, this study suggests that AITC has several roles in plant defense and add evidence to the growing data supporting a multifunctional role of glucosinolates and their degradation products in plants.

  11. Influence of the antimicrobial compound allyl isothiocyanate against the Aspergillus parasiticus growth and its aflatoxins production in pizza crust.

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    Quiles, Juan M; Manyes, Lara; Luciano, Fernando; Mañes, Jordi; Meca, Giuseppe

    2015-09-01

    Aflatoxins (AFs) are secondary metabolites produced by different species of Aspergillus, such as Aspergillus flavus and Aspergillus parasiticus, which possess mutagenic, teratogenic and carcinogenic activities in humans. In this study, active packaging devices containing allyl isothiocyanate (AITC) or oriental mustard flour (OMF) + water were tested to inhibit the growth of A. parasiticus and AFs production in fresh pizza crust after 30 d. The antimicrobial and anti-aflatoxin activities were compared to a control group (no antimicrobial treatment) and to a group added with commercial preservatives (sorbic acid + sodium propionate). A. parasiticus growth was only inhibited after 30 d by AITC in filter paper at 5 μL/L and 10 μL/L, AITC sachet at 5 μL/L and 10 μL/L and OMF sachet at 850 mg + 850 μL of water. However, AFs production was inhibited by all antimicrobial treatments in a dose-dependent manner. More importantly, AITC in a filter paper at 10 μL/L, AITC sachet at 10 μL/L, OMF sachet at 850 mg + 850 μL of water and sorbic acid + sodium propionate at 0.5-2.0 g/Kg completely inhibited AFs formation. The use of AITC in active packaging devices could be a natural alternative to avoid the growth of mycotoxinogenic fungi in refrigerated bakery products in substitution of common commercial preservatives. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Contact and fumigant toxicity of Armoracia rusticana essential oil, allyl isothiocyanate and related compounds to Dermatophagoides farinae.

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    Yun, Yeon-Kyeong; Kim, Hyun-Kyung; Kim, Jun-Ran; Hwang, Kumnara; Ahn, Young-Joon

    2012-05-01

    The toxicity to adult Dermatophagoides farinae of allyl isothiocyanate identified in horseradish, Armoracia rusticana, oil and another 27 organic isothiocyanates was evaluated using contact + fumigant and vapour-phase mortality bioassays. Results were compared with those of two conventional acaricides, benzyl benzoate and dibutyl phthalate. Horseradish oil (24 h LC(50), 1.54 µg cm(-2)) and allyl isothiocyanate (2.52 µg cm(-2)) were highly toxic. Benzyl isothiocyanate (LC(50) , 0.62 µg cm(-2)) was the most toxic compound, followed by 4-chlorophenyl, 3-bromophenyl, 3,5-bis(trifluoromethyl)phenyl, cyclohexyl, 2-chlorophenyl, 4-bromophenyl and 2-bromophenyl isothiocyanates (0.93-1.41 µg cm(-2)). All were more effective than either benzyl benzoate (LC(50) , 4.58 µg cm(-2)) or dibutyl phthalate (24.49 µg cm(-2)). The structure-activity relationship indicates that types of functional group and chemical structure appear to play a role in determining the isothiocyanate toxicities to adult D. farinae. In the vapour-phase mortality bioassay, these isothiocyanates were consistently more toxic in closed versus open containers, indicating that their mode of delivery was, in part, a result of vapour action. In the light of global efforts to reduce the level of highly toxic synthetic acaricides in indoor environments, the horseradish oil-derived compounds and the isothiocyanates described herein merit further study as potential acaricides for the control of house dust mite populations as fumigants with contact action. Copyright © 2011 Society of Chemical Industry.

  13. Therapeutic Efficacy of Allyl Isothiocyanate Evaluated on N-Nitrosodiethylamine/Phenobarbitol induced Hepatocarcinogenesis in Wistar Rats

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    G. Thiyagarajan

    2010-07-01

    Full Text Available N-nitrosodiethylamine (NDEA is a potential carcinogenic agent that induces liver cancer. To evaluate the chemotherapeutic effect of Allyl isothiocyanate in the experimental model, Wistar male rats were administered single dose of intraperitoneal (IP injection of NDEA. Two weeks after administration of NDEA, Phenobarbital at the concentration of 0.05% was incorporated in rat chow for up to 14 successive weeks to promote liver cancer. Allyl isothiocyanate (AITC (2mg/kg body weight in addition with 0.5ml of corn oil was given orally on a daily basis. At the end of this experimental period, the rats were sacrificed and the blood samples were taken for biochemical studies. The levels of the marker enzymes for liver function were measured in serum. The results of the biochemical studies showed that NDEA administration followed by phenobarbital induces macro and microscopic liver tumors that increase the levels of marker enzymes and decreases the level of antioxidant in the serum in addition to loss of body weight. Conclusively, the administration of AITC as therapeutic treatment for hepatocarcinoma has significantly reduced the tumor development and counteracted all the biochemical effects induced by NDEA.

  14. Inactivation of Salmonella in tomato stem scars by organic acid wash and chitosan-allyl isothiocyanate coating

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    The objective of this study was to evaluate inactivation of inoculated Salmonella enterica on tomato stem scars exploiting integrated treatment of organic acid wash (AW) followed by chitosan-allyl isothiocyanate (CT-AIT) coating. The treatment effect on microbial loads and fruit quality during 21 d...

  15. Allyl Isothiocyanate Inhibits Actin-Dependent Intracellular Transport in Arabidopsis thaliana

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    Bjørnar Sporsheim

    2015-12-01

    Full Text Available Volatile allyl isothiocyanate (AITC derives from the biodegradation of the glucosinolate sinigrin and has been associated with growth inhibition in several plants, including the model plant Arabidopsis thaliana. However, the underlying cellular mechanisms of this feature remain scarcely investigated in plants. In this study, we present evidence of an AITC-induced inhibition of actin-dependent intracellular transport in A. thaliana. A transgenic line of A. thaliana expressing yellow fluorescent protein (YFP-tagged actin filaments was used to show attenuation of actin filament movement by AITC. This appeared gradually in a time- and dose-dependent manner and resulted in actin filaments appearing close to static. Further, we employed four transgenic lines with YFP-fusion proteins labeling the Golgi apparatus, endoplasmic reticulum (ER, vacuoles and peroxisomes to demonstrate an AITC-induced inhibition of actin-dependent intracellular transport of or, in these structures, consistent with the decline in actin filament movement. Furthermore, the morphologies of actin filaments, ER and vacuoles appeared aberrant following AITC-exposure. However, AITC-treated seedlings of all transgenic lines tested displayed morphologies and intracellular movements similar to that of the corresponding untreated and control-treated plants, following overnight incubation in an AITC-absent environment, indicating that AITC-induced decline in actin-related movements is a reversible process. These findings provide novel insights into the cellular events in plant cells following exposure to AITC, which may further expose clues to the physiological significance of the glucosinolate-myrosinase system.

  16. Increased presevation of sliced mozzarella cheese by antimibrobial sachet incorporated with allyl isothiocyanate

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    Ana Clarissa dos Santos Pires

    2009-12-01

    Full Text Available There is an increasing tendency to add natural antimicrobials of plant origin into food. The objective of this work was to develop a microbial sachet incorporated with allyl isothiocyanate (AIT, a volatile compound of plant origin, and to test its efficiency against growth of yeasts and molds, Staphylococcus sp. and psychrotrophic bacteria on sliced mozzarella cheese. Another objective was to quantify the concentration of AIT in the headspace of cheese packaging. A reduction of 3.6 log cycles was observed in yeasts and molds counts in the mozzarella packed with the antimicrobial sachet over 15-day storage time. The sachet also showed an antibacterial effect on Staphylococcus sp., reducing 2.4 log cycles after 12-day storage. Psychrotrophic bacteria species were the most resistant to the antimicrobial action. The highest concentration of AIT (0.08µg.mL-1 inside the active packaging system was observed at the 6-day of storage at 12 ºC ± 2 ºC. At the end of the storage time, AIT concentration decreased to only 10% of the initial concentration. Active packaging containing antimicrobial sachet has a potential use for sliced mozzarella, with molds and yeasts being the most sensitive to the antimicrobial effects.

  17. Effect of allyl isothiocyanate on ultra-structure and the activities of four enzymes in adult Sitophilus zeamais.

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    Wu, Hua; Liu, Xue-ru; Yu, Dong-dong; Zhang, Xing; Feng, Jun-tao

    2014-02-01

    Rarefaction and vacuolization of the mitochondrial matrix of AITC-treated (allyl isothiocyanate-treated) adult Sitophilus zeamais were evident according to the ultra-structural by TEM. Four important enzymes in adult S. zeamais were further studied after fumigation treatment with allyl isothiocyanate (AITC) extracted from Armoracia rusticana roots and shoots. The enzymes were glutathione S-transferase (GST), catalase (CAT), cytochrome c oxidase, and acetylcholinesterase (AChE). The results indicated that the activities of the four enzymes were strongly time and dose depended. With prolonged exposure time, treatment with 0.74μg/mL AITC inhibited the activities of cytochrome c oxidase, AChE, and CAT, but induced the activity of GST. The activities of cytochrome c oxidase, AChE, and CAT were remarkably induced at a low AITC dosage (0.25μg/mL), but were restrained with increased AITC dosage. The activity of GST was inhibited at a low AITC dosage (0.5μg/mL), but was induced at a high AITC dosage (1.5μg/mL). According to the results of TEM, toxic symptoms and enzymes activities, it suggested that mitochondrial maybe the one site of action of AITC against the adult S. zeamais and it also suggested that cytochrome c oxidase maybe one target protein of AITC against the adult S. zeamais, which need to further confirmed by protein function tested. Copyright © 2014 Elsevier Inc. All rights reserved.

  18. Comparative studies on mitochondrial electron transport chain complexes of Sitophilus zeamais treated with allyl isothiocyanate and calcium phosphide.

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    Zhang, Chao; Wu, Hua; Zhao, Yuan; Ma, Zhiqing; Zhang, Xing

    2016-01-01

    With Sitophilus zeamais as the target organism, the present study for the first time attempted to elucidate the comparative effects between allyl isothiocyanate (AITC) and calcium phosphide (Ca3P2), exposure on mitochondrial electron transport chain (ETC.) complex I & IV and their downstream effects on enzymes relevant to reactive oxygen species (ROS). In vivo, both AITC and Ca3P2 inhibited complex I and IV with similar downstream effects. In contrast with Ca3P2, the inhibition of complex I caused by AITC was dependent on time and dose. In vitro, AITC inhibited complex IV more significantly than complex I. These results indicate that mitochondrial complex IV is the primary target of AITC, and that complex I is another potential target. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Correlation of quinone reductase activity and allyl isothiocyanate formation among different genotypes and grades of horseradish roots.

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    Ku, Kang-Mo; Jeffery, Elizabeth H; Juvik, John A; Kushad, Mosbah M

    2015-03-25

    Horseradish (Armoracia rusticana) is a perennial crop and its ground root tissue is used in condiments because of the pungency of the glucosinolate (GS)-hydrolysis products allyl isothiocyanate (AITC) and phenethyl isothiocyanate (PEITC) derived from sinigrin and gluconasturtiin, respectively. Horseradish roots are sold in three grades: U.S. Fancy, U.S. No. 1, and U.S. No. 2 according to the USDA standards. These grading standards are primarily based on root diameter and length. There is little information on whether root grades vary in their phytochemical content or potential health promoting properties. This study measured GS, GS-hydrolysis products, potential anticancer activity (as quinone reductase inducing activity), total phenolic content, and antioxidant activities from different grades of horseradish accessions. U.S. Fancy showed significantly higher sinigrin and AITC concentrations than U.S. No. 1 ,whereas U.S. No. 1 showed significantly higher concentrations of 1-cyano 2,3-epithiopropane, the epithionitrile hydrolysis product of sinigrin, and significantly higher total phenolic concentrations than U.S. Fancy.

  20. Brown seaweed (Saccharina japonica) as an edible natural delivery matrix for allyl isothiocyanate inhibiting food-borne bacteria.

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    Siahaan, Evi Amelia; Pendleton, Phillip; Woo, Hee-Chul; Chun, Byung-Soo

    2014-01-01

    The edible, brown seaweed Saccharina japonica was prepared as powder in the size range 500-900 μm for the desorption release of allyl isothiocyanate (AITC). Powders were used as raw (containing lipids) and as de-oiled, where the lipid was removed. In general, de-oiled powders adsorbed larger masses of AITC after vapour or solution contact. Mass adsorbed due to solution contact exceeded vapour contact. Larger particles adsorbed more than smaller particles. No chemical bonding between AITC and the powder surface occurred. Release from vapour deposited particles reached 70-85% available within 72 h; solution deposited reached 70-90% available at 192 h. The larger amounts of AITC adsorbed via solution deposition resulted in greater vapour-phase concentrations at 72 h for antimicrobial activity studies. No loss of activity was detected against Escherichia coli, Salmonella Typhimurium or Bacillus cereus. Only a nominal activity against Staphylococcus aureus was demonstrated. S. japonica powder could be used as an edible, natural vehicle for AITC delivery. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Allyl isothiocyanate that induces GST and UGT expression confers oxidative stress resistance on C. elegans, as demonstrated by nematode biosensor.

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    Koichi Hasegawa

    Full Text Available BACKGROUND: Electrophilic xenobiotics and endogenous products from oxidative stresses induce the glutathione S-transferases (GSTs, which form a large family within the phase II enzymes over both animal and plant kingdoms. The GSTs thus induced in turn detoxify these external as well as internal stresses. Because these stresses are often linked to ageing and damage to health, the induction of phase II enzymes without causing adverse effects would be beneficial in slowing down ageing and keeping healthy conditions. METHODOLOGY/PRINCIPAL FINDINGS: We have tested this hypothesis by choosing allyl isothiocyanate (AITC, a functional ingredient in wasabi, as a candidate food ingredient that induces GSTs without causing adverse effects on animals' lives. To monitor the GST induction, we constructed a gst::gfp fusion gene and used it to transform Caenorhabditis elegans for use as a nematode biosensor. With the nematode biosensor, we found that AITC induced GST expression and conferred tolerance on the nematode against various oxidative stresses. We also present evidence that the transcription factor SKN-1 is involved in regulating the GST expression induced by AITC. CONCLUSIONS/SIGNIFICANCE: We show the applicability of the nematode biosensor for discovering and evaluating functional food substances and chemicals that would provide anti-ageing or healthful benefits.

  2. Synthesis of 2-(2-R1-Hydrazino-5-(R2-benzyl-2-thiazolines on the Basis of Meerweins Arylation Products of Allyl Isothiocyanate

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    Mykola I. Ganushchak

    2003-02-01

    Full Text Available 3-Aryl-2-chloropropylisothiocyanates (1 are formed by interaction of arenediazonium chlorides with allyl isothiocyanate. Adducts 1 react with monoacylhydrazines to form 1-acyl-4-(3-aryl-2-chloropropylthiosemicarbazides (2a–d. Thiosemicarbazides 2a–d in the presence of bases selectively transform into 2-(2-R1-hydrazino-5-(R2-benzyl-2-thiazolines (3a–d.

  3. Response ofMeteorus leviventris, (Hymenoptera: Braconidae) to mustard oils in field trapping experiments.

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    Pivnick, K A

    1993-09-01

    Trapping experiments were carried out near Saskatoon, Canada, from May through August 1990 to assess the response of the braconid wasp,Meteorus leviventris, to four selected mustard oils or isothiocyanates (IC) at a release rate of 4 mg/day, and for allyl IC only, at 40 mg/day. Only allyl IC at 4 mg/day was significantly attractive when trap captures were compared to the captures in the control traps. The others (n-propyl IC, 2-phenylethyl IC., and ethyl IC) were not attractive, nor was allyl IC at the higher dose, although trap captures with the latter bait were the second highest.

  4. Extraction of allyl isothiocyanate from horseradish (Armoracia rusticana) and its fumigant insecticidal activity on four stored-product pests of paddy.

    Science.gov (United States)

    Wu, Hua; Zhang, Guo-An; Zeng, Shuiyun; Lin, Kai-chun

    2009-09-01

    Isothiocyanates (ITCs) extracted from Armoracia rusticana Gaertn., May & Scherb. have been shown previously to have insecticidal activity. Allyl isothiocyanate (AITC), a major component of ITCs with high volatility, was therefore extracted using different methods and tested as a fumigant against four major pest species of stored products, maize weevil Sitophilus zeamais (Motsch.), lesser grain borer Rhizopertha dominica (F.), Tribolium ferrugineum (F.) and book louse Liposcelis entomophila (Enderlein). Whereas there was no significant difference between hydrodistillation and supercritical carbon dioxide fluid extraction in extraction rate for AITC from A. rusticana, both methods resulted in higher extraction efficiency than water extraction. AITC fumigation showed strong toxicity to the four species of stored-product pests. Adult mortality of 100% of all four pest species, recorded after 72 h exposure to AITC fumes at an atmospheric concentration of 3 microg mL(-1), showed no significant difference from that of insects exposed to phosphine at 5 microg mL(-1), the recommended dose for phosphine. The results suggest good insecticidal efficacy of AITC against the four stored-product pests, with non-gaseous residuals on stored products. AITC obtained from A. rusticana may be an alternative to phosphine and methyl bromide against the four pest species. Copyright 2009 Society of Chemical Industry.

  5. Toxic effects of a horseradish extract and allyl isothiocyanate in the urinary bladder after 13-week administration in drinking water to F344 rats.

    Science.gov (United States)

    Hasumura, Mai; Imai, Toshio; Cho, Young-Man; Ueda, Makoto; Hirose, Masao; Nishikawa, Akiyoshi; Ogawa, Kumiko

    2011-01-01

    Subchronic toxicity of a horseradish extract (HRE), consisting mainly of a mixture of allyl isothiocyanate (AITC) and other isothiocyanates, was investigated with administration at concentrations of 0, 0.0125, 0.025 and 0.05% of HRE in drinking water for 13 weeks to male and female F344 rats. For comparison, treatment with 0.0425% of AITC was similarly performed. Body weight gain was reduced in the 0.05% HRE and AITC males as compared to the 0% controls, and the cause was considered at least partly related to decreased water consumption due to the acrid smell of the test substance and decreased food consumption. Serum biochemistry demonstrated increased urea nitrogen in 0.025 and 0.05% HRE and AITC males and 0.0125-0.05% HRE and AITC females, along with decreased total cholesterol in 0.0125-0.05% HRE females. On histopathological assessment, papillary/nodular hyperplasia of bladder mucosa was observed in 0.05% HRE and AITC males and females, in addition to simple mucosal hyperplasia found in all treated groups. Based on the above findings, no-observed-adverse-effect levels (NOAELs) were estimated to be below 0.0125% of HRE for both males and females, corresponding to 9.4 and 8.0 mg/kg body weight/day, respectively, and there appeared to be comparable toxicological properties of HRE to AITC, such as the inductive effect of significant proliferative lesions in the urinary bladder.

  6. Evaluation of allyl isothiocyanate as a soil fumigant against soil-borne diseases in commercial tomato (Lycopersicon esculentum Mill.) production in China.

    Science.gov (United States)

    Ren, Zongjie; Li, Yuan; Fang, Wensheng; Yan, Dongdong; Huang, Bin; Zhu, Jiahong; Wang, Xiaoning; Wang, Xianli; Wang, Qiuxia; Guo, Meixia; Cao, Aocheng

    2018-03-12

    Root-knot nematodes (Meloidogyne spp.), soil-borne diseases and weeds seriously reduce the commercial yield of tomatoes grown under protected cultivation in China. Allyl isothiocyanate (AITC), a natural product obtained from damaged Brassica tissues, was evaluated as a potential replacement for the fumigant methyl bromide (MB) for use in the greenhouse production of tomatoes in China. The dose-response assay indicates that AITC has high biological activity against major bacterial and fungal pathogens (EC 50 of 0.225-4.199 mg L -1 ). The bioassay results indicate that AITC has good efficacy against root-knot nematodes (LC 50 of 18.046 mg kg -1 ), and moderate efficacy against fungal pathogens (LC 50 of 27.999-29.497 mg kg -1 ) and weeds (LC 50 of 17.300-47.660 mg kg -1 ). The potting test indicates that AITC significantly improved plant vigor. Field trials indicate that AITC showed good efficacy against Meloidogyne spp. and Fusarium spp. (both ∼ 80%) as well as Phytophthora spp. and Pythium spp. (both ∼ 70%), and improved plant vigor and marketable yield. AITC used as a soil fumigant (30-50 g m -2 ) effectively controlled major bacterial and fungal pathogens, root-knot nematode, weeds and increased plant vigor, yield and farmers' income in tomato cultivated under protected agriculture in China. © 2018 Society of Chemical Industry. © 2018 Society of Chemical Industry.

  7. Degradation of Biofumigant Isothiocyanates and Allyl Glucosinolate in Soil and Their Effects on the Microbial Community Composition.

    Directory of Open Access Journals (Sweden)

    Franziska S Hanschen

    Full Text Available Brassicales species rich in glucosinolates are used for biofumigation, a process based on releasing enzymatically toxic isothiocyanates into the soil. These hydrolysis products are volatile and often reactive compounds. Moreover, glucosinolates can be degraded also without the presence of the hydrolytic enzyme myrosinase which might contribute to bioactive effects. Thus, in the present study the stability of Brassicaceae plant-derived and pure glucosinolates hydrolysis products was studied using three different soils (model biofumigation. In addition, the degradation of pure 2-propenyl glucosinolate was investigated with special regard to the formation of volatile breakdown products. Finally, the influence of pure glucosinolate degradation on the bacterial community composition was evaluated using denaturing gradient gel electrophoresis of 16S rRNA gene amplified from total community DNA. The model biofumigation study revealed that the structure of the hydrolysis products had a significant impact on their stability in the soil but not the soil type. Following the degradation of pure 2-propenyl glucosinolate in the soils, the nitrile as well as the isothiocyanate can be the main degradation products, depending on the soil type. Furthermore, the degradation was shown to be both chemically as well as biologically mediated as autoclaving reduced degradation. The nitrile was the major product of the chemical degradation and its formation increased with iron content of the soil. Additionally, the bacterial community composition was significantly affected by adding pure 2-propenyl glucosinolate, the effect being more pronounced than in treatments with myrosinase added to the glucosinolate. Therefore, glucosinolates can have a greater effect on soil bacterial community composition than their hydrolysis products.

  8. Diffusion and sorption of allyl isothiocyanate in the process of fumigation of maize Difusão e sorção do isotiocianato alilo no processo de fumigação do milho

    Directory of Open Access Journals (Sweden)

    Juliana L. Paes

    2011-03-01

    Full Text Available The purpose of this work was to evaluate the transport of allyl isothiocyanate (AITC by means of the sorption mechanism and the diffusion of AITC through maize grains. The experimental procedure to study the sorption mechanism was conducted by injection of AITC in glass flasks containing the grains. Kinetic models of zero, first and second order were fitted to AITC concentration data, with the purpose of determining the sorption rate (k. For the study of diffusion, a prototype was utilized in which the components are a gas chamber and a cylindrical column in which the grains were stored. At the interval of 110 min, samples in the chamber and in the column were collected, which were immediately injected into the gas chromatograph. In order to determine the effective diffusion coefficient (Def of AITC through maize grains, the term referring to the sorption rate was added to the diffusion equation. The kinetic model of the first order was the one that best fitted the experimental data for the sorption mechanism, and k was 6.26 x 10-4 s-1. The Def of AITC through grains was 7.2 x 10-3 cm² s-1. It was concluded that the transport of AITC through maize grains is slow, due to the low value of Def and high sorption rate of this component by the grains.Neste trabalho o propósito foi avaliar o transporte do isotiocianato alilo (AITC, por meio do estudo do mecanismo de sorção e da difusão do AITC, nos grãos de milho. O procedimento experimental para o estudo da sorção foi conduzido pela injeção de AITC em frascos de vidro contendo os grãos. Modelos cinéticos de ordem zero, de primeira e de segunda ordem, foram ajustados aos dados de concentração do AITC com a finalidade de determinar a taxa de sorção (k. Para o estudo da difusão utilizou-se um protótipo em que os componentes são uma câmara de gás e uma coluna cilíndrica, para contenção dos grãos. A cada 110 min amostras na câmara e na coluna foram coletadas e imediatamente

  9. Antifungal Activity of Volatile Oil of Mustard (VOM)

    National Research Council Canada - National Science Library

    Sikes, A; Yang, T; Richardson, M; Ehioba, R

    2005-01-01

    .... The active volatile antimicrobial factor in VOM is allyl isothiocyanate (AIT). To evaluate the efficacy of VOM as a fungistatic agent, military-type sandwiches and commercial cheddar cheese samples were inoculated with several mold isolates...

  10. Isothiocyanates: a review

    OpenAIRE

    Chandra Kala*; Syed Salman Ali; Nabeel Ahmad; Sadaf Jamal Gilani; Najam Ali Khan

    2018-01-01

    Isothiocyanates (ITCs) are naturally occurring molecules belonging to highly reactive organosulphur synthons, with the general structure R–N=C=S. The precursor molecule glucosinolate anions are hydrolyzed enzymatically (under the effect of myrosinase enzymes) or unenzymatically to produce nitriles or isothiocyanates depending upon conditions such as pH and temperature. Brassicaceae  Family is known to contain abundant ITCs. A significant number of isothiocyanates has been isolated from differ...

  11. Isothiocyanates: a review

    Directory of Open Access Journals (Sweden)

    Chandra Kala*

    2018-04-01

    Full Text Available Isothiocyanates (ITCs are naturally occurring molecules belonging to highly reactive organosulphur synthons, with the general structure R–N=C=S. The precursor molecule glucosinolate anions are hydrolyzed enzymatically (under the effect of myrosinase enzymes or unenzymatically to produce nitriles or isothiocyanates depending upon conditions such as pH and temperature. Brassicaceae  Family is known to contain abundant ITCs. A significant number of isothiocyanates has been isolated from different plant sources and some of them have been synthesized. Several isothiocyanates have demonstrated significant pharmacological activities including anti-cancer, anti-inflammatory, anti-microbial activities, etc. Pharmacokinetic profiles of these sulphur containing compounds are well established. However, safety profiles of ITCs need consideration and a well-designed study with appropriate control, for their production as lead compounds. This review summarises the chemistry, sources, pharmacokinetics, pharmacological activity and toxicity profiles of the isothiocyanates.

  12. Sulfur Mustard

    Science.gov (United States)

    ... in of the vapors can cause chronic respiratory disease, repeated respiratory infections, or death. Extensive eye exposure can cause permanent blindness. Exposure to sulfur mustard may increase a person’s risk for lung and respiratory cancer. ...

  13. The effect of allyl isothiocyanate on RNA | Habibi | Journal of ...

    African Journals Online (AJOL)

    In this study, the interaction of Allylisothiocyanate with yeast RNA in aqueous solution at physiological conditions using constant RNA concentration and various molar ratios of AITC/RNA complexes are examine. Fourier transform infrared (FTIR) and uv-visible difference spectroscopic methods are used to determine the ...

  14. Antimicrobial Activity of Isothiocyanates from Cruciferous Plants against Methicillin-Resistant Staphylococcus aureus (MRSA

    Directory of Open Access Journals (Sweden)

    Carla Dias

    2014-10-01

    Full Text Available Purified isothiocyanates from cruciferous plants (Brassicacea, Syn. Cruciferae plants were evaluated against 15 isolates of methicillin-resistant S. aureus isolated from diabetic foot-ulcer patients aiming the study of the potential usage of allyl-isothiocyanate, benzyl-isothiocyanate and 2-phenylethyl-isothiocyanate against this important bacteria. Disc diffusion and minimum inhibitory concentration methods were used to access the antimicrobial activity. The index (Ia and rate (Ra of the antibacterial activity for each compound were calculated. The results showed a highly dose-dependent compound and chemical structure antibacterial effectiveness. The results showed a strong relation between the chemical structure of isothiocyanates and its antibacterial effectiveness. The benzyl-isothiocyanate was the most effective with a minimum inhibitory concentration varying between 2.9 and 110 µg·mL−1 with an antibacterial activity rate up to 87%. Moreover, their antibacterial activity was mainly bactericidal. This study provides scientific evidence that isothiocyanates have an interesting biological value and must be considered as an important tool to be used against MRSA.

  15. Antimicrobial activities of isothiocyanates against Campylobacter jejuni isolates

    Directory of Open Access Journals (Sweden)

    Virginie eDufour

    2012-04-01

    Full Text Available Food-borne human infection with Campylobacter jejuni is a medical concern in both industrialized and developing countries. Efficient eradication of C. jejuni reservoirs within live animals and processed foods is limited by the development of antimicrobial resistances and by practical problems related to the use of conventional antibiotics in food processes.We have investigated the bacteriostatic and bactericidal activities of two phytochemicals, allyl-isothiocyanate (AITC and benzyl-isothiocyanate (BITC, against 24 C. jejuni isolates from chicken feces, human infections and contaminated foods, as well as two reference strains NCTC11168 and 81-176.Both AITC and BITC displayed a potent antibacterial activity against C. jejuni. BITC showed a higher overall antibacterial effect (MIC of 2.5 to 5 g mL-1 compared to AITC (MIC of 50 to 200 g mL-1. Interestingly, the 24 C. jejuni isolates could be classified in 3 groups according to their sensitivity levels to both compounds, suggesting that AITC and BITC shared identical activity mechanisms and consequently faced similar resistance processes in bacterial cells.The sensitivity levels of C. jejuni strains against isothiocyanates were neither correlated with the presence of a GGT (-Glutamyl Transpeptidase encoding gene in the genome nor with the origin of the biological sample. However the ggt mutant of C. jejuni 81-176 displayed a decreased survival rate compared to WT when exposed to ITC.

  16. Regiospecific decarboxylative allylation of nitriles

    Science.gov (United States)

    Recio, Antonio; Tunge, Jon A.

    2009-01-01

    Palladium-catalyzed decarboxylative α-allylation of nitriles readily occurs using Pd2(dba)3 and rac-BINAP. This catalyst mixture also allows the highly regiospecific α-allylation of nitriles in the presence of much more acidic α-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement. PMID:19921827

  17. Contact Hwersensitaity to Mustard Khal and Mustard Oil

    Directory of Open Access Journals (Sweden)

    J S Pasricha

    1985-01-01

    Full Text Available This report describes 2 females patients having contact dermatitis due to mustard khal the residue of,mustard seeds after the oil hasbeen extracted out. The dermatitis was caused by mbdng mustard khal with the cattle feed and was occurring on the hands and forearms, though the face, ear lobules and neck were also mvolved because of the practice of applying mustard oil on the hair. Patch tests were positive with the mustard khal and its fractionation products in both the patients and with mustard oil in one patient.

  18. Consumer acceptability and sensory profile of cooked broccoli with mustard seeds added to improve chemoprotective properties.

    Science.gov (United States)

    Ghawi, Sameer Khalil; Shen, Yuchi; Niranjan, Keshavan; Methven, Lisa

    2014-09-01

    Broccoli, a rich source of glucosinolates, is a commonly consumed vegetable of the Brassica family. Hydrolysis products of glucosinolates, isothiocyanates, have been associated with health benefits and contribute to the flavor of Brassica. However, boiling broccoli causes the myrosinase enzyme needed for hydrolysis to denature. In order to ensure hydrolysis, broccoli must either be mildly cooked or active sources of myrosinase, such as mustard seed powder, can be added postcooking. In this study, samples of broccoli were prepared in 6 different ways; standard boiling, standard boiling followed by the addition of mustard seeds, sous vide cooking at low temperature (70 °C) and sous vide cooking at higher temperature (100 °C) and sous vide cooking at higher temperature followed by the addition of mustard seeds at 2 different concentrations. The majority of consumers disliked the mildly cooked broccoli samples (70 °C, 12 min, sous vide) which had a hard and stringy texture. The highest mean consumer liking was for standard boiled samples (100 °C, 7 min). Addition of 1% mustard seed powder developed sensory attributes, such as pungency, burning sensation, mustard odor, and flavor. One cluster of consumers (32%) found mustard seeds to be a good complement to cooked broccoli; however, the majority disliked the mustard-derived sensory attributes. Where the mustard seeds were partially processed, doubling the addition to 2% led to only the same level of mustard and pungent flavors as 1% unprocessed seeds, and mean consumer liking remained unaltered. This suggests that optimization of the addition level of partially processed mustard seeds may be a route to enhance bioactivity of cooked broccoli without compromising consumer acceptability. © 2014 Institute of Food Technologists®

  19. Preconditioning with subneurotoxic allyl nitrile: protection against allyl nitrile neurotoxicity.

    Science.gov (United States)

    Tanii, H; Higashi, T; Saijoh, K

    2010-02-01

    High-dose cruciferous allyl nitrile can induce behavioral abnormalities in rodents, while repeated exposure to allyl nitrile at subneurotoxic levels can increase phase 2 detoxification enzymes in many tissues, although the brain has not been investigated yet. In the present study, we examined the effect of 5 days repeated exposure to subneurotoxic allyl nitrile (0-400 micromol/kg/day) on the brain. Elevated glutathione S-transferase activity was recorded in the striatum, hippocampus, medulla oblongata plus pons, and cortex. Enhancement of quinone reductase activity was observed in the medulla oblongata plus pons, hippocampus, and cortex. In the medulla oblongata plus pons, elevated glutathione levels were recorded. Following repeated subneurotoxic allyl nitrile exposure (0-400 micromol/kg/day), mice were administered a high-dose allyl nitrile (1.2 mmol/kg) which alone led to appearance of behavioral abnormalities. Compared with the 0 micromol/kg/day group, animals in the 200 and 400 micromol/kg/day pre-treatment groups exhibited decreased behavioral abnormalities and elevated GABA-positive cell counts in the substantia nigra pars reticulata and the interpeduncular nucleus. These data suggest that repeated exposure to subneurotoxic levels of allyl nitrile can induce phase 2 enzymes in the brain, which together with induction in other tissues, may contribute to protection against allyl nitrile neurotoxicity. Copyright 2009 Elsevier Ltd. All rights reserved.

  20. Soil bacterial and fungal communities respond differently to various isothiocyanates added for biofumigation

    Directory of Open Access Journals (Sweden)

    Ping eHu

    2015-01-01

    Full Text Available The meals from many oilseed crops have potential for biofumigation due to their release of biocidal compounds such as isothiocyanates (ITCs. Various ITCs are known to inhibit numerous pathogens; however, much less is known about how the soil microbial community responds to the different types of ITCs released from oilseed meals (SMs. To simulate applying ITC-releasing SMs to soil, we amended soil with 1% flax SM (contains no biocidal chemicals along with four types of ITCs (allyl, butyl, phenyl, and benzyl ITC in order to determine their effects on soil fungal and bacterial communities in a replicated microcosm study. Microbial communities were analyzed based on the ITS region for fungi and 16S rRNA gene for bacteria using qPCR and tag-pyrosequencing with 454 GS FLX titanium technology. A dramatic decrease in fungal populations (~85% reduction was observed after allyl ITC addition. Fungal community compositions also shifted following ITC amendments (e.g., Humicola increased in allyl and Mortierella in butyl ITC amendments. Bacterial populations were less impacted by ITCs, although there was atransient increase in the proportion of Firmicutes, related to bacteria know to be antagonistic to plant pathogens, following amendment with allyl ITC. Our results indicate that the type of ITC released from SMs can result in differential impacts on soil microorganisms. This information will aid selection and breeding of plants for biofumigation-based control of soil-borne pathogens while minimizing the impacts on non-target microorganisms.

  1. Tsuji-Trost N-allylation with allylic acetates using cellulose-Pd catalyst

    Science.gov (United States)

    Allylic amines are synthesized using heterogeneous cellulose-Pd catalyst via N-allylation of amines; aliphatic and benzyl amines undergo facile reaction with substituted and unsubstituted allyl acetates in high yields.

  2. Contact Hwersensitaity to Mustard Khal and Mustard Oil

    OpenAIRE

    J S Pasricha; Ramji Gupta; S K Gupta

    1985-01-01

    This report describes 2 females patients having contact dermatitis due to mustard khal the residue of,mustard seeds after the oil hasbeen extracted out. The dermatitis was caused by mbdng mustard khal with the cattle feed and was occurring on the hands and forearms, though the face, ear lobules and neck were also mvolved because of the practice of applying mustard oil on the hair. Patch tests were positive with the mustard khal and its fractionation products in both the patients and with must...

  3. Brassicaceae Mustards: Traditional and Agronomic Uses in Australia and New Zealand

    OpenAIRE

    Mahmudur Rahman; Amina Khatun; Lei Liu; Bronwyn J. Barkla

    2018-01-01

    Commonly cultivated Brassicaceae mustards, namely garlic mustard (Alliaria petiolata), white mustard (Brassica alba), Ethiopian mustard (B. carinata), Asian mustard (B. juncea), oilseed rape (B. napus), black mustard (B. nigra), rapeseed (B. rapa), white ball mustard (Calepina irregularis), ball mustard (Neslia paniculata), treacle mustard (Erysimum repandum), hedge mustard (Sisymbrium officinale), Asian hedge mustard (S. orientale), smooth mustard (S. erysimoides) and canola are the major ec...

  4. Optimized Formation of Benzyl Isothiocyanate by Endogenous ...

    African Journals Online (AJOL)

    The formed benzyl isothiocyanate was extracted by steam distillation method and purified by thin-layer chromatography (TLC). Relevant process variables were also studied. Finally, the purified benzyl isothiocyanate was analyzed by gas chromatography-mass spectrometer (GC-MS) and compared to BITC standard.

  5. Endophytic fungi from the roots of horseradish (Armoracia rusticana) and their interactions with the defensive metabolites of the glucosinolate - myrosinase - isothiocyanate system.

    Science.gov (United States)

    Szűcs, Zsolt; Plaszkó, Tamás; Cziáky, Zoltán; Kiss-Szikszai, Attila; Emri, Tamás; Bertóti, Regina; Sinka, László Tamás; Vasas, Gábor; Gonda, Sándor

    2018-05-09

    The health of plants is heavily influenced by the intensively researched plant microbiome. The microbiome has to cope with the plant's defensive secondary metabolites to survive and develop, but studies that describe this interaction are rare. In the current study, we describe interactions of endophytic fungi with a widely researched chemical defense system, the glucosinolate - myrosinase - isothiocyanate system. The antifungal isothiocyanates are also of special interest because of their beneficial effects on human consumers. Seven endophytic fungi were isolated from horseradish roots (Armoracia rusticana), from the genera Fusarium, Macrophomina, Setophoma, Paraphoma and Oidiodendron. LC-ESI-MS analysis of the horseradish extract incubated with these fungi showed that six of seven strains could decompose different classes of glucosinolates. Aliphatic, aromatic, thiomethylalkyl and indolic glucosinolates were decomposed by different strains at different rates. SPME-GC-MS measurements showed that two strains released significant amounts of allyl isothiocyanate into the surrounding air, but allyl nitrile was not detected. The LC-ESI-MS analysis of many strains' media showed the presence of allyl isothiocyanate - glutathione conjugate during the decomposition of sinigrin. Four endophytic strains also accepted sinigrin as the sole carbon source. Isothiocyanates inhibited the growth of fungi at various concentrations, phenylethyl isothiocyanate was more potent than allyl isothiocyanate (mean IC 50 was 2.30-fold lower). As a control group, ten soil fungi from the same soil were used. They decomposed glucosinolates with lower overall efficiency: six of ten strains had insignificant or weak activities and only three could use sinigrin as a carbon source. The soil fungi also showed lower AITC tolerance in the growth inhibition assay: the median IC 50 values were 0.1925 mM for endophytes and 0.0899 mM for soil fungi. The host's glucosinolates can be used by the tested

  6. Allyl nitrile: Toxicity and health effects.

    Science.gov (United States)

    Tanii, Hideji

    2017-03-28

    Allyl nitrile (3-butenenitrile) occurs naturally in the environment, in particular, in cruciferous vegetables, indicating a possible daily intake of the compound. There is no report on actual health effects of allyl nitrile in humans, although it is possible that individuals in the environment are at a risk of exposure to allyl nitrile. However, little is known about its quantitative assessment for the environment and bioactivity in the body. This study provides a review of previous accumulated studies on allyl nitrile. Published literature on allyl nitrile was examined for findings on toxicity, metabolism, risk of various cancers, generation, intake estimates, and low-dose effects in the body. High doses of allyl nitrile produce toxicity characterized by behavioral abnormalities, which are considered to be produced by an active metabolite, 3,4-epoxybutyronitrile. Cruciferous vegetables have been shown to have a potential role in reducing various cancers. Hydrolysis of the glucosinolate sinigrin, rich in cruciferous vegetables, results in the generation of allyl nitrile. An intake of allyl nitrile is estimated at 0.12 μmol/kg body weight in Japan. Repeated exposure to low doses of allyl nitrile upregulates antioxidant/phase II enzymes in various tissues; this may contribute to a reduction in neurotoxicity and skin inflammation. These high and low doses are far more than the intake estimate. Allyl nitrile in the environment is a compound with diverse bioactivities in the body, characterized by inducing behavioral abnormalities at high doses and some antioxidant/phase II enzymes at low doses.

  7. The rapid generation of isothiocyanates in flow

    Directory of Open Access Journals (Sweden)

    Marcus Baumann

    2013-08-01

    Full Text Available Isothiocyanates are versatile starting materials for a wide range of chemical reactions. However, their high nucleophilic susceptibility means they are best prepared and used immediately. We report here on a flow platform for the fast and efficient formation of isothiocyanates by the direct conversion of easily prepared chloroximes. To expedite this chemistry a flow insert cartridge containing two immobilised reagents is used to affect the chemical transformation which typically eliminates the requirements for any conventional work-up or purification of the reaction stream.

  8. Optimized Formation of Benzyl Isothiocyanate by Endogenous ...

    African Journals Online (AJOL)

    Purpose: To use endogenous myrosinase in Carica papaya seed to convert benzyl glucosinolate (BG) to benzyl isothiocyanate (BITC) and then extract it for further studies. Methods: Process variables including seed powder particle size, sample-to-solvent ratio, pH of buffer solution, enzymolysis temperature, enzymolysis ...

  9. Dietary isothiocyanate sulforaphene induces reactive oxygen ...

    African Journals Online (AJOL)

    Purpose: To investigate the apoptotic activity, cell proliferation inhibition and different signaling protein expressions after treatment with a new isothiocyanate, sulforaphene, in human cervical cancer (HeLa) cells. Methods: Cytotoxicity was analyzed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay ...

  10. Compound list: naphthyl isothiocyanate [Open TG-GATEs

    Lifescience Database Archive (English)

    Full Text Available naphthyl isothiocyanate ANIT 00009 ftp://ftp.biosciencedbc.jp/archive/open-tggates/...LATEST/Human/in_vitro/naphthyl_isothiocyanate.Human.in_vitro.Liver.zip ftp://ftp.biosciencedbc.jp/archive/op...en-tggates/LATEST/Rat/in_vitro/naphthyl_isothiocyanate.Rat.in_vitro.Liver.zip ftp://ftp.biosciencedbc.jp/arc...hive/open-tggates/LATEST/Rat/in_vivo/Liver/Single/naphthyl_isothiocyanate.Rat.in_...vivo.Liver.Single.zip ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Liver/Repeat/naphthyl_isothiocyanate.Rat.in_vivo.Liver.Repeat.zip ...

  11. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu

    2013-05-17

    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  12. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu; Zhu, Bo; Lee, Richmond; Yang, Wenguo; Tan, Davin; Yang, Caiyun; Han, Zhiqiang; Yan, Lin; Huang, Kuo-Wei; Jiang, Zhiyong

    2013-01-01

    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  13. Compound list: allyl alcohol [Open TG-GATEs

    Lifescience Database Archive (English)

    Full Text Available allyl alcohol AA 00010 ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Human/in_vitro/allyl_alcohol....Human.in_vitro.Liver.zip ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vitro/allyl_alcohol...dbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Liver/Repeat/allyl_alcohol.Rat.in_vivo.Liver.Repeat.zip ftp:/.../ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Kidney/Single/allyl_alcohol.Rat.in_vivo.Kidney....Single.zip ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Kidney/Repeat/allyl_alcohol.Rat.in_vivo.Kidney.Repeat.zip ...

  14. Effect of white mustard essential oil on inoculated Salmonella sp. in a sauce with particulates.

    Science.gov (United States)

    David, Jairus R D; Ekanayake, Athula; Singh, Indarpal; Farina, Brian; Meyer, Michael

    2013-04-01

    White mustard essential oil (WMEO), from white mustard seed (Sinapis alba L.), is obtained by solvent extraction of defatted and wetted ground mustard; endogenous myrosinase catalyzes the hydrolysis of the glucosinolate sinalbin to yield 4-hydroxybenzyl isothiocyanate (4-HBITC), the antimicrobial component of WMEO. Sauce with particulates was made by mixing sauce, which served as the carrier for WMEO, with frozen vegetable and chicken particulates inoculated with Salmonella sp. WMEO (at 250 to 750 ppm of 4-HBITC) was able to reduce inoculated Salmonella counts by 0.8 to 2.7 log (CFU/g) in a frozen sauce with particulates in a dose-dependent manner, starting from the point of formulating the sauce through the microwave cooking step. High-pressure liquid chromatography-based analytical data confirmed that 4-HBITC was present in all of the samples in the expected concentrations and was completely hydrolyzed after the recommended cooking time in microwave ovens. In another experiment simulating unintentional abuse conditions, where the WMEO containing sauce with particulates was kept at room temperature for 5 h, WMEO (at 250 to 750 ppm of 4-HBITC) was able to reduce inoculated Salmonella counts from the point of first contact and up to 5 h by 0.7 to 2.4 log (CFU/g). Despite the known hydrolytic instability of the active component 4-HBITC, particularly at close to neutral pH values, WMEO was effective in controlling deliberately inoculated Salmonella sp. in a frozen sauce with particulates.

  15. Glucosinolates and isothiocyanates from broccoliseed extractsuppressproteinglycationand carbonylation

    Directory of Open Access Journals (Sweden)

    Marina Hirano,

    2018-01-01

    Full Text Available Background: Glucosinolates from brassica plants are hydrolyzed by internal or salivary myrosinase to produce isothiocyanates. Glucoraphanin, a major glucosinolate in broccoli, is hydrolyzed to sulforaphane (SFN, which exhibits antitumor and detoxification activities. Regarding the influence of broccoli and its constituents on the skin, a few studies have reported anti-inflammatory and antioxidant effects. Recently, advanced glycation end products (AGEs and carbonyl proteins have been reported to accelerate skin aging. Objective: We evaluated the effects of broccoli seed extract (BSE and glucosinolates on protein glycation and carbonylation in vitro. Methods: To evaluate the effects of BSE and its constituents, protein glycation and carbonylation were induced by mixing fructose with bovine serum albumin (BSA and then measuring production of AGEs, fructosamine, and carbonyl proteins (CP. Production of CP after mixing fatty acids with BSA was also assessed. Furthermore, the effect of BSE and its constituents on CP production by human fibroblasts (TIG103 was examined. Results: BSE suppressed the production of AGEs, fructosamine, and CP after mixing fructose and BSA. BSE also suppressed production of CP when oxidized linoleic acid was mixed with BSA. Isothiocyanates, including SFN and iberin, suppressed fructose-based CP production, but SFN had no effect on CP production stimulated by oxidized linoleic acid. In contrast, glucosinolates from BSE did not suppress fructose-based CP production, but suppressed CP production due to oxidized linoleic acid. Among the glucosinolates in BSE, glucoberteroin showed the strongest suppression of CP production. CP production in fibroblasts was also suppressed by glucosinolates, including glucoiberin and glucoberteroin. Conclusions: BSE demonstrated anti-glycation and anti-carbonylation effects on protein reactions with fructose and oxidized fatty acids. Isothiocyanates suppressed protein carbonylation induced by

  16. Two-dimensional NMR studies of allyl palladium complexes of ...

    Indian Academy of Sciences (India)

    Administrator

    h3-Allyl complexes are intermediates in organic synthetic reactions such as allylic alkylation and amination. There is growing interest in understanding the structures of chiral h3-allyl intermediates as this would help to unravel the mechanism of enantioselective C–C bond forming reactions. Two-dimensional NMR study is a.

  17. Palladium-catalyzed allylation of tautomerizable heterocycles with alkynes.

    Science.gov (United States)

    Lu, Chuan-Jun; Chen, Dong-Kai; Chen, Hong; Wang, Hong; Jin, Hongwei; Huang, Xifu; Gao, Jianrong

    2017-07-21

    A method for the allylic amidation of tautomerizable heterocycles was developed by a palladium catalyzed allylation reaction with 100% atom economy. A series of structurally diverse N-allylic substituted heterocycles can be synthesized in good yields with high chemo-, regio-, and stereoselectivities under mild conditions.

  18. Ocular Effects of Sulfur Mustard

    Directory of Open Access Journals (Sweden)

    Yunes Panahi

    2013-06-01

    Full Text Available Purpose: To review current knowledge about ocular effects of sulfur mustard (SM and the associated histopathologic findings and clinical manifestationsMethods: Literature review of medical articles (human and animal studies was accomplished using PubMed, Scopus and ISI databases. A total of 274 relevant articles in English were retrieved and reviewed thoroughly.Results: Eyes are the most sensitive organs to local toxic effects of mustard gas. Ocular injuries are mediated through different toxic mechanisms including: biochemical damages, biomolecular and gene expression modification, induction of immunologic and inflammatory reactions, disturbing ultrastructural architecture of the cornea, and long-lasting corneal denervation. The resulting ocular injuries can roughly be categorized into acute or chronic complications. Most of the patients recover from acute injuries, but a minority of victims will suffer from chronic ocular complications. Mustard gas keratopathy (MGK is a devastating late complication of SM intoxication that proceeds from limbal stem cell deficiency (LSCD.Conclusion: SM induces several different damaging changes in case of ocular exposure; hence leading to a broad spectrum of ocular manifestations in terms of severity, timing and form. Unfortunately, no effective strategy has been introduced yet to inhibit or restore these damaging changes.

  19. Fluorescein isothiocyanate: Molecular characterization by theoretical calculations

    Energy Technology Data Exchange (ETDEWEB)

    Casanovas, Jordi [Departament de Quimica, Escola Politecnica Superior, Universitat de Lleida, c/Jaume II No 69, Lleida E-25001 (Spain); Jacquemin, Denis [Laboratoire de Chimie Theorique Appliquee, Facultes Universitaires Notre-Dame de la Paix, rue de Bruxelles, 61, B-5000 Namur (Belgium)], E-mail: denis.jacquemin@fundp.ac.be; Perpete, Eric A. [Laboratoire de Chimie Theorique Appliquee, Facultes Universitaires Notre-Dame de la Paix, rue de Bruxelles, 61, B-5000 Namur (Belgium); Aleman, Carlos [Departament d' Enginyeria Quimica, E. T. S. d' Enginyeria Industrial de Barcelona, Universitat Politecnica de Catalunya, Diagonal 647, Barcelona E-08028 (Spain)], E-mail: carlos.aleman@upc.edu

    2008-12-10

    Quantum mechanical calculations have been used to investigate the conformation, molecular geometry, basicity and spectroscopic properties of fluorescein isothiocyanate in both the gas-phase and aqueous solution. Specifically, calculations have been performed considering the neutral, monoanionic and dianionic forms of this important fluorescent compound. Results reveal that for the neutral form multiple conformational states are possible, all them with significant contributions, and the stability of the different conformers is similar in the gas-phase and aqueous solution. Calculation of the excitation energies revealed that spectroscopic properties are very sensitive to the relaxation effect in solution. A good agreement has been reached obtained between the experimental and theoretical values derived from time-dependent density functional theory methods for the neutral form, whereas for charged species the calculations fail to accurately reproduce the measured trends.

  20. Sinalbin degradation products in mild yellow mustard paste

    OpenAIRE

    Paunović, Dragana; Šolević-Knudsen, Tatjana; Krivokapić, Mirjana; Zlatković, Branislav; Antić, Mališa

    2012-01-01

    Sinalbin degradation products in mild yellow mustard paste were investigated. The analyzed material consisted of a mild yellow mustard paste condiment and ground white mustard seeds which were originally used in the mustard paste production process. The samples were extracted in a Soxhlet extraction system and analyzed by gas chromatography - mass spectrometry (GC-MS) technique. The only sinalbin degradation product in ground mustard seeds was 2-(4-hydroxyphenyl)acetonitrile. The most a...

  1. Peptide Reactivity of Isothiocyanates - Implications for Skin Allergy

    Science.gov (United States)

    Karlsson, Isabella; Samuelsson, Kristin; Ponting, David J.; Törnqvist, Margareta; Ilag, Leopold L.; Nilsson, Ulrika

    2016-02-01

    Skin allergy is a chronic condition that affects about 20% of the population of the western world. This disease is caused by small reactive compounds, haptens, able to penetrate into the epidermis and modify endogenous proteins, thereby triggering an immunogenic reaction. Phenyl isothiocyanate (PITC) and ethyl isothiocyanate (EITC) have been suggested to be responsible for allergic skin reactions to chloroprene rubber, the main constituent of wetsuits, orthopedic braces, and many types of sports gear. In the present work we have studied the reactivity of the isothiocyanates PITC, EITC, and tetramethylrhodamine-6-isothiocyanate (6-TRITC) toward peptides under aqueous conditions at physiological pH to gain information about the types of immunogenic complexes these compounds may form in the skin. We found that all three compounds reacted quickly with cysteine moieties. For PITC and 6-TRITC the cysteine adducts decomposed over time, while stable adducts with lysine were formed. These experimental findings were verified by DFT calculations. Our results may suggest that the latter are responsible for allergic reactions to isothiocyanates. The initial adduct formation with cysteine residues may still be of great importance as it prevents hydrolysis and facilitates the transport of isothiocyanates into epidermis where they can form stable immunogenic complexes with lysine-containing proteins.

  2. Effects of Brassicaceae Isothiocyanates on Prostate Cancer

    Directory of Open Access Journals (Sweden)

    Silvia Novío

    2016-05-01

    Full Text Available Despite the major progress made in the field of cancer biology, cancer is still one of the leading causes of mortality, and prostate cancer (PCa is one of the most encountered malignancies among men. The effective management of this disease requires developing better anticancer agents with greater efficacy and fewer side effects. Nature is a large source for the development of chemotherapeutic agents, with more than 50% of current anticancer drugs being of natural origin. Isothiocyanates (ITCs are degradation products from glucosinolates that are present in members of the family Brassicaceae. Although they are known for a variety of therapeutic effects, including antioxidant, immunostimulatory, anti-inflammatory, antiviral and antibacterial properties, nowadays, cell line and animal studies have additionally indicated the chemopreventive action without causing toxic side effects of ITCs. In this way, they can induce cell cycle arrest, activate apoptosis pathways, increase the sensitivity of resistant PCa to available chemodrugs, modulate epigenetic changes and downregulate activated signaling pathways, resulting in the inhibition of cell proliferation, progression and invasion-metastasis. The present review summarizes the chemopreventive role of ITCs with a particular emphasis on specific molecular targets and epigenetic alterations in in vitro and in vivo cancer animal models.

  3. Pressure Dependent Product Formation in the Photochemically Initiated Allyl + Allyl Reaction

    Directory of Open Access Journals (Sweden)

    Thomas Zeuch

    2013-11-01

    Full Text Available Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn’s largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions. The allyl radicals were produced from laser flash photolysis of three different precursors allyl bromide (C3H5Br, allyl chloride (C3H5Cl, and 1,5-hexadiene (CH2CH(CH22CHCH2 at 193 nm. Stable products were identified by their characteristic vibrational modes and quantified using FTIR spectroscopy. In addition to the (re- combination pathway C3H5+C3H5 → C6H10 we found at low pressures around 1 mbar the highest final product yields for allene and propene for the precursor C3H5Br. A kinetic analysis indicates that the end product formation is influenced by specific reaction kinetics of photochemically activated allyl radicals. Above 10 mbar the (re- combination pathway becomes dominant. These findings exemplify the specificities of reaction kinetics involving chemically activated species, which for certain conditions cannot be simply deduced from combustion kinetics or atmospheric chemistry on Earth.

  4. SYNTHESIS OF ALLYL PHENYL ETHER AND CLAISEN REARRANGEMENT

    Directory of Open Access Journals (Sweden)

    Gagik Torosyan

    2011-12-01

    Full Text Available It has been established the possibility for phenol allylation on natural zeolites and them analogs. Here is demonstrated the synthesis of allyl phenol, which has wide industrial applications. The offered method in comparison with the traditional methods has more advantages – higher selectivity, smaller material and power resources consumption. It has been obtained the mixture of allylating phenols (30% in general with allyl phenyl ether (1 with 80% yields. At 600 K is obtained allylphenyl ether, at 700 K beginning the formation of allyl phenols, which is the result of direct C-allylation of the aromatic ring. It has been investigated the possibility of Claisen rearrangement in the same conditions. All of that are established by gas-liquid chromatography and liquid chromatography data.

  5. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...... for the development of allylic C-H alkylation into a widely applicable methodology, thus providing a means to enhance synthetic efficiency in these reactions....

  6. Sulfur Mustard Damage to Cornea: Preventive Studies

    National Research Council Canada - National Science Library

    Varma, Shambhu

    2004-01-01

    Studies are in progress to determine the efficacy and mechanism of a formulation containing anti-alkylating, antioxidants and metabolic accelerators present in VM against mustard induced skin toxicity...

  7. Sinalbin degradation products in mild yellow mustard paste

    Directory of Open Access Journals (Sweden)

    Paunović Dragana

    2012-01-01

    Full Text Available Sinalbin degradation products in mild yellow mustard paste were investigated. The analyzed material consisted of a mild yellow mustard paste condiment and ground white mustard seeds which were originally used in the mustard paste production process. The samples were extracted in a Soxhlet extraction system and analyzed by gas chromatography - mass spectrometry (GC-MS technique. The only sinalbin degradation product in ground mustard seeds was 2-(4-hydroxyphenylacetonitrile. The most abundant sinalbin degradation product in yellow mustard paste was 4-(hydroxymethylphenol. Other compounds identified in this sample were: 4-methyl phenol, 4-ethyl phenol, 4-(2-hydroxyethylphenol and 2-(4-hydroxyphenyl ethanoic acid.

  8. Reactions of sulphur mustard on impregnated carbons.

    Science.gov (United States)

    Prasad, G K; Singh, Beer

    2004-12-31

    Activated carbon of surface area 1100 m2/gm is impregnated with 4% sodium hydroxide plus 3% Cr(VI) as CrO3 with and without 5% ethylene diamine (EDA), 4% magnesium nitrate and 5% ruthenium chloride by using their aqueous solutions. These carbons are characterized for surface area analysis by BET conventional method and exposed to the vapours of sulphur mustard (HD) at room temperature (30 degrees C). After 24 h, the reaction products are extracted in dichloromethane and analyzed using gas chromatography and mass spectrometry (GC-MS). Hemisulphur mustard, thiodiglycol, 1,4-oxathiane are observed to be the products of reaction between sulphur mustard and NaOH/CrO3/C system, whereas on NaOH/CrO3/EDA/C system HD reacted to give 1,4-thiazane. On Mg(NO3)2/C system it gave hemisulphur mustard and thiodiglycol. On RuCl3/C system it degraded to divinyl sulphone. Residual sulphur mustard is observed along with reaction products in all systems studied. Reaction mechanisms are also proposed for these interesting surface reactions. Above-mentioned carbons can be used in filtration systems for protection against hazardous gases such as sulphur mustard.

  9. Reactions of sulphur mustard on impregnated carbons

    International Nuclear Information System (INIS)

    Prasad, G.K.; Singh, Beer

    2004-01-01

    Activated carbon of surface area 1100 m 2 /gm is impregnated with 4% sodium hydroxide plus 3% Cr(Vi) as CrO 3 with and without 5% ethylene diamine (EDA), 4% magnesium nitrate and 5% ruthenium chloride by using their aqueous solutions. These carbons are characterized for surface area analysis by BET conventional method and exposed to the vapours of sulphur mustard (HD) at room temperature (30 deg. C). After 24 h, the reaction products are extracted in dichloromethane and analyzed using gas chromatography and mass spectrometry (GC-MS). Hemisulphur mustard, thiodiglycol, 1,4-oxathiane are observed to be the products of reaction between sulphur mustard and NaOH/CrO 3 /C system, whereas on NaOH/CrO 3 /EDA/C system HD reacted to give 1,4-thiazane. On Mg(NO 3 ) 2 /C system it gave hemisulphur mustard and thiodiglycol. On RuCl 3 /C system it degraded to divinyl sulphone. Residual sulphur mustard is observed along with reaction products in all systems studied. Reaction mechanisms are also proposed for these interesting surface reactions. Above-mentioned carbons can be used in filtration systems for protection against hazardous gases such as sulphur mustard

  10. Tribological Characteristics Evaluation of Mustard Oil Blends

    Directory of Open Access Journals (Sweden)

    Mohammed Hassan Jabal

    2018-03-01

    Full Text Available A progressive increase in the desire for environmentally friendly lubricants by users and strict government regulations for the use of these lubricants has provided an opportunity to use plant oils as biodegradable lubricants, therefore vegetable oils have been investigated to replace oil lubricants because of their maintaining the conditions of nature (environment properties. In this paper, the influences of the blending ratio of mustard seeds oil with commercial mineral oil (SAE40 on the tribological characteristics were investigated and compared with mineral oil using the four-ball tribotester. Mustard seeds oil was blended with mineral oil at a volumetric ratio ranging from 22.5 to 90%. All experimental works were confirmed to ASTM D4172-B standard. The results exhibit that some blends of mustard seeds oil with mineral oil have lower wear scar diameter, friction torque, Friction coefficient and a higher parameter of flash temperature value compared to mineral oil and neat mustard seed oil. In conclusion, the mustard seed oil blend (MU22.5 shows a better anti-wear and anti-friction performance compared to oil samples. Therefore, mustard seeds oil has the potential to be used as a lubricant of mating surfaces.

  11. Asymmetric synthesis of allylic sulfonic acids: enantio- and regioselective iridium-catalyzed allylations of Na2SO3.

    Science.gov (United States)

    Liu, Wei; Zhao, Xiao-ming; Zhang, Hong-bo; Zhang, Liang; Zhao, Ming-zhu

    2014-12-15

    An enantioselective allylation reaction of allylic carbonates with sodium sulfite (Na2 SO3 ) catalyzed by Ir complex was accomplished, providing allylic sulfonic acids in good to excellent yields with a high level of enantio- and regioselectivities. (R)-2-Phenyl-2-sulfoacetic acid, a key intermediate for the synthesis of Cefsulodin and Sulbenicillin, was synthesized as well. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Mustard gas or sulfur mustard: an old chemical agent as a new terrorist threat.

    Science.gov (United States)

    Wattana, Monica; Bey, Tareg

    2009-01-01

    Sulfur mustard is a member of the vesicant class of chemical warfare agents that causes blistering to the skin and mucous membranes. There is no specific antidote, and treatment consists of systematically alleviating symptoms. Historically, sulfur mustard was used extensively in inter-governmental conflicts within the trenches of Belgium and France during World War I and during the Iran-Iraq conflict. Longitudinal studies of exposed victims show that sulfur mustard causes long-term effects leading to high morbidity. Given that only a small amount of sulfur mustard is necessary to potentially cause an enormous number of casualties, disaster-planning protocol necessitates the education and training of first-line healthcare responders in the recognition, decontamination, triage, and treatment of sulfur mustard-exposed victims in a large-scale scenario.

  13. Preliminary Investigation on the Use of Allyi Isothiocyanate to Increase the Shelf-Life of Gilthead Sea Bream (Sparus Aurata) Fillets.

    Science.gov (United States)

    Giarratana, Filippo; Crinò, Chiara; Muscolino, Daniele; Beninati, Chiara; Ziino, Graziella; Giuffrida, Alessandro; Panebianco, Antonio

    2015-06-30

    The aim of this work is to evaluate the activity of allyl isothiocyanate (AITC) against fish spoilage bacteria (specific spoilage organisms; SSOs) as well as its possible use in gilthead sea bream ( Sparus aurata ) fillets to extend their shelf-life. In this regard, in vitro tests are carried out in order to evaluate the inhibitory activity of AITC and its vapours on several strains of SSOs. The AITC effect on the shelf-life of sea bream fillets was made by putting them in plastic trays hermetically closed with the addition AITC. Microbiological and sensorial evaluations were made on fish fillets during storage. Treated fillets maintained microbial populations at a significantly lower level compared with the control samples during storage, showing better sensorial characteristics. Therefore, the use of AITC's vapours seems to be a new and interesting alternative way to increase fish product shelf-life.

  14. Allyl borates: a novel class of polyhomologation initiators

    KAUST Repository

    Wang, De

    2016-12-24

    Allyl borates, a new class of monofunctional polyhomologation initiators, are reported. These monofunctional initiators are less sensitive and more effective towards polymethylene-based architectures. As an example, the synthesis of α-vinyl-ω-hydroxypolymethylenes is given. By designing/synthesizing different allylic borate initiators, and using 1H and 11B NMR spectroscopy, the initiation mechanism was elucidated.

  15. Carbocyclization cascades of allyl ketenimines via aza-Claisen rearrangements of N-phosphoryl-N-allyl-ynamides.

    Science.gov (United States)

    DeKorver, Kyle A; Wang, Xiao-Na; Walton, Mary C; Hsung, Richard P

    2012-04-06

    A series of carbocyclization cascades of allyl ketenimines initiated through a thermal aza-Claisen rearrangement of N-phosphoryl-N-allyl ynamides is described. Interceptions of the cationic intermediate via Meerwein-Wagner rearrangements and polyene-type cyclizations en route to fused bi- and tricyclic frameworks are featured.

  16. Sulfur mustard and respiratory diseases.

    Science.gov (United States)

    Tang, Feng Ru; Loke, Weng Keong

    2012-09-01

    Victims exposed to sulfur mustard (HD) in World War I and Iran-Iraq war, and those suffered occupational or accidental exposure have endured discomfort in the respiratory system at early stages after exposure, and marked general physical deterioration at late stages due to pulmonary fibrosis, bronchiolitis obliterans or lung cancer. At molecule levels, significant changes of cytokines and chemokines in bronchoalveolar lavage and serum, and of selectins (in particular sE-selectin) and soluble Fas ligand in the serum have been reported in recent studies of patients exposed to HD in Iran-Iraq war, suggesting that these molecules may be associated with the pathophysiological development of pulmonary diseases. Experimental studies in rodents have revealed that reactive oxygen and nitrogen species, their product peroxynitrite (ONOO(-)), nitric oxide synthase, glutathione, poly (adenosine diphosphate-ribose) polymerase, activating protein-1 signaling pathway are promising drug targets for preventing HD-induced toxicity, whereas N-acetyl cysteine, tocopherols, melatonin, aprotinin and many other molecules have been proved to be effective in prevention of HD-induced damage to the respiratory system in different animal models. In this paper, we will systemically review clinical and pathophysiological changes of respiratory system in victims exposed to HD in the last century, update clinicians and researchers on the mechanism of HD-induced acute and chronic lung damages, and on the relevant drug targets for future development of antidotes for HD. Further research directions will also be proposed.

  17. Hypothermia reduces sulphur mustard toxicity

    International Nuclear Information System (INIS)

    Mi Lei; Gong Wenrong; Nelson, Peggy; Martin, Leanne; Sawyer, Thomas W.

    2003-01-01

    The effect of temperature on the development of sulphur mustard (HD)-induced toxicity was investigated in first passage cultures of human skin keratinocytes and on hairless guinea pig skin. When cells exposed to HD were incubated at 37 deg. C, a concentration-dependent decline in viability was observed that was maximal by 2 days. In contrast, no significant HD-induced toxicity was evident up to 4 days posttreatment when the cells were incubated at 25 deg. C. However, these protective effects were lost by 24 h when the cells were switched back to 37 deg. C. The protective effects of hypothermia were also demonstrated when apoptotic endpoints were examined. The HD concentration-dependent induction of fragmented DNA (as quantitated using soluble DNA and the TUNEL reaction), morphology, and p53 expression were all significantly depressed when cell cultures were incubated at 25 deg. C compared to 37 deg. C. When animals were exposed to HD vapour for 2, 4, and 6 min and left at room temperature, lesions were produced whose severity was dependent on exposure time and that were maximal by 72 h posttreatment. Moderate cooling (5-10 deg. C) of HD exposure sites posttreatment (4-6 h) significantly reduced the severity of the resultant lesions. However, in contrast to the in vitro results, these effects were permanent. It appears that the early and noninvasive act of cooling HD-exposed skin may provide a facile means of reducing the severity of HD-induced cutaneous lesions

  18. Effect of Betong Watercress and Phenethyl Isothiocyanate on N ...

    African Journals Online (AJOL)

    Purpose: To investigate the effect of Betong watercress and phenethyl isothiocyanate (PEITC) on the N-demethylation of caffeine (CF) in rats. Methods: Male Wistar rats were subjected to 2 phases of experiment. Phase I, they received a single oral dose of CF (10 mg/kg), while in phase II, they were pretreated with the ...

  19. Propargylamine-isothiocyanate reaction: efficient conjugation chemistry in aqueous media

    DEFF Research Database (Denmark)

    Viart, Helene Marie-France; Larsen, T. S.; Tassone, Chiara

    2014-01-01

    A coupling reaction between secondary propargyl amines and isothiocyanates in aqueous media is described. The reaction is high-yielding and affords cyclized products within 2-24 h. A functionalized ether lipid was synthesized in 8 steps, formulated as liposomes with POPC and conjugated to FITC un...

  20. Catalytic Oxidation of Allylic Alcohols to Methyl Esters

    DEFF Research Database (Denmark)

    Gallas-Hulin, Agata; Kotni, Rama Krishna; Nielsen, Martin

    2017-01-01

    Aerobic oxidation of allylic alcohols to methyl esters using gold nanoparticles supported on different metal oxide carriers has been performed successfully under mild conditions (room temperature, 0.1 MPa O2) without significant loss of catalytic activity. The effects of different reaction...... parameters are studied to find the suitable reaction conditions. All catalysts are characterised by XRD, XRF and TEM. Among these catalysts, Au/TiO2 showed the most efficient catalytic activity towards the selective oxidation of allylic alcohols to the corresponding esters. Moreover, the same Au/TiO2...... to synthesize methyl esters from allylic alcohols....

  1. Spasmolytic, antimicrobial and cytotoxic activities of 5-phenylpentyl isothiocyanate, a new glucosinolate autolysis product from horseradish (Armoracia rusticana P. Gaertn., B. Mey. & Scherb., Brassicaceae).

    Science.gov (United States)

    Dekić, Milan S; Radulović, Niko S; Stojanović, Nikola M; Randjelović, Pavle J; Stojanović-Radić, Zorica Z; Najman, Stevo; Stojanović, Sanja

    2017-10-01

    Detailed analyses of horseradish autolysates led to the identification of a new natural product, 5-phenylpentyl isothiocyanate (PhPeITC). The structural assignment was corroborated by synthesis, and the identity unequivocally established by spectral means. The occurrence of PhPeITC is the first direct proof of the existence of a 5-phenylpentyl glucosinolate in the aerial parts of this species as one of the possible "mustard oil" precursors. To verify its possible contribution to the horseradish functional food status, horseradish above- and underground autolysates, together with five ω-phenylalkyl isothiocyanates were tested for their spasmolytic, cytotoxic and antimicrobial activities. Specifically, the cytotoxic effect on Caco-2, HeLa (cancer) and MDCK (non-cancer) cell lines was established. Additionally, the five tested ITCs exerted significant spasmolytic activity (on rat distal colon), with PhPeITC being almost 100 times more potent than papaverine. A non-selective antimicrobial activity of all ITCs was revealed in the case of 6 bacterial and 2 fungal strains. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter

    2011-01-01

    are highlighted with emphasis on those leading to C-C bond formation, but where it was deemed necessary for the general understanding of the process closely related C-H oxidations and aminations are also included. It is found that C-H cleavage is most likely achieved by ligand participation which could involve......-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation...... an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence...

  3. Novel Molecular Strategies Against Sulfur Mustard Toxicity

    Directory of Open Access Journals (Sweden)

    Zeki Ilker Kunak

    2012-04-01

    Full Text Available Among the available chemical warfare agents, sulfur mustard (SM, also known as mustard gas, has been widely used chemical weapon. In our laboratory, we have shown that, acute toxicity of SM is related to reactive oxygen and nitrogen species, DNA damage, poly(ADP-ribose polymerase activation and energy depletion within the affected cell. In spite of the knowledge about acute SM-induced cellular toxicity, unfortunately, it is not clear how mustard gas causes severe multi-organ damage years after even a single exposure. A variety of treatment modalities including antioxidants, anti-inflammatory drugs and others have resulted no promising results. We, therefore, made an attempt whether epigenetic aberrations may contribute to pathogenesis of mustard poisoning. The term epigenetic describes the study of inheritable alterations in gene expression that occur in the absence of changes in genome sequence. Therefore, epigenetic gene regulation requires molecular mechanisms that encode information in addition to the DNA base sequence and can be propagated through mitosis and meiosis. Our current understanding of epigenetic regulation of gene expression involves basically two classes of molecular mechanisms: histone modifications and DNA methylation. Preliminary evidence obtained from our laboratory reveals that exposure to mustards may not only cause nitro-oxidative stress and DNA (genetic damage, but epigenetic perturbations as well. Epigenetic therapy is a new and rapidly developing field in pharmacology. Epigenetic drugs alone or in combination with conventional drugs may prove to be a significant advance over the conventional drugs used to treat both acute and delayed SM toxicity. Future studies are urgently needed to clarify the mechanism of delayed SM-induced toxicity and novel treatment modalities. [TAF Prev Med Bull 2012; 11(2.000: 231-236

  4. REACTIVITY OF (η3-ALLYL)DICARBONYLNITROSYL IRON ...

    African Journals Online (AJOL)

    metal complexes can be synthesized from various organic precursors. Iron allyl ... iron complexes to develop a green chemistry approach [7]. Catalysis ...... Akermark, B.; Jutand, A. Addition of ketone enolates to π-allylpalladlum compounds.

  5. Allyl borates: a novel class of polyhomologation initiators

    KAUST Repository

    Wang, De; Hadjichristidis, Nikolaos

    2016-01-01

    Allyl borates, a new class of monofunctional polyhomologation initiators, are reported. These monofunctional initiators are less sensitive and more effective towards polymethylene-based architectures. As an example, the synthesis of α

  6. Zinc Mediated Tandem Fragmentation-Allylation of Methyl 5-Iodopentofuranosides

    DEFF Research Database (Denmark)

    Hyldtoft, Lene; Madsen, Robert

    1999-01-01

    In the presence of zinc and allyl bromide methyl 5-iodopentofuranosides undergo a tandem fragmentation alkylation to give functionalized dienes. These can undergo ring-closing olefin metathesis to produce cyclohexenes which on dihydroxylation give quercitols.......In the presence of zinc and allyl bromide methyl 5-iodopentofuranosides undergo a tandem fragmentation alkylation to give functionalized dienes. These can undergo ring-closing olefin metathesis to produce cyclohexenes which on dihydroxylation give quercitols....

  7. Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

    Science.gov (United States)

    Soltanzadeh, Bardia; Jaganathan, Arvind; Staples, Richard J.

    2016-01-01

    An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. PMID:26110812

  8. General Allylic C–H Alkylation with Tertiary Nucleophiles

    Science.gov (United States)

    2015-01-01

    A general method for intermolecular allylic C–H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C–H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C–H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C–H reactivity are illustrated in an allylic C–H alkylation/Diels–Alder reaction cascade: a reactive diene is generated via intermolecular allylic C–H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids. PMID:24641574

  9. General allylic C-H alkylation with tertiary nucleophiles.

    Science.gov (United States)

    Howell, Jennifer M; Liu, Wei; Young, Andrew J; White, M Christina

    2014-04-16

    A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.

  10. Laminin-5 Degradation Due to Mustard in Cultured Normal Human Epidermal Keratinocytes (NHEK)

    National Research Council Canada - National Science Library

    Ray, Prabhati; Jin, Xiannu; Leng, Yan; Li, Zhuangwu; Ray, Radharaman

    2003-01-01

    .... We observed that in NHEK, mustards degrade laminin-5. Calmodulin antagonist, W7 or the serine protease inhibitor, TLCK prior to mustard exposure prevented mustard-induced degradation of laminin-5...

  11. Molecular Mechanics and Quantum Chemistry Based Study of Nickel-N-Allyl Urea and N-Allyl Thiourea Complexes

    Directory of Open Access Journals (Sweden)

    P. D. Sharma

    2009-01-01

    Full Text Available Eigenvalue, eigenvector and overlap matrix of nickel halide complex of N-allyl urea and N-allyl thiourea have been evaluated. Our results indicate that ligand field parameters (Dq, B’ and β evaluated earlier by electronic spectra are very close to values evaluated with the help of eigenvalues and eigenvectors. Eigenvector analysis and population analysis shows that in bonding 4s, 4p, and 3dx2-y2, 3dyz orbitals of nickel are involved but the coefficient values differ in different complexes. Out of 4px, 4py, 4pz the involvement of either 4pz or 4py, is noticeable. The theoretically evaluated positions of infrared bands indicate that N-allyl urea is coordinated to nickel through its oxygen and N-allyl thiourea is coordinated to nickel through its sulphur which is in conformity with the experimental results.

  12. 7 CFR 201.56-3 - Mustard family, Brassicaceae (Cruciferae).

    Science.gov (United States)

    2010-01-01

    ..., Chinese cabbage, cauliflower, collards, garden cress, upland cress, water cress, kale, Chinese kale, Siberian kale, kohlrabi, mustard, pakchoi, radish, rape, rutabaga, and turnip. (a) General description. (1...

  13. The nature of resonance in allyl ions and radical.

    Science.gov (United States)

    Linares, Mathieu; Humbel, Stéphane; Braïda, Benoît

    2008-12-18

    A recent valence bond scheme based on Lewis structures, the valence bond BOND (VBB) method (BOND: Breathing Orbitals Naturally Delocalized) method (Linares, M.; Braida, B.; Humbel, S. J. Phys. Chem. A 2006, 110, 2505-2509), is applied to explore the nature of resonance in allyl systems. Whereas allyl radical is correctly described by the resonance between the two traditional Lewis structures, a third "long-bonded" structure, which apparently creates a pi bond between the two distant carbon atoms, appears to plays an important role in allyl ions description. The similar vertical resonance energy (VRE) for both allyl ions is rather moderate (approximately 37 kcal/mol) in the two-structure description but is significantly enhanced when the long-bonded structure is included into the VBB wave function (by up to 20 kcal/mol). The allyl radical is much less resonant and is correctly described by the traditional two-structure picture. The development of VBB Lewis structures into "pure" valence bond determinants enlightens the role of the third structure in the description of allyl ions. The existence of a long bond between the two distant carbon atoms is clearly ruled out. Charge equilibration effect is shown to be a minor factor. The third structure is finally attributed to one- and three-electron bonding character revealed in the pi systems of the cation and anion, respectively. This makes these systems two surprising examples of odd electron bonding within a singlet state. Last, the two-structure description of allyl radical is improved by addition of missing ionic structures.

  14. Features of accumulation of inorganic elements in seeds of white mustard (Sinapis alba L.) and black mustard (Brassica nigra L.)

    OpenAIRE

    О. І. Рудник-Іващенко; Л. М. Михальська; В. В. Швартау

    2016-01-01

    Purpose. To investigate special aspects of accumulation of inorganic elements including heavy metals in seeds of white and black mustard to be grown for obtaining drugs. Methods. Field experiments, microwave digestion, ICP-MS and statistical analysis. Results. The content of inorganic elements including heavy metals was determined in the seeds of white and black mustard grown in Kiev Oblast. It was revealed that during the growing season plants of white mustard were able to accumulate...

  15. Tribological Characteristics Evaluation of Mustard Oil Blends

    OpenAIRE

    Mohammed Hassan Jabal; Muhannad Zaidan Khalefa

    2018-01-01

    A progressive increase in the desire for environmentally friendly lubricants by users and strict government regulations for the use of these lubricants has provided an opportunity to use plant oils as biodegradable lubricants, therefore vegetable oils have been investigated to replace oil lubricants because of their maintaining the conditions of nature (environment) properties. In this paper, the influences of the blending ratio of mustard seeds oil with commercial mineral oil (SAE40) on the ...

  16. Water promoted allylic nucleophilic substitution reactions of (E)-1,3 diphenylallyl acetate

    KAUST Repository

    Ghorpade, Seema Arun; Sawant, Dinesh N; Makki, Arwa; Sekar, N; Eppinger, Jö rg

    2017-01-01

    Transition metal free, water based, greener protocol for allylic alkylation, allylic amination, O-allylation of (E)-1,3-diphenylallyl acetate is described. The developed methodology is applicable for a wide range of nucleophiles furnishing excellent yields of corresponding products up to 87% under mild reaction conditions. A Distinct effect of water and base is explored for allylic nucleophilic substitution reactions of (E)-1,3-diphenylallyl acetate.

  17. Water promoted allylic nucleophilic substitution reactions of (E)-1,3 diphenylallyl acetate

    KAUST Repository

    Ghorpade, Seema Arun

    2017-11-30

    Transition metal free, water based, greener protocol for allylic alkylation, allylic amination, O-allylation of (E)-1,3-diphenylallyl acetate is described. The developed methodology is applicable for a wide range of nucleophiles furnishing excellent yields of corresponding products up to 87% under mild reaction conditions. A Distinct effect of water and base is explored for allylic nucleophilic substitution reactions of (E)-1,3-diphenylallyl acetate.

  18. Rapid synthesis of polyprenylated acylphloroglucinol analogs via dearomative conjunctive allylic annulation.

    Science.gov (United States)

    Grenning, Alexander J; Boyce, Jonathan H; Porco, John A

    2014-08-20

    Polyprenylated acylphloroglucinols (PPAPs) are structurally complex natural products with promising biological activities. Herein, we present a biosynthesis-inspired, diversity-oriented synthesis approach for rapid construction of PPAP analogs via double decarboxylative allylation (DcA) of acylphloroglucinol scaffolds to access allyl-desoxyhumulones followed by dearomative conjunctive allylic alkylation (DCAA).

  19. Urinary excretion of N-acetyl-S-allyl-L-cystein upon garlic consumption by human volunteers.

    NARCIS (Netherlands)

    de Rooij, B.M.; Boogaard, P.J.; Rijksen, D.A.; Commandeur, J.N.M.; Vermeulen, N.P.E.

    1996-01-01

    N-Acetyl-S-allyl-L-cysteine (allylmercapturic acid, ALMA) was previously detected in urine from humans consuming garlic. Exposure of rats to allyl halides is also known to lead to excretion of ALMA in urine. ALMA is a potential biomarker for exposure assessment of workers exposed to allyl halides.

  20. Palladium-Catalyzed Anti-Markovnikov Oxidation of Allylic Amides to Protected beta-Amino Aldehydes

    NARCIS (Netherlands)

    Dong, Jiajia; Harvey, Emma C.; Fananas-Mastral, Martin; Browne, Wesley R.; Feringa, Bernard

    2014-01-01

    A general method for the preparation of N-protected beta-amino aldehydes from allylic amines or linear allylic alcohols is described. Here the Pd(II)-catalyzed oxidation of N-protected allylic amines with benzoquinone is achieved in tBuOH under ambient conditions with excellent selectivity toward

  1. 40 CFR 721.7000 - Polymer of disodium maleate, allyl ether, and ethylene oxide.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymer of disodium maleate, allyl... New Uses for Specific Chemical Substances § 721.7000 Polymer of disodium maleate, allyl ether, and... substance identified generically as a polymer of disodium maleate, allyl ether, and ethylene oxide (P-91...

  2. Redox-Neutral Rh(III)-Catalyzed Olefination of Carboxamides with Trifluoromethyl Allylic Carbonate.

    Science.gov (United States)

    Park, Jihye; Han, Sangil; Jeon, Mijin; Mishra, Neeraj Kumar; Lee, Seok-Yong; Lee, Jong Suk; Kwak, Jong Hwan; Um, Sung Hee; Kim, In Su

    2016-11-18

    The rhodium(III)-catalyzed olefination of various carboxamides with α-CF 3 -substituted allylic carbonate is described. This reaction provides direct access to linear CF 3 -allyl frameworks with complete trans-selectivity. In particular, a rhodium catalyst provided Heck-type γ-CF 3 -allylation products via the β-O-elimination of rhodacycle intermediate and subsequent olefin migration process.

  3. Development of an enzyme-linked immunosorbent assay method to detect mustard protein in mustard seed oil

    NARCIS (Netherlands)

    Koppelman, S.J.; Vlooswijk, R.; Bottger, G.; Duijn, G. van; Schaft, P. van der; Dekker, J.; Bemgen, H. van

    2007-01-01

    An enzyme-linked immunosorbent assay for the detection of mustard protein was developed. The assay is based on a polyclonal antiserum directed against a mixture of mustard proteins raised in rabbits. The assay has a detection limit of 1.5 ppm (milligrams per kilogram) and is suitable for the

  4. Antitrypanosomal isothiocyanate and thiocarbamate glycosides from Moringa peregrina.

    Science.gov (United States)

    Ayyari, Mahdi; Salehi, Peyman; Ebrahimi, Samad Nejad; Zimmermann, Stefanie; Portmann, Lena; Krauth-Siegel, R Luise; Kaiser, Marcel; Brun, Reto; Rezadoost, Hassan; Rezazadeh, Shamsali; Hamburger, Matthias

    2014-01-01

    O-Methyl (1), O-ethyl (2), and O-butyl (3) 4-[(α-L-rhamnosyloxy) benzyl] thiocarbamate (E), along with 4-(α-L-rhamnosyloxy) benzyl isothiocyanate (4) have been isolated from the aerial parts of Moringa peregrina. The compounds were tested for in vitro activity against Trypanosoma brucei rhodesiense and cytotoxicity in rat skeletal myoblasts (L6 cells). The most potent compound was 4 with an IC50 of 0.10 µM against T.b. rhodesiense and a selectivity index of 73, while the thiocarbamate glycosides 1, 2, and 3 showed only moderate activity. Intraperitoneal administration of 50 mg/kg body weight/day of 4 in the T.b. rhodesiense STIB 900 acute mouse model revealed significant in vivo toxicity. Administration of 10 mg/kg body weight/day resulted in a 95% reduction of parasitemia on day 7 postinfection, but did not cure the animals. Because of its high in vitro activity and its ability to irreversibly inhibit trypanothione reductase, an attractive parasite-specific target enzyme, 4-[(α-L-rhamnosyloxy) benzyl] isothiocyanate (4), can be considered as a lead structure for the development and characterization of novel antitrypanosomal drugs. Georg Thieme Verlag KG Stuttgart · New York.

  5. Metabolic Activity of Radish Sprouts Derived Isothiocyanates in Drosophila melanogaster

    Directory of Open Access Journals (Sweden)

    Nieves Baenas

    2016-02-01

    Full Text Available We used Drosophila melanogaster as a model system to study the absorption, metabolism and potential health benefits of plant bioactives derived from radish sprouts (Raphanus sativus cv. Rambo, a Brassicaceae species rich in glucosinolates and other phytochemicals. Flies were subjected to a diet supplemented with lyophilized radish sprouts (10.6 g/L for 10 days, containing high amounts of glucoraphenin and glucoraphasatin, which can be hydrolyzed by myrosinase to the isothiocyanates sulforaphene and raphasatin, respectively. We demonstrate that Drosophila melanogaster takes up and metabolizes isothiocyanates from radish sprouts through the detection of the metabolite sulforaphane-cysteine in fly homogenates. Moreover, we report a decrease in the glucose content of flies, an upregulation of spargel expression, the Drosophila homolog of the mammalian PPARγ-coactivator 1 α, as well as the inhibition of α-amylase and α-glucosidase in vitro. Overall, we show that the consumption of radish sprouts affects energy metabolism in Drosophila melanogaster which is reflected by lower glucose levels and an increased expression of spargel, a central player in mitochondrial biogenesis. These processes are often affected in chronic diseases associated with aging, including type II diabetes mellitus.

  6. Metabolic Activity of Radish Sprouts Derived Isothiocyanates in Drosophila melanogaster

    Science.gov (United States)

    Baenas, Nieves; Piegholdt, Stefanie; Schloesser, Anke; Moreno, Diego A.; García-Viguera, Cristina; Rimbach, Gerald; Wagner, Anika E.

    2016-01-01

    We used Drosophila melanogaster as a model system to study the absorption, metabolism and potential health benefits of plant bioactives derived from radish sprouts (Raphanus sativus cv. Rambo), a Brassicaceae species rich in glucosinolates and other phytochemicals. Flies were subjected to a diet supplemented with lyophilized radish sprouts (10.6 g/L) for 10 days, containing high amounts of glucoraphenin and glucoraphasatin, which can be hydrolyzed by myrosinase to the isothiocyanates sulforaphene and raphasatin, respectively. We demonstrate that Drosophila melanogaster takes up and metabolizes isothiocyanates from radish sprouts through the detection of the metabolite sulforaphane-cysteine in fly homogenates. Moreover, we report a decrease in the glucose content of flies, an upregulation of spargel expression, the Drosophila homolog of the mammalian PPARγ-coactivator 1 α, as well as the inhibition of α-amylase and α-glucosidase in vitro. Overall, we show that the consumption of radish sprouts affects energy metabolism in Drosophila melanogaster which is reflected by lower glucose levels and an increased expression of spargel, a central player in mitochondrial biogenesis. These processes are often affected in chronic diseases associated with aging, including type II diabetes mellitus. PMID:26901196

  7. PERFORMANCE AND ANALYSIS OF MUSTARD FARMING IN JAYAPURA PAPUA

    Directory of Open Access Journals (Sweden)

    Herman Tangkelayuk

    2014-01-01

    Full Text Available Research aim was to see variability, feasibility, and mustard farm income cultivated in Jayapura . The experiment was conducted in Kampung Yobeh, District of Sentani, Jayapura regency, on November to December 2013, using data growing season in October 2013, in form of a survey involving 30 mustard farmers as respondents . Determination of respondent using simple random method by getting farmers planting mustard continuously. Results: average mustard farmers area of 0,099 ha, seed expenses of IDR 37,400, the use of 9.20 kg Urea, NPK 2.80 kg, 526 kg manure , and cost of medicines IDR 26.366, male workers 2.66 HOK and women 2.03 HOK , and other expenses (shrinkage values and land tax .The level of productivity of mustard is 538.6 kg/0.99 ha/cropping season. Total revenue mustard farming with land size 0,099 ha/growing season is IDR 1.615.800, total spending is IDR 562 18. Benefit of farmers is IDR 1,053,618 with value of R/C ratio of 2.87. Analysis shows that mustard farming in Yobeh village, Sentani, Jayapura profitable, it is advisable for further development. Need guidance from Field Extension so that increased production increased.

  8. Mustard Group Chemical War Agents from Preventive Medicine Perspective

    Directory of Open Access Journals (Sweden)

    Muharrem Ucar

    2007-06-01

    Full Text Available Although many preventive efforts and treaties, chemical warfare agents have still been a severe assault form against both military and civilian individuals. The most important chemical warfare agents sulphur mustard and others are easy to handle and cheap those the important reasons to accept sulphur mustard as a chemical warfare agent. Many individuals attacked by sulphur mustard have severe health problems such as respiratory system diseases. After ten years of sulphur mustard exposure, several health problems such as respiratory tract problems (%42.5, eye problems (%40 and other systemic diseases have been observed to insist on induviduals when examined. Exposure of even single sulphur mustard exposure has been seen to result high level of disability and early deaths. In spite of the fact that there is no available antidote and/or remedy against sulphur mustard exposure, our country has an incremental chemical assault threat for both military personels and civilians because of its jeopolitics position. Experimental studies regarding sulphur mustard toxicity will be helpful for novel preventive strategies and antidot devolepment. [TAF Prev Med Bull 2007; 6(3.000: 209-214

  9. Direct activation of allylic alcohols in palladium catalyzed coupling reactions

    NARCIS (Netherlands)

    Gümrükçü, Y.

    2014-01-01

    The direct use of allylic alcohols in substitution reactions without pre-activation of the hydroxyl-group into a better leaving group or the use of additional stoichiometric in situ activators remains challenging due to the poor leaving group ability of the hydroxyl-group. Hence, it is important to

  10. Can Mustard Gas Induce Late Onset Polyneuropathy?

    Directory of Open Access Journals (Sweden)

    SJ. Mousavi

    2007-11-01

    Full Text Available Background:Mustard gas, lethal in high doses, affects multiple organs such as skin, eye and respiratory system. We studied the development of late onset mustardinduced polyneuropathy among chemically wounded Iranian veterans.Methods:In this descriptive study,100 chemically wounded Iranian veterans with severe eye involvement were examined for any signs and symptoms of polyneuropathy by an internist.20 patients were suspected to have neurological symptoms or signs.These patients were examined by a neurologist again. 13 showed abnormal neurological symptoms. Electrodiagnostic exams were performed for this group by another physician.Results:13 veterans had abnormal neurological exam results with prominent sensory signs and symptoms in almost all of them. Brisk deep tendon reflexes were found in 3 cases. Electrodiagnostic studies were compatible with axonal type distal sensory polyneuropathy in 6 subjects. Conclusion: To the best of our knowledge, this is the first report of late onset polyneuropathy among chemically-wounded victims who were exposed to mustard gas. The pathophysiology of this form of neuropathy is still unknown. Unlike most toxic neuropathies,obvious clinical signs and symptoms appeared several years after exposure. No specific treatment for.polyneuropathy due to chemical weapons exposure has been described to date.

  11. Combustion characteristics of the mustard methyl esters

    International Nuclear Information System (INIS)

    Bannikov, M.G.; Vasilev, I.P.

    2011-01-01

    Mustard Methyl Esters (further bio diesel) and regular diesel fuel were tested in direct injection diesel engine. Analysis of experimental data was supported by an analysis of fuel injection and combustion characteristics. Engine fuelled with bio diesel had increased brake specific fuel consumption, reduced nitrogen oxides emission and smoke opacity, moderate increase in carbon monoxide emission with essentially unchanged unburned hydrocarbons emission. Increase in fuel consumption was attributed to lesser heating value of bio diesel and partially to decreased fuel conversion efficiency. Analysis of combustion characteristics revealed earlier start of injection and shorter ignition delay period of bio diesel. Resulting decrease in maximum rate of heat release and cylinder pressure was the most probable reason for reduced emission of nitrogen oxides. Analysis of combustion characteristics also showed that cetane index determined by ASTM Method D976 is not a proper measure of ignition quality of bio diesel. Conclusion was made on applicability of mustard oil as a source for commercial production of bio diesel in Pakistan. Potentialities of on improving combustion and emissions characteristics of diesel engine by reformulating bio diesel were discussed. (author)

  12. Models of invasion and establishment of African Mustard (Brassica tournefortii)

    Science.gov (United States)

    Berry, Kristin H.; Gowan, Timothy A.; Miller, David M.; Brooks, Matthew L.

    2015-01-01

    Introduced exotic plants can drive ecosystem change. We studied invasion and establishment ofBrassica tournefortii (African mustard), a noxious weed, in the Chemehuevi Valley, western Sonoran Desert, California. We used long-term data sets of photographs, transects for biomass of annual plants, and densities of African mustard collected at irregular intervals between 1979 and 2009. We suggest that African mustard may have been present in low numbers along the main route of travel, a highway, in the late 1970s; invaded the valley along a major axial valley ephemeral stream channel and the highway; and by 2009, colonized 22 km into the eastern part of the valley. We developed predictive models for invasibility and establishment of African mustard. Both during the initial invasion and after establishment, significant predictor variables of African mustard densities were surficial geology, proximity to the highway and axial valley ephemeral stream channel, and number of small ephemeral stream channels. The axial valley ephemeral stream channel was the most vulnerable of the variables to invasions. Overall, African mustard rapidly colonized and quickly became established in naturally disturbed areas, such as stream channels, where geological surfaces were young and soils were weakly developed. Older geological surfaces (e.g., desert pavements with soils 140,000 to 300,000 years old) were less vulnerable. Microhabitats also influenced densities of African mustard, with densities higher under shrubs than in the interspaces. As African mustard became established, the proportional biomass of native winter annual plants declined. Early control is important because African mustard can colonize and become well established across a valley in 20 yr.

  13. Pityriasis rosea-like eruptions due to mustard oil application

    Directory of Open Access Journals (Sweden)

    Zawar Vijay

    2005-01-01

    Full Text Available A young man employed in a construction company, presented with cutaneous lesions clinically simulating pityriasis rosea. Satisfactory and complete response to corticosteroids and antihistamines was followed by recurrence. Multiple recurrences within a short span of time arose a suspicion of alternative diagnosis. Site visit helped us to rule out occupational contact dermatitis. Further history taking revealed that he was recently using mustard oil for body massage. Subsequent patch testing confirmed contact hypersensitivity to mustard oil. Avoidance of the contact with mustard oil arrested appearance of further skin lesions. We stress the importance of taking a good history in clinical practice in disclosing a possible contactant.

  14. The Mustard Consortium’s Elucidation of the Pathophysiology of Sulfur Mustard and Antidote Development

    Science.gov (United States)

    2006-09-01

    fibrosis is well documented (4). Not unexpectedly, HD is radiomimetic, teratogenic and mutagenic (5,6). Currently, there is no effective therapy ...available. The long term goals are to further define the mode of action of mustard gas and to develop a therapy using liposomes containing both lipid...unilamellar antioxidant liposomes containing 6.6 mole percent RRR-alpha- tocopherol (as well as 66.6, 26.5 and 0.66 mole percent of soy lecithin

  15. Stable, water extractable isothiocyanates from Moringa oleifera leaves attenuate inflammation in vitro.

    Science.gov (United States)

    Waterman, Carrie; Cheng, Diana M; Rojas-Silva, Patricio; Poulev, Alexander; Dreifus, Julia; Lila, Mary Ann; Raskin, Ilya

    2014-07-01

    Moringa (Moringa oleifera Lam.) is an edible plant used as both a food and medicine throughout the tropics. A moringa concentrate (MC), made by extracting fresh leaves with water, utilized naturally occurring myrosinase to convert four moringa glucosinolates into moringa isothiocyanates. Optimum conditions maximizing MC yield, 4-[(α-L-rhamnosyloxy)benzyl]isothiocyanate, and 4-[(4'-O-acetyl-α-L-rhamnosyloxy)benzyl]isothiocyanate content were established (1:5 fresh leaf weight to water ratio at room temperature). The optimized MC contained 1.66% isothiocyanates and 3.82% total polyphenols. 4-[(4'-O-acetyl-α-L-rhamnosyloxy)benzyl]isothiocyanate exhibited 80% stability at 37°C for 30 days. MC, and both of the isothiocyanates described above significantly decreased gene expression and production of inflammatory markers in RAW macrophages. Specifically, both attenuated expression of iNOS and IL-1β and production of nitric oxide and TNFα at 1 and 5 μM. These results suggest a potential for stable and concentrated moringa isothiocyanates, delivered in MC as a food-grade product, to alleviate low-grade inflammation associated with chronic diseases. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Carcinogenicity of Mustard Gas: Report of the Cancer Registry Project Among Mustard Gas Exposed Iranian Veterans

    International Nuclear Information System (INIS)

    Soroush, M. R.

    2007-01-01

    Since 2003 The Janbazan Medical and Engineering Research Center in collaboration with Tehran University has conducted a nationwide cancer registry project among all Iranian Veterans with history of exposure to mustard gas during 1980-1988 Iran Iraq war. The mixed cohort study has a retrospective phase from the exposure time to 2003 and a prospective phase from 2003 to 2013. The main goal is to find any possible relationship between exposure to mustard gas and developing cancer as a long term health effect. A total number of 7500 individual (both military and civilians) with confirmed medical records of exposure to mustard gas have been included in the study to be compared with the same number of control population as well as the statistics of the national cancer registry system. The follow up of all cases is being done as a part of the national health monitoring program of the Janbazan (veterans) organization. In this report the latest findings of this project will be presented.(author)

  17. Brassicaceae Mustards: Traditional and Agronomic Uses in Australia and New Zealand

    Directory of Open Access Journals (Sweden)

    Mahmudur Rahman

    2018-01-01

    Full Text Available Commonly cultivated Brassicaceae mustards, namely garlic mustard (Alliaria petiolata, white mustard (Brassica alba, Ethiopian mustard (B. carinata, Asian mustard (B. juncea, oilseed rape (B. napus, black mustard (B. nigra, rapeseed (B. rapa, white ball mustard (Calepina irregularis, ball mustard (Neslia paniculata, treacle mustard (Erysimum repandum, hedge mustard (Sisymbrium officinale, Asian hedge mustard (S. orientale, smooth mustard (S. erysimoides and canola are the major economically important oilseed crops in many countries. Mustards were naturalized to Australia and New Zealand and Australia is currently the second largest exporter of Brassicaceae oilseeds to meet the global demand for a healthy plant-derived oil, high in polyunsaturated fats. Apart from providing edible oil, various parts of these plants and many of their phytochemicals have been used traditionally for both agronomic as well as medicinal purposes, with evidence of their use by early Australian and New Zealand settlers and also the indigenous population. This review provides an overview of the current knowledge of traditional and agronomic uses of Brassicaceae oilseeds and mustards with a focus on their importance in Australia and New Zealand.

  18. Brassicaceae Mustards: Traditional and Agronomic Uses in Australia and New Zealand.

    Science.gov (United States)

    Rahman, Mahmudur; Khatun, Amina; Liu, Lei; Barkla, Bronwyn J

    2018-01-21

    Commonly cultivated Brassicaceae mustards, namely garlic mustard ( Alliaria petiolata ), white mustard ( Brassica alba ), Ethiopian mustard ( B. carinata ), Asian mustard ( B. juncea ), oilseed rape ( B. napus ), black mustard ( B. nigra ), rapeseed ( B. rapa ), white ball mustard ( Calepina irregularis ), ball mustard ( Neslia paniculata ), treacle mustard ( Erysimum repandum ), hedge mustard ( Sisymbrium officinale ), Asian hedge mustard ( S. orientale ), smooth mustard ( S. erysimoides ) and canola are the major economically important oilseed crops in many countries. Mustards were naturalized to Australia and New Zealand and Australia is currently the second largest exporter of Brassicaceae oilseeds to meet the global demand for a healthy plant-derived oil, high in polyunsaturated fats. Apart from providing edible oil, various parts of these plants and many of their phytochemicals have been used traditionally for both agronomic as well as medicinal purposes, with evidence of their use by early Australian and New Zealand settlers and also the indigenous population. This review provides an overview of the current knowledge of traditional and agronomic uses of Brassicaceae oilseeds and mustards with a focus on their importance in Australia and New Zealand.

  19. Development of Biological Control for Alliaria petiolata (Garlic Mustard)

    National Research Council Canada - National Science Library

    Blossey, Bernd; Nuzzo, Victoria; Hinz, Harriet; Gerber, Esther

    2003-01-01

    Alliaria petiolata, garlic mustard, a biennial plant of European origin accidentally introduced to North America, has spread throughout much of eastern and midwestern North America and is now recorded...

  20. Dehalogenase: The Follow-Up Enzyme After Mustard Oxidation

    National Research Council Canada - National Science Library

    Elashvili, Ilya; DeFrank, Joseph J

    2002-01-01

    Sulfur mustard (HD) has been used as a chemical warfare agent since 1917. Currently fielded M258A1 and M280 decontamination kits and prospective oxidative decontaminants convert HD to HD sulfoxide (HDSO...

  1. Diversity Analysis of Ethiopian Mustard Breeding Lines Using RAPD ...

    African Journals Online (AJOL)

    Ethiopian mustard (Brassica carinata A. Braun) is an oilseed crop less known to the ... have also been used for cultivar identification in B. napus (Ren et al. ..... of Brassica oleracea L. group (2n=18) using random amplified polymorphic DNA.

  2. TREATMENT OF BIODIESEL WASTEWATER USING YELLOW MUSTARD SEEDS

    OpenAIRE

    SAVCI, Serpil

    2017-01-01

    In thisstudy, removal of original biodiesel wastewater (BOD, COD, oil&greas) by yellow mustard seeds was examined bya batch system. The effect of the adsorption time 300 minutes, adsorbent dose(1.0 g/L) and mixing rate (120 rpm) on the adsorption capacity of pollutants.The applicability of the Langmuir and Freundlich isotherms were examined.According to the data obtained from experiments, biodiesel wastewater can betreated by adsorption using yellow mustard seeds.

  3. Phytocontact Dermatitis due to Mustard Seed Mimicking Burn Injury: Report of a Case

    OpenAIRE

    Yabanoglu, Hakan; Akbulut, Sami; Karakayali, Feza

    2012-01-01

    Mustard seeds have been used in traditional folk medicine as a stimulant, diuretic, and purgative and to treat a variety of ailments including peritonitis and neuralgia. Mustards are still used today in mustard plasters to treat rheumatism, arthritis, chest congestion, aching back, and sore muscles. To make a mustard plaster, mix equal parts of flour and powdered mustard and spread it as a paste on a doubled piece of soft cloth. Apply mustard plaster to the affected area for a maximum of 15 m...

  4. Ionic dependence of sulphur mustard cytotoxicity

    International Nuclear Information System (INIS)

    Sawyer, Thomas W.; Nelson, Peggy; Bjarnason, Stephen; Vair, Cory; Shei Yimin; Tenn, Catherine; Lecavalier, Pierre; Burczyk, Andrew

    2010-01-01

    The effect of ionic environment on sulphur mustard (bis 2-chloroethyl sulphide; HD) toxicity was examined in CHO-K1 cells. Cultures were treated with HD in different ionic environments at constant osmolar conditions (320 mOsM, pH 7.4). The cultures were refed with fresh culture medium 1 h after HD exposure, and viability was assessed. Little toxicity was apparent when HD exposures were carried out in ion-free sucrose buffer compared to LC 50 values of ∼ 100-150 μM when the cultures were treated with HD in culture medium. Addition of NaCl to the buffer increased HD toxicity in a salt concentration-dependent manner to values similar to those obtained in culture medium. HD toxicity was dependent on both cationic and anionic species with anionic environment playing a much larger role in determining toxicity. Substitution of NaI for NaCl in the treatment buffers increased HD toxicity by over 1000%. The activity of the sodium hydrogen exchanger (NHE) in recovering from cytosolic acidification in salt-free and in different chloride salts did not correlate with the HD-induced toxicity in these buffers. However, the inhibition by HD of intracellular pH regulation correlated with its toxicity in NaCl, NaI and sucrose buffers. Analytical chemical studies and the toxicity of the iodine mustard derivative ruled out the role of chemical reactions yielding differentially toxic species as being responsible for the differences in HD toxicity observed. This work demonstrates that the early events that HD sets into motion to cause toxicity are dependent on ionic environment, possibly due to intracellular pH deregulation.

  5. Features of accumulation of inorganic elements in seeds of white mustard (Sinapis alba L. and black mustard (Brassica nigra L.

    Directory of Open Access Journals (Sweden)

    О. І. Рудник-Іващенко

    2016-12-01

    Full Text Available Purpose. To investigate special aspects of accumulation of inorganic elements including heavy metals in seeds of white and black mustard to be grown for obtaining drugs. Methods. Field experiments, microwave digestion, ICP-MS and statistical analysis. Results. The content of inorganic elements including heavy metals was determined in the seeds of white and black mustard grown in Kiev Oblast. It was revealed that during the growing season plants of white mustard were able to accumulate such elements as aluminum, barium, strontium, zinc in seeds in concentrations that exceed their content in black mustard seeds, while compounds of calcium, cesium, iron, magnesium, manganese, potassium in a greater degree were accumulated in black mustard seeds. Conclusions. As legal and regulatory documents for important chemical elements don’t contain the maximum permissible limits of their content in medicinal plants, it would make sense to launch a comprehensive research with the involvement of specia­lists of relevant profiles in order to establish such a gradation. Plants of white and black mustard in Kiev Oblast have accumulated high levels of such metals as Ba, Cu, Fe, Mn, Mo, Sr, Zn that exceed the known limits of accumulation, indicating a partial contamination of soils in the region. Consequently, these plants can be used for phytoremediation of soils. Considering the fact that in the pharmaceutical practice refined mustard seed oil is used, revealed alterations of metal accumulation in seeds will not affect the quality of the final drugs. According to the research results, white and black mustard is promising for cultivation in Kiev Oblast with a view to obtain raw material that can be processed into drugs.

  6. ION EXCHANGE SUBSTANCES BY SAPONIFICATION OF ALLYL PHOSPHATE POLYMERS

    Science.gov (United States)

    Kennedy, J.

    1959-04-14

    An ion exchange resin having a relatively high adsorption capacity tor uranyl ion as compared with many common cations is reported. The resin comprises an alphyl-allyl hydrogen phosphate polymer, the alphyl group being either allyl or a lower alkyl group having up to 5 carbon atoins. The resin is prepared by polymerizing compounds such as alkyl-diallyl phosphate and triallyl phosphate in the presence of a free radical generating substance and then partially hydrolyzing the resulting polymer to cause partial replacement of organic radicals by cations. A preferred free radical gencrating agent is dibenzoyl peroxide. The partial hydrolysis is brought about by refluxing the polymer with concentrated aqueous NaOH for three or four hours.

  7. Radiation initiated copolymerization of allyl alcohol with acrylonitrile

    International Nuclear Information System (INIS)

    Solpan, Dilek; Guven, Olgun

    1996-01-01

    Copolymerization of allyl alcohol (AA) with acrylonitrile (AN) initiated by γ-rays has been investigated to determine the respective reactivity ratios. Three different experimental techniques, namely Fourier Transform Infrared (FTIR), Ultraviolet (UV/vis) and elemental analysis (EA) have been used for the determination of copolymer compositions. Fineman-Ross (FR), Kelen-Tudos (KT), Non-Linear Least Square (NLLS) Analysis and Q-e methods have been applied to the three sets of experimental data. It has been concluded that data obtained from elemental analysis as applied to the Non-Linear Least Square approach gave the most reliable reactivity ratios as 2.09 and 0.40 for acrylonitrile and allyl alcohol, respectively. (Author)

  8. Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

    International Nuclear Information System (INIS)

    Fujimura, T.; Hayakawa, N.; Kuriyama, I.

    1978-01-01

    The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed. (author)

  9. Functionality of whey proteins covalently modified by allyl isothiocyanate. Part 1 physicochemical and antibacterial properties of native and modified whey proteins at pH 2 to 7

    NARCIS (Netherlands)

    Keppler, Julia Katharina; Martin, Dierk; Garamus, Vasil M.; Berton-Carabin, Claire; Nipoti, Elia; Coenye, Tom; Schwarz, Karin

    2017-01-01

    Whey protein isolate (WPI) (∼75% β-lactoglobulin (β-LG)) is frequently used in foods as a natural emulsifying agent. However, at an acidic pH value, its emulsification capacity is greatly reduced. The covalent attachment of natural electrophilic hydrophobic molecules to WPI proteins is a

  10. Preservation of acidified cucumbers with a natural preservative combination of fumaric acid and allyl isothiocyanate that target lactic acid bacteria and yeasts

    Science.gov (United States)

    Without the addition of preservative compounds cucumbers acidified with 150 mM acetic acid with pH adjusted to 3.5 typically undergo fermentation by lactic acid bacteria. Fumaric acid (20 mM) inhibited growth of Lactobacillus plantarum and the lactic acid bacteria present on fresh cucumbers, but sp...

  11. Isothiocyanates: An Overview of Their Antimicrobial Activity against Human Infections

    Directory of Open Access Journals (Sweden)

    Letizia Romeo

    2018-03-01

    Full Text Available The use of plant-derived products as antimicrobial agents has been investigated in depth. Isothiocyanates (ITCs are bioactive products resulting from enzymatic hydrolysis of glucosinolates (GLs, the most abundant secondary metabolites in the botanical order Brassicales. Although the antimicrobial activity of ITCs against foodborne and plant pathogens has been well documented, little is known about their antimicrobial properties against human pathogens. This review collects studies that focus on this topic. Particular focus will be put on ITCs’ antimicrobial properties and their mechanism of action against human pathogens for which the current therapeutic solutions are deficient and therefore of prime importance for public health. Our purpose was the evaluation of the potential use of ITCs to replace or support the common antibiotics. Even though ITCs appear to be effective against the most important human pathogens, including bacteria with resistant phenotypes, the majority of the studies did not show comparable results and thus it is very difficult to compare the antimicrobial activity of the different ITCs. For this reason, a standard method should be used and further studies are needed.

  12. Sulforaphane (SFN: An Isothiocyanate in a Cancer Chemoprevention Paradigm

    Directory of Open Access Journals (Sweden)

    Mohammad Fahad Ullah

    2015-07-01

    Full Text Available The International Agency for Research on Cancer (IARC in its latest World Cancer Report (2014 has projected the increase in the global cancer burden from 14 million (2012 to 22 million incidence annually within the next two decades. Such statistics warrant a collaborative engagement of conventional and complementary and alternative therapies to contain and manage cancer. In recent years, there has been a shift in the cancer chemoprevention paradigm with a significant focus turning towards bioactive components of human diets for their anticancer properties. Since diet is an integral part of lifestyle and given that an estimated one third of human cancers are believed to be preventable though appropriate lifestyle modification including dietary habits, the current shift in the conventional paradigm assumes significance. Several epidemiological studies have indicated that consumption of broccoli is associated with a lower risk of cancer incidence including breast, prostate, lung, stomach and colon cancer. The edible plant belonging to the family of cruciferae such as broccoli is a rich source of glucoraphanin, a precursor of isothiocyanate sulforaphane which is considered to be a potent anti-cancer agent. Plant-based dietary agents such as sulforaphane mimic chemotherapeutic drugs such as vorinostat, possessing histone deacetylase inhibition activity. Evidence from epidemiological and experimental studies have emerged, enhancing the clinical plausibility and translational value of sulforaphane in cancer chemoprevention. The present review provides the current understanding of the cancer chemopreventive pharmacology of sulforaphane towards its potential as an anticancer agent.

  13. The systemic nature of mustard lung: Comparison with COPD patients

    Directory of Open Access Journals (Sweden)

    Shahriary Alireza

    2017-11-01

    Full Text Available Sulphur mustard (SM is a powerful blister-causing alkylating chemical warfare agent used by Iraqi forces against Iran. One of the known complications of mustard gas inhalation is mustard lung which is discussed as a phenotype of chronic obstructive pulmonary disease (COPD. In this complication, there are clinical symptoms close to COPD with common etiologies, such as in smokers. Based on information gradually obtained by conducting the studies on mustard lung patients, systemic symptoms along with pulmonary disorders have attracted the attention of researchers. Changes in serum levels of inflammatory markers, such as C-reactive protein (CRP, tumor necrosis factor alpha (TNF-α, nuclear factor κB (NF-κB, matrix metalloproteinases (MMPs, interleukin (IL, chemokines, selectins, immunoglobulins, and signs of imbalance in oxidant-antioxidant system at serum level, present the systemic changes in these patients. In addition to these, reports of extra-pulmonary complications, such as osteoporosis and cardiovascular disease are also presented. In this study, the chance of developing the systemic nature of this lung disease have been followed on using the comparative study of changes in the mentioned markers in mustard lung and COPD patients at stable phases and the mechanisms of pathogenesis and phenomena, such as airway remodeling in these patients.

  14. Thermal and pressure stability of myrosinase enzymes from black mustard (Brassica nigra L. W.D.J Koch. var. nigra), brown mustard (Brassica juncea L. Czern. var. juncea) and yellow mustard (Sinapsis alba L. Subsp Maire) seeds

    OpenAIRE

    Okunade, O. A.; Ghawi, S. K.; Methven, Lisa; Niranjan, Keshavan

    2015-01-01

    This study investigates the effects of temperature and pressure on inactivation of myrosinase extracted from black, brown and yellow mustard seeds. Brown mustard had higher myrosinase activity (2.75 un/mL) than black (1.50 un/mL) and yellow mustard (0.63 un/mL). The extent of enzyme inactivation increased with pressure (600-800 MPa) and temperature (30-70 °C) for all the mustard seeds. However, at combinations of lower pressures (200-400 MPa) and high temperatures (60-80 °C), there was less i...

  15. Vapor-liquid equilibria of the binary system 1,5-hexadiene + allyl chloride

    NARCIS (Netherlands)

    Raeissi, S.; Florusse, L.J.; Peters, C.J.

    2014-01-01

    Knowledge of accurate vapor–liquid equilibrium data for mixtures of allyl chloride and 1,5-hexadiene is important for several industrial purposes. The bubble points of binary mixtures of allyl chloride and 1,5-hexadiene have been measured experimentally using a synthetic method. Measurements were

  16. Memory effects in palladium-catalyzed allylic Alkylations of 2-cyclohexen-1-yl acetate

    DEFF Research Database (Denmark)

    Svensen, Nina; Fristrup, Peter; Tanner, David Ackland

    2007-01-01

    The objective of this work was to characterize the enantiospecificity of the allylic alkylation of enantioenriched 2-cyclohexen-1-yl acetate with the enolate ion of dimethyl malonate catalyzed by unsymmetrical palladium catalysts. The precatalysts employed were (eta(3)-allyl)PdLCl, where L...

  17. Practical Stannylation of Allyl Acetates Catalyzed by Nickel with Bu3 SnOMe.

    Science.gov (United States)

    Komeyama, Kimihiro; Itai, Yuuhei; Takaki, Ken

    2016-06-27

    A practical and scalable nickel-catalyzed allylic stannylation of allyl acetates with Bu3 SnOMe is described. A variety of acyclic and cyclic allyl acetates, even with base-sensitive moieties, undergoes the stannylation by using NiBr2 /4,4'-di-tert-butylbipyridine (dtbpy)/Mn catalyst system to afford highly functionalized allyl stannanes with excellent regioselectivity and yields. Furthermore, the scope of protocol is also extended by the reaction of propargyl acetates, giving rise to propargyl or allenyl stannanes. Additionally, a unique diastereoselectivity using the nickel catalyst different from the palladium was demonstrated for the stannylation of cyclic allyl acetates. In the reaction, inexpensive and stable nickel complexes, abundant reductant (Mn), and atom-economical stannyl source were used. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Construction of an Asymmetric Quaternary Carbon Center via Allylation of Hydrazones

    International Nuclear Information System (INIS)

    Kim, Jin Bum; Satyender, Apuri; Jang, Doo Ok

    2013-01-01

    Asymmetric indium-mediated allylation of imine derivatives bearing a chiral auxiliary is a reliable strategy for the synthesis of chiral homoallylic amines. Various techniques for indium-mediated stereoselective allylation of imines bearing a chiral auxiliary have been reported. In 1997 Loh and co-workers reported indium-mediated allylation with imines derived from L-valine methyl ester. Since then, many forms of indium-mediated allylation bearing a chiral auxiliary have been reported, including imines derived from (S)-valinol, (R)-phenylglycinol, uracil, (R)-phenylglycinol methyl ester, N-tert-butanesufinamide, and (1R,2S)-1-amino-2-indanol. However, the synthesis of chiral auxiliaries often involves a laborious multi-step synthesis with expensive reagents. Therefore, the development of readily accessible chiral auxiliaries for asymmetric indium-mediated all-ylation is in high demand

  19. Applications of deuterium labeling in studies of drug metabolism: metabolism of trideuteroaniline mustard

    International Nuclear Information System (INIS)

    Cox, P.J.; Farmer, P.B.; Foster, A.B.; Jarman, M.

    1977-01-01

    In a continuation of a study of aniline mustard, the metabolism of 2,4,6-trideuteroaniline mustard [N-N-di-(2-chloroethyl)-2,4,6-trideuteroaniline] was investigated. Measurements of the ratios of deuterated to nondeuterated species in p-hydroxyaniline mustard and N-(2-chloroethyl)-4-hydroxyaniline isolated following in vitro metabolism of a mixture of aniline mustard and aniline mustard-d 3 enabled a determination both of the kinetic isotope effect and of the extents of NIH shifts and indicated the probable metabolite sequence

  20. Mugwort-Mustard Allergy Syndrome due to Broccoli Consumption

    Directory of Open Access Journals (Sweden)

    Yuri Sugita

    2016-01-01

    Full Text Available Pollen-food allergy syndrome (PFAS is a relatively rare form of food allergy which develops in individuals who are sensitized to pollen. Tree pollens, especially birch pollen, frequently induce PFAS; however, the incidence of PFAS due to grass or weed pollens such as ragweed or mugwort is relatively rare. Mugwort-mustard allergy syndrome (MMAS is an example of a PFAS in which individuals sensitized to mugwort may develop an allergy to mustard and experience severe reactions. We herein describe a case of MMAS due to broccoli consumption.

  1. Urease from Helicobacter pylori is inactivated by sulforaphane and other isothiocyanates

    Science.gov (United States)

    Fahey, Jed W.; Stephenson, Katherine K.; Wade, Kristina L.; Talalay, Paul

    2013-01-01

    Infections by Helicobacter pylori are very common, causing gastroduodenal inflammation including peptic ulcers, and increasing the risk of gastric neoplasia. The isothiocyanate (ITC) sulforaphane [SF; 1-isothiocyanato-4-(methylsulfinyl)butane] derived from edible crucifers such as broccoli is potently bactericidal against Helicobacter, including antibiotic-resistant strains, suggesting a possible dietary therapy. Gastric H. pylori infections express high urease activity which generates ammonia, neutralizes gastric acidity, and promotes inflammation. The finding that SF inhibits (inactivates) urease (jack bean and Helicobacter) raised the issue of whether these properties might be functionally related. The rates of inactivation of urease activity depend on enzyme and SF concentrations and show first order kinetics. Treatment with SF results in time-dependent increases in the ultraviolet absorption of partially purified Helicobacter urease in the 280–340 nm region. This provides direct spectroscopic evidence for the formation of dithiocarbamates between the ITC group of SF and cysteine thiols of urease. The potencies of inactivation of Helicobacter urease by isothiocyanates structurally related to SF were surprisingly variable. Natural isothiocyanates closely related to SF, previously shown to be bactericidal (berteroin, hirsutin, phenethyl isothiocyanate, alyssin, and erucin), did not inactivate urease activity. Furthermore, SF is bactericidal against both urease positive and negative H. pylori strains. In contrast, some isothiocyanates such as benzoyl-ITC, are very potent urease inactivators, but are not bactericidal. The bactericidal effects of SF and other ITC against Helicobacter are therefore not obligatorily linked to urease inactivation, but may reduce the inflammatory component of Helicobacter infections. PMID:23583386

  2. Copper-catalyzed decarboxylative trifluoromethylation of allylic bromodifluoroacetates.

    Science.gov (United States)

    Ambler, Brett R; Altman, Ryan A

    2013-11-01

    The development of new synthetic fluorination reactions has important implications in medicinal, agricultural, and materials chemistries. Given the prevalence and accessibility of alcohols, methods to convert alcohols to trifluoromethanes are desirable. However, this transformation typically requires four-step processes, specialty chemicals, and/or stoichiometric metals to access the trifluoromethyl-containing product. A two-step copper-catalyzed decarboxylative protocol for converting allylic alcohols to trifluoromethanes is reported. Preliminary mechanistic studies distinguish this reaction from previously reported Cu-mediated reactions.

  3. Oral Administration of (S)-Allyl-l-Cysteine and Aged Garlic Extract to Rats: Determination of Metabolites and Their Pharmacokinetics.

    Science.gov (United States)

    Park, Taehoon; Oh, Ju-Hee; Lee, Joo Hyun; Park, Sang Cheol; Jang, Young Pyo; Lee, Young-Joo

    2017-11-01

    ( S )-Allyl-l-cysteine is the major bioactive compound in garlic. ( S )-Allyl-l-cysteine is metabolized to ( S )-allyl-l-cysteine sulfoxide, N -acetyl-( S )-allyl-l-cysteine, and N -acetyl-( S )-allyl-l-cysteine sulfoxide after oral administration. An accurate LC-MS/MS method was developed and validated for the simultaneous quantification of ( S )-allyl-l-cysteine and its metabolites in rat plasma, and the feasibility of using it in pharmacokinetic studies was tested. The analytes were quantified by multiple reaction monitoring using an atmospheric pressure ionization mass spectrometer. Because significant quantitative interference was observed between ( S )-allyl-l-cysteine and N -acetyl-( S )-allyl-l-cysteine as a result of the decomposition of N -acetyl-( S )-allyl-l-cysteine at the detector source, chromatographic separation was required to discriminate ( S )-allyl-l-cysteine and its metabolites on a reversed-phase C 18 analytical column with a gradient mobile phase consisting of 0.1% formic acid and acetonitrile. The calibration curves of ( S )-allyl-l-cysteine, ( S )-allyl-l-cysteine sulfoxide, N -acetyl-( S )-allyl-l-cysteine, and N -acetyl-( S )-allyl-l-cysteine sulfoxide were linear over each concentration range, and the lower limits of quantification were 0.1 µg/mL [( S )-allyl-l-cysteine and N -acetyl-( S )-allyl-l-cysteine] and 0.25 µg/mL [( S )-allyl-l-cysteine sulfoxide and N -acetyl-( S )-allyl-l-cysteine sulfoxide]. Acceptable intraday and inter-day precisions and accuracies were obtained at three concentration levels. The method satisfied the regulatory requirements for matrix effects, recovery, and stability. The validated LC-MS/MS method was successfully used to determine the concentration of ( S )-allyl-l-cysteine and its metabolites in rat plasma samples after the administration of ( S )-allyl-l-cysteine or aged garlic extract. Georg Thieme Verlag KG Stuttgart · New York.

  4. 27 CFR 21.65 - Formula No. 38-B.

    Science.gov (United States)

    2010-04-01

    .... Cinnamic aldehyde, N.F. IX. Cinnamon oil, N.F. Citronella oil, natural. Clove oil, N.F. Coal tar, U.S.P....P. Methyl salicylate, N.F. Mustard oil, volatile (allyl isothiocyanate), U.S.P. XII. Peppermint oil... pounds of any one, or a total of 10 pounds of two or more, of the oils and substances listed below: Alpha...

  5. In vitro assessment of antiproliferative action selectivity of dietary isothiocyanates for tumor versus normal human cells

    Directory of Open Access Journals (Sweden)

    Konić-Ristić Aleksandra

    2016-01-01

    Full Text Available Background/Aim. Numerous epidemiological studies have shown beneficial effects of cruciferous vegetables consumption in cancer chemoprevention. Biologically active compounds of different Brassicaceae species with antitumor potential are isothiocyanates, present in the form of their precursors - glucosinolates. The aim of this study was to determine the selectivity of antiproliferative action of dietary isothiocyanates for malignant versus normal cells. Methods. Antiproliferative activity of three isothiocyanates abundant in human diet: sulforaphane, benzyl isothiocyanate (BITC and phenylethyl isothiocyanate, on human cervix carcinoma cell line - HeLa, melanoma cell line - Fem-x, and colon cancer cell line - LS 174, and on peripheral blood mononuclear cells (PBMC, with or without mitogen, were determined by MTT colorimetric assay 72 h after their continuous action. Results. All investigated isothiocyanates inhibited the proliferation of HeLa, Fem-x and LS 174 cells. On all cell lines treated, BITC was the most potent inhibitor of cell proliferation with half-maximum inhibitory concentration (IC50 values of 5.04 mmoL m-3 on HeLa cells, 2.76 mmol m-3 on Fem-x, and 14.30 mmol m-3 on LS 174 cells. Antiproliferative effects on human PBMC were with higher IC50 than on malignant cells. Indexes of selectivity, calculated as a ratio between IC50 values obtained on PBMC and malignant cells, were between 1.12 and 16.57, with the highest values obtained for the action of BITC on melanoma Fem-x cells. Conclusion. Based on its antiproliferative effects on malignant cells, as well as the selectivity of the action to malignant vs normal cells, benzyl isothiocyanate can be considered as a promising candidate in cancer chemoprevention. In general, the safety of investigated compounds, in addition to their antitumor potential, should be considered as an important criterion in cancer chemoprevention. Screening of selectivity is a plausible approach to the evaluation

  6. Genetic diversity analysis of mustard ( Brassica spp.) germplasm ...

    African Journals Online (AJOL)

    Molecular characterization of 16 mustard (Brassica spp.) genotypes by using 12 RAPD markers revealed that three primers GLA-11, OPB-04 and OPD-02 showed good technical resolution and sufficient variations among different genotypes. A total of 40 RAPD bands were scored of which 38 (94.87%) polymorphic ...

  7. Sulphur Mustard Poisoning and Its Complications in Iranian Veterans

    Directory of Open Access Journals (Sweden)

    Beeta Balali-Mood

    2009-09-01

    Full Text Available Sulphur mustard is a chemical warfare agent, which was largelyused during the World War One and in Iraq-Iran conflict. It mayalso be used as a chemical terrorism agent. Therefore, medicalprofessions should have sufficient knowledge and be preparedfor medical intervention of any such chemical attack.Sulphur mustard exerts direct toxic effects on the eyes, skin,and respiratory tract, with subsequent systemic actions on thenervous, immunologic, hematologic, digestive, and reproductivesystems. It is an alkylating agent that affects DNA synthesis andthus, delayed complications have been considered since theWorld War One. Cases of malignancies in the target organs particularlyin hematopoietic, respiratory, and digestive systemswere reported. Common delayed respiratory complications includechronic bronchitis, bronchiectasis, frequent bronchopneumonia,and pulmonary fibrosis, all of which tend to deterioratewith time. Severe dry skin, delayed keratitis, and reduction ofnatural killer cells with subsequent increased risk of infectionsand malignancies are also among the most distressing long-termconsequences of sulphur mustard intoxication. However, despiteextensive research that has been conducted on Iranian veteransduring the past decades, major gaps continue to remain in thesulphur mustard literature. Immunological and neurological dysfunctionsand the relationship between exposure to sulphur mustardand mutagenicity, carcinogenicity, and teratogenicity areimportant fields that require further studies, particularly on Iranianveterans with chronic health problems caused by sulphurmustard poisoning. There is also a paucity of information on themedical management of acute and delayed toxic effects of sulphurmustard poisoning, a subject that greatly challenges themedical professions.

  8. Genetic diversity analysis of mustard (Brassica spp.) germplasm ...

    African Journals Online (AJOL)

    sunny t

    successfully cultivated between Aman and Boro rice rotation without affecting this popular cropping pattern. So, it is urgent to analyze the genetic diversity and its response for the selection of short duration mustard genotypes for increasing our cropping intensity. Diversity at marker loci is currently the most feasible strategy ...

  9. Onion and weed response to mustard (Sinapis alba) seed meal

    Science.gov (United States)

    Weed control in organic onion production is often difficult and expensive, requiring numerous cultivations and extensive hand-weeding. Onion safety and weed control with mustard seed meal (MSM) derived from Sinapis alba was evaluated in greenhouse and field trials. MSM applied at 110, 220, and 440 g...

  10. Response of bread wheat to increasing mustard meal nitrogen ...

    African Journals Online (AJOL)

    Greenhouse experiment on the nitrogen uptake from the mustard meal using 15N showed significant difference on both soil types. On the Vertisol the per cent nitrogen derived from the meal and per cent nitrogen use efficiency varied from 18 to 40 and from 18 to 62%, respectively. On the Nitosol, these values varied from 25 ...

  11. Genetic diversity in Ethiopian mustard ( Bbrassica carinata a. braun ...

    African Journals Online (AJOL)

    In this study, genetic diversity in 60 Ethiopian mustard genotypes, collected from 16 regions of Ethiopia, were assessed using the techniques of cluster and ... for the majority of traits of interest: seed yield/plot, seed yield/plant, biomass/plot, biomass/plant, plant height, number of pods/plant, 1000 seeds' weight and oil content ...

  12. 7 CFR 457.168 - Mustard crop insurance provisions.

    Science.gov (United States)

    2010-01-01

    ... amount of production delivered, and the processor contract provides for delivery of the mustard under... that are identified by the Food and Drug Administration or other public health organizations of the... FCIC including, but not limited to, protein and oil will not be considered. (e) Any production...

  13. Pulmonary Complications of Mustard Gas Exposure: A Study on Cadavers

    Directory of Open Access Journals (Sweden)

    Behnam Behnoush

    2011-04-01

    Full Text Available Sulfur mustard gas is one of the chemical warfare gases that roughly about 45000 soldiers continue to suffer long-lasting consequences of exposure during the Iran-Iraq war between 1980 and 1988. According to the common pulmonary lesions due to this gas exposure, we studied gross and microscopic pulmonary lesions in cadavers and also assessed the main causes of mortality caused by mustard gas exposure. A case-series study was performed on hospital record files of 100 cadavers that were exposed with documented sulfur mustard gas during the Iran-Iraq war from 1979 to 1988 and autopsied in legal medicine organization In Tehran between 2005 and 2007 and gross and microscopic pathological findings of autopsied organs such as hematological, pulmonary, hepatic, and renal changes were evaluated. All cases were male with the mean age of 43 years. The time interval between the gas exposure and death was almost 20years. The most frequent pulmonary complication was chronic bronchitis in 81% of autopsied cadavers. Other pulmonary findings were progressive pulmonary fibrosis (9%, pulmonary infections and tuberculosis (29%, malignant cellular infiltration (4%, and aspergilloma (1%. According to the chronic progressive lesions caused by mustard gas exposure such as pulmonary lesions and also its high mortality rate, suitable programming for protection of the gas exposed persons and prohibiting chemical warfare are recommended.

  14. Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

    Science.gov (United States)

    Sharma, Ankit; Hartwig, John F

    2013-11-27

    We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

  15. Decarbonylation and hydrogenation reactions of allyl alcohol and acrolein on Pd(110)

    Science.gov (United States)

    Shekhar, Ratna; Barteau, Mark A.

    1994-11-01

    Allyl alcohol and acrolein reactions on the Pd(110) surface were investigated using temperature programmed desorption. For both unsaturated oxygenates, three coverage-dependent reaction pathways were observed. At low coverages, allyl alcohol decomposed completely to CO, hydrogen and carbonaceous species on the surface. For θ > 0.15 monolayer, ethylene (and small amounts of ethane) desorbed at ca. 295 K. Near saturation coverages, desorption of propanal was detected at ca. 235 K. The parent molecule, allyl alcohol, desorbed only after exposures sufficient to saturate these channels. Acrolein decomposition spectra were similar to those observed for allyl alcohol decomposition on the clean surface. Additional experiments with allyl alcohol on hydrogen- and deuterium-precoveredPd(110) surfaces demonstrated increased hydrogenation of the C 2-hydrocarbon products along with hydrogenation of allyl alcohol to 1-propanol. However, in contrast to previous results for allyl alcohol on the Pd(111) surface, there was no evidence for C-O scission reactions of any C 3 oxygenate on Pd(110).

  16. Therapeutic journery of nitrogen mustard as alkylating anticancer agents: Historic to future perspectives.

    Science.gov (United States)

    Singh, Rajesh K; Kumar, Sahil; Prasad, D N; Bhardwaj, T R

    2018-05-10

    Cancer is considered as one of the most serious health problems today. The discovery of nitrogen mustard as an alkylating agent in 1942, opened a new era in the cancer chemotherapy. This valuable class of alkylating agent exerts its biological activity by binding to DNA, cross linking two strands, preventing DNA replication and ultimate cell death. At the molecular level, nitrogen lone pairs of nitrogen mustard generate a strained intermediate "aziridinium ion" which is very reactive towards DNA of tumor cell as well as normal cell resulting in various adverse side effects alogwith therapeutic implications. Over the last 75 years, due to its high reactivity and peripheral cytotoxicity, numerous modifications have been made in the area of nitrogen mustard to improve its efficacy as well as enhancing drug delivery specifically to tumor cells. This review mainly discusses the medicinal chemistry aspects in the development of various classes of nitrogen mustards (mechlorethamine, chlorambucil, melphalan, cyclophosphamide and steroidal based nitrogen mustards). The literature collection includes the historical and the latest developments in these areas. This comprehensive review also attempted to showcase the recent progress in the targeted delivery of nitrogen mustards that includes DNA directed nitrogen mustards, antibody directed enzyme prodrug therapy (ADEPT), gene directed enzyme prodrug therapy (GDEPT), nitrogen mustard activated by glutathione transferase, peptide based nitrogen mustards and CNS targeted nitrogen mustards. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

  17. Reaction of aryl diazonium tetrafluoro borates with allyl methacrylate in the presence of rhodanide-anion

    International Nuclear Information System (INIS)

    Grishchuk, B.D.; Baranovskij, V.S.; Simchak, R.V.; Tulajdan, G.N.; Gorbovoj, P.M.

    2006-01-01

    Reaction of aryl diazonium tetrafluoro borates (I) with allyl ester of methacrylic acid in the water-acetone (1:5) medium is studied by means of IR spectroscopy and 1 H NMR. It is established that (I) reacts with aryl methacrylate in the presence of rhodanide-anion and catalytic quantities of copper salts with the formation of allyl esters of 2-thiocyanato-2-methyl-3-aryl propionic acids with the yield of 32-56%. Allyl fragment of biunsaturated compound shows no reaction under the tested conditions [ru

  18. A Facile and Mild Synthesis of Trisubstituted Allylic Sulfones from Morita-Baylis-Hillman Carbonates

    Directory of Open Access Journals (Sweden)

    Lin Jiang

    2015-05-01

    Full Text Available An efficient and catalyst-free synthesis of trisubstituted allylic sulfones through an allylic sulfonylation reaction of Morita-Baylis-Hillman (MBH carbonates with sodium sulfinates has been developed. Under the optimized reaction conditions, a series of trisubstituted allylic sulfones were rapidly prepared in good to excellent yields (71%–99% with good to high selectivity (Z/E from 79:21 to >99:1. Compared with known synthetic methods, the current protocol features mild reaction temperature, high efficiency and easily available reagents.

  19. A facile and mild synthesis of trisubstituted allylic sulfones from Morita-Baylis-Hillman carbonates.

    Science.gov (United States)

    Jiang, Lin; Li, Yong-Gen; Zhou, Jiang-Feng; Chuan, Yong-Ming; Li, Hong-Li; Yuan, Ming-Long

    2015-05-07

    An efficient and catalyst-free synthesis of trisubstituted allylic sulfones through an allylic sulfonylation reaction of Morita-Baylis-Hillman (MBH) carbonates with sodium sulfinates has been developed. Under the optimized reaction conditions, a series of trisubstituted allylic sulfones were rapidly prepared in good to excellent yields (71%-99%) with good to high selectivity (Z/E from 79:21 to >99:1). Compared with known synthetic methods, the current protocol features mild reaction temperature, high efficiency and easily available reagents.

  20. Effects of native herbs and light on garlic mustard (Alliaria petiolata) invasion

    Science.gov (United States)

    Phillips-Mao, Laura; Larson, Diane L.; Jordan, Nicholas R.

    2014-01-01

    The degree to which invasive species drive or respond to environmental change has important implications for conservation and invasion management. Often characterized as a driver of change in North American woodlands, the invasive herb garlic mustard may instead respond to declines in native plant cover and diversity. We tested effects of native herb cover, richness, and light availability on garlic mustard invasion in a Minnesota oak woodland. We planted 50 garlic mustard seeds into plots previously planted with 0 to 10 native herb species. We measured garlic mustard seedling establishment, survival to rosette and adult stages, and average (per plant) and total (per plot) biomass and silique production. With the use of structural equation models, we analyzed direct, indirect, and net effects of native cover, richness, and light on successive garlic mustard life stages. Native plant cover had a significant negative effect on all life stages. Species richness had a significant positive effect on native cover, resulting in indirect negative effects on all garlic mustard stages, and net negative effects on adult numbers, total biomass, and silique production. Light had a strong negative effect on garlic mustard seedling establishment and a positive effect on native herb cover, resulting in significant negative net effects on garlic mustard rosette and adult numbers. However, light's net effect on total garlic mustard biomass and silique production was positive; reproductive output was high even in low-light/high-cover conditions. Combined effects of cover, richness, and light suggest that native herbs provide biotic resistance to invasion by responding to increased light availability and suppressing garlic mustard responses, although this resistance may be overwhelmed by high propagule pressure. Garlic mustard invasion may occur, in part, in response to native plant decline. Restoring native herbs and controlling garlic mustard seed production may effectively reduce

  1. Facile synthesis of aliphatic isothiocyanates and thioureas on solid phase using peptide coupling reagents

    DEFF Research Database (Denmark)

    Boas, Ulrik; Andersen, Heidi Gertz; Christensen, Jørn B.

    2004-01-01

    Peptide coupling reagents can be used as versatile reagents for the formation of aliphatic isothiocyanates and thioureas on solid phase from the corresponding solid-phase anchored aliphatic primary amines. The formation of the thioureas is fast and highly chemoselective, and proceeds via formatio...

  2. Bioavailability of Isothiocyanates From Broccoli Sprouts in Protein, Lipid, and Fiber Gels

    NARCIS (Netherlands)

    Oliviero, Teresa; Lamers, Simone; Capuano, Edoardo; Dekker, Matthijs; Verkerk, Ruud

    2018-01-01

    Scope: Optimization of bioavailability of dietary bioactive health-beneficial compounds is as important as increasing their concentration in foods. The aim of this study is to explore the change in bioavailability of isothiocyanates (ITCs) in broccoli sprouts incorporated in protein, fiber, and

  3. A new efficient synthesis of isothiocyanates from amines using di-tert-butyl dicarbonate

    DEFF Research Database (Denmark)

    Munch, Henrik; Hansen, Jon S.; Pittelkow, Michael

    2008-01-01

    Alkyl and aryl amines are converted smoothly to the corresponding isothiocyanates via the dithiocarbamates in good to excellent yields using di-tert-butyl dicarbonate (Boc(2)O) and 1-3 mol% of DMAP or DABCO as catalyst. As most of the byproducts are volatile, the work-up involves simple evaporation...

  4. Microbial- and isothiocyanate-mediated control of Phytophthora and Pythium species

    Science.gov (United States)

    M.F. Cohen; E. Yamamoto; E. Condeso; B.L. Anacker; N. Rank; M. Mazzola

    2008-01-01

    Plant pathogens of the oomycete lineage share common susceptibilities to many biotic and abiotic stresses. We are investigating the potential of antagonistic bacteria, isothiocyanates, and mycophagous amoebae to control diseases caused by Phytophthora spp., including the etiologic agent of sudden oak death, Phytophthora ramorum (...

  5. Pseudomonas sax genes overcome aliphatic isothiocyanate-mediated non-host resistance in Arabidopsis

    Science.gov (United States)

    Jun Fan; Casey Crooks; Gary Creissen; Lionel Hill; Shirley Fairhurst; Peter Doerner; Chris Lamb

    2011-01-01

    Most plant-microbe interactions do not result in disease; natural products restrict non-host pathogens. We found that sulforaphane (4-methylsulfinylbutyl isothiocyanate), a natural product derived from aliphatic glucosinolates, inhibits growth in Arabidopsis of non-host Pseudomonas bacteria in planta. Multiple sax genes (saxCAB/F/D/G) were identified in Pseudomonas...

  6. Polymerization of allyl alcohol by radiation to obtain microencapsulated structure

    International Nuclear Information System (INIS)

    Usanmaz, A.; Saricilar, S.

    1989-01-01

    Allyl alcohol was polymerized by radiation under various conditions. The limiting conversions were about 30 % in bulk, 35 % when containing 0.03 mole fraction AlCl 3 and 50 % when water was contained at 27 % (v/v). Irradiation was done with Co-60 gamma rays at room temperature and under vacuum. The presence of oxygen did not cause any change in the reaction rate. Molecular weights were determined by viscosity and cryoscopic methods. K and α values were found to be 3.57 x 10 -4 and 0.62 for solutions in methanol at 25degC. The polymers up to about 10 % conversion were viscous liquids having microcapsular structures: at high conversions, they became hard and glassy. The microencapsulated structures were also retained in solutions in methanol, acetone, and isopropyl alcohol. The samples were insoluble in water, benzene, and toluence. (author)

  7. Competitive Interactions of Garlic Mustard (Alliaria petiolata) and Damesrocket (Hesperis matronalis)

    Science.gov (United States)

    Leicht-Young, Stacey A.; Pavlovic, Noel B.; Adams, Jean V.

    2012-01-01

    Competitive interactions between native plants and nonnative, invasive plant species have been extensively studied; however, within degraded landscapes, the effect of interspecific interactions among invasive plants is less explored. We investigated a competitive interaction between two sympatric, invasive mustard species that have similar life history strategies and growth forms: garlic mustard and damesrocket. Greenhouse experiments using a full range of reciprocal density ratios were conducted to investigate interspecific competition. Garlic mustard had a negative effect on the final biomass, number of leaves, and relative growth rate in height of damesrocket. Survival of damesrocket was not negatively affected by interspecific competition with garlic mustard; however, garlic mustard showed higher mortality because of intraspecific competition. These results indicated that although garlic mustard has been observed to be the dominant species in this landscape, it may not completely outcompete damesrocket in all situations. Studies of invasive species in competition are important in degraded landscapes because this is the common situation in many natural areas.

  8. A convenient procedure for the synthesis of allyl and benzyl ethers ...

    Indian Academy of Sciences (India)

    Unknown

    Department of Chemistry, Pondicherry University, Pondicherry 605 014, .... organic synthesis we hope that the procedure described in this paper will find ... Allyl bromide (Fluka) and benzyl bromide (E Merck) were freshly distilled before use.

  9. Biomarkers derived from heterolytic and homolytic cleavage of allylic hydroperoxides resulting from alkenone autoxidation

    Digital Repository Service at National Institute of Oceanography (India)

    Rontania, J.F.; Harji, R.; Volkmanc, J.K.

    Laboratory incubation of alkenone mixtures with tert-butyl hydroperoxide and di-tert-butyl nitroxide (radical initiator) in hexane, as a means to simulate alkenone autoxidation processes, rapidly led to the formation of allylic hydroperoxides, whose...

  10. α,β-Unsaturated imines via Ru-catalyzed coupling of allylic alcohols and amines.

    Science.gov (United States)

    Rigoli, Jared W; Moyer, Sara A; Pearce, Simon D; Schomaker, Jennifer M

    2012-03-07

    A convenient synthesis of α,β-unsaturated imines requiring only an allylic alcohol, an amine and a Ru catalyst has been developed. The use of large excesses of oxidant and the purification of sensitive intermediates can be avoided.

  11. Development of chiral terminal-alkene-phosphine hybrid ligands for palladium-catalyzed asymmetric allylic substitutions.

    Science.gov (United States)

    Liu, Zhaoqun; Du, Haifeng

    2010-07-02

    A variety of novel chiral terminal-alkene-phosphine hybrid ligands were successfully developed from diethyl L-tartrate for palladium-catalyzed asymmetric allylic alkylations, etherifications, and amination to give the desired products in excellent yields and ee's.

  12. Total synthesis of broussonetine F: the orthoamide Overman rearrangement of an allylic diol.

    Science.gov (United States)

    Hama, Naoto; Aoki, Toshihiro; Miwa, Shohei; Yamazaki, Miki; Sato, Takaaki; Chida, Noritaka

    2011-02-18

    A first total synthesis of broussonetine F from diethyl L-tartrate was achieved. The cornerstone of our synthesis was an orthoamide Overman rearrangement, which provided an allylic amino alcohol with complete diastereoselectivity.

  13. Vanadium-Catalyzed Enantioselective Desymmetrization of meso-Secondary Allylic Alcohols and Homoallylic Alcohols

    OpenAIRE

    Li, Zhi; Zhang, Wei; Hisashi Yamamoto, H.

    2008-01-01

    Vanadium-catalyzed epoxidation has extended substrate scope. In addition to various bis-allylic alcohols, bis-homoallylic alcohols can also be desymmetrized using our Vanadium-Bis-hydroxamic acid complexes.

  14. Solid radiation curable polyene compositions containing liquid polythiols and solid styrene-allyl copolymer based polyenes

    International Nuclear Information System (INIS)

    Morgan, C.R.

    1977-01-01

    Novel styrene-allyl alcohol copolymer based solid polyene compositions which when mixed with liquid polythiols can form solid curable polyene-polythiol systems are claimed. These solid polyenes, containing at least two reactive carbon-to-carbon unsaturated bonds, are urethane or ester derivatives of styrene-allyl alcohol copolymers. The solid polyenes are prepared by treating the hydroxyl groups of a styrene-allyl alcohol copolymer with a reactive unsaturated isocyanate, e.g., allyl isocyanate or a reactive unsaturated carboxylic acid, e.g., acrylic acid. Upon exposure to a free radical generator, e.g., actinic radiation, the solid polyene-polythiol compositions cure to solid, insoluble, chemically resistant, cross-linked polythioether products. Since the solid polyene-liquid polythiol composition can be cured in a solid state, such a curable system finds particular use in preparation of coatings, imaged surfaces such as photoresists, particularly solder-resistant photoresists, printing plates, etc

  15. Enantioselective synthesis of almorexant via iridium-catalysed intramolecular allylic amidation

    NARCIS (Netherlands)

    Fananas Mastral, Martin; Teichert, Johannes F.; Fernandez-Salas, Jose Antonio; Heijnen, Dorus; Feringa, Ben L.

    2013-01-01

    An enantioselective synthesis of almorexant, a potent antagonist of human orexin receptors, is presented. The chiral tetrahydroisoquinoline core structure was prepared via iridium-catalysed asymmetric intramolecular allylic amidation. Further key catalytic steps of the synthesis include an oxidative

  16. Computational estimation of soybean oil adulteration in Nepalese mustard seed oil based on fatty acid composition

    OpenAIRE

    Shrestha, Kshitij; De Meulenaer, Bruno

    2011-01-01

    The experiment was carried out for the computational estimation of soybean oil adulteration in the mustard seed oil using chemometric technique based on fatty acid composition. Principal component analysis and K-mean clustering of fatty acid composition data showed 4 major mustard/rapeseed clusters, two of high erucic and two of low erucic mustard type. Soybean and other possible adulterants made a distinct cluster from them. The methodology for estimation of soybean oil adulteration was deve...

  17. Selective epoxidation of allylic alcohols with a titania-silica aerogel

    Energy Technology Data Exchange (ETDEWEB)

    Dusi, M.; Mallat, T.; Baiker, A. [Lab. of Technical Chemistry, Swiss Federal Inst. of Technology, ETH-Zentrum, Zuerich (Switzerland)

    1998-12-31

    An amorphous mesoporous titania-silica aerogel (20 wt%TiO{sub 2} - 80 wt% SiO{sub 2}) and tert.-butylhydroperoxide (TBHP) have been used for the epoxidation of various allylic alcohols. Allylic alcohols possessing an internal double bond were more reactive than those with a terminal C=C bond. Epoxide selectivities could be improved by addition of (basic) zeolite 4 A and NaHCO{sub 3} to the reaction mixture. (orig.)

  18. Glucosinolate-derived isothiocyanates impact mitochondrial function in fungal cells and elicit an oxidative stress response necessary for growth recovery

    Directory of Open Access Journals (Sweden)

    Benoit eCalmes

    2015-06-01

    Full Text Available Glucosinolates are brassicaceous secondary metabolites that have long been considered as chemical shields against pathogen invasion. Isothiocyanates, are glucosinolate-breakdown products that have negative effects on the growth of various fungal species. We explored the mechanism by which isothiocyanates could cause fungal cell death using Alternaria brassicicola, a specialist Brassica pathogens, as model organism. Exposure of the fungus to isothiocyanates led to a decreased oxygen consumption rate, intracellular accumulation of reactive oxygen species and mitochondrial-membrane depolarization. We also found that two major regulators of the response to oxidative stress, i.e. the MAP kinase AbHog1 and the transcription factor AbAP1, were activated in the presence of isothiocyanates. Once activated by isothiocyanate-derived reactive oxygen species, AbAP1 was found to promote the expression of different oxidative-response genes. This response might play a significant role in the protection of the fungus against isothiocyanates as mutants deficient in AbHog1 or AbAP1 were found to be hypersensitive to these metabolites. Moreover, the loss of these genes was accompanied by a significant decrease in aggressiveness on Brassica. We suggest that the robust protection response against isothiocyanate-derived oxidative stress might be a key adaptation mechanism for successful infection of host plants by Brassicaceae-specialist necrotrophs like A. brassicicola.

  19. Teratology Studies on Lewisite and Sulfur Mustard Agents: Effects of Sulfur Mustard in Rats and Rabbits

    Energy Technology Data Exchange (ETDEWEB)

    Hackett, P. L.; Rommereim, R. L.; Burton, F. G.; Buschbom, R. L.; Sasser, L . B.

    1987-09-30

    Sulfur mustard (HD) was administered to rats and rabbits by intragastric intubation. Rats were dosed daily from 6 through 15 days of gestation (dg) with 0. 0.5, 1.0 or 2.0 mg of HD/kg; rabbits were dosed with 0, 0.4, 0.6 or 0.8 mg/kg on 6 through 19 dg. Maternal animals were weighed periodically and, at necropsy, were examined for gross lesions of major organs and reproductive performance; live fetuses were weighed and examined for external, internal and skeletal defects. In rats, reductions in body weights were observed in maternal animals and their female fetuses at the lowest administered dose (0.5 mg/kg), but the incidence of fetal malformations was not increased. In rabbits the highest administered dose (0.8 mg/kg) induced maternal mortality and depressed body weight measures but did not affect fetal development. These results suggest that orally administered HD is not teratogenic in rats and rabbits since fetal effects were observed only at dose levels that induced frank maternal toxicity. Estimations of dose ranges for "no observable effects levels" in rats and rabbits, respectively, were: < 0.5 and < 0.4 mg/kg in maternal animals and < 0.5 and > 0.8 mg/kg in their fetuses.

  20. Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

    Science.gov (United States)

    Bayeh, Liela; Le, Phong Q.; Tambar, Uttam K.

    2017-07-01

    The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years. Inspired by nature, enantioselective dihydroxylations, epoxidations and other oxidations of unsaturated hydrocarbons have been developed. More recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streamlined the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral building blocks with a newly formed stereocentre from petrochemical feedstocks while preserving the olefin functionality as a handle for further chemical elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation using the more common internal alkenes remains elusive. Here we report the enantioselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a catalytic hetero-ene reaction with a chalcogen-based oxidant. Our method enables non-symmetric internal alkenes to be selectively converted into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the resulting multifunctional chiral building blocks highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be used in the synthesis of complex target molecules.

  1. Mercury-induced oxidative stress in Indian mustard (Brassica juncea L.).

    Science.gov (United States)

    Shiyab, Safwan; Chen, Jian; Han, Fengxiang X; Monts, David L; Matta, Fank B; Gu, Mengmeng; Su, Yi; Masad, Motasim A

    2009-10-01

    Mercury, a potent neurotoxin, is released to the environment in significant amounts by both natural processes and anthropogenic activities. No natural hyperaccumulator plant has been reported for mercury phytoremediation. Few studies have been conducted on the physiological responses of Indian mustard, a higher biomass plant with faster growth rates, to mercury pollution. This study investigated the phytotoxicity of mercury to Indian mustard (Brassica juncea L.) and mercury-induced oxidative stress in order to examine the potential application of Indian mustard to mercury phytoremediation. Two common cultivars (Florida Broadleaf and Longstanding) of Indian mustard were grown hydroponically in a mercury-spiked solution. Plant uptake, antioxidative enzymes, peroxides, and lipid peroxidation under mercury stress were investigated. Antioxidant enzymes (catalase, CAT; peroxidase, POD; and superoxide dismutase, SOD) were the most sensitive indices of mercury-induced oxidative response of Indian mustard plants. Indian mustard effectively generated an enzymatic antioxidant defense system (especially CAT) to scavenge H(2)O(2), resulting in lower H(2)O(2) in shoots with higher mercury concentrations. These two cultivars of Indian mustard demonstrated an efficient metabolic defense and adaptation system to mercury-induced oxidative stress. A majority of Hg was accumulated in the roots and low translocations of Hg from roots to shoots were found in two cultivars of Indian mustard. Thus Indian mustard might be a potential candidate plant for phytofiltration/phytostabilization of mercury contaminated waters and wastewater.

  2. Sensory evaluation of dry-fermented sausage containing ground deodorized yellow mustard.

    Science.gov (United States)

    Li, Shuliu; Aliani, Michel; Holley, Richard A

    2013-10-01

    Ground deodorized yellow mustard is used as a binder and meat protein substitute in cooked processed meat products. Recent studies have shown that it has the potential to be used in uncooked processed meat products because of its natural antimicrobial properties. In the present study, ground deodorized yellow mustard was added to uncooked dry-fermented sausage during manufacture at 1% to 4% (w/w) and analyzed for its effects on starter cultures, physico-chemical properties, and consumer acceptability. Mustard had a nondose-dependent inhibitory effect on the Staphylococcus starter culture, had no effect on water activity or instrumental texture, and tended to accelerate sausage pH reduction. At 3% and 4% mustard, consumer scores on all sensory attributes as well as overall acceptability were significantly lower. The appearance and color of 3% and 4% mustard-treated sausages were liked slightly, whereas flavor, texture, and overall acceptability scores were reduced. The control without mustard and 1% mustard-treated sausages had similar sensory properties and were the most acceptable, while 2% mustard-treated sausages were given "like moderately" and "like slightly" descriptors. Sensory results mean that at concentrations necessary for mandated regulatory control of Escherichia coli O157:H7 in dry sausages, mustard may have a negative effect on consumer acceptance. © 2013 Institute of Food Technologists®

  3. Biodiesel from Mustard oil: a Sustainable Engine Fuel Substitute for Bangladesh

    Directory of Open Access Journals (Sweden)

    M.M. Alam

    2013-10-01

    Full Text Available Various attractive features of mustard oil based biodiesel as a potential substitute for engine fuel are investigated in this paper for use in Bangladesh. Although the use of mustard oil as edible oil has been reduced, Bangladesh still produces 0.22 million metric tons of mustard oil per year. This surplus mustard oil would satisfactorily be used as an alternative to diesel fuel, and thus could contribute in reducing the expenses for importing fuel from foreign countries. Moreover, the rural people of Bangladesh are capable of producing mustard oil themselves using indigenous machines. Fuel properties of biodiesel obtained from mustard oil were determined in the laboratory using standard procedure and an experimental setup was constructed to study the performance of a small diesel engine. It is observed that with biodiesel, the engine is capable of running without difficulty. Initially different lower blends of biodiesel (e.g., B20, B30 etc. have been used to avoid complicated modification of the engine and the fuel supply system. It is also found in some condition that mustard oil based biodiesel have better properties than those made from other vegetable oils. These properties of mustard oil based biodiesel were evaluated to validate its sustainability in Bangladesh. Keywords: biodiesel, indigenous machines, mustard oil, renewable energy policy, sustainability

  4. Platinum bioaccumulation by mustard plants (Sinapis alba L.)

    International Nuclear Information System (INIS)

    Hawienczyk, M.; Bystrzejewska-Piotrowska, G.; Kowalska, J.; Asztemborska, M.

    2005-01-01

    The ability of hydroponically cultivated Indian mustard plants (Sinapis alba L.) to accumulate platinum was investigated. The Pt-bioaccumulation in leaves, stem and shoots of plants growing for 2 and 4 weeks at Pt-concentration of 50 and 500 μg/L was compared. The relation between dry and fresh weight was also estimated. Adsorptive stripping voltammetry (AdSV) and mass spectrometry with inductively coupled plasma (ICP-MS) were applied for determination of Pt. Increasing Pt-concentration from 50 to 500 μg/L in the medium causes: (1) reduction of the root tissue hydration level at unchanged modification in aboveground parts of the plants and (2) decrease of the Pt transfer factor (TF) for roots and increase for leaves and stem. Duration of the culture influenced on Pt-accumulation in roots and in aboveground organs of mustard plants. Transfer factor for Pt between 560 and 1600 makes Indian mustard plants one at Pt-hyperaccumulators. Distribution of Pt-bioaccumulation in the plant organs may be useful for biomonitoring of platinum in the environment. (author)

  5. Mustard vesicant-induced lung injury: Advances in therapy

    International Nuclear Information System (INIS)

    Weinberger, Barry; Malaviya, Rama; Sunil, Vasanthi R.; Venosa, Alessandro; Heck, Diane E.; Laskin, Jeffrey D.; Laskin, Debra L.

    2016-01-01

    Most mortality and morbidity following exposure to vesicants such as sulfur mustard is due to pulmonary toxicity. Acute injury is characterized by epithelial detachment and necrosis in the pharynx, trachea and bronchioles, while long-term consequences include fibrosis and, in some instances, cancer. Current therapies to treat mustard poisoning are primarily palliative and do not target underlying pathophysiologic mechanisms. New knowledge about vesicant-induced pulmonary disease pathogenesis has led to the identification of potentially efficacious strategies to reduce injury by targeting inflammatory cells and mediators including reactive oxygen and nitrogen species, proteases and proinflammatory/cytotoxic cytokines. Therapeutics under investigation include corticosteroids, N-acetyl cysteine, which has both mucolytic and antioxidant properties, inducible nitric oxide synthase inhibitors, liposomes containing superoxide dismutase, catalase, and/or tocopherols, protease inhibitors, and cytokine antagonists such as anti-tumor necrosis factor (TNF)-α antibody and pentoxifylline. Antifibrotic and fibrinolytic treatments may also prove beneficial in ameliorating airway obstruction and lung remodeling. More speculative approaches include inhibitors of transient receptor potential channels, which regulate pulmonary epithelial cell membrane permeability, non-coding RNAs and mesenchymal stem cells. As mustards represent high priority chemical threat agents, identification of effective therapeutics for mitigating toxicity is highly significant.

  6. Mustard vesicant-induced lung injury: Advances in therapy

    Energy Technology Data Exchange (ETDEWEB)

    Weinberger, Barry, E-mail: bweinberger@northwell.edu [Division of Neonatal and Perinatal Medicine, Hofstra Northwell School of Medicine, Cohen Children' s Medical Center of New York, New Hyde Park, NY 11040 (United States); Malaviya, Rama; Sunil, Vasanthi R.; Venosa, Alessandro [Department of Pharmacology and Toxicology, Ernest Mario School of Pharmacy, Rutgers University, Piscataway, NJ 08854 (United States); Heck, Diane E. [Department of Environmental Health Science, New York Medical College, School of Public Health, Valhalla, NY 10595 (United States); Laskin, Jeffrey D. [Department of Environmental and Occupational Health, School of Public Health, Rutgers University, Piscataway, NJ 08854 (United States); Laskin, Debra L. [Department of Pharmacology and Toxicology, Ernest Mario School of Pharmacy, Rutgers University, Piscataway, NJ 08854 (United States)

    2016-08-15

    Most mortality and morbidity following exposure to vesicants such as sulfur mustard is due to pulmonary toxicity. Acute injury is characterized by epithelial detachment and necrosis in the pharynx, trachea and bronchioles, while long-term consequences include fibrosis and, in some instances, cancer. Current therapies to treat mustard poisoning are primarily palliative and do not target underlying pathophysiologic mechanisms. New knowledge about vesicant-induced pulmonary disease pathogenesis has led to the identification of potentially efficacious strategies to reduce injury by targeting inflammatory cells and mediators including reactive oxygen and nitrogen species, proteases and proinflammatory/cytotoxic cytokines. Therapeutics under investigation include corticosteroids, N-acetyl cysteine, which has both mucolytic and antioxidant properties, inducible nitric oxide synthase inhibitors, liposomes containing superoxide dismutase, catalase, and/or tocopherols, protease inhibitors, and cytokine antagonists such as anti-tumor necrosis factor (TNF)-α antibody and pentoxifylline. Antifibrotic and fibrinolytic treatments may also prove beneficial in ameliorating airway obstruction and lung remodeling. More speculative approaches include inhibitors of transient receptor potential channels, which regulate pulmonary epithelial cell membrane permeability, non-coding RNAs and mesenchymal stem cells. As mustards represent high priority chemical threat agents, identification of effective therapeutics for mitigating toxicity is highly significant.

  7. Panceratic Complications of Mustard Gas Exposure: A Study on Cadavers

    Directory of Open Access Journals (Sweden)

    Amir Farshid Fayyaz

    2015-06-01

    Full Text Available Background: Sulfur mustard is one of the chemical warfare gases that has been known as a vesicant or blistering agents. It is a chemical alkylating compound agent that can be frequently absorbed through skin, respiratory system, genital tract, and ocular system. This study was done to pathologically analyze the microscopic pancreatic lesions in cadavers. Methods: This case series study was performed during 2007 to 2012 in Legal Medicine Organization. Exposure was confirmed by the written reports of the field hospitals, based on acute presentation of eye, skin and pulmonary symptoms of the exposure. Results: Pancreatic autopsy findings were chronic inflammation, fibrosis and duct ectasia; acinar atrophy was also seen in 4 cases. All 4 cases had chronic pancreatic disease with abdominal pain, steatorrhea and weight loss that was confirmed by sonography. CT scan and Endoscopic Retrograde Cholangio-Pancreatography (ERCP have also demonstrated the chronic pancreatitis. Conclusion: According to the chronic progressive lesions caused by mustard gas exposure such as pulmonary lesions and also its high mortality rate, suitable programming for protection of the mustard gas exposed people in chemical factories is necessary.

  8. Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements

    Directory of Open Access Journals (Sweden)

    Jungho Jun

    2013-08-01

    Full Text Available Gold-catalyzed intermolecular couplings of sulfonylacetylenes with allyl ethers are reported. A cooperative polarization of alkynes both by a gold catalyst and a sulfonyl substituent resulted in an efficient intermolecular tandem carboalkoxylation. Reactions of linear allyl ethers are consistent with the [3,3]-sigmatropic rearrangement mechanism, while those of branched allyl ethers provided [3,3]- and [1,3]-rearrangement products through the formation of a tight ion–dipole pair.

  9. Ketenimines from Isocyanides and Allyl Carbonates: Palladium-Catalyzed Synthesis of β,γ-Unsaturated Amides and Tetrazoles.

    Science.gov (United States)

    Qiu, Guanyinsheng; Mamboury, Mathias; Wang, Qian; Zhu, Jieping

    2016-12-05

    The reaction of allyl ethyl carbonates with isocyanides in the presence of a catalytic amount of Pd(OAc) 2 provided ketenimines through β-hydride elimination of the allyl imidoylpalladium intermediates. The insertion of the isocyanide into the π-allyl Pd complex proceeded via an unusual η 1 -allyl Pd species. The resulting ketenimines were hydrolyzed to β,γ-unsaturated carboxamides during purification by flash column chromatography on silica gel or converted in situ into 1,5-disubstituted tetrazoles by [3+2] cycloaddition with hydrazoic acid or trimethylsilyl azide. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Radiation synthesis and characterization of new hydrogels based on acrylamide copolymers cross-linked with 1-allyl-2-thiourea

    Energy Technology Data Exchange (ETDEWEB)

    Sahiner, Nurettin [Department of Chemistry, Faculty of Science, Hacettepe University, Beytepe Campus, 0653 Ankara (Turkey); Malci, Savas [Department of Chemistry, Faculty of Science, Hacettepe University, Beytepe Campus, 0653 Ankara (Turkey); Celikbicak, Oemuer [Department of Chemistry, Faculty of Science, Hacettepe University, Beytepe Campus, 0653 Ankara (Turkey); Kantoglu, Oemer [Ankara Nuclear Research Center, Turkish Atomic Energy Authority, 06983 Ankara (Turkey); Salih, Bekir [Department of Chemistry, Faculty of Science, Hacettepe University, Beytepe Campus, 0653 Ankara (Turkey)]. E-mail: bekir@hacettepe.edu.tr

    2005-10-01

    Poly(acrylamide-1-allyl-2-thiourea) hydrogels, Poly(AA-AT), were synthesized by gamma irradiation using {sup 60}Co {gamma} source in different irradiation dose and at different 1-allyl-2-thiourea content in the monomer mixture. For the characterization of the hydrogels, Fourier transform infrared spectrometer (FT-IR), thermogravimetric analyzer (TGA), elemental analyzer and the swellability of the hydrogels were used. It was noted that 1-allyl-2-thiourea in the synthesized hydrogels was increased by the increasing the content of the 1-allyl-2-thiourea in the irradiation monomer mixture and increasing the radiation dose for the hydrogel synthesis. sis.

  11. Declines in a ground-dwelling arthropod community during an invasion by Sahara mustard (Brassica tournefortii) in aeolian sand habitats

    Science.gov (United States)

    Heather L. Hulton VanTassel; Anne M. Hansen; Cameron W. Barrows; Quresh Latif; Margaret W. Simon; Kurt E. Anderson

    2014-01-01

    Sahara Mustard (Brassica tournefortii; hereafter mustard), an exotic plant species, has invaded habitats throughout the arid southwestern United States. Mustard has reached high densities across aeolian sand habitats of southwestern deserts, including five distinct sand habitats in the eastern Coachella Valley, California. We examined trends in ground-dwelling...

  12. Bioavailability of Isothiocyanates From Broccoli Sprouts in Protein, Lipid, and Fiber Gels

    OpenAIRE

    Oliviero, Teresa; Lamers, Simone; Capuano, Edoardo; Dekker, Matthijs; Verkerk, Ruud

    2018-01-01

    Scope: Optimization of bioavailability of dietary bioactive health-beneficial compounds is as important as increasing their concentration in foods. The aim of this study is to explore the change in bioavailability of isothiocyanates (ITCs) in broccoli sprouts incorporated in protein, fiber, and lipid gels. Methods and results: Five participants took part in a cross-over study and collected timed urine samples up to 24 h after consumption of proteins, dietary fibers, and lipid gels containing ...

  13. A highly selective and sensitive "turn-on" fluorescence chemodosimeter for the detection of mustard gas.

    Science.gov (United States)

    Raghavender Goud, D; Purohit, Ajay Kumar; Tak, Vijay; Dubey, Devendra Kumar; Kumar, Pravin; Pardasani, Deepak

    2014-10-21

    A new chemodosimetric protocol based on a tandem S-alkylation followed by desulfurisation reaction of rhodamine-thioamide with mustard gas is reported. The chemodosimeter is highly selective for potential DNA alkylating agents like sulfur mustard, over other simple alkyl halides with the limit of detection of 4.75 μM.

  14. Phytocontact Dermatitis due to Mustard Seed Mimicking Burn Injury: Report of a Case

    Directory of Open Access Journals (Sweden)

    Hakan Yabanoglu

    2012-01-01

    Full Text Available Mustard seeds have been used in traditional folk medicine as a stimulant, diuretic, and purgative and to treat a variety of ailments including peritonitis and neuralgia. Mustards are still used today in mustard plasters to treat rheumatism, arthritis, chest congestion, aching back, and sore muscles. To make a mustard plaster, mix equal parts of flour and powdered mustard and spread it as a paste on a doubled piece of soft cloth. Apply mustard plaster to the affected area for a maximum of 15 minutes. Prolonged application can result in burns to the skin and nerve damage. Skin lesions occur within hours after exposure, and there is no significant therapy procedure. This case report is about a patient with second-degree burn, occurred when a mixture including mustard seed was exposed to her skin in the pain therapy of the osteoarthritis in her left knee. There are no studies analyzing treatment of skin burns induced by mustard seed in the literature. While in this type of burns our experience is limited, we think that conservative approach should be first choice of treatment.

  15. Direct and indirect antioxidant activity of polyphenol- and isothiocyanate-enriched fractions from Moringa oleifera.

    Science.gov (United States)

    Tumer, Tugba Boyunegmez; Rojas-Silva, Patricio; Poulev, Alexander; Raskin, Ilya; Waterman, Carrie

    2015-02-11

    Moringa oleifera Lam. is a fast-growing, tropical tree with various edible parts used as nutritious food and traditional medicine. This study describes an efficient preparatory strategy to extract and fractionate moringa leaves by fast centrifugal partition chromatography (FCPC) to produce polyphenol and isothiocyanate (ITC) rich fractions. Characterization and further purification of these fractions showed that moringa polyphenols were potent direct antioxidants assayed by oxygen radical absorbance capacity (ORAC), whereas moringa ITCs were effective indirect antioxidants assayed by induction of NAD(P)H quinone oxidoreductase 1 (NQO1) activity in Hepa1c1c7 cells. In addition, purified 4-[(α-l-rhamnosyloxy)benzyl]isothiocyanate and 4-[(4'-O-acetyl-α-l-rhamnosyloxy)benzyl]isothiocyanate were further evaluated for their ORAC and NQO1 inducer potency in comparison with sulforaphane (SF). Both ITCs were as potent as SF in inducing NQO1 activity. These findings suggest that moringa leaves contain a potent mixture of direct and indirect antioxidants that can explain its various health-promoting effects.

  16. Effect of Wasabi Component 6-(Methylsulfinylhexyl Isothiocyanate and Derivatives on Human Pancreatic Cancer Cells

    Directory of Open Access Journals (Sweden)

    Yu-Jen Chen

    2014-01-01

    Full Text Available The naturally occurring compound 6-(methylsulfinylhexyl isothiocyanate (6-MITC was isolated from Wasabia japonica (Wasabi, a pungent spice used in Japanese food worldwide. The synthetic derivatives 6-(methylsulfenylhexyl isothiocyanate (I7447 and 6-(methylsulfonylhexyl isothiocyanate (I7557 are small molecule compounds derived from 6-MITC. This study aimed to evaluate the effect of these compounds on human pancreatic cancer cells. Human pancreatic cancer cell lines PANC-1 and BxPC-3 were used to perform an MTT assay for cell viability and Liu’s stain for morphological observation. The cell cycle was analyzed by DNA histogram. Aldehyde dehydrogenase (ALDH activity was used as a marker for cancer stem cells (CSC. Western blotting was performed for the expression of proteins related to CSC signaling. The results showed that compounds 6-MITC and I7557, but not I7447, inhibited viability of both PANC-1 and BxPC-3 cells. Morphological observation showed mitotic arrest and apoptosis in 6-MITC- and I7557-treated cells. These two compounds induced G2/M phase arrest and hypoploid population. Percentages of ALDH-positive PANC-1 cells were markedly reduced by 6-MITC and I7557 treatment. The expression of CSC signaling molecule SOX2, but not NOTCH1, ABCG2, Sonic hedgehog, or OCT4, was inhibited by 6-MITC and I7557. In conclusion, wasabi compounds 6-MITC and I7557 may possess activity against the growth and CSC phenotypes of human pancreatic cancer cells.

  17. Dietary Broccoli Alters Rat Cecal Microbiota to Improve Glucoraphanin Hydrolysis to Bioactive Isothiocyanates

    Directory of Open Access Journals (Sweden)

    Xiaoji Liu

    2017-03-01

    Full Text Available Broccoli consumption brings many health benefits, including reducing the risk of cancer and inflammatory diseases. The objectives of this study were to identify global alterations in the cecal microbiota composition using 16S rRNA sequencing analysis and glucoraphanin (GRP hydrolysis to isothiocyanates ex vivo by the cecal microbiota, following different broccoli diets. Rats were randomized to consume AIN93G (control or different broccoli diets; AIN93G plus cooked broccoli, a GRP-rich powder, raw broccoli, or myrosinase-treated cooked broccoli. Feeding raw or cooked broccoli for four days or longer both changed the cecal microbiota composition and caused a greater production of isothiocyanates ex vivo. A more than two-fold increase in NAD(PH: quinone oxidoreductase 1 activity of the host colon mucosa after feeding cooked broccoli for seven days confirmed the positive health benefits. Further studies revealed that dietary GRP was specifically responsible for the increased microbial GRP hydrolysis ex vivo, whereas changes in the cecal microbial communities were attributed to other broccoli components. Interestingly, a three-day withdrawal from a raw broccoli diet reversed the increased microbial GRP hydrolysis ex vivo. Findings suggest that enhanced conversion of GRP to bioactive isothiocyanates by the cecal microbiota requires four or more days of broccoli consumption and is reversible.

  18. Dietary Broccoli Alters Rat Cecal Microbiota to Improve Glucoraphanin Hydrolysis to Bioactive Isothiocyanates.

    Science.gov (United States)

    Liu, Xiaoji; Wang, Yanling; Hoeflinger, Jennifer L; Neme, Bárbara P; Jeffery, Elizabeth H; Miller, Michael J

    2017-03-10

    Broccoli consumption brings many health benefits, including reducing the risk of cancer and inflammatory diseases. The objectives of this study were to identify global alterations in the cecal microbiota composition using 16S rRNA sequencing analysis and glucoraphanin (GRP) hydrolysis to isothiocyanates ex vivo by the cecal microbiota, following different broccoli diets. Rats were randomized to consume AIN93G (control) or different broccoli diets; AIN93G plus cooked broccoli, a GRP-rich powder, raw broccoli, or myrosinase-treated cooked broccoli. Feeding raw or cooked broccoli for four days or longer both changed the cecal microbiota composition and caused a greater production of isothiocyanates ex vivo. A more than two-fold increase in NAD(P)H: quinone oxidoreductase 1 activity of the host colon mucosa after feeding cooked broccoli for seven days confirmed the positive health benefits. Further studies revealed that dietary GRP was specifically responsible for the increased microbial GRP hydrolysis ex vivo, whereas changes in the cecal microbial communities were attributed to other broccoli components. Interestingly, a three-day withdrawal from a raw broccoli diet reversed the increased microbial GRP hydrolysis ex vivo. Findings suggest that enhanced conversion of GRP to bioactive isothiocyanates by the cecal microbiota requires four or more days of broccoli consumption and is reversible.

  19. Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Hansen, E. Louise; Kane, John

    2001-01-01

    A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed by asy...... the allylic stereocenter and the alkene geometry. Thus, a single $gamma@-substituted ester was obtained as the overall product, in high isomeric purity. The method was applied to a synthesis of a subunit of the iejimalides, a group of cytotoxic macrolides.......A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed...... by asymmetric HWE reactions into mixtures of two major $alpha@,$beta@-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution...

  20. SYNTHESIS OF 4-ALLYL-2-METHOXY-6-AMINOPHENOL FROM NATURAL EUGENOL

    Directory of Open Access Journals (Sweden)

    I Made Sudarma

    2010-06-01

    Full Text Available The aim of this preliminary research was to synthesize derivatives of eugenol such as 4-allyl-2-methoxy-6-nitrophenol (2 and 4-allyl-2-methoxy-6-aminophenol (3. The result could be used as a reference on the transformation of eugenol to its derivatives. Theoriticaly nitration of eugenol (1 by nitric acid could produced 4-allyl-2-methoxy-6-nitrophenol (2 and followed by reduction could achieved 4-allyl-2-mehtoxy-6-aminophenol (3. The formation of this product was analyzed by analytical thin layer chromatography (TLC and GC-MS. These analysis showed the formation of product (2 and (3 were visible. TLC showed product (1 less polar than eugenol and gave orange colour, and supported by GC-MS which showed molecular ion at m/z 209 due to the presence of -NO2 by replacing one H at 6 position of eugenol. Product (3 was afforded by reduction of (2 with Sn/HCl and tlc analysis showed compound (3 more polar than eugenol (1 and (2 and supported by GC-MS which showed molecular ion at m/z 179 due to the presence of -NH2.   Keywords: Synthesis, 4-allyl-2-methoxy-6-aminophenol, Eugenol

  1. Novel liquid chromatography–mass spectrometry method for sensitive determination of the mustard allergen Sin a 1 in food

    OpenAIRE

    Alvarez-Llamas, Gloria; Maes, Xavier; Muñoz-García, Esther; Villalba, Mayte; Rodríguez, Rosalía; Pérez-Gordo, Marina; Vivanco, Fernando; Pérez-Gordo, Carlos; Cuesta-Herranz, Javier

    2015-01-01

    Mustard is a condiment added to a variety of foodstuffs and a frequent cause of food allergy. A new strategy for the detection of mustard allergen in food products is presented. The methodology is based on liquid chromatography analysis coupled to mass spectrometry. Mustard allergen Sin a 1 was purified from yellow mustard seeds. Sin a 1 was detected with a total of five peptides showing a linear response (lowest LOD was 5 ng). Sin a 1 was detected in mustard sauces and salty biscuit (19 ± 3 ...

  2. On the Nature of the Intermediates and the Role of Chloride Ions in Pd-Catalyzed Allylic Alkylations: Added Insight from Density Functional Theory

    DEFF Research Database (Denmark)

    Fristrup, Peter; Ahlquist, Mårten Sten Gösta; Tanner, David Ackland

    2008-01-01

    The reactivity of intermediates in palladium-catalyzed allylic alkylation was investigated using DFT (B3LYP) calculations including a PB-SCRF solvation model. In the presence of both phosphine and chloride ligands, the allyl intermediate is in equilibrium between a cationic eta(3)-allylPd complex...

  3. Arsenic and Old Mustard: Chemical Problems of Old Arsenical and 'Mustard' Munitions (Joseph F. Bunnett and Marian Mikotajczyk, Eds.)

    Science.gov (United States)

    Garrett, Benjamin

    1999-10-01

    What do Knute Rockne, Notre Dame's famed football coach, and Lewisite, a chemical warfare agent dubbed "the dew of death", have in common? Both owe their discovery to Father Julius Arthur Nieuwland.1 Rockne's legacy lives on in the Fighting Irish and their tradition of excellence on the gridiron. Lewisite, together with other arsenical- and mustard-type chemical warfare agents, provide a legacy that lives on, too, but with less cheerful consequences. The book Arsenic and Old Mustard: Chemical Problems of Old Arsenical and 'Mustard' Munitions makes clear the challenges faced in dealing with those consequences. This book documents the proceedings of a workshop devoted to arsenical- and mustard-type chemical warfare agents and their associated munitions. The workshop, held in Poland in 1996, included nine lectures, eight posters, and three discussion groups; and the contents of all these are presented. Major support for the workshop came from the Scientific Affairs Division of NATO as part of on ongoing series of meetings, cooperative research projects, and related efforts dealing with problems leftover from the Cold War and, in the case of the arsenicals and mustards, from conflicts dating to World War I. These problems can be seen in contemporary accounts, including a January 1999 news report that the U.S. Department of Defense intends to survey Washington, DC, areas near both American University and the Catholic University of America (CUA), site of the original synthesis of Lewisite, for chemical warfare agents and other materials disposed at the end of World War I.2 The first nine chapters of the book present the workshop's lectures. Of these, readers interested in chemical weapon destruction might find especially useful the first chapter, in which Ron Mansley of the Organisation for the Prohibition of Chemical Weapons presents a scholarly overview covering historical aspects of the arsenicals and mustards; their production and use; prospective destruction

  4. An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.

    Science.gov (United States)

    DeKorver, Kyle A; Hsung, Richard P; Song, Wang-Ze; Wang, Xiao-Na; Walton, Mary C

    2012-06-15

    A cascade of Pd-catalyzed N-to-C allyl transfer-intramolecular ketenimine-[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines.

  5. An Efficient Synthesis of de novo Imidates via Aza-Claisen Rearrangements of N-Allyl Ynamides

    Science.gov (United States)

    DeKorver, Kyle A.; North, Troy D.; Hsung, Richard P.

    2010-01-01

    A novel thermal 3-aza-Claisen rearrangement of N-allyl ynamides for the synthesis of α-allyl imidates is described. Also, a sequential aza-Claisen, Pd-catalyzed Overman rearrangement is described for the synthesis of azapine-2-ones. PMID:21278848

  6. Dual platinum and pyrrolidine catalysis in the direct alkylation of allylic alcohols: selective synthesis of monoallylation products.

    Science.gov (United States)

    Shibuya, Ryozo; Lin, Lu; Nakahara, Yasuhito; Mashima, Kazushi; Ohshima, Takashi

    2014-04-22

    A dual platinum- and pyrrolidine-catalyzed direct allylic alkylation of allylic alcohols with various active methylene compounds to produce products with high monoallylation selectivity was developed. The use of pyrrolidine and acetic acid was essential, not only for preventing undesirable side reactions, but also for obtaining high monoallylation selectivity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Formation of gas-phase π-allyl radicals from propylene over bismuth oxide and γ-bismuth molybdate catalysts

    International Nuclear Information System (INIS)

    Martir, W.; Lunsford, J.H.

    1981-01-01

    Gas-phase π-allyl radicals were produced when propylene reacted over Bi 2 O 3 and γ-bismuth molybdate catalysts at 723 K. The pressure in the catalyst zone was varied between 5 x 10 -3 and 1 torr. The radicals were detected by EPR spectroscopy together with a matrix isolation technique in which argon was used as the diluent. The matrix was formed on a sapphire rod at 12 K which was located 33-cm downstream from the catalyst. Bismuth oxide was more effective in the production of gas-phase allyl radicals than γ-bismuth molybdate. By contrast α-bismuth molybdate was ineffective in forming allyl radicals and MoO 3 acted as a sink for radicals which were produced elsewhere in the system. Comparison of the π-allyl radical and the stable product concentrations over Bi 2 O 3 revealed that gas-phase radical recombination reactions served as a major pathway for the formation of 1,5-hexadiene. Addition of small amounts of gas-phase oxygen increased the concentration of allyl radicals, and at greater oxygen levels allyl peroxy radicals were detected. Because of the effect of temperature on the equilibrium between allyl and allyl peroxy radicals, the latter product must be formed in the cooler part of the system

  8. Regio- and Enantioselective N-Allylations of Imidazole, Benzimidazole, and Purine Heterocycles Catalyzed by Single-Component Metallacyclic Iridium Complexes

    Science.gov (United States)

    Stanley, Levi M.

    2010-01-01

    Highly regio- and enantioselective iridium-catalyzed N-allylations of benzimidazoles, imidazoles, and purines have been developed. N-Allylated benzimidazoles and imidazoles were isolated in high yields (up to 97%) with high branched-to-linear selectivity (up to 99:1) and enantioselectivity (up to 98% ee) from the reactions of benzimidazole and imidazole nucleophiles with unsymmetrical allylic carbonates in the presence of single component, ethylene-bound, metallacyclic iridium catalysts. N-Allylated purines were also obtained in high yields (up to 91%) with high N9:N7 selectivity (up to 96:4), high branched-to-linear selectivity (98:2), and high enantioselectivity (up to 98% ee) under similar conditions. The reactions encompass a range of benzimidazole, imidazole, and purine nucleophiles, as well as a variety of unsymmetrical aryl, heteroaryl, and aliphatic allylic carbonates. Competition experiments between common amine nucleophiles and the heterocyclic nitrogen nucleophiles studied in this work illustrate the effect of nucleophile pKa on the rate of iridium-catalyzed N-allylation reactions. Kinetic studies on the allylation of benzimidazole catalyzed by metallacyclic iridium-phosphoramidite complexes, in combination with studies on the deactivation of these catalysts in the presence of heterocyclic nucleophiles, provide insight into the effects of the structure of the phosphoramidite ligands on the stability of the metallacyclic catalysts. The data obtained from these studies has led to the development of N-allylations of benzimidazoles and imidazoles in the absence of an exogenous base. PMID:19480431

  9. Zinc and application to optimize seed yield of mustard

    International Nuclear Information System (INIS)

    Nawaz, N.; Nawaz, M.S.; Cheema, N.M.

    2012-01-01

    A study was conducted on a sandy clay loam soil at the National Agricultural Research Centre, Islamabad, Pakistan, during 2005 and 2006. The mustard (Brassica juncea) variety BARD-1 was treated with various levels of Zn and Fe, (0-0, 0-1.5, 0-3, 2.5-0, 2.5-1.5, 2.5-3, 5-0, 5-1.5 kgha/sup -1/ and 5-3 kgha/sup -1/, respectively. A basal dose of 90N and 60P kgha/sup -1/ was applied, in the form of Urea and triple super phosphate (TSP) with Zn and Fe. The increase in Zn and Fe fertility from 0-1.5 to 5-1.5 kg ha/sup -1/ increased yield of BARD-I. The maximum yield response was recorded when 5 kg ha/sup -1/ Zn and 1.5 kg ha/sup -1/ Fe were applied. Beyond this level, no further increase in yield was recorded in any mustard traits. A positive correlation was recorded between seed yield and 1000-seed weight with the application of 5 kg Zn ha-1 and 1.5 kg Fe ha/sup -1/ in combination at the time of sowing. It can therefore be concluded that 100 % seed yield of mustard variety BARD-l increased at 5 Zn: 1.5 Fc kg ha-1 as a result of increased pods plant/sup -l/, number of seeds pod-1 and 1000-seed weight. (author)

  10. Sulphur mustard degradation on zirconium doped Ti-Fe oxides

    Energy Technology Data Exchange (ETDEWEB)

    Stengl, Vaclav, E-mail: stengl@iic.cas.cz [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR v.v.i 250 68 Husinec-Rez (Czech Republic); Grygar, Tomas Matys [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR v.v.i 250 68 Husinec-Rez (Czech Republic); Oplustil, Frantisek; Nemec, Tomas [Military Technical Institute of Protection Brno Veslarska 230, 628 00 Brno (Czech Republic)

    2011-09-15

    Highlights: {yields} New stechiometric materials for sulphur mustard degradation. {yields} High degree of degradation, more then 95% h{sup -1}. {yields} One-pot synthesis procedure. - Abstract: Zirconium doped mixed nanodispersive oxides of Ti and Fe were prepared by homogeneous hydrolysis of sulphate salts with urea in aqueous solutions. Synthesized nanodispersive metal oxide hydroxides were characterised as the Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared (IR) spectroscopy, scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) microanalysis, and acid-base titration. These oxides were taken for an experimental evaluation of their reactivity with sulphur mustard (chemical warfare agent HD or bis(2-chloroethyl)sulphide). The presence of Zr{sup 4+} dopant tends to increase both the surface area and the surface hydroxylation of the resulting doped oxides in such a manner that it can contribute to enabling the substrate adsorption at the oxide surface and thus accelerate the rate of degradation of warfare agents. The addition of Zr{sup 4+} to the hydrolysis of ferric sulphate with urea shifts the reaction route and promotes formation of goethite at the expense of ferrihydrite. We discovered that Zr{sup 4+} doped oxo-hydroxides of Ti and Fe exhibit a higher degradation activity towards sulphur mustard than any other yet reported reactive sorbents. The reaction rate constant of the slower parallel reaction of the most efficient reactive sorbents is increased with the increasing amount of surface base sites.

  11. Protein Changes in Sulfur Mustard Exposure: Diagnostic and Therapeutic Implications

    International Nuclear Information System (INIS)

    Ray, P.; Jin, X.; Ray, R.

    2007-01-01

    Laminin-5, a heterotrimer of laminin α3, β3, and γ2 subunits, is a component of the skin basal epithelium. Laminin-5 functions as a ligand of the α3β1 and α6β4 integrins in epidermal keratinocytes to regulate cell adhesion, migration, morphogenesis, and assembly of basement membranes; thus it is essential for a stable attachment of the epidermis to the dermis and recovery of damaged skin. Sulfur mustard (SM), also known as mustard gas, is a vesicant chemical warfare and terrorism agent. Skin exposure to SM results in fluid-filled blisters; proposed mechanisms are inflammation, protease stimulation, basal cell death, and separation of the epidermis from the dermis apparently due to the degradation of attachment proteins like laminin-5. Therefore, we investigated the effects of SM exposure on the degradation of laminin-5 by exposing normal human epidermal keratinocytes (NHEK) to SM (0-300 μM, 1-24 hours). We found that SM degraded laminin-5 and its two subunits β3 and γ2, but not α3. Preincubation of cells with a serine protease inhibitor (PMSF), or a metalloprotease inhibitor (1, 10-phenanthroline) prior to SM exposure partially prevented SM-induced degradation of laminin-5 subunits, β3 and γ2. Regarding specificity, laminin-5 γ2 was degraded due to a bifunctional mustard compound like SM, but not due to the other alkylating agents tested. Our results support that laminin-5 degradation is an important mechanism of SM injury as well as a useful biomarker of SM exposure. This knowledge of the mechanism of laminin-5 degradation due to SM has potential application in developing cutaneous therapeutics against SM.(author)

  12. Capsaicinoids, chloropicrin and sulfur mustard: Possibilities for exposure biomarkers

    Directory of Open Access Journals (Sweden)

    Maija Pesonen

    2010-12-01

    Full Text Available Incapacitating and irritating agents produce temporary disability persisting for hours to days after the exposure. One can be exposed to these agents occupationally in industrial or other working environments. Also general public can be exposed in special circumstances, like industrial accidents or riots. Incapacitating and irritating agents discussed in this review are chloropicrin and capsaicinoids. In addition, we include sulfur mustard, which is an old chemical warfare agent and known to cause severe long-lasting injuries or even death. Chloropicrin that was used as a warfare agent in the World War I is currently used mainly as a pesticide. Capsaicinoids, components of hot pepper plants, are used by police and other law enforcement personnel as riot control agents. Toxicity of these chemicals is associated particularly with the respiratory tract, eyes and skin. Their acute effects are relatively well known but the knowledge of putative long-term effects is almost non-existent. Also, mechanisms of effects at cellular level are not fully understood. There is a need for further research to get better idea of health risks, particularly of long-term and low-level exposures to these chemicals. For this, exposure biomarkers are essential. Validated exposure biomarkers for capsaicinoids, chloropicrin and sulfur mustard do not exist so far. Metabolites and macromolecular adducts have been suggested biomarkers for sulfur mustard and these can already be measured qualitatively, but quantitative biomarkers await further development and validation. The purpose of this review is, based on the existing mechanistic and toxicokinetic information, to shed light on the possibilities for developing biomarkers for exposure biomonitoring of these compounds. It is also of interest to find ideas for early effect biomarkers considering the need for studies on subchronic and chronic toxicity.

  13. Theoretical Studies of [2,3]-Sigmatropic Rearrangements of Allylic Selenoxides and Selenimides

    Directory of Open Access Journals (Sweden)

    Sonia Antony

    2009-08-01

    Full Text Available Density-functional theory is used to model the endo and exo transition states for [2,3]-sigmatropic rearrangement of allylic aryl-selenoxides and -selenimides. The endo transition state is generally preferred for selenoxides if there is no substitution at the 2 position of the allyl group. Based upon the relative energies of the endo and exo transition states, enantioselectivity of rearrangements is expected to be greatest for molecules with substitutions at the 1- or (E-3- position of the allyl group. Ortho substitution of a nitro group on the ancillary selenoxide phenyl ring reduces the activation barriers, increases the difference between the endo and exo activation barriers and shifts the equilibrium toward products.

  14. How phenyl makes a difference: mechanistic insights into the ruthenium( ii )-catalysed isomerisation of allylic alcohols

    KAUST Repository

    Manzini, Simone

    2013-10-16

    [RuCl(η5-3-phenylindenyl)(PPh3)2] (1) has been shown to be a highly active catalyst for the isomerisation of allylic alcohols to the corresponding ketones. A variety of substrates undergo the transformation, typically with 0.25-0.5 mol% of catalyst at room temperature, outperforming commonly-used complexes such as [RuCl(Cp)(PPh3) 2] and [RuCl(η5-indenyl)(PPh3) 2]. Mechanistic experiments and density functional theory have been employed to investigate the mechanism and understand the effect of catalyst structure on reactivity. These investigations suggest a oxo-π-allyl mechanism is in operation, avoiding intermediate ruthenium hydride complexes and leading to a characteristic 1,3-deuterium shift. Important mechanistic insights from DFT and experiments also allowed for the design of a protocol that expands the scope of the transformation to include primary allylic alcohols. © 2013 The Royal Society of Chemistry.

  15. A Green Approach for Allylations of Aldehydes and Ketones: Combining Allylborate, Mechanochemistry and Lanthanide Catalyst

    Directory of Open Access Journals (Sweden)

    Viviane P. de Souza

    2016-11-01

    Full Text Available Secondary and tertiary alcohols synthesized via allylation of aldehydes and ketones are important compounds in bioactive natural products and industry, including pharmaceuticals. Development of a mechanochemical method using potassium allyltrifluoroborate salt and water, to successfully perform the allylation of aromatic and aliphatic carbonyl compounds is reported for the first time. By controlling the grinding parameters, the methodology can be selective, namely, very efficient for aldehydes and ineffective for ketones, but by employing lanthanide catalysts, the reactions with ketones can become practically quantitative. The catalyzed reactions can also be performed under mild aqueous stirring conditions. Considering the allylation agent and its by-products, aqueous media, energy efficiency and use of catalyst, the methodology meets most of the green chemistry principles.

  16. How phenyl makes a difference: mechanistic insights into the ruthenium( ii )-catalysed isomerisation of allylic alcohols

    KAUST Repository

    Manzini, Simone; Poater, Albert; Nelson, David J.; Cavallo, Luigi; Nolan, Steven P.

    2013-01-01

    [RuCl(η5-3-phenylindenyl)(PPh3)2] (1) has been shown to be a highly active catalyst for the isomerisation of allylic alcohols to the corresponding ketones. A variety of substrates undergo the transformation, typically with 0.25-0.5 mol% of catalyst at room temperature, outperforming commonly-used complexes such as [RuCl(Cp)(PPh3) 2] and [RuCl(η5-indenyl)(PPh3) 2]. Mechanistic experiments and density functional theory have been employed to investigate the mechanism and understand the effect of catalyst structure on reactivity. These investigations suggest a oxo-π-allyl mechanism is in operation, avoiding intermediate ruthenium hydride complexes and leading to a characteristic 1,3-deuterium shift. Important mechanistic insights from DFT and experiments also allowed for the design of a protocol that expands the scope of the transformation to include primary allylic alcohols. © 2013 The Royal Society of Chemistry.

  17. The effects of γ-irradiation on the garlic oil contents in garlic bulbs and the radiolysis of allyl trisulfide

    International Nuclear Information System (INIS)

    Wei Genshuan, Wang Guanghui; Yang Ruipu; Wu Jilan

    1995-01-01

    The study of the effects of γ-irradiation on the garlic oil contents in the garlic bulbs and the radiolysis of allyl trisulfide and disulfide were carried out. The content of garlic oil in fresh garlic bulbs treated by gamma ray keeps nearly constant as stored for 10 months long. The main components of the garlic oil are allyl trisulfide (about 60%) and allyl disulfide (about 30%). The G values of radiolysis products of allyl disulfide and trisulfide in ethanol system were determined. The results show that allyl trisulfide is a very effective solvated electron scavenger and can oxidize CH 3 C HOH radical into acetaldehyde, which causes that the formation of 2,3-butanediol is extensively inhibited. (author)

  18. The effects of γ-irradiation on garlic oil content in garlic bulbs and on the radiolysis of allyl trisulfide

    International Nuclear Information System (INIS)

    Wei Genshuan; Wang Guanghui; Yang Ruipu; Wu Jilan

    1996-01-01

    A study of the effects of γ-irradiation on garlic oil content in garlic bulbs and on the radiolysis of allyl trisufide and disulfide was carried out. The content of garlic oil in fresh garlic bulbs treated by gamma ray keeps nearly constant when stored for 10 months. The main components of garlic oil are allyl trisulfide (about 60%) and allyl disulfide (about 30%). The G values of radiolysis products of allyl disulfide and trisulfide in ethanol system were determined. The results show that allyl trisulfide is a very effective solvated electron scavenger and can oxidize CH 3 C . HOH radical into acetaldehyde, which means that the formation of 2,3-butanediol is extensively inhibited. (author)

  19. Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters.

    Science.gov (United States)

    Thomas, Bryce N; Moon, Patrick J; Yin, Shengkang; Brown, Alex; Lundgren, Rylan J

    2018-01-07

    A well-defined Ir-allyl complex catalyzes the Z -selective cross-coupling of allyl carbonates with α-aryl diazo esters. The process overrides the large thermodynamic preference for E -products typically observed in metal-mediated coupling reactions to enable the synthesis of Z , E -dieneoates in good yield with selectivities consistently approaching or greater than 90 : 10. This transformation represents the first productive merger of Ir-carbene and Ir-allyl species, which are commonly encountered intermediates in allylation and cyclopropanation/E-H insertion catalysis. Potentially reactive functional groups (aryl halides, ketones, nitriles, olefins, amines) are tolerated owing to the mildness of reaction conditions. Kinetic analysis of the reaction suggests oxidative addition of the allyl carbonate to an Ir-species is rate-determining. Mechanistic studies uncovered a pathway for catalyst activation mediated by NEt 3 .

  20. Transient overexpression of adh8a increases allyl alcohol toxicity in zebrafish embryos.

    Directory of Open Access Journals (Sweden)

    Nils Klüver

    Full Text Available Fish embryos are widely used as an alternative model to study toxicity in vertebrates. Due to their complexity, embryos are believed to more resemble an adult organism than in vitro cellular models. However, concerns have been raised with respect to the embryo's metabolic capacity. We recently identified allyl alcohol, an industrial chemical, to be several orders of magnitude less toxic to zebrafish embryo than to adult zebrafish (embryo LC50 = 478 mg/L vs. fish LC50 = 0.28 mg/L. Reports on mammals have indicated that allyl alcohol requires activation by alcohol dehydrogenases (Adh to form the highly reactive and toxic metabolite acrolein, which shows similar toxicity in zebrafish embryos and adults. To identify if a limited metabolic capacity of embryos indeed can explain the low allyl alcohol sensitivity of zebrafish embryos, we compared the mRNA expression levels of Adh isoenzymes (adh5, adh8a, adh8b and adhfe1 during embryo development to that in adult fish. The greatest difference between embryo and adult fish was found for adh8a and adh8b expression. Therefore, we hypothesized that these genes might be required for allyl alcohol activation. Microinjection of adh8a, but not adh8b mRNA led to a significant increase of allyl alcohol toxicity in embryos similar to levels reported for adults (LC50 = 0.42 mg/L in adh8a mRNA-injected embryos. Furthermore, GC/MS analysis of adh8a-injected embryos indicated a significant decline of internal allyl alcohol concentrations from 0.23-58 ng/embryo to levels below the limit of detection (< 4.6 µg/L. Injection of neither adh8b nor gfp mRNA had an impact on internal allyl alcohol levels supporting that the increased allyl alcohol toxicity was mediated by an increase in its metabolization. These results underline the necessity to critically consider metabolic activation in the zebrafish embryo. As demonstrated here, mRNA injection is one useful approach to study the role of candidate enzymes

  1. Tandem catalytic allylic amination and [2,3]-Stevens rearrangement of tertiary amines.

    Science.gov (United States)

    Soheili, Arash; Tambar, Uttam K

    2011-08-24

    We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.

  2. Scope and mechanism in palladium-catalyzed isomerizations of highly substituted allylic, homoallylic, and alkenyl alcohols.

    Science.gov (United States)

    Larionov, Evgeny; Lin, Luqing; Guénée, Laure; Mazet, Clément

    2014-12-03

    Herein we report the palladium-catalyzed isomerization of highly substituted allylic alcohols and alkenyl alcohols by means of a single catalytic system. The operationally simple reaction protocol is applicable to a broad range of substrates and displays a wide functional group tolerance, and the products are usually isolated in high chemical yield. Experimental and computational mechanistic investigations provide complementary and converging evidence for a chain-walking process consisting of repeated migratory insertion/β-H elimination sequences. Interestingly, the catalyst does not dissociate from the substrate in the isomerization of allylic alcohols, whereas it disengages during the isomerization of alkenyl alcohols when additional substituents are present on the alkyl chain.

  3. Allylic azides as potential building blocks for the synthesis of nitrogenated compounds

    Directory of Open Access Journals (Sweden)

    Sá Marcus M.

    2003-01-01

    Full Text Available The synthetic potential of multifunctional allylic azides and imines in attempted intramolecular cyclizations to nitrogen-containing heterocycles was investigated. Tandem Staudinger/aza-Wittig reaction of (E-3-aryl-2-(azidomethylpropenoates with triphenylphosphine and aldehydes yielded N-allylic imines in good yield. The (E-stereochemistry of C=C and C=N bonds was assigned based on NOESY experiments. AlCl3 mediated formation of 3-carbomethoxyquinoline from methyl (E-2-(azidomethyl-3-phenylpropenoate is also described.

  4. Advances in Agronomic Management of Indian Mustard (Brassica juncea (L. Czernj. Cosson: An Overview

    Directory of Open Access Journals (Sweden)

    Kapila Shekhawat

    2012-01-01

    Full Text Available India is the fourth largest oilseed economy in the world. Among the seven edible oilseeds cultivated in India, rapeseed-mustard contributes 28.6% in the total oilseeds production and ranks second after groundnut sharing 27.8% in the India’s oilseed economy. The mustard growing areas in India are experiencing the vast diversity in the agro climatic conditions and different species of rapeseed-mustard are grown in some or other part of the country. Under marginal resource situation, cultivation of rapeseed-mustard becomes less remunerative to the farmers. This results in a big gap between requirement and production of mustard in India. Therefore site-specific nutrient management through soil-test recommendation based should be adopted to improve upon the existing yield levels obtained at farmers field. Effective management of natural resources, integrated approach to plant-water, nutrient and pest management and extension of rapeseed-mustard cultivation to newer areas under different cropping systems will play a key role in further increasing and stabilizing the productivity and production of rapeseed-mustard. The paper reviews the advances in proper land and seedbed preparation, optimum seed and sowing, planting technique, crop geometry, plant canopy, appropriate cropping system, integrated nutrient management and so forth to meet the ever growing demand of oil in the country and to realize the goal of production of 24 million tonnes of oilseed by 2020 AD through these advanced management techniques.

  5. Anionic carbonato and oxalato cobalt(III) nitrogen mustard complexes.

    Science.gov (United States)

    Craig, Peter R; Brothers, Penelope J; Clark, George R; Wilson, William R; Denny, William A; Ware, David C

    2004-02-21

    Synthetic approaches to cobalt(III) complexes [Co(L)(L')2] containing the bidentate dialkylating nitrogen mustard N,N-bis(2-chloroethyl)-1,2-ethanediamine (L = dce) together with anionic ancilliary ligands (L') which are either carbonato (CO3(2-)), oxalato (ox2-), bis(2-hydroxyethyl)dithiocarbamato (bhedtc-), 2-pyridine carboxylato (pico-) or 2-pyrazine carboxylato (pyzc-) were investigated. Synthetic routes were developed using the related amines N,N-diethyl-1,2-ethanediamine (dee) and 1,2-ethanediamine (en). The complexes [Co(CO3)2(L)]- (L = dee 1, dce 2), [Co(ox)2(L)]- (L = dee 3, dce 4), [Co(bhedtc)2(dee)]+ 5, [Co(bhedtc)2(en)]+ 6, mer-[Co(pico)3], mer-[Co(pyzc)]3 7 and [Co(pico)2(dee)]+ 8 were prepared and were characterised by IR, UV-Vis, 1H and 13C[1H] NMR spectroscopy, mass spectrometry and cyclic voltammetry. [Co(bhedtc)2(en)]BPh4 6b and trans(O)-[Co(pico)2(dee)]ClO4 8 were characterised by X-ray crystallography. In vitro biological tests were carried out on complexes 1-4 in order to assess the degree to which coordination of the mustard to cobalt attenuated its cytotoxicity, and the differential toxicity in air vs. nitrogen.

  6. Breeding strategy for the improvement of mustard (Brassica Juncea Coss.)

    International Nuclear Information System (INIS)

    Nayar, G.G.

    1980-01-01

    Mutants having desirable agronomic characters were obtained in the high yielding, recommended mustard (B. juncea) varieties Rai 5, RL 9 and Varuna (T 59). Following hybridizations between induced mutants or mutants with other promising varieties, recombinants having superior agronomic traits have been developed. The parent varieties are characterised by open pod arrangement and blackish brown seeds. The mutants and the recombinants have desirable agronomic characters like compact plant type, appressed pods with less shattering nature, yellow seeds, higher oil content and lighter coloured oil. Among the 12 new strains developed at this centre, five have been tested at various locations in the country. At many places, TM-(Trombay Mustard-) cultures outyielded or were at par with the local check varieties. TM-2-11 (Appressed pod mutant) and TM-4 (Yellow bold seeded Mutant) have also been included in the Initial Evaluation Trial of the All India Co-ordinated Research Project in Oilseeds (AICORPO) improvement. Reports so far received from various locations in the country indicate that TM-strains, being relatively early cultures, are suited more for states of Rajasthan, Gujarat, U.P. and Bihar. (author)

  7. Sulfur Mustard Exposure from Dredged Artillery Shell in a Commercial Clammer

    Directory of Open Access Journals (Sweden)

    Jenna Otter

    2017-09-01

    Full Text Available A 40-year-old commercial fisherman presented with a blistering second degree burn to the right arm after handling a dredged and undetonated World War I-era sulfur mustard artillery shell. He sustained isolated second degree cutaneous injury requiring wound care and skin grafting. Sulfur mustard, or dichlorethylsulphide, is a vesicant chemical warfare agent that causes significant cutaneous chemical burn and is managed with burn wound care. Long-term effects include cosmetic disfigurement and increased risk of developing cancer. Sulfur mustard exposure is a rare but devastating injury when discarded artillery shells are encountered in coastal waters.

  8. New Mild and Simple Approach to Isothiocyanates: A Class of Potent Anticancer Agents

    Directory of Open Access Journals (Sweden)

    Bingling Luo

    2017-06-01

    Full Text Available In our current work, acetyl chloride-mediated synthesis of phenethyl isothiocyanate (PEITC derivatives proves to be convenient and provides the expected products at good to excellent yields. Biological evaluation and structure-activity relationship analysis found that the novel compound 7 showed the best anticancer activity against human cancer cell line Panc1 and HGC27 compared with PEITC. Compounds 6 and 7 induced more apoptosis in pancreatic cancer cells but less toxicity in non-cancer cells. Further biological study demonstrated that 7 substantially increased intracellular reactive oxygen species (ROS and depleted glutathione (GSH, leading to an oxidative stress to kill cancer cell.

  9. Synthesis, crystal structure, and photoluminescence of a lithium isothiocyanate compound with 18-crown-6

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Shan; Fu, Bo; Zhao, Zhen; Liu, Xi [Chongqing Normal Univ. (China). Chongqing Key Lab. of Inorganic Functional Materials

    2018-04-01

    The investigation of the supramolecular interactions between the lithium isothiocyanate salt and 18-crown-6 (18C-6) in commercial tetrahydrofuran leads to the formation of a lithium compound, LiNCS(H{sub 2}O)(18C-6) (1). In the crystal structure the asymmetric unit contains two similar LiNCS(H{sub 2}O)(18C-6) molecules. Solid-state photoluminescence experiments have shown that compound 1 emits violet luminescence, and its possible emission mechanism was investigated in detail based on theoretical calculations.

  10. Crystal structure of 4′-allyl-4,5,6,7,2′,7′-hexachlorofluorescein allyl ester unknown solvate

    Directory of Open Access Journals (Sweden)

    Lili Wang

    2018-01-01

    Full Text Available In the title compound, 4′-allyl-4,5,6,7,2′,7′-hexachlorofluorescein allyl ester {systematic name: prop-2-en-1-yl 2,3,4,5-tetrachloro-6-[2,7-dichloro-6-hydroxy-3-oxo-4-(prop-2-en-1-yl-3H-xanthen-9-yl]benzoate}, C26H14Cl6O5, accompanied by unknown solvate molecules, the dihedral angle between the xanthene ring system (r.m.s. deviation = 0.046 Å and the pentasubstituted benzene ring is 71.67 (9°. Both allyl groups are disordered over two sets of sites in statistical ratios. The scattering contributions of the disordered solvent molecules (both Ph2O and CHCl3, as identified by NMR were removed with the PLATON SQUEEZE algorithm [Spek (2015. Acta Cryst. C71, 9–18]. In the crystal, tetrameric supramolecular aggregates linked by O—H...O hydrogen bonds occur; these further interact with neighboring aggregates through C—Cl...π interactions arising from the benzene rings, forming infinite two-dimensional sheets. Each C6Cl4 ring shifts in the direction perpendicular to the two-dimensional sheet, exhibiting a helical chain in which every C6Cl4 ring is utilized as both a donor and an acceptor of Cl...π contacts. Thus, these two-dimensional sheets pack in a helical fashion, constructing a three-dimensional network.

  11. Toxicology Studies on Lewisite and Sulfur Mustard Agents: Subchronic Toxicity of Sulfur Mustard (HD) In Rats Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Sasser, L. B.; Miller, R. A.; Kalkwarf, D, R.; Buschbom, R. L.; Cushing, J. A.

    1989-06-30

    Occupational health standards have not been established for sulfur mustard [bis(2- chlorethyl)-sulfide], a strong alkylating agent with known mutagenic properties. Seventytwo Sprague-Dawley rats of each sex, 6-7 weeks old, were divided into six groups (12/group/ sex) and gavaged with either 0, 0.003 , 0.01 , 0.03 , 0.1 or 0.3 mg/kg of sulfur mustard in sesame oil 5 days/week for 13 weeks. No dose-related mortality was observed. A significant decrease (P ( 0.05) in body weight was observed in both sexes of rats only in the 0.3 mg/kg group. Hematological evaluations and clinical chemistry measurements found no consistent treatment-related effects at the doses studied. The only treatment-related lesion associated with gavage exposure upon histopathologic evaluation was epithelial hyperplasia of the forestomach of both sexes at 0.3 mg/kg and males at 0.1 mg/kg. The hyperplastic change was minimal and characterized by cellular disorganization of the basilar layer, an apparent increase in mitotic activity of the basilar epithelial cells, and thickening of the epithelial layer due to the apparent increase in cellularity. The estimated NOEL for HD in this 90-day study is 0.1 mg/kg/day when administered orally.

  12. Method of preparing water purification membranes. [polymerization of allyl amine as thin films in plasma discharge

    Science.gov (United States)

    Hollahan, J. R.; Wydeven, T. J., Jr. (Inventor)

    1974-01-01

    Allyl amine and chemically related compounds are polymerized as thin films in the presence of a plasma discharge. The monomer compound can be polymerized by itself or in the presence of an additive gas to promote polymerization and act as a carrier. The polymerized films thus produced show outstanding advantages when used as reverse osmosis membranes.

  13. Mechanistic Investigation of Palladium–Catalyzed Allylic C–H Activation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Jensen, Thomas; Rodríguez-Rodríguez, Sergio

    2013-01-01

    The mechanism for the palladium–catalyzed allylic C–H activation was investigated using a combination of experimental and theoretical methods. A Hammett study revealed a buildup of a partial negative charge in the rate-determining step, while determination of the kinetic isotope effect (KIE...

  14. Synthesis of Chromane Derivatives via Indium-mediated Intramolecular Allenylation and Allylation to Imines

    International Nuclear Information System (INIS)

    Kang, Han Young; Yu, Yeon Kwon

    2004-01-01

    The results of preparing chromans by intramolecular allylation are shown in Table 2. The results indicated that the indium-mediated allylation was not as efficient as the allenylation. About 10-20% decrease in yields was observed. As mentioned above, in each case only a single isomer was observed, and the stereochemistry of the product was determined as cis by analysis of 1 H NMR and NOE spectra. There are, however, still some limitations in these transformations. Especially, in the case of allylation mixtures of cis and trans isomers are always produced in about 2 : 1 ratio (cis/trans). The ratio was not improved under the various reaction conditions we attempted. Since the indium-mediated addition to carbonyl groups has been successful, it occurred to us that it would be worthwhile to test the addition to carbon-nitrogen double bonds, that is, imine groups. We wish to report here the results of the investigations on allylation and allenylation to C=N bond to provide the chromane structures. The whole transformations

  15. Organocatalytic asymmetric allylic amination of Morita–Baylis–Hillman carbonates of isatins

    Directory of Open Access Journals (Sweden)

    Hang Zhang

    2012-08-01

    Full Text Available The investigation of a Lewis base catalyzed asymmetric allylic amination of Morita–Baylis–Hillman carbonates derived from isatins afforded an electrophilic pathway to access multifunctional oxindoles bearing a C3-quaternary stereocenter, provided with good to excellent enantioselectivity (up to 94% ee and in high yields (up to 97%.

  16. In(OTf)3 catalyzed allylation reaction of imines with tetraallyltin

    Institute of Scientific and Technical Information of China (English)

    Xiao Ning Wei; Ling Yan Liu; Bing Wang; Wei Xing Chang; Jing Li

    2009-01-01

    In the presence of catalytic amount of In(OTf)3 (10 mol%), a series of aldimines reacted with tetraallyltin in a 2:1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom efficiency was achieved under mild reaction conditions and a new protocol (allyl)4Sn/In(OTf)3 for simple imines was developed.

  17. Chalcogen-containing oxazolines in the palladium-catalyzed asymmetric allylic alkylation

    Directory of Open Access Journals (Sweden)

    Braga Antonio L.

    2006-01-01

    Full Text Available A comparative study about the ability of chiral chalcogen-containing oxazolines to act as chiral ligands in the palladium-catalyzed allylic alkylation of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate is reported. Differences in the catalytic performance are observed with sulfur, selenium and tellurium analogues.

  18. The Defense Metabolite, Allyl Glucosinolate, Modulates Arabidopsis thaliana Biomass Dependent upon the Endogenous Glucosinolate Pathway.

    Science.gov (United States)

    Francisco, Marta; Joseph, Bindu; Caligagan, Hart; Li, Baohua; Corwin, Jason A; Lin, Catherine; Kerwin, Rachel; Burow, Meike; Kliebenstein, Daniel J

    2016-01-01

    Glucosinolates (GSLs) play an important role in plants as direct mediators of biotic and abiotic stress responses. Recent work is beginning to show that the GSLs can also inducing complex defense and growth networks. However, the physiological significance of these GSL-induced responses and the molecular mechanisms by which GSLs are sensed and/or modulate these responses are not understood. To identify these potential mechanisms within the plant and how they may relate to the endogenous GSLs, we tested the regulatory effect of exogenous allyl GSL application on growth and defense metabolism across sample of Arabidopsis thaliana accessions. We found that application of exogenous allyl GSL had the ability to initiate changes in plant biomass and accumulation of defense metabolites that genetically varied across accessions. This growth effect was related to the allyl GSL side-chain structure. Utilizing this natural variation and mutants in genes within the GSL pathway we could show that the link between allyl GSL and altered growth responses are dependent upon the function of known genes controlling the aliphatic GSL pathway.

  19. Solvent-controlled regioselective protection of allyl-4,6-benzylidene glucopyranosides

    Directory of Open Access Journals (Sweden)

    Migaud Marie E

    2007-09-01

    Full Text Available Abstract We wish to report a simple synthetic procedure, which permits the regiospecific mono-acylation, alkylation and silylation at the 2-position of allyl 4,6-O-benzylidene α-D-glucopyranoside in high yields and which does not require the use of catalysts.

  20. Cu-Catalyzed Asymmetric Allylic Alkylation of Phosphonates and Phosphine Oxides with Grignard Reagents

    NARCIS (Netherlands)

    Hornillos, Valentin; Perez, Manuel; Fananas-Mastral, Martin; Feringa, Ben L.

    An efficient and highly enantioselective copper-catalyzed allylic alkylation of phosphonates and phosphine oxides with Grignard reagents and Taniaphos or phosphoramidites as chiral ligands is reported. Transformation of these products leads to a variety of new phosphorus-containing chiral

  1. Enantioselective Allylation of Thiophene-2-carbaldehyde: Formal Total Synthesis of Duloxetine

    Czech Academy of Sciences Publication Activity Database

    Motloch, P.; Valterová, Irena; Kotora, M.

    2014-01-01

    Roč. 356, č. 1 (2014), s. 199-204 ISSN 1615-4150 Grant - others:GA ČR(CZ) GAP207/11/0587 Institutional support: RVO:61388963 Keywords : aldehydes * allylation * Lewis bases * organocatalysis * synthetic methods Subject RIV: CC - Organic Chemistry Impact factor: 5.663, year: 2014

  2. 1-Allyl-3-amino-1H-pyrazole-4-carboxylic acid

    Directory of Open Access Journals (Sweden)

    Feng-Ling Yang

    2008-12-01

    Full Text Available The title compound, C7H9N3O2, was prepared by alkaline hydrolysis of ethyl 1-allyl-3-amino-1H-pyrazole-4-carboxylate. The crystal structure is stabilized by three types of intermolecular hydrogen bond (N—H...O, N—H...N and O—H...N.

  3. Combined experimental and theoretical mechanistic investigation of the Barbier allylation in aqueous media

    DEFF Research Database (Denmark)

    Dam, Johan Hygum; Fristrup, Peter; Madsen, Robert

    2008-01-01

    -determining step. For Zn, In, Sn, Sb, and Bi, an inverse secondary kinetic isotope effect was found (k(H)/k(D) = 0.75-0.95), which was compatible with the formation of a discrete organometallic species prior to allylation via a closed six-membered transition state. With Mg, a significantly larger build...

  4. Reactivity of olefin and allyl ligands in π-complexes of metals

    International Nuclear Information System (INIS)

    Kukushkin, Yu.N.

    1987-01-01

    The data on reactivity of olefin and allyl ligands in transition metal (Ru, W) π-complexes, published up to 1984 are presented. Metal ion coordination of olefins causes their appreciable reactivity change. Transformations of π-olefin ligands into σ-alkyl ones, interaction of π-complexes with oxygen nucleophilic reagents, amines, halogenides and pseudohalogenides are considered

  5. Preparation of pyrrolizinone derivatives via sequential transformations of cyclic allyl imides: synthesis of quinolactacide and marinamide.

    Science.gov (United States)

    Simic, Milena; Tasic, Gordana; Jovanovic, Predrag; Petkovic, Milos; Savic, Vladimir

    2018-03-28

    A facile synthetic route has been developed for the preparation of pyrrolizinone derivatives employing N-allyl imides as starting materials. The nucleophilic addition of a vinyl Grignard reagent/RCM/elimination sequence afforded pyrrolizinones in good yields and has been applied for the preparation of naturally occurring quinolactacide and marinamide.

  6. Catalytic Enantioselective Synthesis of Naturally Occurring Butenolides via Hetero-Allylic Alkylation and Ring Closing Metathesis

    NARCIS (Netherlands)

    Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; Zijl, Anthoni W. van; Fletcher, Stephen P.; Minnaard, Adriaan J.; Feringa, Bernard

    2011-01-01

    An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey

  7. 31P NMR study of phosphate metabolites in intact developing seeds of wheat, soybean and mustard

    International Nuclear Information System (INIS)

    Gambhir, P.N.; Pande, P.C.; Ratcliffe, R.G.

    1994-01-01

    The study of 31 P NMR spectra of intact developing seeds of wheat, soybean and mustard and its possible use for assessing the relative degree of hypoxia under in vivo conditions are reported. 7 refs., 2 figs

  8. Fluorogenic dansyl-ligated gold nanoparticles for the detection of sulfur mustard by displacement assay.

    Science.gov (United States)

    Knighton, Richard C; Sambrook, Mark R; Vincent, Jack C; Smith, Simon A; Serpell, Christopher J; Cookson, James; Vickers, Matthew S; Beer, Paul D

    2013-03-21

    The dansyl fluorophore ligated to gold nanoparticles via imidazole and amine groups affords conjugates capable of detecting micromolar concentrations of the chemical warfare agent sulfur mustard by a fluorescence switching 'ON' displacement assay.

  9. Deconvoluting the memory effect in Pd-catalyzed allylic alkylation; effect of leaving group and added chloride

    DEFF Research Database (Denmark)

    Fristrup, Peter; Jensen, Thomas; Hoppe, Jakob

    2006-01-01

    An analysis of product distributions in the Tsuji-Trost reaction indicates that several instances of reported memory effects can be attributed to slow interconversion of the initially formed syn- and anti-[Pd(eta3-allyl)] complexes. Addition of chloride triggers a true memory effect, in which...... the allylic terminus originally bearing the leaving group has a higher reactivity. The latter effect, termed regioretention, can be rationalized by ionization from a palladium complex bearing a chloride ion, forming an unsymmetrically substituted [Pd(eta3-allyl)] complex. DFT calculations verify...

  10. Metabolism, excretion, and pharmacokinetics of S-allyl-L-cysteine in rats and dogs.

    Science.gov (United States)

    Amano, Hirotaka; Kazamori, Daichi; Itoh, Kenji; Kodera, Yukihiro

    2015-05-01

    The metabolism, excretion, and pharmacokinetics of S-allyl-l-cysteine (SAC), an active key component of garlic supplements, were examined in rats and dogs. A single dose of SAC was administered orally or i.v. to rats (5 mg/kg) and dogs (2 mg/kg). SAC was well absorbed (bioavailability >90%) and its four metabolites-N-acetyl-S-allyl-l-cysteine (NAc-SAC), N-acetyl-S-allyl-l-cysteine sulfoxide (NAc-SACS), S-allyl-l-cysteine sulfoxide (SACS), and l-γ-glutamyl-S-allyl-l-cysteine-were identified in the plasma and/or urine. Renal clearance values (l/h/kg) of SAC indicated its extensive renal reabsorption, which contributed to the long elimination half-life of SAC, especially in dogs (12 hours). The metabolism of SAC to NAc-SAC, principal metabolite of SAC, was studied in vitro and in vivo. Liver and kidney S9 fractions of rats and dogs catalyzed both N-acetylation of SAC and deacetylation of NAc-SAC. After i.v. administration of NAc-SAC, SAC appeared in the plasma and its concentration declined in parallel with that of NAc-SAC. These results suggest that the rate and extent of the formation of NAc-SAC are determined by the N-acetylation and deacetylation activities of liver and kidney. Also, NAc-SACS was detected in the plasma after i.v. administration of either NAc-SAC or SACS, suggesting that NAc-SACS could be formed via both N-acetylation of SACS and S-oxidation of NAc-SAC. In conclusion, this study demonstrated that the pharmacokinetics of SAC in rats and dogs is characterized by its high oral bioavailability, N-acetylation and S-oxidation metabolism, and extensive renal reabsorption, indicating the critical roles of liver and kidney in the elimination of SAC. Copyright © 2015 by The American Society for Pharmacology and Experimental Therapeutics.

  11. Natural isothiocyanates express antimicrobial activity against developing and mature biofilms of Pseudomonas aeruginosa.

    Science.gov (United States)

    Kaiser, Stefan J; Mutters, Nico T; Blessing, Brigitte; Günther, Frank

    2017-06-01

    The antimicrobial properties of natural isothiocyanates (ITCs) found in plants such as nasturtium (Tropaeolum majus) and horseradish (Armoracia rusticana), and the need of new chemotherapeutic options for treatment of infections caused by multidrug-resistant and biofilm-forming Gram-negative bacteria such as Pseudomonas aeruginosa (Pa), led us to evaluate the effects of three major ITCs, allylisothiocyanate (AITC), benzylisothiocyanate (BITC), and phenylethyl-isothiocyanate (PEITC), and a mixture (ITCM) adapted to the ITC composition after release of active components out of natural sources. Out of 105Pa isolates 27 isolates with increased biofilm formation were selected for testing. The effects of ITCs on Pa were evaluated regarding (1) planktonic bacterial proliferation, (2) biofilm formation, (3) metabolic activity in mature biofilms, and (4) synergism of ITCs and antibiotics. (1) Each ITC had anti-Pa activity. Mean minimum inhibitory concentrations (MICs) were (μg/ml, mean±standard deviation): AITC 103±6.9; BITC, 2145±249; PEITC 29,423±1652; and ITCM, 140±5. (2) Treating bacteria with PEITC and ITCM in concentrations below the MIC significantly inhibited biofilm formation. Particularly, ITCM reduced biofilm mass and bacterial proliferation. (3) ITCs significantly inhibited metabolic activity in mature biofilms. (4) Combining ITCs with meropenem synergistically increased antimicrobial efficacy on Pa biofilms. ITCs represent a promising group of natural anti-infective compounds with activity against Pa biofilms. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  12. Pathogenesis of Acute and Delayed Corneal Lesions after Ocular Exposure to Sulfur Mustard Vapor

    Science.gov (United States)

    2012-01-01

    14. ABSTRACT See reprint. 15. SUBJECT TERMS mustard gas keratopathy, ocular toxicity , vapor exposure , sulfur mustard, chemical warfare agent, medical...had poor outcomes . Using a rabbit corneal vapor exposure model, we previously demonstrated a clinical progression with acute and chronic sequelae...the appearance of BCN between one and two weeks suggests that necrosis is either due to delayed SM toxicity or a second-order effect indirectly

  13. Quantum molecular modeling of the interaction between guanine and alkylating agents--2--nitrogen mustard.

    Science.gov (United States)

    Hamza, A; Broch, H; Vasilescu, D

    1996-06-01

    The alkylation mechanism of guanine by nitrogen mustard (HN2) was studied by using a supermolecular modeling at the ab initio 6-31G level. Our computations show that interaction of guanine with the aziridinium form of HN2 necessitates a transition state for the N7 alkylation route. The pathway of N7-guanine alkylation by nitrogen and sulfur mustards is discussed on the basis of the Molecular Electrostatic Potential and HOMO-LUMO properties of these molecules.

  14. Dermatotoxicology of sulfur mustard: Historical perspectives from World War I.

    Science.gov (United States)

    Jiang, Austin; Maibach, Howard

    2018-01-01

    Sulfur mustard has been used as a chemical warfare agent for the past century. After its introduction by the Germans in World War I, investigators quickly began studying its impact on the human body including its deleterious effects on skin. This review focuses on two groups in particular who conducted experiments from 1917 to 1918: the United States Army at the American University Experiment Station Laboratories and Torald Sollmann at Western Reserve University. Through this work, these researchers proved far ahead of their time by anticipating dermatologic phenomena not described in the literature until later in the twentieth century. These include regional variation of percutaneous penetration, effect of vehicle on penetration and predicting immunologic contact urticaria. The work conducted by these researchers set the groundwork for much of twentieth century dermatotoxicology. Copyright © 2017 John Wiley & Sons, Ltd.

  15. Sulfur mustard-induced poikiloderma: a case report.

    Science.gov (United States)

    Emadi, Seyed Naser; Kaffashi, Mohammad; Poursaleh, Zohreh; Akhavan-Moghaddam, Jamal; Soroush, Mohammad Reza; Emadi, Seyed Emad; Taghavi, Nez'hat-o-Sadat

    2011-06-01

    Sulfur mustard (SM) is a potent chemical warfare agent that was widely used during the First World War and the Iran-Iraq conflict. This vesicant agent causes several acute and chronic effects on the skin, eye, and respiratory system. We report the case of a 41-year-old man who was injured with SM in Iraq chemical attack in 1988. After exposure, he developed severe skin blisters on his upper trunk, dorsum of hands, and genitalia. Based on several clinical observations, such as atrophy, pigmentation, and vascular changes on genitalia with relevant findings in histopathological studies, persistent pigmentation, and damaged skin appendix in hand lesions, a diagnosis of "SM-induced poikiloderma" was postulated. The absence of any complication on the palmar aspect of hands is another remarkable finding in presented case, which suggests a plausible role of the palms as a vector for transporting SM to other sites of the skin.

  16. Advanced biotherapy for the treatment of sulfur mustard poisoning.

    Science.gov (United States)

    Sun, Mingxue; Yang, Yuyan; Meng, Wenqi; Xu, Qingqiang; Lin, Fengwu; Chen, Yongchun; Zhao, Jie; Xiao, Kai

    2018-04-25

    Sulfur mustard (SM), a bifunctional alkylating agent, can react with a variety of biochemical molecules (DNA, RNA, proteins and other cell components) to cause a series of serious health issues or even death. Although a plethora of research has been done, the pathogenesis of SM poisoning has yet to be fully understood due to its high complexity. As a consequence, a specific antidote has not yet been developed and the treatment of SM poisoning remains a medical challenge. In recent years, various biological products and cell transplantation in the treatment of SM poisoning offered a significant clinical treatment progress. By highlighting these and other research studies, we hereby summarize the progress in this field in an effort to provide useful information on the clinical treatment of SM poisoning. This review summarizes the major advances of SM poisoning therapy by means of biological products (peptide and protein drugs, polysaccharides drugs, nucleic acid drugs, etc.), and cell transplantation (e.g., bone marrow, limbal stem cells, mesenchymal stem cells), as well as other relevant biotherapeutic approaches. We searched the database PubMed for published domestic and international articles using web based resources for information on histological, immunochemical, ultrastructural, and treatment features of SM-induced manifestations in both animal models and human tissues. To this end, we applied keywords containing mustard gas, chemical warfare, SM, eye, lung and skin. Our review provides a comprehensive understanding of the advances of available biotherapies in SM poisoning, and its potential for the treatment of SM-induced injuries. Potentially, our review will provide new insights for future research studies in this field. Copyright © 2018. Published by Elsevier B.V.

  17. Impact of Indian Mustard (Brassica juncea and Flax (Linum usitatissimum Seed Meal Applications on Soil Carbon, Nitrogen, and Microbial Dynamics

    Directory of Open Access Journals (Sweden)

    Autumn S. Wang

    2012-01-01

    Full Text Available There is a critical need to investigate how land application of dedicated biofuel oilseed meals affects soil ecosystems. In this study, mustard (Brassica juncea and flax (Linum usitatissimum seed meals and sorghum-sudangrass (Sorghum bicolor were added to soil at levels of 0, 1, 2.5, and 5% (w/w. Both the type of amendment and application rate affected soil organic C, total C & N, and C & N mineralization. Mustard meal amendment initially inhibited C mineralization as compared to flax, but >50% of mustard and flax organic C was mineralized within 51 d. Nitrogen mineralization was similar for flax and mustard, except for the 2.5% rate for which a lower proportion of mustard N was converted to nitrate. The mustard meal greatly impacted microbial community composition, appearing to select for specific fungal populations. The potential varying impacts of different oilseed meals on soil ecosystems should be considered when developing recommendations for land application.

  18. Mesoporous CuO–ZnO binary metal oxide nanocomposite for decontamination of sulfur mustard

    International Nuclear Information System (INIS)

    Praveen Kumar, J.; Prasad, G.K.; Ramacharyulu, P.V.R.K.; Garg, P.; Ganesan, K.

    2013-01-01

    Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. They were prepared by precipitation pyrolysis method and characterized by means of X-ray diffraction, transmission electron microscopy, nitrogen adsorption, Fourier transform infrared spectroscopy techniques. Obtained data indicated the presence of mesopores with diameter ranging from 2 to 80 nm and the materials exhibited relatively high surface area 86 m 2 g −1 when compared to the individual metal oxide nanoparticles. Reactive sites of mesoporous CuO–ZnO binary metal oxide nanocomposites were studied by infrared spectroscopy technique using pyridine as a probe molecule. These materials demonstrated superior decontamination properties against sulfur mustard when compared to single component metal oxides and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Graphical abstract: Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. These materials demonstrated superior decontamination properties against sulfur mustard and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Highlights: • Preparation of mesoporous CuO–ZnO binary metal oxide nanocomposite. • CuO–ZnO with better surface area was synthesized by precipitation pyrolysis. • Decontamination of HD using mesoporous CuO–ZnO binary metal oxide nanocomposite. • HD decontaminated by elimination and hydrolysis reactions

  19. Mesoporous CuO–ZnO binary metal oxide nanocomposite for decontamination of sulfur mustard

    Energy Technology Data Exchange (ETDEWEB)

    Praveen Kumar, J.; Prasad, G.K., E-mail: gkprasad2001@yahoo.com; Ramacharyulu, P.V.R.K.; Garg, P.; Ganesan, K.

    2013-11-01

    Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. They were prepared by precipitation pyrolysis method and characterized by means of X-ray diffraction, transmission electron microscopy, nitrogen adsorption, Fourier transform infrared spectroscopy techniques. Obtained data indicated the presence of mesopores with diameter ranging from 2 to 80 nm and the materials exhibited relatively high surface area 86 m{sup 2} g{sup −1} when compared to the individual metal oxide nanoparticles. Reactive sites of mesoporous CuO–ZnO binary metal oxide nanocomposites were studied by infrared spectroscopy technique using pyridine as a probe molecule. These materials demonstrated superior decontamination properties against sulfur mustard when compared to single component metal oxides and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Graphical abstract: Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. These materials demonstrated superior decontamination properties against sulfur mustard and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Highlights: • Preparation of mesoporous CuO–ZnO binary metal oxide nanocomposite. • CuO–ZnO with better surface area was synthesized by precipitation pyrolysis. • Decontamination of HD using mesoporous CuO–ZnO binary metal oxide nanocomposite. • HD decontaminated by elimination and hydrolysis reactions.

  20. Cascade synthesis of dihydrobenzofuran via Claisen rearrangement of allyl aryl ethers using FeCl3/MCM-41 catalyst

    Directory of Open Access Journals (Sweden)

    Sachin S. Sakate

    2018-05-01

    Full Text Available Dihydrobenzofuran as one of the active ingredients of the naturally occurring motif is synthesized by using in situ generation of ortho allyl phenols. Aryl allyl ethers on reacting with catalytic amounts of non noble metal iron (III chloride supported on MCM-41 under moderate reaction conditions yield dihydrobenzofuran. First step via Claisen rearrangement gives ortho allyl phenol followed by its in situ cyclization to yield dihydrobenzofuran in very good yields. Both Lewis as well as Brønsted acidity of the catalyst as evidenced by Py-FTIR studies was found to catalyze the cascade synthesis of dihydrobenzofuran. The scope of the present strategy was successfully demonstrated for several substrates with varying electronic effects for the synthesis of corresponding dihydrobenzofuran with high yields in a range of 71–86%. Keywords: Claisen rearrangement, Dihydrobenzofuran, Aryl allyl ether, MCM-41, Ferric chloride

  1. Chemoenzymatic one-pot synthesis in an aqueous medium: combination of metal-catalysed allylic alcohol isomerisation-asymmetric bioamination.

    Science.gov (United States)

    Ríos-Lombardía, Nicolás; Vidal, Cristian; Cocina, María; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier

    2015-07-11

    The ruthenium-catalysed isomerisation of allylic alcohols was coupled, for the first time, with asymmetric bioamination in a one-pot process in an aqueous medium. In the cases involving prochiral ketones, the ω-TA exhibited excellent enantioselectivity, identical to that observed in the single step. As a result, amines were obtained from allylic alcohols with high overall yields and excellent enantiomeric excesses.

  2. Allylic chlorination of terpenic olefins using a combination of MoCl{sub 5} and NaOCl

    Energy Technology Data Exchange (ETDEWEB)

    Boualy, Brahim; Firdoussi, Larbi El; Ali, Mustapha Ait; Karim, Abdellah, E-mail: elfirdoussi@ucam.ac.m [Universite Cadi Ayyad, Marrakech (Morocco). Faculte des Sciences Semlalia. Lab. de Chimie de Coordination

    2011-07-01

    MoCl{sub 5} is applied as efficient agent in allylic chlorination of terpenic olefins in the presence of NaOCl as chlorine donor. Various terpenes are converted to the corresponding allylic chlorides in moderate to good yield under mild and optimized reaction conditions. Different molybdenum precursors are also studied. Among them, MoO{sub 3} gives good yield, but after a longer reaction time. (author)

  3. Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: synergetic effect of ligands and barium enolates.

    Science.gov (United States)

    Chen, Wenyong; Chen, Ming; Hartwig, John F

    2014-11-12

    We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

  4. Contents of Sulforaphane and Total Isothiocyanates, Antimutagenic Activity, and Inhibition of Clastogenicity in Pulp Juices from Cruciferous Plants

    Czech Academy of Sciences Publication Activity Database

    Totušek, J.; Tříska, Jan; Lefnerová, D.; Strohalm, J.; Vrchotová, Naděžda; Zendulka, O.; Průchová, J.; Chaloupková, J.; Novotná, P.; Houška, M.

    2011-01-01

    Roč. 29, č. 5 (2011), s. 548-556 ISSN 1212-1800 R&D Projects: GA MZe QF3287 Institutional research plan: CEZ:AV0Z60870520 Keywords : cruciferous vegetables * juice * antimutagenic effects * sulforaphane * isothiocyanates Subject RIV: GM - Food Processing Impact factor: 0.522, year: 2011

  5. The addition of organotin hydrides to isocyanates and isothiocyanates: synthesis and structure of some organotin-substituted amides

    NARCIS (Netherlands)

    Noltes, J.G.; Janssen, M.J.

    Organotin hydrides add across the carbon---nitrogen double bond of aryl isocyanates (tin---nitrogen bond formation) and hexyl isocyanate (tin---carbon bond formation) and across the carbon---sulfur double bond of phenyl isothiocyanate (tin---sulfur bond formation) to afford in excellent yield 1:1

  6. Taste detection of the non-volatile isothiocyanate moringin results in deterrence to glucosinolate-adapted insect larvae

    NARCIS (Netherlands)

    Müller, Caroline; Loon, Van Joop; Ruschioni, Sara; Nicola, De Gina Rosalinda; Olsen, Carl Erik; Iori, Renato; Agerbirk, Niels

    2015-01-01

    Isothiocyanates (ITCs), released from Brassicales plants after hydrolysis of glucosinolates, are known for their negative effects on herbivores but mechanisms have been elusive. The ITCs are initially present in dissolved form at the site of herbivore feeding, but volatile ITCs may subsequently

  7. Relationship between Chemical Structure and Antimicrobial Activities of Isothiocyanates from Cruciferous Vegetables against Oral Pathogens.

    Science.gov (United States)

    Ko, Mi-Ok; Kim, Mi-Bo; Lim, Sang-Bin

    2016-12-28

    We evaluated the potentials of 10 isothiocyanates (ITCs) from cruciferous vegetables and radish root hydrolysate for inhibiting the growth of oral pathogens, with an emphasis on assessing any structure-function relationship. Structural differences in ITCs impacted their antimicrobial activities against oral pathogens differently. The indolyl ITC (indol-3-carbinol) was the most potent inhibitor of the growth of oral pathogens, followed by aromatic ITCs (benzyl ITC (BITC) and phenylethyl ITC (PEITC)) and aliphatic ITCs (erucin, iberin, and sulforaphene). Sulforaphene, which is similar in structure, but has one double bond, showed higher antimicrobial activity than sulforaphane. Erucin, which has a thiol group, showed higher antimicrobial activity than sulforaphane, which has a sulfinyl group. BITC and iberin with a short chain exhibited higher antimicrobial potential than PEITC and sulforaphane with a longer chain, respectively. ITCs have strong antimicrobial activities and may be useful in the prevention and management of dental caries.

  8. Lipid Profile Status in Mustard Lung Patients and its Relation to Severity of Airflow Obstruction

    Directory of Open Access Journals (Sweden)

    Davood Attaran

    2014-02-01

    Full Text Available Introduction: Chronic obstructive pulmonary disease (COPD secondary to sulfur mustard gas poisoning, known as mustard lung, is a major late pulmonary complications in chemical warfare patients. Serious comorbidities like dyslipidemia are frequently encountered in COPD. The aim of this study was to measure the serum lipid profile and evaluate the relation of lipid parameters with the severity of airway obstruction in mustard lung patients. Materials and Methods: Thirty-six non-smoker mustard lung patients with no history of cardiovascular disease, diabetes mellitus, and dyslipidemia were entered into this cross-sectional study. Control group consisted of 36 healthy non-smoker men were considered in this study. Serum lipid profile was performed in the patients and the controls. Spirometry was done in mustard lung patients. Results: The mean age of the patients was 47±6.80 SD years. The mean duration of COPD was 18.50±7.75 SD years. There were statistically significant differences in mean serum triglycerides and total cholesterol levels between patients and controls (p=0.04 and p=0.03, respectively.The mean levels of lipid parameters were not statistically significant different among the 4 stages of COPD severity (p>0.05. Conclusion: The current study revealed that the serum levels of triglycerides and cholesterol are elevated in mustard lung patients compared with the healthy controls. Since lipid profile abnormalities are considered as a major risk factor for cardiovascular disease, especial attention to this matter is recommended in mustard lung patients

  9. Mesoporous binary metal oxide nanocomposites: Synthesis, characterization and decontamination of sulfur mustard

    Energy Technology Data Exchange (ETDEWEB)

    Praveen Kumar, J., E-mail: praveenjella10@gmail.com; Prasad, G.K.; Ramacharyulu, P.V.R.K.; Singh, Beer; Gopi, T.; Krishna, R.

    2016-04-15

    Mesoporous MnO{sub 2}–ZnO, Fe{sub 2}O{sub 3}–ZnO, NiO–ZnO, and CeO{sub 2}–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard. They were synthesized by precipitation pyrolysis method and characterized by means of transmission electron microscopy, scanning electron microscopy coupled with energy dispersive analysis of X rays, X ray diffraction, and nitrogen adsorption techniques. The transmission electron microscopy and nitrogen adsorption data indicated the presence of pores with diameter ranging from 10 to 70 nm in the binary metal oxide nanocomposites and these materials exhibited surface area values in the range of 76–134 m{sup 2}/g. These binary metal oxide nanocomposites demonstrated large decontamination efficiencies against sulfur mustard when compared to their single component metal oxide nanoparticles. The binary metal oxide nanocomposites effectively decontaminated sulfur mustard into relatively non toxic products such as chloro ethyl vinyl sulfide, divinyl sulfide, 1,4-oxathiane, etc. The promising decontamination properties of binary metal oxide nanocomposites against sulfur mustard were attributed to the basic sites, Lewis acid sites, and the presence of these sites was confirmed by CO{sub 2} and NH{sub 3} temperature programmed desorption. - Graphical abstract: Mesoporous MnO{sub 2}–ZnO, Fe{sub 2}O{sub 3}–ZnO, NiO–ZnO, and CeO{sub 2}–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard. - Highlights: • Binary metal oxide nanocomposites were synthesized by co-precipitation method. • They were studied as sorbent decontaminants against sulfur mustard. • They decontaminated sulfur mustard into non toxic products. • MnO{sub 2}–ZnO and CeO{sub 2}–ZnO nanocomposites showed greater decontamination efficiency.

  10. Biochemical characterization and anti-inflammatory properties of an isothiocyanate-enriched moringa (Moringa oleifera) seed extract.

    Science.gov (United States)

    Jaja-Chimedza, Asha; Graf, Brittany L; Simmler, Charlotte; Kim, Youjin; Kuhn, Peter; Pauli, Guido F; Raskin, Ilya

    2017-01-01

    Moringa oleifera Lam. is a tropical plant, used for centuries as food and traditional medicine. The aim of this study was to develop, validate and biochemically characterize an isothiocyanate-enriched moringa seed extract (MSE), and to compare the anti-inflammatory effects of MSE-containing moringa isothiocyanate-1 (MIC-1) with a curcuminoid-enriched turmeric extract (CTE), and a material further enriched in its primary phytochemical, curcumin (curcumin-enriched material; CEM). MSE was prepared by incubating ground moringa seeds with water to allow myrosinase-catalyzed enzymatic formation of bioactive MIC-1, the predominant isothiocyanate in moringa seeds. Optimization of the extraction process yielded an extract of 38.9% MIC-1. Phytochemical analysis of MSE revealed the presence of acetylated isothiocyanates, phenolic glycosides unique to moringa, flavonoids, fats and fatty acids, proteins and carbohydrates. MSE showed a reduction in the carrageenan-induced rat paw edema (33% at 500 mg/kg MIC-1) comparable to aspirin (27% at 300 mg/kg), whereas CTE did not have any significant effect. In vitro, MIC-1 at 1 μM significantly reduced the production of nitric oxide (NO) and at 5 μM, the gene expression of LPS-inducible nitric oxide synthase (iNOS) and interleukins 1β and 6 (IL-1β and IL-6), whereas CEM did not show any significant activity at all concentrations tested. MIC-1 (10μM) was also more effective at upregulating the nuclear factor (erythroid-derived 2)-like 2 (Nrf2) target genes NAD(P)H:quinone oxidoreductase 1 (NQO1), glutathione S-transferase pi 1 (GSTP1), and heme oxygenase 1 (HO1) than the CEM. Thus, in contrast to CTE and CEM, MSE and its major isothiocyanate MIC-1 displayed strong anti-inflammatory and antioxidant properties in vivo and in vitro, making them promising botanical leads for the mitigation of inflammatory-mediated chronic disorders.

  11. Biochemical characterization and anti-inflammatory properties of an isothiocyanate-enriched moringa (Moringa oleifera seed extract.

    Directory of Open Access Journals (Sweden)

    Asha Jaja-Chimedza

    Full Text Available Moringa oleifera Lam. is a tropical plant, used for centuries as food and traditional medicine. The aim of this study was to develop, validate and biochemically characterize an isothiocyanate-enriched moringa seed extract (MSE, and to compare the anti-inflammatory effects of MSE-containing moringa isothiocyanate-1 (MIC-1 with a curcuminoid-enriched turmeric extract (CTE, and a material further enriched in its primary phytochemical, curcumin (curcumin-enriched material; CEM. MSE was prepared by incubating ground moringa seeds with water to allow myrosinase-catalyzed enzymatic formation of bioactive MIC-1, the predominant isothiocyanate in moringa seeds. Optimization of the extraction process yielded an extract of 38.9% MIC-1. Phytochemical analysis of MSE revealed the presence of acetylated isothiocyanates, phenolic glycosides unique to moringa, flavonoids, fats and fatty acids, proteins and carbohydrates. MSE showed a reduction in the carrageenan-induced rat paw edema (33% at 500 mg/kg MIC-1 comparable to aspirin (27% at 300 mg/kg, whereas CTE did not have any significant effect. In vitro, MIC-1 at 1 μM significantly reduced the production of nitric oxide (NO and at 5 μM, the gene expression of LPS-inducible nitric oxide synthase (iNOS and interleukins 1β and 6 (IL-1β and IL-6, whereas CEM did not show any significant activity at all concentrations tested. MIC-1 (10μM was also more effective at upregulating the nuclear factor (erythroid-derived 2-like 2 (Nrf2 target genes NAD(PH:quinone oxidoreductase 1 (NQO1, glutathione S-transferase pi 1 (GSTP1, and heme oxygenase 1 (HO1 than the CEM. Thus, in contrast to CTE and CEM, MSE and its major isothiocyanate MIC-1 displayed strong anti-inflammatory and antioxidant properties in vivo and in vitro, making them promising botanical leads for the mitigation of inflammatory-mediated chronic disorders.

  12. Use of Fluorescein Isothiocyanate-Inulin as a Marker for Intestinal Ischemic Injury.

    Science.gov (United States)

    AlKukhun, Abedalrazaq; Caturegli, Giorgio; Munoz-Abraham, Armando Salim; Judeeba, Sami; Patron-Lozano, Roger; Morotti, Raffaella; Rodriguez-Davalos, Manuel I; Geibel, John P

    2017-06-01

    Intestinal ischemia is observed in conditions such as mesenteric ischemia, or during traumatic events such as intestinal transplantation. Intestinal ischemia leads to pathophysiologic disruptions that present as increased fluid secretion into the intestinal lumen. We propose a novel method to detect real-time ischemic injury that is used in an in vitro model applicable to intestinal transplantation. Small intestine segments from rats were procured. The segments were attached to customized perfusion chambers. Both intestines were perfused on the vascular side with a Ringer buffer solution. The experimental buffer solution was bubbled with 100% nitrogen to mimic ischemia. Both lumens were perfused with 3 mL HEPES-Ringer solution containing 50 μM fluorescein isothiocyanate (FITC)-inulin. Intraluminal samples were collected at 15-minute intervals to measure FITC-inulin concentration using a nanofluorospectrophotometer. Intestinal tissue samples were processed and evaluated by a blinded pathologist using the Park/Chiu scoring system for grading intestinal ischemia. Samples collected from the ischemic intestine showed a significant decrease in FITC-inulin fluorescence compared with the control intestine, indicating enhanced fluid secretion. Histopathologic samples from the experimental arm exhibited higher scores of ischemic injury in comparison with the control arm, confirming the FITC-inulin as a correlation to ischemia. Fluorescein isothiocyanate-inulin can be used as a real-time volume marker to monitor the ischemic state of intestinal tissue. A positive correlation between the degree of fluid shift and presence of ischemic injury. The changes in fluorescence signal provide a potential selective method to measure real-time fluid changes inside an intestinal graft to evaluate viability. Copyright © 2016 American College of Surgeons. Published by Elsevier Inc. All rights reserved.

  13. Apoptotic role of natural isothiocyanate from broccoli (Brassica oleracea italica) in experimental chemical lung carcinogenesis.

    Science.gov (United States)

    Kalpana Deepa Priya, D; Gayathri, R; Gunassekaran, G R; Murugan, S; Sakthisekaran, D

    2013-05-01

    Sulforaphane (SFN) [1-isothiocyanato-4-(methylsulfinyl)butane] is a naturally occurring isothiocyanate found in cruciferous vegetables such as broccoli [Brassica oleracea L. var. italica Plenck. (Brassicaceae)]. Since it is among the most potent bioactive components with antioxidant and antitumor properties, it has received intense attention in the recent years for its chemopreventive properties. The present work determined the rehabilitating role in alleviating the oxidative damage caused by benzo(a)pyrene [B(a)P] to biomolecules and the apoptotic cascade mediated by orally administered isothiocyanate-SFN (9 µmol/mouse/day) against B(a)P (100 mg/kg body weight, i.p.) induced pulmonary carcinogenesis in Swiss albino mice. Oxidative damage was assessed by measuring lipid peroxidation, 8-hydroxydeoxyguanosine, hydrogen peroxide (H2O2) production, glycoprotein components, protein carbonyl levels and DNA-protein crosslinks. DNA fragmentation by agarose gel electrophoresis and caspase-3 activity by ELISA proved apoptotic induction by SFN along with the protein expression of Bcl-2, Bax and Cyt c. SFN treatment was found to decrease the H2O2 production (p < 0.001) in cancer induced animals, proving its antioxidant potential. Apoptosis was induced by increasing the release of Cyt c (p < 0.001) from mitochondria, decreasing and increasing the expression of Bcl-2 (p < 0.01) and Bax (p < 0.001), respectively. Caspase-3 activity was also enhanced (p < 0.001) which leads to DNA fragmentation in SFN treated groups. Our results reflect the rehabilitating role of SFN in B(a)P induced lung carcinogenesis.

  14. Retrospective detection of exposure to sulfur mustard: Improvements on an assay for liquid chromatography-tandem mass spectrometry analysis of albumin/sulfur mustard adducts

    NARCIS (Netherlands)

    Noort, D.; Fidder, A.; Hulst, A.G.; Woolfitt, A.R.; Ash, D.; Barr, J.R.

    2004-01-01

    We here report on the further development of the method comprising the pronase digestion of albumin alkylated by sulfur mustard and the subsequent mass spectrometric analysis of an adducted tripeptide. This includes significant improvements in both the albumin isolation procedure and the automation

  15. Synthesis of praseodymium allyl iodide complex and its use in piperilene polymerization

    International Nuclear Information System (INIS)

    Gajlyunas, G.A.; Biktimirov, R.Kh.; Khajrullina, R.M.; Marina, N.G.; Manakov, Yu.B.; Tolstikov, G.A.

    1987-01-01

    Synthesis, structure and catalytic properties of tetrahydrofuran praseodymium allyl iodine complex (1) are described and studied. Complex 1 is formed during interaction of allyl iodine with metal praseodymium (the molar ratio is 2:1) in THF at room temperature with 97% yield. It represents the solid powder-like substance of the light-brown colour with a pale green shade, being sensitive to moisture and oxygen and decomposing at temperature >120 deg. On the basis of the IR-spectroscopy data the supposition about the dimeric (or n-dimensional) complex structure is made. The complex prepared in combination with tributyl aluminium during piperylene polymerization gives a high-stereoregular and high-molecular polypiperylene

  16. Optimizing isothiocyanate formation during enzymatic glucosinolate breakdown by adjusting pH value, temperature and dilution in Brassica vegetables and Arabidopsis thaliana

    Science.gov (United States)

    Hanschen, Franziska S.; Klopsch, Rebecca; Oliviero, Teresa; Schreiner, Monika; Verkerk, Ruud; Dekker, Matthijs

    2017-01-01

    Consumption of glucosinolate-rich Brassicales vegetables is associated with a decreased risk of cancer with enzymatic hydrolysis of glucosinolates playing a key role. However, formation of health-promoting isothiocyanates is inhibited by the epithiospecifier protein in favour of nitriles and epithionitriles. Domestic processing conditions, such as changes in pH value, temperature or dilution, might also affect isothiocyanate formation. Therefore, the influences of these three factors were evaluated in accessions of Brassica rapa, Brassica oleracea, and Arabidopsis thaliana. Mathematical modelling was performed to determine optimal isothiocyanate formation conditions and to obtain knowledge on the kinetics of the reactions. At 22 °C and endogenous plant pH, nearly all investigated plants formed nitriles and epithionitriles instead of health-promoting isothiocyanates. Response surface models, however, clearly demonstrated that upon change in pH to domestic acidic (pH 4) or basic pH values (pH 8), isothiocyanate formation considerably increases. While temperature also affects this process, the pH value has the greatest impact. Further, a kinetic model showed that isothiocyanate formation strongly increases due to dilution. Finally, the results show that isothiocyanate intake can be strongly increased by optimizing the conditions of preparation of Brassicales vegetables.

  17. Iron(III) chloride catalyzed glycosylation of peracylated sugars with allyl/alkynyl alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Narayanaperumal, Senthil; Silva, Rodrigo Cesar da; Monteiro, Julia L.; Correa, Arlene G.; Paixao, Marcio W., E-mail: mwpaixao@ufscar.br [Universidade Federal de Sao Carlos (UFSCAR), SP (Brazil). Dept. de Quimica

    2012-11-15

    In this work, the use of ferric chloride as an efficient catalyst in glycosylation reactions of sugars in the presence of allyl and alkynyl alcohols is described. The corresponding glycosides were obtained with moderate to good yields. This new procedure presented greater selectivity when compared to classic methods found in the literature. Principal features of this simple method include non-hazardous reaction conditions, low-catalyst loading, good yields and high anomeric selectivity (author)

  18. Tether-directed synthesis of highly substituted oxasilacycles via an intramolecular allylation employing allylsilanes

    Directory of Open Access Journals (Sweden)

    Cox Liam R

    2007-02-01

    Full Text Available Abstract Background Using a silyl tether to unite an aldehyde electrophile and allylsilane nucleophile into a single molecule allows a subsequent Lewis-acid-mediated allylation to proceed in an intramolecular sense and therefore receive all the benefits associated with such processes. However, with the ability to cleave the tether post allylation, a product that is the result of a net intermolecular reaction can be obtained. In the present study, four diastereoisomeric β-silyloxy-α-methyl aldehydes, which contain an allylsilane tethered through the β-carbinol centre, have been prepared, in order to probe how the relative configuration of the two stereogenic centres affects the efficiency and selectivity of the intramolecular allylation. Results Syn-aldehydes, syn-4a and syn-4b, both react poorly, affording all four possible diastereoisomeric oxasilacycle products. In contrast, the anti aldehydes anti-4a and anti-4b react analogously to substrates that lack substitution at the α-site, affording only two of the four possible allylation products. Conclusion The outcome of the reaction with anti-aldehydes is in accord with reaction proceeding through a chair-like transition state (T.S.. In these systems, the sense of 1,3-stereoinduction can be rationalised by the aldehyde electrophile adopting a pseudoaxial orientation, which will minimise dipole-dipole interactions in the T.S. The 1,4-stereoinduction in these substrates is modest and seems to be modulated by the R substituent in the starting material. In the case of the syn-substrates, cyclisation through a chair T.S. is unlikely as this would require the methyl substituent α to the reacting carbonyl group to adopt an unfavourable pseudoaxial position. It is therefore proposed that these substrates react through poorly-defined T.S.s and consequently exhibit essentially no stereoselectivity.

  19. Antiviral activity of an N-allyl acridone against dengue virus

    OpenAIRE

    Mazzucco, María Belén; Talarico, Laura Beatriz; Vatansever, Sezen; Carro, Ana Clara; Fascio, Mirta Liliana; D'Accorso, Norma Beatriz; Garcia, Cybele; Damonte, Elsa Beatriz

    2016-01-01

    Dengue virus (DENV), a member of the family Flaviviridae, is at present the most widespread causative agent of a human viral disease transmitted by mosquitoes. Despite the increasing incidence of this pathogen, there are no antiviral drugs or vaccines currently available for treatment or prevention. In a previous screening assay, we identified a group of N-allyl acridones as effective virus inhibitors. Here, the antiviral activity and mode of action targeted to viral RNA replication of one of...

  20. Surprisingly Mild Enolate-Counterion-Free Pd(0)-Catalyzed Intramolecular Allylic Alkylations

    DEFF Research Database (Denmark)

    Madec, David; Prestat, Guillaume; Martini, Elisabetta

    2005-01-01

    Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence of a crown ether. These new reaction conditions are milder and higher yielding than those previously reported. A rationalization for such an...... for such an unexpected result is put forth and validated by DFT-B3LYP calculations. The results suggest cyclization via a counterion-free (E)-enolate TS....

  1. Lewis base catalyzed enantioselective allylic hydroxylation of Morita-Baylis-Hillman carbonates with water

    KAUST Repository

    Zhu, Bo

    2011-08-19

    A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using 18O-labeling experiments. © 2011 American Chemical Society.

  2. An iron/amine-catalyzed cascade process for the enantioselective functionalization of allylic alcohols.

    Science.gov (United States)

    Quintard, Adrien; Constantieux, Thierry; Rodriguez, Jean

    2013-12-02

    Three is a lucky number: An enantioselective transformation of allylic alcohols into β-chiral saturated alcohols has been developed by combining two distinct metal- and organocatalyzed catalytic cycles. This waste-free triple cascade process merges an iron-catalyzed borrowing-hydrogen step with an aminocatalyzed nucleophilic addition reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. An XPS study of pulsed plasma polymerised allyl alcohol film growth on polyurethane

    Energy Technology Data Exchange (ETDEWEB)

    Watkins, Lucy [Department of Chemistry, University of York, Heslington, York YO10 5DD (United Kingdom); Bismarck, Alexander [Department of Chemical Engineering, Polymer and Composite Engineering (PaCE) Group, Imperial College London, London SW7 2AZ (United Kingdom); Lee, Adam F. [Department of Chemistry, University of York, Heslington, York YO10 5DD (United Kingdom); Wilson, Darren [Smith and Nephew Research Centre, York Science Park, Heslington, York YO10 5DF (United Kingdom); Wilson, Karen [Department of Chemistry, University of York, Heslington, York YO10 5DD (United Kingdom)]. E-mail: kw13@york.ac.uk

    2006-09-30

    The growth of highly functionalised poly allyl alcohol films by pulsed plasma polymerisation of CH{sub 2} =CHCH{sub 2}OH on biomedical grade polyurethane has been followed by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. Film thickness is observed to increase approximately linearly with plasma modification time, suggesting a layer-by-layer growth mode of poly allyl alcohol. Water contact angle measurements reveal the change in the surface free energy of wetting decreases linearly with plasma modification up to the monolayer point after which a constant limiting value of -24 mJ m{sup -2} was attained. Films prepared at 20 W plasma power with a duty cycle of 10 {mu}s:500 {mu}s exhibit a high degree of hydroxyl (-OH) retention with minimal fragmentation of the monomer observed. Increasing the plasma power up to 125 W is found to improve -OH retention at the expense of ether formation generating films close to the monomer stoichiometry. Duty cycle plays an important role in controlling both film composition and thickness, with longer off times increasing -OH retention, while longer on times enhance allyl alcohol film growth.

  4. Synthesis of a Novel Allyl-Functionalized Deep Eutectic Solvent to Promote Dissolution of Cellulose

    Directory of Open Access Journals (Sweden)

    Hongwei Ren

    2016-08-01

    Full Text Available Deep eutectic solvents (DESs offer attractive options for the “green” dissolution of cellulose. However, the protic hydroxyl group causes weak dissolving ability of DESs, requiring the substitution of hydroxyl groups in the cation. In this study, a novel allyl-functionalized DES was synthesized and characterized, and its possible effect on improved dissolution of cellulose was investigated. The DES was synthesized by a eutectic mixture of allyl triethyl ammonium chloride ([ATEAm]Cl and oxalic acid (Oxa at a molar ratio of 1:1 and a freezing point of 49 °C. The [ATEAm]Cl-Oxa exhibited high polarity (56.40 kcal/mol, dipolarity/polarizability effects (1.10, hydrogen-bond donating acidity (0.41, hydrogen-bond basicity (0.89, and low viscosity (76 cP at 120 °C owing to the π-π conjugative effect induced by the allyl group. The correlation between temperature and viscosity on the [ATEAm]Cl-Oxa fit the Arrhenius equation well. The [ATEAm]Cl-Oxa showed low pseudo activation energy for viscous flow (44.56 kJ/mol. The improved properties of the [ATEAm]Cl-Oxa noticeably promoted the solubility (6.48 wt.% of cellulose.

  5. N-Boc Amines to Oxazolidinones via Pd(II)/Bis-sulfoxide/Brønsted Acid Co-Catalyzed Allylic C–H Oxidation

    Science.gov (United States)

    2015-01-01

    A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C–H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C–H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C–H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration. PMID:24999765

  6. N-Boc amines to oxazolidinones via Pd(II)/bis-sulfoxide/Brønsted acid co-catalyzed allylic C-H oxidation.

    Science.gov (United States)

    Osberger, Thomas J; White, M Christina

    2014-08-06

    A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C-H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C-H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C-H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration.

  7. Interaction between copper and radiocesium in Indian mustard and sunflower grown in the hydroponic solution

    International Nuclear Information System (INIS)

    Shirong Tang; Xiaochang Wang

    2002-01-01

    Both Indian mustard and sunflower were grown in a hydroponic solution treated with different concentration activities of 134 Cs or with different amounts of copper or with both in order to investigate the interaction between copper and radiocesium. It was found that 134 Cs activity concentration applied in the nutrient solution exerted more influence on the uptake and translocation of copper by Indian mustard than by sunflower. Indian mustard grown in hydroponic solution containing certain levels of copper and being treated with higher 134 Cs activity concentration showed higher uptake of copper than sunflower. However, in the case of root copper concentrations, sunflower showed significantly higher copper immobilization by roots than Indian mustard. It was also found that the presence of copper the the hydroponic solution did modify radiocesium uptake by both species. The application of 1 mg/l in the growth medium could greatly increase the uptake of 134 Cs by both species. With 3 mg/l concentration of copper amended to the solution, the accumulation of 134 Cs by both species was decreased compared to the 1 mg/l copper treatment. These lines of evidence show that there is stronger interaction between copper and radiocesium in Indian mustard than in sunflower during the root uptake through nutrient solution. (author)

  8. The GC/AED studies on the reactions of sulfur mustard with oxidants

    International Nuclear Information System (INIS)

    Popiel, StanisIaw; Witkiewicz, Zygfryd; Szewczuk, Aleksander

    2005-01-01

    A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive

  9. New studies on mustard gold from the Dongping Mines, Hebei Province, China: The tellurian, plumbian, manganoan and mixed varieties

    DEFF Research Database (Denmark)

    Li, Jiuling; Makovicky, Emil

    2001-01-01

    geologi, Dongping gold tellurite deposit, mustard gold, calaverite, Fe-Pb-Te minerals, alteration, tellurium, filling in micro-porous, composite varieties, particles of gold......geologi, Dongping gold tellurite deposit, mustard gold, calaverite, Fe-Pb-Te minerals, alteration, tellurium, filling in micro-porous, composite varieties, particles of gold...

  10. 38 CFR 3.316 - Claims based on chronic effects of exposure to mustard gas and Lewisite.

    Science.gov (United States)

    2010-07-01

    ... effects of exposure to mustard gas and Lewisite. 3.316 Section 3.316 Pensions, Bonuses, and Veterans... Compensation Ratings and Evaluations; Service Connection § 3.316 Claims based on chronic effects of exposure to mustard gas and Lewisite. (a) Except as provided in paragraph (b) of this section, exposure to the...

  11. Characterization of sulfur mustard induced structural modifications in human hemoglobin by liquid chromatography-tandem mass spectrometry

    NARCIS (Netherlands)

    Noort, D.; Verheij, E.R.; Hulst, A.G.; Jong, L.P.A. de; Benschop, H.P.

    1996-01-01

    In this paper we describe the use of tandem mass spectrometry to identify modified sites in human hemoglobin after in vitro exposure to bis(2- chloroethyl) sulfide (sulfur mustard). Globin isolated from human whole blood which had been exposed to sulfur mustard was degraded with trypsin, and the

  12. The effect of mustard seed meal (Sinapis arvensis on thyroid hormones and liver enzymes in Japanese quails (Coturnix coturnix japonica

    Directory of Open Access Journals (Sweden)

    Sajjad Mohebali

    2016-07-01

    Full Text Available Objective: To investigate the effect of wild black mustard seed meal on thyroid hormones (thyroxine and thyroid-stimulating hormone in Japanese quails and also study the ability of FeSO4 to alleviate the possible negative effect of mustard meal on thyroid hormones in these birds for the first time. Methods: The experimental procedure was undertaken on 28 quails which were randomly assigned to a control and 6 test groups with 4 quails in each group for 28 days, during which the control group received basic diet with no mustard meal whereas the test groups (No. 2, 3 and 4 received mustard meal (5%, 10% and 15%, respectively and test groups (No. 5, 6 and 7 received FeSO4 (1%-treated mustard meal (5%, 10% and 15%, respectively on the basic of basic diet. Results: The group fed on 15% non-treated mustard seed meal had the least thyroxine level and its level backed to normal in group fed on 15% FeSO4-treated mustard seed meal although this group had the highest alanine transaminase and aspartate transaminase levels. Conclusions: We concluded that up to 10% FeSO4 mustard seed meal could be incorporated in the quail diet successfully with the least damage to thyroids and livers, but further investigations on these birds are still needed to confirm this hypothesis.

  13. Genotypic variation of nitrogen use efficiency in Indian mustard

    International Nuclear Information System (INIS)

    Ahmad, Altaf; Khan, Ishrat; Abrol, Yash P.; Iqbal, Muhammad

    2008-01-01

    This experiment was conducted to investigate the variation of nitrogen efficiency (NE), nitrogen uptake efficiency (UE), physiological nitrogen use efficiency (PUE) among Indian mustard genotypes, grown under N-insufficient and N-sufficient conditions. Nitrogen efficiency varied from 52.7 to 92.8. Seed yield varied from 1.14 t ha -1 to 3.21 t ha -1 under N-insufficient condition, while 2.14 t ha -1 -3.33 t ha -1 under N-sufficient condition. Physiological basis of this difference was explained in terms of nitrogen uptake efficiency and physiological nitrogen use efficiency, and their relationship with the growth and yield characteristics. While nitrogen uptake efficiency was positively correlated with plant biomass (0.793**), leaf area index (0.664*), and leaf nitrogen content (0.783**), physiological nitrogen use efficiency is positively correlated with photosynthetic rate (0.689**) and yield (0.814**). This study suggests that genotype having high nitrogen uptake efficiency and high physiological nitrogen use efficiency might help in reducing the nitrogen load on soil without any penalty on the yield. - Nitrogen efficient crop plants may help in reducing environmental contamination of nitrate without any penalty on seed yield

  14. Reduction and Coordination of Arsenic in Indian Mustard1

    Science.gov (United States)

    Pickering, Ingrid J.; Prince, Roger C.; George, Martin J.; Smith, Robert D.; George, Graham N.; Salt, David E.

    2000-01-01

    The bioaccumulation of arsenic by plants may provide a means of removing this element from contaminated soils and waters. However, to optimize this process it is important to understand the biological mechanisms involved. Using a combination of techniques, including x-ray absorption spectroscopy, we have established the biochemical fate of arsenic taken up by Indian mustard (Brassica juncea). After arsenate uptake by the roots, possibly via the phosphate transport mechanism, a small fraction is exported to the shoot via the xylem as the oxyanions arsenate and arsenite. Once in the shoot, the arsenic is stored as an AsIII-tris-thiolate complex. The majority of the arsenic remains in the roots as an AsIII-tris-thiolate complex, which is indistinguishable from that found in the shoots and from AsIII-tris-glutathione. The thiolate donors are thus probably either glutathione or phytochelatins. The addition of the dithiol arsenic chelator dimercaptosuccinate to the hydroponic culture medium caused a 5-fold-increased arsenic level in the leaves, although the total arsenic accumulation was only marginally increased. This suggests that the addition of dimercaptosuccinate to arsenic-contaminated soils may provide a way to promote arsenic bioaccumulation in plant shoots, a process that will be essential for the development of an efficient phytoremediation strategy for this element. PMID:10759512

  15. Study on irradiation sterilization of mixture of blanched mustard greed and soybean

    International Nuclear Information System (INIS)

    Li Shurong; Ha Yiming; Wang Shuo; Gao Meixu; Zhou Hongjie; Li Qingpeng

    2010-01-01

    The effects of irradiation on microbiological and sensory qualities of mixture of blanched mustard green and soybean stored at commercial condition and D 10 values of pathogens of Listeria innocua were investigated. The results show that D 10 value of Listeria innocua inoculated in mixture of blanched mustard green and soybean is 0.264 kGy, and fatality rate of the Listeria irradiated by a dose of 1.2 kGy was 99.996%; Irradiation at doses less than 2.0 kGy does not have significant effects on sensory qualities, and this dose is able to decrease microbe and pathogens of Listeria innocua by 2-3 log and 6 log, respectively. A dose of 2.0 kGy might be applied to ensure the hygienic quality of mixture of blanched mustard green and soybean. (authors)

  16. Thermal aromatic Claisen rearrangement and Strecker reaction of alkyl(allyl-aryl ethers under green reaction conditions: Efficient and clean preparation of ortho-allyl phenols (naphthols and alkyl(allyloxyarene-based γ-amino nitriles

    Directory of Open Access Journals (Sweden)

    Kheila N. Silgado-Gómez

    2017-11-01

    Full Text Available Chemical transformations of 13 diverse allyl(alkyl-aryl ethers, easily prepared using Williamson reaction of different hydroxyarenes and allyl bromide and alkyl (n-butyl, n-octyl bromides, were studied. Thermal aromatic Claisen rearrangement of allyl-aryl ethers to obtain ortho-allyl phenols (naphthols employing propylene carbonate as a nontoxic and biodegradable solvent was described for the first time. The use of this green solvent allowed to enhance notably product yields and reduce significantly the reaction time comparing with the use of 1,2-dichlorobenzene, toxic solvent, which is traditionally employed in this type of Claisen rearrangement. Three-component Strecker reaction of selected alkyl(allyl-aryl ethers with formyl function on aryl fragment and, piperidine and potassium cyanide in the presence of sulfuric acid supported on silica gel (SSA, SiO2-O-SO3H under mild reaction conditions was used in the preparation of new γ-amino nitriles, analogues of alkaloid girgensohnine [2-(4-hydroxyphenyl-2-(piperidin-1-ylacetonitrile], a perspective biological model in the search for new insecticidal agrochemicals against Aedes aegypti. The use of SSA, an inexpensive and reusable solid catalyst, allowed to obtain new series of 2-[4-alkyl(allyloxyphenyl]-2-(piperidin-1-ylacetonitriles in short time at room temperature with good yields.

  17. Teratology Studies on Lewisite and Sulfur Mustard Agents: Effects of Sulfur Mustard in Rats and Rabbits - Part 2, Appendices

    Energy Technology Data Exchange (ETDEWEB)

    Hackett, P L; Rommereim, R L; Burton, F G; Buschbom, R L; Sasser, L B

    1987-09-30

    Sulfur mustard (HD) was administered to rats and rabbits by intragastric intubation. Rats were dosed daily from 6 through 15 days of gestation (dg) with o. 0.5, 1 .0 or 2.0 mg of HD/kg; rabbits were dosed with 0, 0.4, 0.6 or 0.8 mg/kg on 6 through 19 dg. Maternal animals were weighed periodically and, at necropsy, were examined for gross lesions of major organs and reproductive performance; live fetuses were weighed and examined for external, internal and skeletal defects. In rats, reductions in body weights were observed in maternal animals and their female fetuses at the lowest administered dose (0.5 mg/kg), but the incidence of fetal malformations was not increased. In rabbits the highest administered dose (0.8 mg/kg) induced maternal mortality and depressed body weight measures but did not affect fetal development These results suggest that orally administered HD is not teratogenic in rats • and rabbits since fetal effects were obs~rved only at dose levels that induced frank maternal toxicity. Estimations of dose ranges for •no observable effects levers· in rats and rabbits, respectively, were: < 0.5 and < 0.4 mg/kg in maternal animals and < 0.5 and > 0.8 mg/kg in their fetuses.

  18. Phytoextraction potential of sunflower and white mustard plants in zinc-contaminated soil

    Directory of Open Access Journals (Sweden)

    Marta Zalewska

    2014-12-01

    Full Text Available Phytoextraction relies on plants with a high capacity to absorb heavy metals and remove them from the soil. The objective of this study was to analyze the potential of sunflower (Helianthus annuus L. and white mustard (Sinapis alba L. for phytoextraction of Zn-contaminated soil. Research was based on a strict pot experiment conducted in a greenhouse. Seven treatments were established with increasing Zn concentrations: 0, 25, 50, 100, 200, 400, and 600 mg Zn kg-1 air-dry soil. The first tested plant was fodder sunflower. In the following year, white mustard was sown in the same pots. Plants were harvested at the end of the flowering stage. The toxic effect of Zn on sunflower yields occurred at the contamination level of 200 mg Zn kg-1 soil. In the second year of the experiment, a significant decrease in mustard biomass took place in response to 400 mg Zn kg-1 soil. The contamination level of 600 mg Zn kg-1 soil resulted in complete plant death. Plant growth was not inhibited even at high tissue Zn concentrations of 515 mg Zn kg-1 sunflower DM and 422 mg Zn kg-1 mustard DM. The 2-yr cropping system did not contribute to a significant decrease in soil Zn content. Despite high concentrations of Zn in sunflower and mustard plants, total Zn uptake accounted for only 1% to 8% of the Zn rate introduced into the soil. However, in the long run, the growing of crops could reduce Zn contamination levels in the soil. The relatively high tolerance of sunflower and white mustard for Zn contamination and rapid growth of these species are possible alternatives for phytoextraction and phytostabilization of Zn-contaminated soil.

  19. Kinetics of the degradation of sulfur mustard on ambient and moist concrete

    International Nuclear Information System (INIS)

    Brevett, Carol A.S.; Sumpter, Kenneth B.; Nickol, Robert G.

    2009-01-01

    The rate of degradation of the chemical warfare agent sulfur mustard, bis(2-chloroethyl) sulfide, was measured on ambient and moist concrete using 13 C Solid State Magic Angle Spinning Nuclear Magnetic Resonance (SSMAS NMR). Three samples of concrete made by the same formulation, but differing in age and alkalinity were used. The sulfur mustard eventually degraded to thiodiglycol and 1,4-oxathiane via the intermediate sulfonium ions CH-TG, H-TG, H-2TG and O(CH 2 CH 2 ) 2 S + CH 2 CH 2 OH on all of the concrete samples, and in addition formed 8-31% vinyl moieties on the newer, more alkaline concrete samples. This is the first observation of the formation of O(CH 2 CH 2 ) 2 S + CH 2 CH 2 OH on a solid substrate. The addition of 2-chloroethanol to concrete on which mustard had fully degraded to thiodiglycol and 1,4-oxathiane resulted in the formation of O(CH 2 CH 2 ) 2 S + CH 2 CH 2 OH, thus demonstrating the reversibility of sulfur mustard degradation pathways. The sulfur mustard degradation half-lives on ambient concrete at 22 deg. C ranged from 3.5 to 54 weeks. When the substrates were moistened, the degradation half-lives at 22 deg. C ranged from 75 to 350 h. The degradation of sulfur mustard occurred more quickly at elevated temperatures and with added water. The non-volatile toxic sulfonium ions persisted for months to years on concrete at 22 deg. C and weeks to months on concrete at 35 deg. C, before decomposing to the relatively non-toxic compounds thiodiglycol and 1,4-oxathiane

  20. Kinetics of the degradation of sulfur mustard on ambient and moist concrete

    Energy Technology Data Exchange (ETDEWEB)

    Brevett, Carol A.S. [SAIC, Gunpowder Branch, P.O. Box 68, APG, MD 21010-0068 (United States)], E-mail: carol.brevett@us.army.mil; Sumpter, Kenneth B. [U.S. Army Edgewood Chemical Biological Center, 5183 Blackhawk Road, Aberdeen Proving Ground, MD 21010-5424 (United States); Nickol, Robert G. [SAIC, Gunpowder Branch, P.O. Box 68, APG, MD 21010-0068 (United States)

    2009-02-15

    The rate of degradation of the chemical warfare agent sulfur mustard, bis(2-chloroethyl) sulfide, was measured on ambient and moist concrete using {sup 13}C Solid State Magic Angle Spinning Nuclear Magnetic Resonance (SSMAS NMR). Three samples of concrete made by the same formulation, but differing in age and alkalinity were used. The sulfur mustard eventually degraded to thiodiglycol and 1,4-oxathiane via the intermediate sulfonium ions CH-TG, H-TG, H-2TG and O(CH{sub 2}CH{sub 2}){sub 2}S{sup +}CH{sub 2}CH{sub 2}OH on all of the concrete samples, and in addition formed 8-31% vinyl moieties on the newer, more alkaline concrete samples. This is the first observation of the formation of O(CH{sub 2}CH{sub 2}){sub 2}S{sup +}CH{sub 2}CH{sub 2}OH on a solid substrate. The addition of 2-chloroethanol to concrete on which mustard had fully degraded to thiodiglycol and 1,4-oxathiane resulted in the formation of O(CH{sub 2}CH{sub 2}){sub 2}S{sup +}CH{sub 2}CH{sub 2}OH, thus demonstrating the reversibility of sulfur mustard degradation pathways. The sulfur mustard degradation half-lives on ambient concrete at 22 deg. C ranged from 3.5 to 54 weeks. When the substrates were moistened, the degradation half-lives at 22 deg. C ranged from 75 to 350 h. The degradation of sulfur mustard occurred more quickly at elevated temperatures and with added water. The non-volatile toxic sulfonium ions persisted for months to years on concrete at 22 deg. C and weeks to months on concrete at 35 deg. C, before decomposing to the relatively non-toxic compounds thiodiglycol and 1,4-oxathiane.

  1. Crystal structure of chlorido(η2-phenyl isothiocyanate-κ2C,S-mer-tris(trimethylphosphane-κPiridium(I

    Directory of Open Access Journals (Sweden)

    Joseph S. Merola

    2014-11-01

    Full Text Available The molecule of the title compound, [IrCl(C7H5NS(C3H9P3], is a distorted octahedral iridium complex with three PMe3 ligands arranged in a meridional geometry, a chloride ion cis to all three PMe3 groups and the phenyl isothiocyanate ligand bonded in an η2-fashion through the C and S atoms. The C atom is trans to the chloride ion and the S atom is responsible for a significant deviation from an ideal octahedral geometry. The geometric parameters for the metal-complexing phenyl isothiocyanate group are compared with other metal-complexed phenyl isothiocyanates, as well as with examples of uncomplexed aryl isothiocyanates.

  2. Chemical Kinetics of Hydrogen Atom Abstraction from Allylic Sites by 3O2; Implications for Combustion Modeling and Simulation.

    Science.gov (United States)

    Zhou, Chong-Wen; Simmie, John M; Somers, Kieran P; Goldsmith, C Franklin; Curran, Henry J

    2017-03-09

    Hydrogen atom abstraction from allylic C-H bonds by molecular oxygen plays a very important role in determining the reactivity of fuel molecules having allylic hydrogen atoms. Rate constants for hydrogen atom abstraction by molecular oxygen from molecules with allylic sites have been calculated. A series of molecules with primary, secondary, tertiary, and super secondary allylic hydrogen atoms of alkene, furan, and alkylbenzene families are taken into consideration. Those molecules include propene, 2-butene, isobutene, 2-methylfuran, and toluene containing the primary allylic hydrogen atom; 1-butene, 1-pentene, 2-ethylfuran, ethylbenzene, and n-propylbenzene containing the secondary allylic hydrogen atom; 3-methyl-1-butene, 2-isopropylfuran, and isopropylbenzene containing tertiary allylic hydrogen atom; and 1-4-pentadiene containing super allylic secondary hydrogen atoms. The M06-2X/6-311++G(d,p) level of theory was used to optimize the geometries of all of the reactants, transition states, products and also the hinder rotation treatments for lower frequency modes. The G4 level of theory was used to calculate the electronic single point energies for those species to determine the 0 K barriers to reaction. Conventional transition state theory with Eckart tunnelling corrections was used to calculate the rate constants. The comparison between our calculated rate constants with the available experimental results from the literature shows good agreement for the reactions of propene and isobutene with molecular oxygen. The rate constant for toluene with O 2 is about an order magnitude slower than that experimentally derived from a comprehensive model proposed by Oehlschlaeger and coauthors. The results clearly indicate the need for a more detailed investigation of the combustion kinetics of toluene oxidation and its key pyrolysis and oxidation intermediates. Despite this, our computed barriers and rate constants retain an important internal consistency. Rate constants

  3. Isothiocyanate-enriched moringa seed extract alleviates ulcerative colitis symptoms in mice.

    Science.gov (United States)

    Kim, Youjin; Wu, Alex G; Jaja-Chimedza, Asha; Graf, Brittany L; Waterman, Carrie; Verzi, Michael P; Raskin, Ilya

    2017-01-01

    Moringa (Moringa oleifera Lam.) seed extract (MSE) has anti-inflammatory and antioxidant activities. We investigated the effects of MSE enriched in moringa isothiocyanate-1 (MIC-1), its putative bioactive, on ulcerative colitis (UC) and its anti-inflammatory/antioxidant mechanism likely mediated through Nrf2-signaling pathway. Dextran sulfate sodium (DSS)-induced acute (n = 8/group; 3% DSS for 5 d) and chronic (n = 6/group; cyclic rotations of 2.5% DSS/water for 30 d) UC was induced in mice that were assigned to 4 experimental groups: healthy control (water/vehicle), disease control (DSS/vehicle), MSE treatment (DSS/MSE), or 5-aminosalicyic acid (5-ASA) treatment (positive control; DSS/5-ASA). Following UC induction, water (vehicle), 150 mg/kg MSE, or 50 mg/kg 5-ASA were orally administered for 1 or 2 wks. Disease activity index (DAI), spleen/colon sizes, and colonic histopathology were measured. From colon and/or fecal samples, pro-inflammatory biomarkers, tight-junction proteins, and Nrf2-mediated enzymes were analyzed at protein and/or gene expression levels. Compared to disease control, MSE decreased DAI scores, and showed an increase in colon lengths and decrease in colon weight/length ratios in both UC models. MSE also reduced colonic inflammation/damage and histopathological scores (modestly) in acute UC. MSE decreased colonic secretions of pro-inflammatory keratinocyte-derived cytokine (KC), tumor necrosis factor (TNF)-α, nitric oxide (NO), and myeloperoxidase (MPO) in acute and chronic UC; reduced fecal lipocalin-2 in acute UC; downregulated gene expression of pro-inflammatory interleukin (IL)-1, IL-6, TNF-α, and inducible nitric oxide synthase (iNOS) in acute UC; upregulated expression of claudin-1 and ZO-1 in acute and chronic UC; and upregulated GSTP1, an Nrf2-mediated phase II detoxifying enzyme, in chronic UC. MSE was effective in mitigating UC symptoms and reducing UC-induced colonic pathologies, likely by suppressing pro-inflammatory biomarkers

  4. Availability and uptake of sulphur by mustard in three soils in Udaipur valley

    International Nuclear Information System (INIS)

    Kataria, S.K.; Shriniwas

    1976-01-01

    The differential behaviour of three soils (Bargaon, Bhatewar red and Bhatewar black) for availability of sulphur to mustard was studied in a greenhouse pot culture experiment using five doses of sulphur (0,20,40,80,120 ppm) applied as 35 S tagged ammonium sulphate. Application of sulphur significantly increased the dry matter of mustard over control, however, maximum dry matter was obtained when sulphur was applied at 40 ppm level, thereafter, any higher doses did not prove beneficial. Sulphur content in the plant tissue and percent of sulphur in the plant derived from fertilizer increased with successive doses of applied sulphur. (author)

  5. Development of new apple beverages rich in isothiocyanates by using extracts obtained from ultrasound-treated cauliflower by-products

    DEFF Research Database (Denmark)

    Amofa-Diatuo, Tracy; Anang, Daniel M.; Barba Orellana, Francisco Jose

    2017-01-01

    The objective of this study was to develop a new apple juice beverage enriched with isothiocyanates (ITC) - rich extracts obtained from cauliflower by-products. Ultrasound-assisted extraction (UAE) at different amplitudes (20-100%) and extraction times (0-10. min) at a frequency of 24. kHz was em......The objective of this study was to develop a new apple juice beverage enriched with isothiocyanates (ITC) - rich extracts obtained from cauliflower by-products. Ultrasound-assisted extraction (UAE) at different amplitudes (20-100%) and extraction times (0-10. min) at a frequency of 24. k......) and UAE (20%, 3. min), respectively. Moreover, the highest recovery of total phenolic compounds (TPC) (≈105. mg gallic acid equivalent (GAE)/L) μM) was found after UAE (100% amplitude, 3. min) of TPC from stems. ITC-rich extracts obtained from caulifower by-products at the optimum UAE conditions were...

  6. Genome Wide Association Mapping in Arabidopsis thaliana Identifies Novel Genes Involved in Linking Allyl Glucosinolate to Altered Biomass and Defense.

    Science.gov (United States)

    Francisco, Marta; Joseph, Bindu; Caligagan, Hart; Li, Baohua; Corwin, Jason A; Lin, Catherine; Kerwin, Rachel E; Burow, Meike; Kliebenstein, Daniel J

    2016-01-01

    A key limitation in modern biology is the ability to rapidly identify genes underlying newly identified complex phenotypes. Genome wide association studies (GWAS) have become an increasingly important approach for dissecting natural variation by associating phenotypes with genotypes at a genome wide level. Recent work is showing that the Arabidopsis thaliana defense metabolite, allyl glucosinolate (GSL), may provide direct feedback regulation, linking defense metabolism outputs to the growth, and defense responses of the plant. However, there is still a need to identify genes that underlie this process. To start developing a deeper understanding of the mechanism(s) that modulate the ability of exogenous allyl GSL to alter growth and defense, we measured changes in plant biomass and defense metabolites in a collection of natural 96 A. thaliana accessions fed with 50 μM of allyl GSL. Exogenous allyl GSL was introduced exclusively to the roots and the compound transported to the leaf leading to a wide range of heritable effects upon plant biomass and endogenous GSL accumulation. Using natural variation we conducted GWAS to identify a number of new genes which potentially control allyl responses in various plant processes. This is one of the first instances in which this approach has been successfully utilized to begin dissecting a novel phenotype to the underlying molecular/polygenic basis.

  7. Genome wide association mapping in Arabidopsis thaliana identifies novel genes involved in linking allyl glucosinolate to altered biomass and defense

    Directory of Open Access Journals (Sweden)

    Marta Francisco

    2016-07-01

    Full Text Available A key limitation in modern biology is the ability to rapidly identify genes underlying newly identified complex phenotypes. Genome wide association studies (GWAS have become an increasingly important approach for dissecting natural variation by associating phenotypes with genotypes at a genome wide level. Recent work is showing that the Arabidopsis thaliana defense metabolite, allyl glucosinolate (GSL, may provide direct feedback regulation, linking defense metabolism outputs to the growth and defense responses of the plant. However, there is still a need to identify genes that underlie this process. To start developing a deeper understanding of the mechanism(s that modulate the ability of exogenous allyl GSL to alter growth and defense, we measured changes in plant biomass and defense metabolites in a collection of natural 96 A. thaliana accessions fed with 50 µM of allyl GSL. Exogenous allyl GSL was introduced exclusively to the roots and the compound transported to the leaf leading to a wide range of heritable effects upon plant biomass and endogenous GSL accumulation. Using natural variation we conducted GWAS to identify a number of new genes which potentially control allyl responses in various plant processes. This is one of the first instances in which this approach has been successfully utilized to begin dissecting a novel phenotype to the underlying molecular/polygenic basis.

  8. One-Pot Multicomponent Coupling Methods for the Synthesis of Diastereo- and Enantioenriched (Z)-Trisubstituted Allylic Alcohols

    Science.gov (United States)

    Kerrigan, Michael H.; Jeon, Sang-Jin; Chen, Young K.; Salvi, Luca; Carroll, Patrick J.; Walsh, Patrick J.

    2009-01-01

    (Z)-Trisubstituted allylic alcohols are widespread structural motifs in natural products and biologically active compounds but are difficult to directly prepare. Introduced herein is a general one-pot multicomponent coupling method for the synthesis of (Z)-α,α,β-trisubstituted allylic alcohols. (Z)-Trisubstituted vinylzinc reagents are formed in situ by initial hydroboration of 1-bromo-1-alkynes. Addition of dialkylzinc reagents induces a 1,2-metallate rearrangement that is followed by a boron-to-zinc transmetallation. The resulting vinylzinc reagents add to a variety of prochiral aldehydes to produce racemic (Z)-trisubstituted allylic alcohols. When enantioenriched aldehyde substrates are employed (Z)-trisubstituted allylic alcohols are isolated with high dr (>20:1 in many cases). For example, vinylation of enantioenriched benzyl protected α- and β-hydroxy propanal derivatives furnished the expected anti-Felkin addition products via chelation control. Surprisingly, silyl protected α-hydroxy aldehydes also afford anti-Felkin addition products. A protocol for the catalytic asymmetric addition of (Z)-trisubstituted vinylzinc reagents to prochiral aldehydes with a (−)-MIB-based catalyst has also been developed. Several additives were investigated as inhibitors of the Lewis acidic alkylzinc halide byproducts, which promote the background reaction to form the racemate. α-Ethyl and α-cyclohexyl (Z)-trisubstituted allylic alcohols can now be synthesized with excellent levels of enantioselectivity in the presence of diamine inhibitors. PMID:19476375

  9. Optimizing isothiocyanate formation during enzymatic glucosinolate breakdown by adjusting pH value, temperature and dilution in Brassica vegetables and Arabidopsis thaliana

    OpenAIRE

    Hanschen, Franziska S.; Klopsch, Rebecca; Oliviero, Teresa; Schreiner, Monika; Verkerk, Ruud; Dekker, Matthijs

    2017-01-01

    Consumption of glucosinolate-rich Brassicales vegetables is associated with a decreased risk of cancer with enzymatic hydrolysis of glucosinolates playing a key role. However, formation of health-promoting isothiocyanates is inhibited by the epithiospecifier protein in favour of nitriles and epithionitriles. Domestic processing conditions, such as changes in pH value, temperature or dilution, might also affect isothiocyanate formation. Therefore, the influences of these three factors were eva...

  10. Isothiocyanates, Nitriles, and Epithionitriles from Glucosinolates Are Affected by Genotype and Developmental Stage in Brassica oleracea Varieties.

    Science.gov (United States)

    Hanschen, Franziska S; Schreiner, Monika

    2017-01-01

    Vegetables of the Brassica oleracea group, such as broccoli, cauliflower, and cabbage, play an important role for glucosinolate consumption in the human diet. Upon maceration of the vegetable tissue, glucosinolates are degraded enzymatically to form volatile isothiocyanates, nitriles, and epithionitriles. However, only the uptake of isothiocyanates is linked to the cancer-preventive effects. Thus, it is of great interest to evaluate especially the isothiocyanate formation. Here, we studied the formation of glucosinolates and their respective hydrolysis products in sprouts and fully developed vegetable heads of different genotypes of the five B. oleracea varieties: broccoli, cauliflower as well as white, red, and savoy cabbages. Further, the effect of ontogeny (developmental stages) during the head development on the formation of glucosinolates and their respective hydrolysis products was evaluated at three different developmental stages (mini, fully developed, and over-mature head). Broccoli and red cabbage were mainly rich in 4-(methylsulfinyl)butyl glucosinolate (glucoraphanin), whereas cauliflower, savoy cabbage and white cabbage contained mainly 2-propenyl (sinigrin) and 3-(methylsulfinyl)propyl glucosinolate (glucoiberin). Upon hydrolysis, epithionitriles or nitriles were often observed to be the main hydrolysis products, with 1-cyano-2,3-epithiopropane being most abundant with up to 5.7 μmol/g fresh weight in white cabbage sprouts. Notably, sprouts often contained more than 10 times more glucosinolates or their hydrolysis products compared to fully developed vegetables. Moreover, during head development, both glucosinolate concentrations as well as hydrolysis product concentrations changed and mini heads contained the highest isothiocyanate concentrations. Thus, from a cancer-preventive point of view, consumption of mini heads of the B. oleracea varieties is recommended.

  11. Metabolomics diagnostic approach to mustard airway diseases: a preliminary study

    Directory of Open Access Journals (Sweden)

    BiBi Fatemeh Nobakht Mothlagh Ghoochani

    2018-01-01

    Full Text Available Objective(s: This study aims to evaluate combined proton nuclear magnetic resonance (1H NMR spectroscopy and gas chromatography-mass spectrometry (GC-MS metabolic profiling approaches, for discriminating between mustard airway diseases (MADs and healthy controls and for providing biochemical information on this disease. Materials and Methods: In the present study, analysis of serum samples collected from 17 MAD subjects and 12 healthy controls was performed using NMR. Of these subjects, 14 (8 patients and 6 controls were analyzed by GC-MS. Then, their spectral profiles were subjected to principal component analysis (PCA and orthogonal partial least squares regression discriminant analysis (OPLS-DA. Results: A panel of twenty eight metabolite biomarkers was generated for MADs, sixteen  NMR-derived metabolites (3-methyl-2-oxovaleric acid, 3-hydroxyisobutyrate, lactic acid, lysine, glutamic acid, proline, hydroxyproline, dimethylamine, creatine, citrulline, choline, acetic acid, acetoacetate, cholesterol, alanine, and lipid (mainly VLDL and twelve GC-MS-derived metabolites (threonine, phenylalanine, citric acid, myristic acid, pentadecanoic acid, tyrosine, arachidonic acid, lactic acid, propionic acid, 3-hydroxybutyric acid, linoleic acid, and oleic acid. This composite biomarker panel could effectively discriminate MAD subjects from healthy controls, achieving an area under receiver operating characteristic curve (AUC values of 1 and 0.79 for NMR and GC-MS, respectively. Conclusion: In the present study, a robust panel of twenty-eight biomarkers for detecting MADs was established. This panel is involved in three metabolic pathways including aminoacyl-tRNA biosynthesis, arginine, and proline metabolism, and synthesis and degradation of ketone bodies, and could differentiate MAD subjects from healthy controls with a higher accuracy.

  12. Whole body exposure of rats to sulfur mustard vapor.

    Science.gov (United States)

    Dachir, Shlomit; Rabinovitz, Ishai; Yaacov, Guy; Gutman, Hila; Cohen, Liat; Horwitz, Vered; Cohen, Maayan; Kadar, Tamar

    2017-11-24

    Sulfur mustard (SM) is an incapacitating chemical warfare agent used in numerous conflicts around the world and it is still a major threat for both, army troops and civilians. To evaluate its multiple targets effects in experimental setup, a model of whole body exposure (WBE) to SM vapor was established in rats and its simultaneous effects on lungs and eyes as well as on general wellbeing were examined. Rats were exposed to SM vapor. Evaluation (up to 10 weeks post-exposure) included body weight, general observation, blood counts and histological analysis. Results showed that following a latency-period of several hours, rats typical symptoms developed over a period of more than one week. The initial symptoms, characterized by swollen and erythematic nose, deteriorated into extensive rhinorrhea, eye closure, excessive lacrimation as well as rhonchi, wheezing and breathing difficulties. Alopecia and behavioral abnormality were also recorded. A weight loss of up to 40% was measured within one week with spontaneous recovery to baseline level within three weeks after exposure. Blood counts revealed leukopenia during the first three days post-exposure. Histological evaluation revealed a long lasting damage to the trachea, lungs and eyes. Thus, WBE to SM, was found to closely mimic the deleterious effects of SM on the sensitive tissues previously described in human victims during WWI and the Iran-Iraq war. The use of this animal model will enable comprehensive characterization of changes in biological processes that may lead to the development of therapeutic measures to ameliorate SM induced multi-system injuries.

  13. Accumulation of Cd in Indian mustard and sunflower for phytoremediation

    International Nuclear Information System (INIS)

    Okada, Satoshi; Fukutani, Satoshi; Takahashi, Tomoyuki; Fukui, Masami

    2004-01-01

    Phytoremediation is a new method that uses plants to remove contaminants from soil without affecting soil fertility. It can therefore be used for contaminated agricultural land. Indian mustard (Brassica juncea) and sunflower (Helianthus annuus L.) are used in phytoremediation to remove Cadmium (Cd), which they can accumulate in large quantities. It is important to know when plants have accumulated significant Cd, so that we can decide when the plants should be harvested and synthetic chelates applied. Brassica juncea seeds and Helianthus annuus L. seeds were planted in a field in Kyoto University Research Reactor Institute (KUR). Brassica juncea and Helianthus annuus L. were collected at time intervals ranging from 1 to 6 months and 2 to 7 weeks, respectively, after seedling emergence and the concentration of Cd in the plants was analyzed. These results indicated that Brassica juncea should be harvested before beginning flowering and Helianthus annuus L. should be harvested after it becomes old enough. The solubility of Cd in soil is enhanced when the soil is heated or dried, and black vinyl mulch was therefore used to absorb the heat from sunlight. The difference in the Cd uptake of Brassica juncea between mulching cultivation and non-mulching cultivation was investigated in a field, and this indicated that there is no probability that mulching enhances Cd uptake in plants. The solubility of Cd in soil decreases over time. Repeated pot experiments were done. We planted Brassica juncea in pots, and investigated the uptake of Cd and the solid phase fractions in which Cd was present in each pot experiment. These did not change considerably over time, indicating that age has a negligible effect on Cd uptake in plants. (author)

  14. Breeding cultivars of barley and mustard containing biochemical mutants

    Energy Technology Data Exchange (ETDEWEB)

    Oram, R N [Division of Plant industry, CSIRO, Canberra (Australia)

    1990-01-01

    Full text: The inactivation of dominant and co-dominant alleles is becoming increasingly important in changing the composition of seed carbohydrates, protein, oil, fibre and secondary products to suit modern food and feed technologies. In barley, breeding lines adapted to south-eastern Australian conditions have been developed containing a waxy endosperm from the Japanese variety 'Sumire Mochi', the high lysine gene lys from cv. 'Hiproly' of Ethiopia, and the induced high lysine mutant gene lys 3a from 'Risoe 1508'. The improved mutant lines yield 12-34% less than the highest yielding feed barley. The lys and lys 3a alleles suppress the formation of prolamins, the waxy allele inhibits the formation of amylose. It seems difficult to modify the background genotype to fully compensate for the reduction of major storage carbohydrate or protein compounds. However, waxy barleys have uses in some human foods and a premium can be paid to producers. The grain of the provisionally-patented waxy cultivar Wasiro is suitable for pearling. It contains 5% {beta}-glucan (soluble fibre) and therefore should be as effective as oat bran for reducing blood cholesterol. In Indian mustard (Brassica juncea), three cultivars differing in date of maturity, each containing the spontaneous mutant alleles for low erucic acid levels in the seed oil, have been developed to produce a high quality, mildly flavoured cooking/salad oil. The concentration of glucosinolates in the seed meal must be reduced to make it palatable and non-toxic to pigs and poultry. Three B. juncea lines were treated in up to four successive generations with gamma rays or EMS. 60,000 seed samples were analysed in subsequent generations. Two induced mutants with reduced glucosinolate concentrations are now available besides 4 naturally-occurring sources with only little reduced yields. Recombination may give a high-yielding low erucic acid and low glucosinolate variety of B. juncea. (author)

  15. Breeding cultivars of barley and mustard containing biochemical mutants

    International Nuclear Information System (INIS)

    Oram, R.N.

    1990-01-01

    Full text: The inactivation of dominant and co-dominant alleles is becoming increasingly important in changing the composition of seed carbohydrates, protein, oil, fibre and secondary products to suit modern food and feed technologies. In barley, breeding lines adapted to south-eastern Australian conditions have been developed containing a waxy endosperm from the Japanese variety 'Sumire Mochi', the high lysine gene lys from cv. 'Hiproly' of Ethiopia, and the induced high lysine mutant gene lys 3a from 'Risoe 1508'. The improved mutant lines yield 12-34% less than the highest yielding feed barley. The lys and lys 3a alleles suppress the formation of prolamins, the waxy allele inhibits the formation of amylose. It seems difficult to modify the background genotype to fully compensate for the reduction of major storage carbohydrate or protein compounds. However, waxy barleys have uses in some human foods and a premium can be paid to producers. The grain of the provisionally-patented waxy cultivar Wasiro is suitable for pearling. It contains 5% β-glucan (soluble fibre) and therefore should be as effective as oat bran for reducing blood cholesterol. In Indian mustard (Brassica juncea), three cultivars differing in date of maturity, each containing the spontaneous mutant alleles for low erucic acid levels in the seed oil, have been developed to produce a high quality, mildly flavoured cooking/salad oil. The concentration of glucosinolates in the seed meal must be reduced to make it palatable and non-toxic to pigs and poultry. Three B. juncea lines were treated in up to four successive generations with gamma rays or EMS. 60,000 seed samples were analysed in subsequent generations. Two induced mutants with reduced glucosinolate concentrations are now available besides 4 naturally-occurring sources with only little reduced yields. Recombination may give a high-yielding low erucic acid and low glucosinolate variety of B. juncea. (author)

  16. Photodissociaton of allyl-d2 iodide excited at 193 nm: Stability of highly rotationally excited H2CDCH2 radicals to C-D fission

    International Nuclear Information System (INIS)

    Szpunar, D.E.; Liu, Y.; McCullagh, M.J.; Butler, L.J.; Shu, J.

    2003-01-01

    The photodissociation of allyl-d2 iodide (H2C=CDCH2I) and the dynamics of the nascent allyl-d2 radical (H2CCDCH2) were studied using photofragment translational spectroscopy. A previous study found the allyl radical stable at internal energies up to 15 kcal/mol higher than the 60 kcal/mol barrier to allene + H formation as the result of a centrifugal barrier. The deuterated allyl radical should then also show a stability to secondary dissociation at internal energies well above the barrier due to centrifugal effects. A comparison in this paper shows the allyl-d2 radical is stable to allene + D formation at energies of 2-3 kcal/mol higher than that of the non-deuterated allyl radical following photolysis of allyl iodide at 193 nm. This is most likely a result of a combination of the slight raising of the barrier from the difference in zero-point levels and a reduction of the impact parameter of the dissociative fragments due to the decrease in frequency of the C-D bending modes, and the refore allene + D product orbital angular momentum. Integrated signal taken at m/e = 40 (allene) and m/e = 41 (allene-d1 and propyne-d3) shows a minor fraction of the allyl-d2 radicals isomerize to the 2-propenyl radical, in qualitative support of earlier conclusions of the domination of direct allene + H formation over isomerization

  17. Expression of liver functions following sub-lethal and non-lethal doses of allyl alcohol and acetaminophen in the rat

    DEFF Research Database (Denmark)

    Tygstrup, N; Jensen, S A; Krog, B

    1997-01-01

    BACKGROUND/AIMS: To relate severity of intoxication with allyl alcohol and acetaminophen to modulated hepatic gene expression of liver functions and regeneration. METHODS: Rats fasted for 12 h received acetaminophen 3.5 or 5.6 g per kg body weight, or allyl alcohol 100 or 125 microl by gastric tu...

  18. Direct preparation of 14C-labelled 5-allyl- and 5-propyl-2'-deoxyuridine from [2-14C]2'-deoxyuridine

    International Nuclear Information System (INIS)

    Ruth, J.L.; White, S.K.; Bergstrom, D.E.

    1982-01-01

    [2- 14 C]5-Allyl-2'-deoxyuridine was synthesized directly from [2- 14 C]2'-deoxyuridine using mercury, palladium, and 3-chloropropene. [2- 14 C]5-Propyl-2'-deoxyuridine was obtained by hydrogenation of the [ 14 C]5-allyl-2'-deoxyuridine. Advantages of the synthetic method and its application to the preparation of other radiolabeled 5-alkyl/alkenyl-2'-deoxyuridines are discussed. (author)

  19. Isothiocyanate-rich Moringa oleifera extract reduces weight gain, insulin resistance, and hepatic gluconeogenesis in mice.

    Science.gov (United States)

    Waterman, Carrie; Rojas-Silva, Patricio; Tumer, Tugba Boyunegmez; Kuhn, Peter; Richard, Allison J; Wicks, Shawna; Stephens, Jacqueline M; Wang, Zhong; Mynatt, Randy; Cefalu, William; Raskin, Ilya

    2015-06-01

    Moringa oleifera (moringa) is tropical plant traditionally used as an antidiabetic food. It produces structurally unique and chemically stable moringa isothiocyanates (MICs) that were evaluated for their therapeutic use in vivo. C57BL/6L mice fed very high fat diet (VHFD) supplemented with 5% moringa concentrate (MC, delivering 66 mg/kg/d of MICs) accumulated fat mass, had improved glucose tolerance and insulin signaling, and did not develop fatty liver disease compared to VHFD-fed mice. MC-fed group also had reduced plasma insulin, leptin, resistin, cholesterol, IL-1β, TNFα, and lower hepatic glucose-6-phosphatase (G6P) expression. In hepatoma cells, MC and MICs at low micromolar concentrations inhibited gluconeogenesis and G6P expression. MICs and MC effects on lipolysis in vitro and on thermogenic and lipolytic genes in adipose tissue in vivo argued these are not likely primary targets for the anti-obesity and anti-diabetic effects observed. Data suggest that MICs are the main anti-obesity and anti-diabetic bioactives of MC, and that they exert their effects by inhibiting rate-limiting steps in liver gluconeogenesis resulting in direct or indirect increase in insulin signaling and sensitivity. These conclusions suggest that MC may be an effective dietary food for the prevention and treatment of obesity and type 2 diabetes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Watercress and Water Quality: The Effect of Phenethyl Isothiocyanate on the Mating Behaviour of Gammarus pulex

    Directory of Open Access Journals (Sweden)

    Melanie J. Dixon

    2011-01-01

    Full Text Available Watercress releases phenethyl isothiocyanate (PEITC upon wounding as a defence against herbivores. PEITC levels released from watercress farms are elevated due to cropping, washing, and processing and are thought to lead to adverse effects on Gammarus pulex in chalk streams. This study elucidates the sublethal effect of PEITC on reproductive behaviour of G. pulex, employing ex situ tests to investigate the disruption of precopular pairing under conditions simulating in situ exposure. Mean time to separation of precopular pairs was 89 ± 6 minutes for watercress wash water (1 g watercress per litre water and 81 ± 15 minutes for pure PEITC (1 μL/L. Re-exposure to watercress wash water to simulate the pulsed operation at a watercress farm did not alter behavioural response. The repeated interruption of reproductive behaviour under in situ conditions would impair long-term reproductive success and could explain in part low abundance of G. pulex downstream of watercress farms.

  1. Antimicrobial activity of isothiocyanates (ITCs) extracted from horseradish (Armoracia rusticana) root against oral microorganisms.

    Science.gov (United States)

    Park, Ho-Won; Choi, Kyu-Duck; Shin, Il-Shik

    2013-01-01

    The antimicrobial activity of isothiocyanates (ITCs) extracted from horseradish root was investigated against oral microorganisms: 6 strains of facultative anaerobic bacteria, Streptococcus mutans, Streptococcus sobrinus, Lactobacillus casei, Staphylococcus aureus, Enterococcus faecalis and Aggregatibacter actinomycetemcomitans; one strain of yeast, Candida albicans, and 3 strains of anaerobic bacteria, Fusobacterium nucleatum, Prevotella nigrescens, and Clostridium perfringens. The ITCs extracted from horseradish root showed antimicrobial activity against all oral microorganisms by the paper disk method. The minimum bactericidal concentration (MBC) of the ITCs extracted from horseradish root ranged from 1.25 to 5.00 mg/ml against 6 strains of facultative anaerobic bacteria and one strain of yeast, and 4.17 to 16.67 mg/ml against 3 strains of anaerobic bacteria. The ITCs extracted from horseradish root showed the strongest antimicrobial activity, with a MBC of 1.25 mg/ml, against C. albicans among facultative microorganisms, and 4.17 mg/ml against F. nucleatum among anaerobic bacteria. These results suggest that the ITCs extracted from horseradish root may be a candidate for use as an antimicrobial agent against oral microorganisms.

  2. UAE-HPLC-UV: New Contribution for Fast Determination of Total Isothiocyanates in Brassicaceae Vegetables

    Directory of Open Access Journals (Sweden)

    Cecilia M. Fusari

    2015-01-01

    Full Text Available Total isothiocyanates content (ITC is considered a good indicator of bioactive compounds responsible for beneficial effects related to Brassicaceae vegetables. Analytical performance is a critical factor for routine analysis in plant tissues. The extraction technique for isolating phytochemicals from Brassicaceae vegetables is currently the bottleneck of the methodology. The aim of this work was to optimize this step in the analytical process. Fast and less expensive alternative, based on ultrasound-assisted extraction technique (UAE for direct extraction of GLS into an aqueous phase and further analysis of the hydrolysis product, was optimized. Full factorial (2k design followed by Central Composite Design (CCD was used to obtain the optimum extraction conditions. Selected conditions were homogenization time (9 min; ultrasound bath time (5 min; and sample-to-solvent ratio (1 : 5 w/v mg mL−1. The proposed analytical methodology exhibits satisfactory analytical performance in terms of linearity, precision (RSD < 2.4%, and limits of detection (26 nmol g−1 w.w.. The new analytical methodology was applied to cauliflower, cabbage, watercress, and broccoli samples with recoveries higher than 86%. The UAE extraction technique was showed to be efficient for real samples analysis leading to sensible, selective, and reproducible methodology for ITC analysis.

  3. Laboratory Measured Emission Losses of Methyl Isothiocyanate at Pacific Northwest Soil Surface Fumigation Temperatures.

    Science.gov (United States)

    Lu, Zhou; Hebert, Vincent R; Miller, Glenn C

    2017-02-01

    Temperature is a major environmental factor influencing land surface volatilization at the time of agricultural field fumigation. Cooler fumigation soil temperatures relevant to Pacific Northwest (PNW) application practices with metam sodium/potassium should result in appreciably reduced methyl isothiocyanate (MITC) emission rates, thus minimizing off target movement and bystander inhalation exposure. Herein, a series of laboratory controlled flow-through soil column assessments were performed evaluating MITC emissions over the range of cooler temperatures (2-13°C). Assessments were also conducted at the maximum allowed label application temperature of 32°C. All assessments were conducted at registration label-specified field moisture capacity, and no more than 50% cumulative MITC loss was observed over the 2-day post-fumigation timeframe. Three-fold reductions in MITC peak fluxes at cooler PNW application temperatures were observed compared to the label maximum temperature. This study supports current EPA metam sodium/potassium label language that indicates surface fumigations during warmer soil conditions should be discouraged.

  4. Nanoemulsions of cancer chemopreventive agent benzyl isothiocyanate display enhanced solubility, dissolution, and permeability.

    Science.gov (United States)

    Qhattal, Hussaini Syed Sha; Wang, Shu; Salihima, Tri; Srivastava, Sanjay K; Liu, Xinli

    2011-12-14

    Benzyl isothiocyanate (BITC), a compound found in cruciferous vegetables, is an effective chemopreventive agent. The objective of this study was to develop nanoemulsion formulations for the oral delivery of BITC. Optimized oil-in-water BITC nanoemulsions were prepared by a spontaneous self-nanoemulsification method and a homogenization-sonication method. Both nanoemulsions entrapped high amounts of BITC (15-17 mg/mL), with low polydispersity and good colloidal stability. The BITC nanoemulsions showed enhanced solubility and dissolution compared to pure BITC. These formulations markedly increased the apical to basolateral transport of BITC in Caco-2 cell monolayers. The apparent permeability values were 3.6 × 10(-6) cm/s for pure BITC and (1.1-1.3) × 10(-5) cm/s for BITC nanoemulsions. The nanoemulsions were easily taken up by human cancer cells A549 and SKOV-3 and inhibited tumor growth in vitro. This work shows for the first time that BITC can be formulated into nanoemulsions and may show promise in enhancing absorption and bioavailability.

  5. Enantioselective epoxidation with chiral MN(III)(salen) catalysts: kinetic resolution of aryl-substituted allylic alcohols.

    Science.gov (United States)

    Adam, W; Humpf, H U; Roschmann, K J; Saha-Möller, C R

    2001-08-24

    A set of aryl-substituted allylic alcohols rac-2 has been epoxidized by chiral Mn(salen*) complexes 1 as the catalyst and iodosyl benzene (PhIO) as the oxygen source. Whereas one enantiomer of the allylic alcohol 2 is preferentially epoxidized to give the threo- or cis-epoxy alcohol 3 (up to 80% ee) as the main product (dr up to >95:5), the other enantiomer of 2 is enriched (up to 53% ee). In the case of 1,1-dimethyl-1,2-dihydronaphthalen-2-ol (2c), the CH oxidation to the enone 4c proceeds enantioselectively and competes with the epoxidation. The absolute configurations of the allylic alcohols 2 and their epoxides 3 have been determined by chemical correlation or CD spectroscopy. The observed diastereo- and enantioselectivities in the epoxidation reactions are rationalized in terms of a beneficial interplay between the hydroxy-directing effect and the attack along the Katsuki trajectory.

  6. catena-Poly[[bromidocopper(I)]-?-?2,?1-3-(2-allyl-2H-tetra?zol-5-yl)pyridine

    OpenAIRE

    Wang, Wei

    2008-01-01

    The title compound, [CuBr(C9H9N5)] n , has been prepared by the solvothermal treatment of CuBr with 3-(2-allyl-2H-tetra?zol-5-yl)pyridine. It is a new homometallic CuI olefin coord?ination polymer in which the CuI atoms are linked by the 3-(2-allyl-2H-tetra?zol-5-yl)pyridine ligands and bonded to one terminal Br atom each. The organic ligand acts as a bidentate ligand connecting two neighboring Cu centers through the N atom of the pyridine ring and the double bond of the allyl group. A three-...

  7. Pathogens present on vegetative organs and seeds of white mustard (Sinapis alba L. and chinese mustad (Brassica juncea L.

    Directory of Open Access Journals (Sweden)

    Barbara Majchrzak

    2013-12-01

    Full Text Available The research was conducted in the years 1999-2001. The aim of the research was to determine the health condition of overground parts and seeds of white niuslard (Sinapis alba L. cv. Metex and chinese mustard (Brassica juncea L. cv. Małopolska. In all the years of the research alternaria blight was found on the leaves of white mustard which injury index ranged from 5,6% in 2001 to 17,6% in 200O. The most dangerous disease of chinese mustard also was alternaria blight and its symptoms were found on leaves and siliques. The strongest infection of leaves was in 2000 (50% and the weakest in 2001 (6,7%. In all the years of the research siliques were rather weak infected (50-8,89%. Besides powdery mildew was found on chinese mustard which injury index ranged from 0,3% in 1999 to 32,3% in 2000. Intensity of diseases was affected generally by the weather conditions. From the seeds of white mustard and chinese mustard were isolated respectively 263 and 137 colonies. Alternaria alternata was the most numerous species which makes respectively 60,9% and 42,3% isolates. Among the fungi pathogenic for white and chinese mustard were also isolated: A. brassicae, Botrytis cinerea and Rhizoctonia solami.

  8. The reactivity of allyl and propargyl alcohols with solvated electrons: temperature and solvent effects

    International Nuclear Information System (INIS)

    Afanassiev, A.M.; Okazaki, K.; Freeman, G.R.

    1979-01-01

    The rate constants K 1 for the reaction of solvated electrons with allyl alcohol in a number of hydroxylic solvents differ by up to two orders of magnitude and decrease in the order tert-butyl alcohol > 2-propanol > l-propanol approximately ethanol > methanol approximately ethylene glycol > water. In methanol and ethylene glycol the rate constants (7 x 10 7 M -1 s -1 at 298 K) and activation energies (16 kJ/mol) are equal, in spite of a 32-fold difference in solvent viscosity (0.54 and 17.3 cP, respectively) and 3-fold difference in its activation energy (11 and 32 kJ/mol, respectively). The reaction in tert-butyl alcohol is nearly diffusion controlled and has a high activation energy that is characteristic of transport in that liquid (E 1 = 31 kJ/mol, E sub(eta) = 39 kJ/mol). The activation energies in the other alcohols are all 16 kJ/mol, and it is 14 kJ/mol in water. They do not correlate with transport properties. The solvent effect is connected primarily with the entropy of activation. The rate constants correlate with the solvated electron trap depth. When the electron affinity of the scavenger is small, a favorable configuration of solvent molecules about the electron/scavenger encounter pair is required for the electron jump to take place. The behavior of the rate parameters for propargyl alcohol is similar to that for allyl alcohol, but k 1 , A 1 , and E 1 are larger for the former. The ratio k(propargyl)/k(allyl) at 298 K equals 10.5 in water and decreases through the series, reaching 1.3 in tert-butyl alcohol. Rate parameters for several other scavengers are also reported. (author)

  9. Unusual selectivity-determining factors in the phosphine-free Heck arylation of allyl ethers

    DEFF Research Database (Denmark)

    Ambrogio, I.; Fabrizi, G.; Cacchi, S.

    2008-01-01

    The Heck reaction of aryl iodides and bromides with allyl ethers has been investigated. Using phosphinefree Pd(OAc)(2) in DNIF at 90 degrees C in the presence of Bu4NOAc, the reaction gave cinnamyl derivatives, usually in good to high yields, with a wide range of aryl halides. The reaction...... tolerates a variety of functional groups, including ether, amide, alcohol, aldehyde, ketone, ester, cyano, carboxylic acid, and nitro groups. Ortho-substituted arylating agents afforded moderate yields in some cases, though good to high yields were obtained with o-iodotoluene, iodovanillin, and 1...

  10. Design of the passive personal dosimeter for miners using an allyl diglycol carbonate plastic. Phase 1

    International Nuclear Information System (INIS)

    1983-12-01

    The report summarizes the results of the feasibility study on the design and development of a passive personal dosimeter incorporating an allyl diglycol carbonate plastic (CR39) detector, for use by uranium miners. Based upon the feasibility study, a passive personal dosimeter using a capacitor-type electrostatic enhancement device has been designed. Preliminary tests indicate that the prototype could be used in the mine environment to differentiate radon and thoron daughters with a detection efficiency comparable to that of a typical active device. Further study is required, however, into the possible influence in the mine environment of local variations in charged fraction, upon the calibration of this dosimeter

  11. Direct asymmetric allylic alkenylation of N-itaconimides with Morita-Baylis-Hillman carbonates

    KAUST Repository

    Yang, Wenguo

    2012-08-03

    The asymmetric allylic alkenylation of Morita-Baylis-Hillman (MBH) carbonates with N-itaconimides as nucleophiles has been developed using a commercially available Cinchona alkaloid catalyst. A variety of multifunctional chiral α-methylene-β-maleimide esters were attained in moderate to excellent yields (up to 99%) and good to excellent enantioselectivities (up to 91% ee). The origin of the regio- and stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed regio- and enantioselectivity. © 2012 American Chemical Society.

  12. Non-thermal plasma destruction of allyl alcohol in waste gas: kinetics and modelling

    Science.gov (United States)

    DeVisscher, A.; Dewulf, J.; Van Durme, J.; Leys, C.; Morent, R.; Van Langenhove, H.

    2008-02-01

    Non-thermal plasma treatment is a promising technique for the destruction of volatile organic compounds in waste gas. A relatively unexplored technique is the atmospheric negative dc multi-pin-to-plate glow discharge. This paper reports experimental results of allyl alcohol degradation and ozone production in this type of plasma. A new model was developed to describe these processes quantitatively. The model contains a detailed chemical degradation scheme, and describes the physics of the plasma by assuming that the fraction of electrons that takes part in chemical reactions is an exponential function of the reduced field. The model captured the experimental kinetic data to less than 2 ppm standard deviation.

  13. Non-thermal plasma destruction of allyl alcohol in waste gas: kinetics and modelling

    International Nuclear Information System (INIS)

    Visscher, A de; Dewulf, J; Durme, J van; Leys, C; Morent, R; Langenhove, H Van

    2008-01-01

    Non-thermal plasma treatment is a promising technique for the destruction of volatile organic compounds in waste gas. A relatively unexplored technique is the atmospheric negative dc multi-pin-to-plate glow discharge. This paper reports experimental results of allyl alcohol degradation and ozone production in this type of plasma. A new model was developed to describe these processes quantitatively. The model contains a detailed chemical degradation scheme, and describes the physics of the plasma by assuming that the fraction of electrons that takes part in chemical reactions is an exponential function of the reduced field. The model captured the experimental kinetic data to less than 2 ppm standard deviation

  14. Lanthanum triflate triggered synthesis of tetrahydroquinazolinone derivatives of N-allyl quinolone and their biological assessment

    Directory of Open Access Journals (Sweden)

    Jardosh Hardik H.

    2012-01-01

    Full Text Available A series of 24 derivatives of tetrahydroquinazolinone has been synthesized by one-pot cyclocondensation reaction of N-allyl quinolones, cyclic β-diketones and (thiourea/N-phenylthiourea in presence of lanthanum triflate catalyst. This methodology allowed us to achieve the products in excellent yield by stirring at room temperature. All the synthesized compounds were investigated against a representative panel of pathogenic strains using broth microdilution MIC (minimum inhibitory concentration method for their in vitro antimicrobial activity. Amongst these sets of heterocyclic compounds 5h, 6b, 6h, 5f, 5l, 5n and 6g found to have admirable activity.

  15. Neutron radiographic characteristics of MA-ND type (allyl-diglycol-carbonate) nuclear track detectors

    Energy Technology Data Exchange (ETDEWEB)

    Ilic, R.; Rant, J.; Humar, M.; Somogyi, G.; Hunyadi, I.

    1986-01-01

    Neutron radiographic properties of recently developed new nuclear track detectors (MA-ND/..cap alpha.., MA-ND/p and MA-ND/p1), manufactured from allyl diglycol carbonate, were studied. It was found that the quality of radiographic image has an optimum at a removed layer thickness of about 0.8 ..mu..m. The image obtained under this condition is characterized by high detection sensitivity to neutrons (approx. 8.10/sup -3/ tracks/nsub(th) when using B converter) and by excellent inherent unsharpness (approx. 5 ..mu..m) as well as high image contrast (maximum value of net optical density is approx. 1.4).

  16. Effect of garlic mustard invasion on ectomycorrhizae in mature pine trees and pine seedlings

    Science.gov (United States)

    Lauren A. Carlson; Kelly D. McConnaughay; Sherri J. Morris

    2014-01-01

    Ectomycorrhizal fungi are mutualistic fungi that colonize the roots of many terrestrial plants. These fungi increase plant vigor by acquiring nutrients from the soil for their hosts in exchange for photosynthates. We studied the effect of garlic mustard (Alliaria petiolata) invasion on the density of ectomycorrhizal symbionts using two approaches. We...

  17. Therapeutic options to treat sulfur mustard poisoning--the road ahead.

    Science.gov (United States)

    Smith, William J

    2009-09-01

    For the past 15 years the international research community has conducted a basic and applied research program aimed at identifying a medical countermeasure against chemical threat vesicant, or blistering, agents. The primary emphasis of this program has been the development of therapeutic protection against sulfur mustard and its cutaneous pathology-blister formation. In addition to the work on a medical countermeasures, significant research has been conducted on the development of topical skin protectants and medical strategies for wound healing. This review will focus on the pharmacological strategies investigated, novel therapeutic targets currently under investigation and therapeutic approaches being considered for transition to advanced development. Additionally, we will review the expansion of our understanding of the pathophysiological mechanisms of mustard injury that has come from this research. While great strides have been made through these investigations, the complexity of the mustard insult demands that further studies extend the inroads made and point the way toward better understanding of cellular and tissue disruptions caused by sulfur mustard.

  18. Analysis of Genetic Parameters on Ethiopian Mustard (Brassica Carinata A. Braun Genotypes in Northwestern Ethiopia

    Directory of Open Access Journals (Sweden)

    Walle Tesfaye

    2014-12-01

    Full Text Available This study was carried out with the objective to estimate the genotypic variability and other yield related traits of Ethiopian mustard in North West Ethiopia. A total of 36 genotypes of Ethiopian mustard were considered for this study. Analysis of variance was computed to contrast the variability within the collected genotypes based on yield and other yield related traits. The results revealed highly significant values(p<0.01 for days to maturity, grain filling period, number of pod per plot, secondary branches per plant, harvest index, seed yield per plot, seed yield per hectare and oil content. Significant differences (p<0.05 were noted for days to flowering, plant height, primary branch per plant, biomass per plot, oil yield per plot differences among the genotypes. Genotypic coefficient of variation (GCV % was lower than phenotypic coefficient of variation (PCV % for all the traits studied. High genetic advance with heritability was observed in the following characters; plant height, biomass of the plant, number of secondary branch per plant and grain filling period. There are variations in the extent of genetic variability, heritability and genetic advance of traits which can facilitate selection for further improvement of important traits of Ethiopian mustard. Therefore, it can be concluded that the variability within Ethiopian mustard genotypes collected from different areas of northern Ethiopia is high and vital for better crop improvement.

  19. Optimisation of ultrasound-assisted extraction of natural antioxidants from mustard seed cultivars.

    Science.gov (United States)

    Szydłowska-Czerniak, Aleksandra; Tułodziecka, Agnieszka; Karlovits, György; Szłyk, Edward

    2015-05-01

    Modified mustard varieties can produce edible oil with reduced amounts of erucic acid and glucosinolates and enhanced antioxidant potential. Therefore, this work focused on the optimisation of the ultrasound-assisted extraction of compounds with high antioxidant capacity from three white mustard seed cultivars using response surface methodology. The predicted optimum solvent polarity (57.2, 56.5 and 57.6) and ultrasound power-to-sonication time ratio (4.5, 4.8 and 4.3 W min(-1)) resulted in antioxidant capacities determined by the ferric-reducing antioxidant power (FRAP) assay [54.37, 65.75 and 68.55 mmol Trolox equivalent (TE) kg(-1)] and the 2,2'-diphenyl-1-picrylhydrazyl (DPPH) method (141.65, 175.26 and 185.10 mmol TE kg(-1)) and total phenolics content (23.70, 27.16 and 11.29 mg sinapic acid g(-1)) for extracts obtained from one traditional and two modified mustard seed varieties. The highest FRAP and DPPH values (69.51 and 197.73 mmol TE kg(-1)) revealed 50% methanolic extract prepared from modified mustard seed cultivar without erucic acid and glucosinolates treated with ultrasound for 30 min (ultrasound power/ultrasound time = 4 W min(-1)). Ultrasound-assisted extraction was found to be a more rapid, convenient and appropriate extraction method with higher yield of antioxidants, shorter time and lower solvent consumption in comparison to conventional extraction. © 2014 Society of Chemical Industry.

  20. Effectiveness of Defatted Mustard Meals Used to Control Fungus Gnats: 2000-2002

    Energy Technology Data Exchange (ETDEWEB)

    McCaffrey, J. P.; Morra, M. J.

    2005-07-01

    Our objective is to develop a pesticidal product from mustard meals that can be used to control insect pests. We have focused our efforts on fungus gnats. This report details our current progress in developing a pesticidal product that can be used to control this plant pest.

  1. Degradation of the blister agent sulfur mustard, bis(2-chloroethyl) sulfide, on concrete

    International Nuclear Information System (INIS)

    Brevett, Carol A.S.; Sumpter, Kenneth B.; Wagner, George W.; Rice, Jeffrey S.

    2007-01-01

    The products formed from the degradation of the blister agent sulfur mustard [bis(2-chloroethyl) sulfide] on concrete were identified using gas chromatography with mass spectrometry detection (GC/MSD), 1 H NMR, 2D 1 H- 13 C NMR and 13 C solid state magic angle spinning (SSMAS) NMR. In situ and extraction experiments were performed. Sulfur mustard was detected in the in situ 13 C SSMAS samples for 12 weeks, whereas less than 5% of the sulfur mustard was detected in extracts from the concrete monoliths after 8 days. Sulfonium ions and (2-chloroethylthio)ethyl ether (T) were observed on the in situ samples after a period of 12 weeks, whereas vinyl species and bis(2-chloroethyl) sulfoxide were observed in the extracts of the concrete monoliths within 24 h. The differences between the extraction and the SSMAS data indicated that the sulfur mustard existed in the concrete in a non-extractable form prior to its degradation. Extraction methods alone were not sufficient to identify the products; methods to identify the presence of non-extractable degradation products were also required

  2. Mustard vesicants alter expression of the endocannabinoid system in mouse skin

    International Nuclear Information System (INIS)

    Wohlman, Irene M.; Composto, Gabriella M.; Heck, Diane E.; Heindel, Ned D.; Lacey, C. Jeffrey; Guillon, Christophe D.; Casillas, Robert P.; Croutch, Claire R.; Gerecke, Donald R.; Laskin, Debra L.; Joseph, Laurie B.; Laskin, Jeffrey D.

    2016-01-01

    Vesicants including sulfur mustard (SM) and nitrogen mustard (NM) are bifunctional alkylating agents that cause skin inflammation, edema and blistering. This is associated with alterations in keratinocyte growth and differentiation. Endogenous cannabinoids, including N-arachidonoylethanolamine (anandamide, AEA) and 2-arachidonoyl glycerol (2-AG), are important in regulating inflammation, keratinocyte proliferation and wound healing. Their activity is mediated by binding to cannabinoid receptors 1 and 2 (CB1 and CB2), as well as peroxisome proliferator-activated receptor alpha (PPARα). Levels of endocannabinoids are regulated by fatty acid amide hydrolase (FAAH). We found that CB1, CB2, PPARα and FAAH were all constitutively expressed in mouse epidermis and dermal appendages. Topical administration of NM or SM, at concentrations that induce tissue injury, resulted in upregulation of FAAH, CB1, CB2 and PPARα, a response that persisted throughout the wound healing process. Inhibitors of FAAH including a novel class of vanillyl alcohol carbamates were found to be highly effective in suppressing vesicant-induced inflammation in mouse skin. Taken together, these data indicate that the endocannabinoid system is important in regulating skin homeostasis and that inhibitors of FAAH may be useful as medical countermeasures against vesicants. - Highlights: • Sulfur mustard and nitrogen mustard are potent skin vesicants. • The endocannabinoid system regulates keratinocyte growth and differentiation. • Vesicants are potent inducers of the endocannabinoid system in mouse skin. • Endocannabinoid proteins upregulated are FAAH, CB1, CB2 and PPARα. • FAAH inhibitors suppress vesicant-induced inflammation in mouse skin.

  3. Covalent binding of nitrogen mustards to the cysteine-34 residue in human serum albumin

    NARCIS (Netherlands)

    Noort, D.; Hulst, A.G.; Jansen, R.

    2002-01-01

    Covalent binding of various clinically important nitrogen mustards to the cysteine-34 residue of human serum albumin, in vitro and in vivo, is demonstrated. A rapid method for detection of these adducts is presented, based on liquid chromatography-tandem mass spectrometry analysis of the adducted

  4. Serum level of substance P in patients with lung injuries due to sulfur mustard

    Directory of Open Access Journals (Sweden)

    Bita Najafian

    2014-01-01

    Conclusion: The SP may have a role in pulmonary complications of mustard gas. The lower level of SP in the moderate to severe patients may be due to corticosteroid consumption in such severe cases. However, further studies are needed to clarify the roles and mechanism of SP in this setting.

  5. Efficacy of white mustard and soybean meal as a bioherbicide in organic broccoli and spinach production

    Science.gov (United States)

    Weed control in organic cropping systems generally rely on mechanical or physical methods because of the lack of reliable organically accepted herbicides. Among the several potential bioherbicides being explored, white mustard (Sinapis alba) seed meal is among those bioherbicides that have been sho...

  6. Detection of sulfur mustard adducts in human callus by phage antibodies

    NARCIS (Netherlands)

    Bikker, F.J.; Mars-Groenendijk, R.H.; Noort, D.; Fidder, A.; Schans, G.P. van der

    2007-01-01

    As part of a research program to develop novel methods for diagnosis of sulfur mustard exposure in the human skin the suitability of phage display was explored. Phage display is a relative new method that enables researchers to quickly evaluate a huge range of potentially useful antibodies, thereby

  7. Isolation of low erucic acid-containing genotype of Indian mustard ...

    African Journals Online (AJOL)

    Reciprocal crosses were done between two cultivars; cv. RJ15 and cv. RLM198 of Indian mustard (Brassica juncea). Anther derived lines designated as A1 plants, were raised through anther culture from these F1 hybrid plants. 45% germination was obtained from distinctly shriveled and small A1 seeds and grown along ...

  8. Space mutation in Sulao mustard, Futian-flowering chinese cabbage and Pachi-radish breeding

    International Nuclear Information System (INIS)

    Zhang Yanrong; Cao Jian; Li Guihua; Zhao Xiujuan

    2004-01-01

    Vegetable seeds of Sulao mustard, Futian flowering Chinese cabbage and Pachi-Radish were mutated by boarding on Shenzhou No.4 Spaceship. The results showed that there were no significant differences between SP 1 and control, however, some variability of plants were found in SP 2

  9. Analysis of esterase isozyme and SSR for mutagenic progenies induced by space mutation in mustard

    International Nuclear Information System (INIS)

    Shen Jinjuan; Liu Yihua; Zhang Zhaorong; Ran Guangkui; Zhao Shouzhong; Xiao Li

    2012-01-01

    Seeds of five mustard (Brassica juncea Coss) varieties were carried into outer space by 'Shijian No.8' satellite. After five years' consecutive planting and selection, ten relatively stable mutant lines were obtained, which had significant variation in agronomic and economic characters. The mutant lines and their original varieties without space mutation treatment as control were studied by esterase isozyme and SSR analyses. Electrophoresis analysis of esterase isozymes indicated that there were differences between mutant lines and their controls in enzyme types and enzyme activity. Different mustard varieties had different enzymographs, and so did the mutants induced by space mutation, which shows different sensitivity among different mustard varieties. The SSR analysis showed that large differences were found in the SSR loci between mutant lines and their original variety, the variation frequency was between 9.52% and 57.14% with an average frequency of 26.19% for all the mutant lines. Among the mutant SSR loci, about 56.36% showed changes in band number and 43.64% in molecular weight. These results indicated that the ten mutant lines had large genetic difference in phenotype, genomic sequence and gene expression, and the outer space mutation would be an effective method to develop new mustard germplasm and variety. (authors)

  10. Further progress in the utilization of yellow seeded Trombay mustard in breeding programmes

    International Nuclear Information System (INIS)

    Abraham, V.; Bhatia, C.R.

    1988-01-01

    Full text: As reported previously the yellow seeded TM (Trombay Mustard) cultivars developed at this centre have been utilized in cross breeding programmes at several other mustard breeding centres in India. According to reports of AICORPO (All India Co-ordinated Research Project on Oilseeds) these cultivars have been used during 1977-87 in over 383 crosses. Derivatives of these crosses in advanced generations were tested in Uttar Pradesh, Rajasthan and West Bengal. In Rajasthan, these derivatives have now reached multilocation trials and three selections RS.64, RS.84, and RS.104 were found promising. In a yield trial under late sown conditions at Phaltan in Maharashtra with 12 varieties, yellow seeded TM-17 was the best yielder with 689 kg/ha compared to 593 kg/ha for Varuna, the national check. One of the objectives of mustard breeding is to evolve early maturing varieties which can be harvested in 100 days. TM-18, a selection from TM-4 x Lethbridge (Canadian cultivar) isolated at our centre, can be harvested in 75 days. It gave 1170 kg/ha seed yield at Trombay. TM-18 is the earliest maturing mustard cultivar available in India. (author)

  11. Mustard vesicants alter expression of the endocannabinoid system in mouse skin

    Energy Technology Data Exchange (ETDEWEB)

    Wohlman, Irene M.; Composto, Gabriella M. [Department of Pharmacology and Toxicology, Ernest Mario School of Pharmacy, Rutgers University, Piscataway, NJ (United States); Heck, Diane E. [Environmental Health Science, New York Medical College, Valhalla, NY (United States); Heindel, Ned D.; Lacey, C. Jeffrey; Guillon, Christophe D. [Department of Chemistry, Lehigh University, Bethlehem, PA (United States); Casillas, Robert P.; Croutch, Claire R. [MRIGlobal, Kansas City, MO (United States); Gerecke, Donald R.; Laskin, Debra L.; Joseph, Laurie B. [Department of Pharmacology and Toxicology, Ernest Mario School of Pharmacy, Rutgers University, Piscataway, NJ (United States); Laskin, Jeffrey D., E-mail: jlaskin@eohsi.rutgers.edu [Environmental and Occupational Health, Rutgers University School of Public Health, Piscataway, NJ (United States)

    2016-07-15

    Vesicants including sulfur mustard (SM) and nitrogen mustard (NM) are bifunctional alkylating agents that cause skin inflammation, edema and blistering. This is associated with alterations in keratinocyte growth and differentiation. Endogenous cannabinoids, including N-arachidonoylethanolamine (anandamide, AEA) and 2-arachidonoyl glycerol (2-AG), are important in regulating inflammation, keratinocyte proliferation and wound healing. Their activity is mediated by binding to cannabinoid receptors 1 and 2 (CB1 and CB2), as well as peroxisome proliferator-activated receptor alpha (PPARα). Levels of endocannabinoids are regulated by fatty acid amide hydrolase (FAAH). We found that CB1, CB2, PPARα and FAAH were all constitutively expressed in mouse epidermis and dermal appendages. Topical administration of NM or SM, at concentrations that induce tissue injury, resulted in upregulation of FAAH, CB1, CB2 and PPARα, a response that persisted throughout the wound healing process. Inhibitors of FAAH including a novel class of vanillyl alcohol carbamates were found to be highly effective in suppressing vesicant-induced inflammation in mouse skin. Taken together, these data indicate that the endocannabinoid system is important in regulating skin homeostasis and that inhibitors of FAAH may be useful as medical countermeasures against vesicants. - Highlights: • Sulfur mustard and nitrogen mustard are potent skin vesicants. • The endocannabinoid system regulates keratinocyte growth and differentiation. • Vesicants are potent inducers of the endocannabinoid system in mouse skin. • Endocannabinoid proteins upregulated are FAAH, CB1, CB2 and PPARα. • FAAH inhibitors suppress vesicant-induced inflammation in mouse skin.

  12. Kinetics of degradation of sulfur mustard and sarin simulants on HKUST-1 metal organic framework.

    Science.gov (United States)

    Roy, Anuradha; Srivastava, Avanish K; Singh, Beer; Shah, Dilip; Mahato, Timir Haran; Srivastava, Anchal

    2012-10-28

    The applicability of HKUST-1 for the degradation of sulfur mustard and sarin simulants was studied with and without coadsorbed water. Degradation was found to be via hydrolysis and dependent on the nucleophilic substitution reaction, vapour pressure and molecular diameter of the toxicants.

  13. A comparison of sulfur mustard and heptane penetrating a dipalmitoylphosphatidylcholine bilayer membrane

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, Thomas J., E-mail: t.mueller@theo.chemie.tu-darmstadt.de [Theoretische Physikalische Chemie, Eduard-Zintl-Institut fuer Anorganische und Physikalische Chemie, Technische Universitaet Darmstadt, Petersenstrasse 20, 64287 Darmstadt (Germany); Mueller-Plathe, Florian [Theoretische Physikalische Chemie, Eduard-Zintl-Institut fuer Anorganische und Physikalische Chemie, Technische Universitaet Darmstadt, Petersenstrasse 20, 64287 Darmstadt (Germany)

    2009-08-30

    In the present molecular dynamics simulations we study the chemical warfare agent sulfur mustard (bis(2-chloroethyl) sulfide) and the alkane heptane inserted into a dipalmitoylphosphatidylcholine (DPPC) bilayer, a generic model for a biological membrane. We investigate the diffusion, the orientation, the preferred positioning, and the end-to-end distance of the solutes within the membrane as well as the corresponding coupling times. We compare results of equilibrium simulations and simulation at different external forces, which drag the solutes through the membrane. These properties lead to a general comparison of the rotational and translational behaviors of the two solutes during the penetration of the membrane. We show that sulfur mustard, due to its atomic charge polarization, its bigger flexibility and its smaller molecular volume, is the faster moving molecule within the membrane. In last consequence, we show that this leads to different limits for the transport mechanism as observed in these simulations. For heptane the hindrance to penetrate into the membrane is significantly higher than for sulfur mustard. In contrast to heptane molecules, which spend the most of the time penetrating the tail groups, sulfur mustard needs more time to escape the tail group-head group interface of the membrane.

  14. Mesoporous titanium-manganese dioxide for sulphur mustard and soman decontamination

    International Nuclear Information System (INIS)

    Stengl, Vaclav; Bludska, Jana; Oplustil, Frantisek; Nemec, Tomas

    2011-01-01

    Highlights: → New nano-dispersive materials for warfare agents decontamination. → 95% decontamination activities for sulphur mustard. → New materials base on titanium and manganese oxides. -- Abstract: Titanium(IV)-manganese(IV) nano-dispersed oxides were prepared by a homogeneous hydrolysis of potassium permanganate and titanium(IV) oxo-sulphate with 2-chloroacetamide. Synthesised samples were characterised using Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), and scanning electron microscopy (SEM). These oxides were taken for an experimental evaluation of their reactivity with sulphur mustard (HD or bis(2-chloroethyl)sulphide) and soman (GD or (3,3'-dimethylbutan-2-yl)-methylphosphonofluoridate). Mn 4+ content affects the decontamination activity; with increasing Mn 4+ content the activity increases for sulphur mustard and decreases for soman. The best decontamination activities for sulphur mustard and soman were observed for samples TiMn 3 7 with 18.6 wt.% Mn and TiMn 5 with 2.1 wt.% Mn, respectively.

  15. Mesoporous titanium-manganese dioxide for sulphur mustard and soman decontamination

    Energy Technology Data Exchange (ETDEWEB)

    Stengl, Vaclav, E-mail: stengl@iic.cas.cz [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR v.v.i., 250 68 Rez (Czech Republic); Bludska, Jana [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR v.v.i., 250 68 Rez (Czech Republic); Oplustil, Frantisek; Nemec, Tomas [Military Technical Institute of Protection Brno, Veslarska 230, 628 00 Brno (Czech Republic)

    2011-11-15

    Highlights: {yields} New nano-dispersive materials for warfare agents decontamination. {yields} 95% decontamination activities for sulphur mustard. {yields} New materials base on titanium and manganese oxides. -- Abstract: Titanium(IV)-manganese(IV) nano-dispersed oxides were prepared by a homogeneous hydrolysis of potassium permanganate and titanium(IV) oxo-sulphate with 2-chloroacetamide. Synthesised samples were characterised using Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), and scanning electron microscopy (SEM). These oxides were taken for an experimental evaluation of their reactivity with sulphur mustard (HD or bis(2-chloroethyl)sulphide) and soman (GD or (3,3'-dimethylbutan-2-yl)-methylphosphonofluoridate). Mn{sup 4+} content affects the decontamination activity; with increasing Mn{sup 4+} content the activity increases for sulphur mustard and decreases for soman. The best decontamination activities for sulphur mustard and soman were observed for samples TiMn{sub 3}7 with 18.6 wt.% Mn and TiMn{sub 5} with 2.1 wt.% Mn, respectively.

  16. Correlations of sleep disorders with severity of obstructive airway disease in mustard gas-injured patients.

    Science.gov (United States)

    Vahedi, Ensieh; Taheri, Saeed; Alaedini, Farshid; Poursaleh, Zohreh; Ameli, Javad; Ghanei, Mostafa

    2012-06-01

    Mustard gas has serious adverse effects on several organs and functions in humans. In this study, we analyzed potential correlations between obstructive airway disease and sleep disorders in Iranian mustard gas-injured patients. We enrolled 30 male mustard gas-injured veterans and civilians from the Chemical Warfare Exposure Clinic at Baqiyatallah Hospital, Tehran. All the subjects underwent comprehensive polysomnographic and spirometric evaluations for diagnosis of sleep disorders. Patients were categorized into three groups according to the severity of their obstructive airway disease based on the Global Initiative for Chronic Obstructive Lung Disease (GOLD) criteria: group 1 (GOLD I and II), group 2 (GOLD III), and group 3 (GOLD IV). Patients with less severe obstructive airway disease had significantly higher rate of hypopnea (p = 0.05) and AHI (p = 0.05). The number of REM events was significantly higher in patients with less severe airway disease (p = 0.028). Stage 1 sleep among patients with higher FEV1 significantly constituted a higher proportion of sleep, and stage 4 sleep was significantly longer in patients with higher DLCO (p = 0.043, both). We found that sleep parameters in SM-exposed patients have some relations with spirometric parameters. Future studies with large patient populations are needed for confirmation of our results, and therapeutic interventions are needed to evaluate endeavors we can do to enhance health and quality of life in our mustard gas-injured population.

  17. Cine computed tomography for diagnosis of superior vena cava obstruction following the mustard operation

    International Nuclear Information System (INIS)

    Matherne, G.P.; Atkins, D.L.; Frey, E.E.; Smith, W.L.

    1987-01-01

    Superior vena caval obstruction is a well described complication following Mustard's repair for transposition of the great arteries. We report a case of a 6-year-old child with superior vena cava obstruction correctly diagnosed by Cine-CT. The advantages of imaging with Cine-CT for this complication are discussed. (orig.)

  18. pH-dependent toxicity of sulphur mustard in vitro

    International Nuclear Information System (INIS)

    Sawyer, Thomas W.; Vair, Cory; Nelson, Peggy; Shei Yimin; Bjarnason, Stephen; Tenn, Catherine; McWilliams, Michael; Villanueva, Mercy; Burczyk, Andrew

    2007-01-01

    The dependence of sulphur mustard (HD) toxicity on intracellular (pH i ) and extracellular pH was examined in CHO-K1 cells. HD produced an immediate and significant concentration-dependent decline in cytosolic pH, and also inhibited the mechanisms responsible for restoring pH i to physiological values. The concentration-response of HD-induced cytosolic acidification, closely paralleled the acidification of the extracellular buffer through HD hydrolysis. A viability study was carried out in order to assess the importance of HD-induced cytosolic acidification. Cultures were exposed to HD for 1 h in media that were adjusted through a pH range (pH 5.0-10), and the 24 h LC 50 values were assessed using the viability indicator dye alamarBlue TM . The toxicity of HD was found to be dependent on extracellular pH, with a greater than eight-fold increase in LD 50 obtained in cultures treated with HD at pH 9.5, compared to those treated at pH 5.0. Assays of apoptotic cell death, including morphology, soluble DNA, caspase-3 activity and TUNEL also showed that as pH was increased, much greater HD concentrations were required to cause cell death. The modest decline in HD half-life measured in buffers of increasing pH, did not account for the protective effects of basic pH. The early event(s) that HD initiates to eventually culminate in cell death are not known. However, based on the data obtained in this study, we propose that HD causes an extracellular acidification through chemical hydrolysis and that this, in both a concentration and temporally related fashion, results in cytosolic acidification. Furthermore, HD also acts to poison the antiporter systems responsible for maintaining physiological pH i , so that the cells are unable to recover from this insult. It is this irreversible decline in pH i that initiates the cascade of events that results in HD-induced cell death

  19. Performance, combustion and emission analysis of mustard oil biodiesel and octanol blends in diesel engine

    Science.gov (United States)

    Devarajan, Yuvarajan; Munuswamy, Dinesh Babu; Nagappan, Beemkumar; Pandian, Amith Kishore

    2018-01-01

    Biodiesels from the mustard oil promise to be an alternative to the conventional diesel fuel due to their similarity in properties. Higher alcohols are added to neat Mustard oil biodiesel (M100) to vary the properties of biodiesel for improving its combustion, emission and performance characteristics. N-Octanol has the ability to act as an oxygen buffer during combustion which contributes to the catalytic effect and accelerates the combustion process. N-Octanol is dispersed to neat Mustard oil biodiesel in the form of emulsions at different dosage levels of 10, 20 and 30% by volume. Three emulsion fuels prepared for engine testing constitutes of 90% of biodiesel and 10% of n-Octanol (M90O10), 80% of biodiesel and 20% of n-Octanol (M80O20) and 70% of biodiesel and 30% of n-Octanol (M70O30) by volume respectively. AVL 5402 diesel engine is made to run on these fuels to study the effect of n-Octanol on combustion, emission and performance characteristics of the mustard oil biodiesel. Experimental results show that addition of n-octanol has a positive effect on performance, combustion and emission characteristics owing to its inbuilt oxygen content. N-octanol was found to be the better oxidizing catalyst as it was more effective in reducing HC and CO emissions. A significant reduction in NOx emission was found when fuelled with emulsion techniques. The blending of n-octanol to neat Mustard oil biodiesel reduces the energy and fuel consumption and a marginal increase in brake thermal efficiency. Further, n-octanol also reduces the ignition delay and aids the combustion.

  20. Effect of Wild Mustard (Sinapis arvensis Competition and Nitrogen Levels on

    Directory of Open Access Journals (Sweden)

    F Soleymani

    2012-06-01

    Full Text Available To investigate the effect of wild mustard plant density and nitrogen fertilizer on morphological characters, yield and yield components of canola a split-plot experiment based on a randomized complete block design with 3 replications was carried out in Bu-Ali Sina university of Hamedan, in 2009. 4 levels of nitrogen fertilization (100, 150, 200 and 250 kgN h-1 were assigned to main-plots and plant density of wild mustard at 5 levels (0, 4, 8, 16 and 32 plants m-2 to the sub-plots. Results showed that the effects of wild mustard competition on yield and components of canola was significant. 32 plants m-2 of wild mustard reduced grain and biologic yield, number of pod per plant, number of seed per pod and 1000seed weight about 28.7, 30, 40.9, 22.2 and 16 percent respectively. With more nitrogen application, number of pod per plant, number of seed per pod, 1000seed weight and grain yield was increased. By increasing nitrogen from 100 to 250 kg ha-1, grain yield was increased more than 53 percent. Increasing density of wild mustard significantly reduced all above mentioned morphological and qualitative characters, except protein percentage. By increasing nitrogen fertilizer, plant height, number of branches per plant, pod length, oil yield and protein percentage of canola were increased significantly. Overall nevertheless negative effect of weed on canola yield, seems that the application 200 kgN/ha in addition to increasing grain yield and canola oil, had less decline in weed interference.

  1. Performance, combustion and emission analysis of mustard oil biodiesel and octanol blends in diesel engine

    Science.gov (United States)

    Devarajan, Yuvarajan; Munuswamy, Dinesh Babu; Nagappan, Beemkumar; Pandian, Amith Kishore

    2018-06-01

    Biodiesels from the mustard oil promise to be an alternative to the conventional diesel fuel due to their similarity in properties. Higher alcohols are added to neat Mustard oil biodiesel (M100) to vary the properties of biodiesel for improving its combustion, emission and performance characteristics. N-Octanol has the ability to act as an oxygen buffer during combustion which contributes to the catalytic effect and accelerates the combustion process. N-Octanol is dispersed to neat Mustard oil biodiesel in the form of emulsions at different dosage levels of 10, 20 and 30% by volume. Three emulsion fuels prepared for engine testing constitutes of 90% of biodiesel and 10% of n-Octanol (M90O10), 80% of biodiesel and 20% of n-Octanol (M80O20) and 70% of biodiesel and 30% of n-Octanol (M70O30) by volume respectively. AVL 5402 diesel engine is made to run on these fuels to study the effect of n-Octanol on combustion, emission and performance characteristics of the mustard oil biodiesel. Experimental results show that addition of n-octanol has a positive effect on performance, combustion and emission characteristics owing to its inbuilt oxygen content. N-octanol was found to be the better oxidizing catalyst as it was more effective in reducing HC and CO emissions. A significant reduction in NOx emission was found when fuelled with emulsion techniques. The blending of n-octanol to neat Mustard oil biodiesel reduces the energy and fuel consumption and a marginal increase in brake thermal efficiency. Further, n-octanol also reduces the ignition delay and aids the combustion.

  2. Benefits and risks of the hormetic effects of dietary isothiocyanates on cancer prevention.

    Directory of Open Access Journals (Sweden)

    Yongping Bao

    Full Text Available The isothiocyanate (ITC sulforaphane (SFN was shown at low levels (1-5 µM to promote cell proliferation to 120-143% of the controls in a number of human cell lines, whilst at high levels (10-40 µM it inhibited such cell proliferation. Similar dose responses were observed for cell migration, i.e. SFN at 2.5 µM increased cell migration in bladder cancer T24 cells to 128% whilst high levels inhibited cell migration. This hormetic action was also found in an angiogenesis assay where SFN at 2.5 µM promoted endothelial tube formation (118% of the control, whereas at 10-20 µM it caused significant inhibition. The precise mechanism by which SFN influences promotion of cell growth and migration is not known, but probably involves activation of autophagy since an autophagy inhibitor, 3-methyladenine, abolished the effect of SFN on cell migration. Moreover, low doses of SFN offered a protective effect against free-radical mediated cell death, an effect that was enhanced by co-treatment with selenium. These results suggest that SFN may either prevent or promote tumour cell growth depending on the dose and the nature of the target cells. In normal cells, the promotion of cell growth may be of benefit, but in transformed or cancer cells it may be an undesirable risk factor. In summary, ITCs have a biphasic effect on cell growth and migration. The benefits and risks of ITCs are not only determined by the doses, but are affected by interactions with Se and the measured endpoint.

  3. Metformin and phenethyl isothiocyanate combined treatment in vitro is cytotoxic to ovarian cancer cultures

    Directory of Open Access Journals (Sweden)

    Chan Daniel K

    2012-07-01

    Full Text Available Abstract Background High mortality rates in ovarian cancer are largely a result of resistance to currently used chemotherapies. Expanding therapies with a variety of drugs has the potential to reduce this high mortality rate. Metformin and phenethyl isothiocyanate (PEITC are both potentially useful in ovarian cancer, and they are particularly attractive because of their safety. Methods Cell proliferation of each drug and drug combination was evaluated by hemacytometry with Trypan blue exclusion or Sytox green staining for cell death. Levels of total and cleaved PARP were measured by Western blot. General cellular and mitochondrial reactive oxygen species were measured by flow cytometry and live cell confocal microscopy with the fluorescent dyes dihydroethidine and MitoSOX. Results Individually, metformin and PEITC each show inhibition of cell growth in multiple ovarian cancer cell lines. Alone, PEITC was also able to induce apoptosis, whereas metformin was primarily growth inhibitory. Both total cellular and mitochondrial reactive oxygen species were increased when treated with either metformin or PEITC. The growth inhibitory effects of metformin were reversed by methyl succinate supplementation, suggesting complex I plays a role in metformin's anti-cancer mechanism. PEITC's anti-cancer effect was reversed by N-acetyl-cysteine supplementation, suggesting PEITC relies on reactive oxygen species generation to induce apoptosis. Metformin and PEITC together showed a synergistic effect on ovarian cancer cell lines, including the cisplatin resistant A2780cis. Conclusions Here we show that when used in combination, these drugs are effective in both slowing cancer cell growth and killing ovarian cancer cells in vitro. Furthermore, the combination of these drugs remains effective in cisplatin resistant cell lines. Novel combinations such as metformin and PEITC show promise in expanding ovarian cancer therapies and overcoming the high incidence of

  4. Moringa isothiocyanate complexed with α-cyclodextrin: a new perspective in neuroblastoma treatment.

    Science.gov (United States)

    Giacoppo, Sabrina; Iori, Renato; Rollin, Patrick; Bramanti, Placido; Mazzon, Emanuela

    2017-07-14

    Several lines of evidence suggest the consume of natural products for cancer prevention or treatment. In particular, isothiocyanates (ITCs) exerting anti-cancer properties, have received great interest as potential chemotherapeutic agents. This study was designed to assess the anti-proliferative activities of a new preparation of Moringa oleifera-derived 4-(α-L-rhamnopyranosyloxy)benzyl ITC (moringin) complexed with alpha-cyclodextrin (moringin + α-CD; MAC) on SH-SY5Y human neuroblastoma cells. This new formulation arises in the attempt to overcome the poor solubility and stability of moringin alone in aqueous media. SH-SY5Y cells were cultured and exposed to increasing concentrations of MAC (1.0, 2.5 and 5.0 μg). Cell proliferation was examined by MTT and cell count assays. The cytotoxic activity of the MAC complex was assessed by lactate dehydrogenase (LDH) assay and trypan blue exclusion test. In addition, western blotting analyses for the main apoptosis-related proteins were performed. Treatment of SH-SY5Y cells with the MAC complex reduced cell growth in concentration dependent manner. Specifically, MAC exhibited a potent action in inhibiting the PI3K/Akt/mTOR pathway, whose aberrant activation was found in many types of cancer. MAC was also found to induce the nuclear factor-κB (NF-κB) p65 activation by phosphorylation and its translocation into the nucleus. Moreover, treatment with MAC was able to down-regulate MAPK pathway (results focused on JNK and p38 expression). Finally, MAC was found to trigger apoptotic death pathway (based on expression levels of cleaved-caspase 3, Bax/Bcl-2 balance, p53 and p21). These findings suggest that use of MAC complex may open novel perspectives to improve the poor prognosis of patients with neuroblastoma.

  5. Ternary Interactions and Energy Transfer between Fluorescein Isothiocyanate, Adenosine Triphosphate, and Graphene Oxide Nanocarriers.

    Science.gov (United States)

    Ratajczak, Katarzyna; Stobiecka, Magdalena

    2017-07-20

    The interactions of fluorescent probes and biomolecules with nanocarriers are of key importance to the emerging targeted drug delivery systems. Graphene oxide nanosheets (GONs) as the nanocarriers offer biocompatibility and robust drug binding capacity. The interactions of GONs with fluorophores lead to strong fluorescence quenching, which may interfere with fluorescence bioimaging and biodetection. Herein, we report on the interactions and energy transfers in a model ternary system: GONs-FITC-ATP, where FITC is a model fluorophore (fluorescein isothiocyanate) and ATP is a common biomolecule (adenosine-5'-triphosphate). We have found that FITC fluorescence is considerably quenched by ATP (the quenching constant K SV = 113 ± 22 M -1 ). The temperature coefficient of K SV is positive (α T = 4.15 M -1 deg -1 ). The detailed analysis of a model for internal self-quenching of FITC indicates that the temperature dependence of the net quenching efficiency η for the FITC-ATP pair is dominated by FITC internal self-quenching modes with their contribution estimated at 79%. The quenching of FITC by GONs is much stronger (K SV = 598 ± 29 M -1 ) than that of FITC-ATP and is associated with the formation of supramolecular assemblies bound with hydrogen bonding and π-π stacking interactions. For the analysis of the complex behavior of the ternary system GONs-FITC-ATP, a model of chemisorption of ATP on GONs, with partial blocking of FITC quenching, has been developed. Our results indicate that ATP acts as a moderator for FITC quenching by GONs. The interactions between ATP, FITC, and GONs have been corroborated using molecular dynamics and quantum mechanical calculations.

  6. Benzylglucosinolate Derived Isothiocyanate from Tropaeolum majus Reduces Gluconeogenic Gene and Protein Expression in Human Cells.

    Directory of Open Access Journals (Sweden)

    Valentina Guzmán-Pérez

    Full Text Available Nasturtium (Tropaeolum majus L. contains high concentrations of benzylglcosinolate. We found that a hydrolysis product of benzyl glucosinolate-the benzyl isothiocyanate (BITC-modulates the intracellular localization of the transcription factor Forkhead box O 1 (FOXO1. FoxO transcription factors can antagonize insulin effects and trigger a variety of cellular processes involved in tumor suppression, longevity, development and metabolism. The current study evaluated the ability of BITC-extracted as intact glucosinolate from nasturtium and hydrolyzed with myrosinase-to modulate i the insulin-signaling pathway, ii the intracellular localization of FOXO1 and, iii the expression of proteins involved in gluconeogenesis, antioxidant response and detoxification. Stably transfected human osteosarcoma cells (U-2 OS with constitutive expression of FOXO1 protein labeled with GFP (green fluorescent protein were used to evaluate the effect of BITC on FOXO1. Human hepatoma HepG2 cell cultures were selected to evaluate the effect on gluconeogenic, antioxidant and detoxification genes and protein expression. BITC reduced the phosphorylation of protein kinase B (AKT/PKB and FOXO1; promoted FOXO1 translocation from cytoplasm into the nucleus antagonizing the insulin effect; was able to down-regulate the gene and protein expression of gluconeogenic enzymes; and induced the gene expression of antioxidant and detoxification enzymes. Knockdown analyses with specific siRNAs showed that the expression of gluconeogenic genes was dependent on nuclear factor (erythroid derived-like2 (NRF2 and independent of FOXO1, AKT and NAD-dependent deacetylase sirtuin-1 (SIRT1. The current study provides evidence that BITC might have a role in type 2 diabetes T2D by reducing hepatic glucose production and increasing antioxidant resistance.

  7. Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism

    Directory of Open Access Journals (Sweden)

    David Porter

    2015-12-01

    Full Text Available Iron(II complexes of the tetradentate amines tris(2-pyridylmethylamine (TPA and N,N′-bis(2-pyridylmethyl-N,N′-dimethylethane-1,2-diamine (BPMEN are established catalysts of C–O bond formation, oxidising hydrocarbon substrates via hydroxylation, epoxidation and dihydroxylation pathways. Herein we report the capacity of these catalysts to promote C–N bond formation, via allylic amination of alkenes. The combination of N-Boc-hydroxylamine with either FeTPA (1 mol % or FeBPMEN (10 mol % converts cyclohexene to the allylic hydroxylamine (tert-butyl cyclohex-2-en-1-yl(hydroxycarbamate in moderate yields. Spectroscopic studies and trapping experiments suggest the reaction proceeds via a nitroso–ene mechanism, with involvement of a free N-Boc-nitroso intermediate. Asymmetric induction is not observed using the chiral tetramine ligand (+-(2R,2′R-1,1′-bis(2-pyridylmethyl-2,2′-bipyrrolidine ((R,R′-PDP.

  8. Polymerizations of beta-substituted allylic arsonium ylides with catalytic amounts of organoboron compounds

    International Nuclear Information System (INIS)

    Mondiere, R.

    2004-01-01

    My Ph.D. work consisted in the generalization and optimization of a new polymerization reaction involving allylic arsonium ylides and catalytic amounts of various boron compounds. Thus, various β-substituted allylic arsonium salts were produced according to synthetic strategies that depended on the nature of the functional group born by the salt. These salts were converted in situ to the corresponding arsonium ylides which were then treated with boron compounds to yield polymers. Our new method of polymerization afforded either non conjugated polyenes that are functionalized every three atoms of carbon, or statistic copolymers, depending on the nature of the group R born on the β position of the ylide. These new polymers cannot be synthesized by usual methods of polymerization. Initial molar ratios of reactants were found to give molar mass control of the synthesized polymers. This controlled polymerization allowed us to produce several bloc copolymers. All the polymers were characterized by NMR techniques, by size exclusion chromatography and, for some of them, by mass spectrometry. Investigation of their physicochemical properties will need additional experiments. (author)

  9. Toxicology Studies on Lewisite and Sulfur Mustard Agents: Modified Dominant Lethal Study of Sulfur Mustard in Rats Final Report

    Energy Technology Data Exchange (ETDEWEB)

    Sasser, L. B.; Cushing, J. A.; Kalkwarf, D. R.; Buschbom, R. L.

    1989-05-01

    Occupational health standards have not been established for sulfur mustard (HD) [bis{2-chloroethyl)-sulfide) ' a strong alkylating agent with known mutagenic properties. Little, however, is known about the mutagenic activity of HD in mammalian species and data regarding the dominant lethal effects of HD are ambiguous. The purpose of this study was to determine the dominant lethal effect in male and female rats orally exposed to HD. The study was conducted in two phases; a female dominant lethal phase and a male dominant lethal phase. Sprague-Dawley rats of each sex were administered 0.08, 0.20, or 0.50 mg/kg HD in sesame oil 5 days/week for 10 weeks. For the female phase, treated or untreated males were mated with treated females and their fetuses were evaluated at approximately 14 days after copulation. For the male dominant lethal phase, treated males cohabited with untreated femal (during 5 days of each week for 10 weeks) and females were sacrificed for fetal evaluation 14 days after the midweek of cohabitation during each of the 10 weeks. The appearance and behavior of the rats were unremarkable throughout the experiment and there were no treatment-related deaths. Growth rates were reduced in both female and male rats treated with 0.50 mg/kg HD. Indicators of reproductive performance did not demonstrate significant female dominant lethal effects, although significant male dominant lethal effects were observed at 2 and 3 week post-exposure. These effects included increases of early fetal resorptions and preimplantation losses and decreases of total live embryo implants. These effects were most consistently observed at a dose of 0.50 mg/kg, but frequently occurred at the lower doses. Although no treatment-related effects on male reproductive organ weights or sperm motility were found, a significant increase in the percentage of abnormal sperm was detected in males exposed to 0. 50 mg/kg HD. The timing of these effects is consistent with an effect during the

  10. Phytotoxic effects of calotropis procera, tamarix aphylla and peganum harmala on plant growth of wheat and mustard

    International Nuclear Information System (INIS)

    Aslam, M.M.; Khatoon, A.; Rehman, A.; Khan, P.; Shakir, S.U.K.; Irfan, S.; Rehman, S.U.; Jamil, M.; Mlaook, I.; Bashar, K.U.; Afridi, M.; Rahim, A.; Ullah, F.

    2016-01-01

    Phytotoxic effects of many plants are known on growth of different useful crops. This research study was designed to find out phytotoxic effects of Calotropis procera, Tamarix aphylla and Peganum harmala on seed germination and seedling length of wheat and mustard. Results showed that seed germination of wheat was significantly decreased by 5 percent, 10 percent, 15 percent, 20 percent and 25 percent while mustard seeds were resistant and were affected by higher dilutions (15 percent, 20 percent and 25 percent) of all plant extracts. Roots of both wheat and mustard were highly affected by plant aqueous extracts at all concentrations (5 percent, 10 percent, 15 percent, 20 percent and 25 percent) but shoots were inhibited by higher concentrations (20 percent and 25 percent). This study revealed that wheat is more sensitive to different plant extracts as compared to mustard. It is thus concluded that inhibitory effect increases with the increase of extracts concentration. (author)

  11. Assay techniques for detection of exposure to sulfur mustard, cholinesterase inhibitors, sarin, soman, GF, and cyanide. Technical bulletin

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-05-01

    This technical bulletin provides analytical techniques to identify toxic chemical agents in urine or blood samples. It is intended to provide the clinician with laboratory tests to detect exposure to sulfur mustard, cholinesterase inhibitors, sarin, soman, GF, and cyanide.

  12. Anti-Inflammatory and Antioxidant Effects of Repeated Exposure to Cruciferous Allyl Nitrile in Sensitizer-Induced Ear Edema in Mice.

    Science.gov (United States)

    Tanii, Hideji; Sugitani, Kayo; Saijoh, Kiyofumi

    2016-02-29

    Skin sensitizers induce allergic reactions through the induction of reactive oxygen species. Allyl nitrile from cruciferous vegetables has been reported to induce antioxidants and phase II detoxification enzymes in various tissues. We assessed the effects of repeated exposure to allyl nitrile on sensitizer-induced allergic reactions. Mice were dosed with allyl nitrile (0-200 µmol/kg), and then received a dermal application of 1 of 3 sensitizers on the left ear or 1 of 2 vehicles on the right ear. Quantitative assessment of edema was carried out by measuring the difference in weight between the portions taken from the right and left ears. We tested enzymes (superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), and thiobarbituric acid reactive substances (TBARS) in ears. Repeated exposure to allyl nitrile reduced edemas induced by glutaraldehyde and by 2, 4-dinitrochlorobenzene (DNCB), but not by formaldehyde. The repeated exposure decreased levels of TBARS, a marker of oxidative stress, induced by glutaraldehyde and by DNCB, but not by formaldehyde. Allyl nitrile elevated SOD levels for the 3 sensitizers, and CAT levels for formaldehyde and DNCB. Allyl nitrile also increased GPx levels for formaldehyde and DNCB, but not for glutaraldehyde. The reduced edemas were associated with changes in oxidative stress levels and antioxidant enzymes. Repeated exposure to allyl nitrile reduced allergic reactions induced by glutaraldehyde and by DNCB, but not by formaldehyde. This reduction was associated with changes in ROS levels and antioxidant enzyme activities.

  13. Aqueous protocol for allylic arylation of cinnamyl acetates with sodium tetraphenylborate using Bedford-type palladacycle catalyst

    KAUST Repository

    Ghorpade, Seema Arun; Sawant, Dinesh N; Renn, Dominik; Zernickel, Anna; Du, Weiyuan; Sekar, Nethi; Eppinger, Jö rg

    2018-01-01

    Allylic arylation of cinnamyl acetates with sodium tetraphenylborate using 0.002 mol % of Bedford-type palladacycle catalyst is described. The developed methodology is applicable for wide range of cinnamyl acetates furnishing excellent yields up to 93%. Notably all reactions proceed smoothly under mild reaction conditions in water under air atmosphere.

  14. Isovanillin derived N-(un)substituted hydroxylamines possessing an ortho-allylic group: valuable precursors to bioactive N-heterocycles.

    Science.gov (United States)

    Dulla, Balakrishna; Tangellamudi, Neelima D; Balasubramanian, Sridhar; Yellanki, Swapna; Medishetti, Raghavender; Kumar Banote, Rakesh; Hari Chaudhari, Girish; Kulkarni, Pushkar; Iqbal, Javed; Reiser, Oliver; Pal, Manojit

    2014-04-28

    The intramolecular 1,3-dipolar cycloaddition of isovanillin derived N-aryl hydroxylamines possessing ortho-allylic dipolarophiles affords novel benzo analogues of tricyclic isoxazolidines that can be readily transformed into functionalized lactams, γ-aminoalcohols and oxazepines. The corresponding N-unsubstituted hydroxylamines give rise to tetrahydroisoquinolines. Anxiogenic properties of these compounds are tested in zebra fish.

  15. Mechanistic Dichotomy in the Asymmetric Allylation of Aldehydes with Allyltrichlorosilanes Catalyzed by Chiral Pyridine N-Oxides

    Czech Academy of Sciences Publication Activity Database

    Malkov, A. V.; Stončius, S.; Bell, M.; Castelluzzo, F.; Ramírez-López, P.; Biedermannová, Lada; Langer, V.; Rulíšek, Lubomír; Kočovský, P.

    2013-01-01

    Roč. 19, č. 28 (2013), s. 9167-9185 ISSN 0947-6539 R&D Projects: GA MŠk LC512 Institutional support: RVO:61388963 ; RVO:86652036 Keywords : allylation * allylsilanes * calculations * organocatalysis * pyridine N-oxides Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.696, year: 2013

  16. A simple approach to unsymmetric atropoisomeric bipyridine N,N'-dioxides and their application in enantioselective allylation of aldehydes

    Czech Academy of Sciences Publication Activity Database

    Hrdina, R.; Valterová, Irena; Hodačová, Jana; Císařová, I.; Kotora, Martin

    2007-01-01

    Roč. 349, č. 6 (2007), s. 822-826 ISSN 1615-4150 R&D Projects: GA ČR(CZ) GA203/05/0102; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40550506 Keywords : allylation * asymmetric catalysis * Lewis bases Subject RIV: CC - Organic Chemistry Impact factor: 4.977, year: 2007

  17. Aqueous protocol for allylic arylation of cinnamyl acetates with sodium tetraphenylborate using Bedford-type palladacycle catalyst

    KAUST Repository

    Ghorpade, Seema Arun

    2018-03-19

    Allylic arylation of cinnamyl acetates with sodium tetraphenylborate using 0.002 mol % of Bedford-type palladacycle catalyst is described. The developed methodology is applicable for wide range of cinnamyl acetates furnishing excellent yields up to 93%. Notably all reactions proceed smoothly under mild reaction conditions in water under air atmosphere.

  18. Aldehyde Selective Wacker Oxidations of Phthalimide Protected Allylic Amines : A New Catalytic Route to beta(3)-Amino Acids

    NARCIS (Netherlands)

    Weiner, Barbara; Baeza Garcia, Alejandro; Jerphagnon, Thomas; Feringa, Ben L.

    2009-01-01

    A new method for the synthesis of B-3-amino acids is presented. Phthalimide protected allylic amines are oxidized under Wacker conditions selectively to aldehydes using PdCl2 and CuCl or Pd(MeCN)(2)Cl(NO2) and CuCl2 as complementary catalyst systems. The aldehydes are produced in excellent yields

  19. Olefination of Electron-Deficient Alkenes with Allyl Acetate: Stereo- and Regioselective Access to (2Z,4E)-Dienamides.

    Science.gov (United States)

    Li, Feifei; Yu, Chunbing; Zhang, Jian; Zhong, Guofu

    2016-09-16

    A Ru-catalyzed direct olefination of electron-deficient alkenes with allyl acetate via C-H bond activation is disclosed. By using N,N-disubstituted aminocarbonyl as the directing group, this external oxidant-free protocol resulted in high reaction efficiency and good stereo- and regioselectivities, which opens a novel synthetic passway for access to (Z,E)-butadiene skeletons.

  20. Endogenous Phenolics in Hulls and Cotyledons of Mustard and Canola: A Comparative Study on Its Sinapates and Antioxidant Capacity

    OpenAIRE

    Mayengbam, Shyamchand; Aachary, Ayyappan; Thiyam-Holländer, Usha

    2014-01-01

    Endogenous sinapic acid (SA), sinapine (SP), sinapoyl glucose (SG) and canolol (CAN) of canola and mustard seeds are the potent antioxidants in various lipid-containing systems. The study investigated these phenolic antioxidants using different fractions of canola and mustard seeds. Phenolic compounds were extracted from whole seeds and their fractions: hulls and cotyledons, using 70% methanol by the ultrasonication method and quantified using HPLC-DAD. The major phenolics from both hulls and...

  1. THE INFLUENCE OF FERTILIZATION WITH SEWAGE SLUDGE AND BIOSOLIDS ON HEAVY METAL CONTENT IN WHITE MUSTARD SEEDS

    Directory of Open Access Journals (Sweden)

    Elżbieta Wołejko

    2017-06-01

    The statistical analysis indicated that the concentrations of Cd in mustard seed was significantly correlated with the concentrations of Ni and Zn (respectively, r=-0.89 and r=-0.54. There were significant positive correlations between soil pH and metal concentrations in the seeds of mustard. The pH was significantly correlated with Ni (r = 0.60 and Zn (r = 0.55 at a p≤ 0.05.

  2. Benzyl isothiocyanate, a major component from the roots of Salvadora persica is highly active against Gram-negative bacteria.

    Directory of Open Access Journals (Sweden)

    Abier Sofrata

    Full Text Available Plants produce a number of antimicrobial substances and the roots of the shrub Salvadora persica have been demonstrated to possess antimicrobial activity. Sticks from the roots of S. persica, Miswak sticks, have been used for centuries as a traditional method of cleaning teeth. Diverging reports on the chemical nature and antimicrobial repertoire of the chewing sticks from S. persica led us to explore its antibacterial properties against a panel of pathogenic or commensal bacteria and to identify the antibacterial component/s by methodical chemical characterization. S. persica root essential oil was prepared by steam distillation and solid-phase microextraction was used to sample volatiles released from fresh root. The active compound was identified by gas chromatography-mass spectrometry and antibacterial assays. The antibacterial compound was isolated using medium-pressure liquid chromatography. Transmission electron microscopy was used to visualize the effect on bacterial cells. The main antibacterial component of both S. persica root extracts and volatiles was benzyl isothiocyanate. Root extracts as well as commercial synthetic benzyl isothiocyanate exhibited rapid and strong bactericidal effect against oral pathogens involved in periodontal disease as well as against other Gram-negative bacteria, while Gram-positive bacteria mainly displayed growth inhibition or remained unaffected. The short exposure needed to obtain bactericidal effect implies that the chewing sticks and the essential oil may have a specific role in treatment of periodontal disease in reducing Gram-negative periodontal pathogens. Our results indicate the need for further investigation into the mechanism of the specific killing of Gram-negative bacteria by S. persica root stick extracts and its active component benzyl isothiocyanate.

  3. Seed rate and nitrogen fertilizer effects on wild mustard (Sinapis arvensis L. and winter wheat (Triticum aestivum L. competition

    Directory of Open Access Journals (Sweden)

    karim moosavi

    2009-06-01

    Full Text Available In order to evaluate wild mustard competitive effect on winter wheat, an additive series experiment was conducted in 2000-2001 at Agricultural Research Station of Mashhad University.The experiment had 3 factor: wheat seed rate (175 , 215 and 255 kg/ha, nitrogen rate (150 and 225 kg/ha, and a range of wild mustard densities. Hyperbolic functions was used to describe yield-weed density relationship. Increasing wild mustard density had a negative , asymptotic – type effect on wheat biomass and grain yield. By increasing wheat seed rate , in optimum nitrogen rate , maximum wheat biomas loss has reduced about 51 %. Maximum yield loss has increased from 42.1 % to 50.4 %, as nitrogen rate incrased from optimum to upper optimum rate of wheat. By increasing of wheat seed rate from 175 to 255 kg/ha, maximum tiller number reduction due to high densities of wild mustard, has decreased by 54 %. Reduction of fertile tiller number was mostly occurred at presence of high nitrogen level, thus, reduction of fertile tiller number compared to control in N1 was 18% , while in N2 has increased to 30%. Wild mustard competition has reduced wheat seed number per ear 30% in compare to weed free control. Results show that wheat 1000 seed weight was more affected by nitrogen rate than plant densities. Apparently, in competition with wheat, wild mustard was better able to utilize the added nitrogen and thus gained a competitive adventage over the wheat.

  4. Complexes of (III) lanthanides isothiocyanate and (III) yttrium with 2,6-lutidine-n-oxide (2,6-LNO)

    International Nuclear Information System (INIS)

    Arico, E.M.

    1990-01-01

    The preparation and characterization of the complexes of yttrium and some lanthanides isothiocyanate with 2,6-lutidine-N-oxide (2,6-LNO) are described. The ligand employed in the synthesis of the compounds were prepared by the reaction of 2,6-lutidine with hydrogen peroxide in glacial acetic acid. The complexes were prepared using the relation 1:3 salt-ligand. Their characterization was made by elemental analysis, electrolytic conductance measurements, X-ray powder patterns, infrared spectra, electronic absorption spectra of the neodymium and fluorescence spectra of the europium compounds. (author)

  5. Improved synthesis methods of standards used for quantitative determination of total isothiocyanates from broccoli in human urine

    DEFF Research Database (Denmark)

    Kristensen, Mette; Krogholm, Kirstine Suszkiewicz; Frederiksen, Hanne

    2007-01-01

    A well-known method for quantification of isothiocyanates (ITCs) and their metabolites is the condensation reaction with 1,2-benzenedithiole to produce 1,3-benzodithiole-2-thione, which can be quantified by high-performance liquid chromatography. Standards of an ITC metabolite and 1,3-benzodithio...... excretion of ITCs from 10 healthy subjects who consumed 350 g broccoli. The excretion was investigated throughout 48 h showing a cumulative urinary ITC excretion of 49.1 +/- 25.2% of the dose....

  6. Chemical Characterization and Release Efficiency of Defatted Mustard Meals: 2000-2002

    Energy Technology Data Exchange (ETDEWEB)

    Morra, M. J.

    2005-07-01

    Glucosinolates, compounds that occur in agronomically important crops, may represent a viable source of allelochemic control for various soil-borne plant pests. Toxicity is not attributed to intact glucosinolates, but instead to biologically active products such as isothiocyanates (ITCs), organic cyanides, oxazolidinethiones, and ionic thiocyanate (SCN-) released upon enzymatic degradation by myrosinase (thioglucoside glucohydrolase, EC 3.2.3.1) in the presence of water.

  7. Benzyl isothiocyanate causes FoxO1-mediated autophagic death in human breast cancer cells.

    Directory of Open Access Journals (Sweden)

    Dong Xiao

    Full Text Available Benzyl isothiocyanate (BITC, a constituent of edible cruciferous vegetables, inhibits growth of breast cancer cells but the mechanisms underlying growth inhibitory effect of BITC are not fully understood. Here, we demonstrate that BITC treatment causes FoxO1-mediated autophagic death in cultured human breast cancer cells. The BITC-treated breast cancer cells (MDA-MB-231, MCF-7, MDA-MB-468, BT-474, and BRI-JM04 and MDA-MB-231 xenografts from BITC-treated mice exhibited several features characteristic of autophagy, including appearance of double-membrane vacuoles (transmission electron microscopy and acidic vesicular organelles (acridine orange staining, cleavage of microtubule-associated protein 1 light chain 3 (LC3, and/or suppression of p62 (p62/SQSTM1 or sequestosome 1 expression. On the other hand, a normal human mammary epithelial cell line (MCF-10A was resistant to BITC-induced autophagy. BITC-mediated inhibition of MDA-MB-231 and MCF-7 cell viability was partially but statistically significantly attenuated in the presence of autophagy inhibitors 3-methyl adenine and bafilomycin A1. Stable overexpression of Mn-superoxide dismutase, which was fully protective against apoptosis, conferred only partial protection against BITC-induced autophagy. BITC treatment decreased phosphorylation of mTOR and its downstream targets (P70s6k and 4E-BP1 in cultured MDA-MB-231 and MCF-7 cells and MDA-MB-231 xenografts, but activation of mTOR by transient overexpression of its positive regulator Rheb failed to confer protection against BITC-induced autophagy. Autophagy induction by BITC was associated with increased expression and acetylation of FoxO1. Furthermore, autophagy induction and cell growth inhibition resulting from BITC exposure were significantly attenuated by small interfering RNA knockdown of FoxO1. In conclusion, the present study provides novel insights into the molecular circuitry of BITC-induced cell death involving FoxO1-mediated autophagy.

  8. The isothiocyanate class of bioactive nutrients covalently inhibit the MEKK1 protein kinase

    Directory of Open Access Journals (Sweden)

    Macdonald Timothy L

    2007-09-01

    Full Text Available Abstract Background Dietary isothiocyanates (ITCs are electrophilic compounds that have diverse biological activities including induction of apoptosis and effects on cell cycle. They protect against experimental carcinogenesis in animals, an activity believed to result from the transcriptional induction of "Phase 2" enzymes. The molecular mechanism of action of ITCs is unknown. Since ITCs are electrophiles capable of reacting with sulfhydryl groups on amino acids, we hypothesized that ITCs induce their biological effects through covalent modification of proteins, leading to changes in cell regulatory events. We previously demonstrated that stress-signaling kinase pathways are inhibited by other electrophilic compounds such as menadione. We therefore tested the effects of nutritional ITCs on MEKK1, an upstream regulator of the SAPK/JNK signal transduction pathway. Methods The activity of MEKK1 expressed in cells was monitored using in vitro kinase assays to measure changes in catalytic activity. The activity of endogenous MEKK1, immunopurified from ITC treated and untreated LnCAP cells was also measured by in vitro kinase assay. A novel labeling and affinity reagent for detection of protein modification by ITCs was synthesized and used in competition assays to monitor direct modification of MEKK1 by ITC. Finally, immunoblots with phospho-specific antibodies were used to measure the activity of MAPK protein kinases. Results ITCs inhibited the MEKK1 protein kinase in a manner dependent on a specific cysteine residue in the ATP binding pocket. Inhibition of MEKK1 catalytic activity was due to direct, covalent and irreversible modification of the MEKK1 protein itself. In addition, ITCs inhibited the catalytic activity of endogenous MEKK1. This correlated with inhibition of the downstream target of MEKK1 activity, i.e. the SAPK/JNK kinase. This inhibition was specific to SAPK, as parallel MAPK pathways were unaffected. Conclusion These results

  9. The isothiocyanate class of bioactive nutrients covalently inhibit the MEKK1 protein kinase

    International Nuclear Information System (INIS)

    Cross, Janet V; Foss, Frank W; Rady, Joshua M; Macdonald, Timothy L; Templeton, Dennis J

    2007-01-01

    Dietary isothiocyanates (ITCs) are electrophilic compounds that have diverse biological activities including induction of apoptosis and effects on cell cycle. They protect against experimental carcinogenesis in animals, an activity believed to result from the transcriptional induction of 'Phase 2' enzymes. The molecular mechanism of action of ITCs is unknown. Since ITCs are electrophiles capable of reacting with sulfhydryl groups on amino acids, we hypothesized that ITCs induce their biological effects through covalent modification of proteins, leading to changes in cell regulatory events. We previously demonstrated that stress-signaling kinase pathways are inhibited by other electrophilic compounds such as menadione. We therefore tested the effects of nutritional ITCs on MEKK1, an upstream regulator of the SAPK/JNK signal transduction pathway. The activity of MEKK1 expressed in cells was monitored using in vitro kinase assays to measure changes in catalytic activity. The activity of endogenous MEKK1, immunopurified from ITC treated and untreated LnCAP cells was also measured by in vitro kinase assay. A novel labeling and affinity reagent for detection of protein modification by ITCs was synthesized and used in competition assays to monitor direct modification of MEKK1 by ITC. Finally, immunoblots with phospho-specific antibodies were used to measure the activity of MAPK protein kinases. ITCs inhibited the MEKK1 protein kinase in a manner dependent on a specific cysteine residue in the ATP binding pocket. Inhibition of MEKK1 catalytic activity was due to direct, covalent and irreversible modification of the MEKK1 protein itself. In addition, ITCs inhibited the catalytic activity of endogenous MEKK1. This correlated with inhibition of the downstream target of MEKK1 activity, i.e. the SAPK/JNK kinase. This inhibition was specific to SAPK, as parallel MAPK pathways were unaffected. These results demonstrate that MEKK1 is directly modified and inhibited by

  10. Fermentation-Assisted Extraction of Isothiocyanates from Brassica Vegetable Using Box-Behnken Experimental Design

    Directory of Open Access Journals (Sweden)

    Amit K. Jaiswal

    2016-11-01

    Full Text Available Recent studies showed that Brassica vegetables are rich in numerous health-promoting compounds such as carotenoids, polyphenols, flavonoids, and glucosinolates (GLS, as well as isothiocyanates (ITCs and are involved in health promotion upon consumption. ITCs are breakdown products of GLS, and typically used in the food industry as a food preservative and colouring agent. They are also used in the pharmaceutical industry due to their several pharmacological properties such as antibacterial, antifungal, antiprotozoal, anti-inflammatory, and chemoprotective effects, etc. Due to their widespread application in food and pharmaceuticals, the present study was designed to extract ITCs from York cabbage. In order to optimise the fermentation-assisted extraction process for maximum yield of ITCs from York cabbage, Box-Behnken design (BBD combined with response surface methodology (RSM was applied. Additionally, the GLS content of York cabbage was quantified and the effect of lactic acid bacteria (LAB on GLS was evaluated. A range of GLS such as glucoraphanin, glucoiberin, glucobrassicin, sinigrin, gluconapin, neoglucobrassicin and 4-methoxyglucobrassicin were identified and quantified in fresh York cabbage. The experimental data obtained were fitted to a second-order polynomial equation using multiple regression analysis, and also examined by appropriate statistical methods. LAB facilitated the degradation of GLS, and the consequent formation of breakdown products such as ITCs. Results showed that the solid-to-liquid (S/L ratio, fermentation time and agitation rate had a significant effect on the yield of ITCs (2.2 times increment. The optimum fermentation conditions to achieve a higher ITCs extraction yield were: S/L ratio of 0.25 w/v, fermentation time of 36 h, and agitation rate of 200 rpm. The obtained yields of ITCs (45.62 ± 2.13 μM sulforaphane equivalent (SFE/mL were comparable to the optimised conditions, indicating the accuracy of the model

  11. Fermentation-Assisted Extraction of Isothiocyanates from Brassica Vegetable Using Box-Behnken Experimental Design.

    Science.gov (United States)

    Jaiswal, Amit K; Abu-Ghannam, Nissreen

    2016-11-04

    Recent studies showed that Brassica vegetables are rich in numerous health-promoting compounds such as carotenoids, polyphenols, flavonoids, and glucosinolates (GLS), as well as isothiocyanates (ITCs) and are involved in health promotion upon consumption. ITCs are breakdown products of GLS, and typically used in the food industry as a food preservative and colouring agent. They are also used in the pharmaceutical industry due to their several pharmacological properties such as antibacterial, antifungal, antiprotozoal, anti-inflammatory, and chemoprotective effects, etc. Due to their widespread application in food and pharmaceuticals, the present study was designed to extract ITCs from York cabbage. In order to optimise the fermentation-assisted extraction process for maximum yield of ITCs from York cabbage, Box-Behnken design (BBD) combined with response surface methodology (RSM) was applied. Additionally, the GLS content of York cabbage was quantified and the effect of lactic acid bacteria (LAB) on GLS was evaluated. A range of GLS such as glucoraphanin, glucoiberin, glucobrassicin, sinigrin, gluconapin, neoglucobrassicin and 4-methoxyglucobrassicin were identified and quantified in fresh York cabbage. The experimental data obtained were fitted to a second-order polynomial equation using multiple regression analysis, and also examined by appropriate statistical methods. LAB facilitated the degradation of GLS, and the consequent formation of breakdown products such as ITCs. Results showed that the solid-to-liquid (S/L) ratio, fermentation time and agitation rate had a significant effect on the yield of ITCs (2.2 times increment). The optimum fermentation conditions to achieve a higher ITCs extraction yield were: S/L ratio of 0.25 w / v , fermentation time of 36 h, and agitation rate of 200 rpm. The obtained yields of ITCs (45.62 ± 2.13 μM sulforaphane equivalent (SFE)/mL) were comparable to the optimised conditions, indicating the accuracy of the model for the

  12. Reprint of: Pendant allyl crosslinking as a tunable shape memory actuator for vascular applications.

    Science.gov (United States)

    Boire, Timothy C; Gupta, Mukesh K; Zachman, Angela L; Lee, Sue Hyun; Balikov, Daniel A; Kim, Kwangho; Bellan, Leon M; Sung, Hak-Joon

    2016-04-01

    Thermo-responsive shape memory polymers (SMPs) can be programmed to fit into small-bore incisions and recover their functional shape upon deployment in the body. This property is of significant interest for developing the next generation of minimally-invasive medical devices. To be used in such applications, SMPs should exhibit adequate mechanical strengths that minimize adverse compliance mismatch-induced host responses (e.g. thrombosis, hyperplasia), be biodegradable, and demonstrate switch-like shape recovery near body temperature with favorable biocompatibility. Combinatorial approaches are essential in optimizing SMP material properties for a particular application. In this study, a new class of thermo-responsive SMPs with pendant, photocrosslinkable allyl groups, x%poly(ε-caprolactone)-co-y%(α-allyl carboxylate ε-caprolactone) (x%PCL-y%ACPCL), are created in a robust, facile manner with readily tunable material properties. Thermomechanical and shape memory properties can be drastically altered through subtle changes in allyl composition. Molecular weight and gel content can also be altered in this combinatorial format to fine-tune material properties. Materials exhibit highly elastic, switch-like shape recovery near 37 °C. Endothelial compatibility is comparable to tissue culture polystyrene (TCPS) and 100%PCL in vitro and vascular compatibility is demonstrated in vivo in a murine model of hindlimb ischemia, indicating promising suitability for vascular applications. With the ongoing thrust to make surgeries minimally-invasive, it is prudent to develop new biomaterials that are highly compatible and effective in this workflow. Thermo-responsive shape memory polymers (SMPs) have great potential for minimally-invasive applications because SMP medical devices (e.g. stents, grafts) can fit into small-bore minimally-invasive surgical devices and recover their functional shape when deployed in the body. To realize their potential, it is imperative to devise

  13. Pendant allyl crosslinking as a tunable shape memory actuator for vascular applications.

    Science.gov (United States)

    Boire, Timothy C; Gupta, Mukesh K; Zachman, Angela L; Lee, Sue Hyun; Balikov, Daniel A; Kim, Kwangho; Bellan, Leon M; Sung, Hak-Joon

    2015-09-01

    Thermo-responsive shape memory polymers (SMPs) can be programmed to fit into small-bore incisions and recover their functional shape upon deployment in the body. This property is of significant interest for developing the next generation of minimally-invasive medical devices. To be used in such applications, SMPs should exhibit adequate mechanical strengths that minimize adverse compliance mismatch-induced host responses (e.g. thrombosis, hyperplasia), be biodegradable, and demonstrate switch-like shape recovery near body temperature with favorable biocompatibility. Combinatorial approaches are essential in optimizing SMP material properties for a particular application. In this study, a new class of thermo-responsive SMPs with pendant, photocrosslinkable allyl groups, x%poly(ε-caprolactone)-co-y%(α-allyl carboxylate ε-caprolactone) (x%PCL-y%ACPCL), are created in a robust, facile manner with readily tunable material properties. Thermomechanical and shape memory properties can be drastically altered through subtle changes in allyl composition. Molecular weight and gel content can also be altered in this combinatorial format to fine-tune material properties. Materials exhibit highly elastic, switch-like shape recovery near 37°C. Endothelial compatibility is comparable to tissue culture polystyrene (TCPS) and 100%PCL in vitro and vascular compatibility is demonstrated in vivo in a murine model of hindlimb ischemia, indicating promising suitability for vascular applications. With the ongoing thrust to make surgeries minimally-invasive, it is prudent to develop new biomaterials that are highly compatible and effective in this workflow. Thermo-responsive shape memory polymers (SMPs) have great potential for minimally-invasive applications because SMP medical devices (e.g. stents, grafts) can fit into small-bore minimally-invasive surgical devices and recover their functional shape when deployed in the body. To realize their potential, it is imperative to devise

  14. Beneficial role of carbon nanotubes on mustard plant growth: an agricultural prospect

    Science.gov (United States)

    Mondal, Anindita; Basu, Ruma; Das, Sukhen; Nandy, Papiya

    2011-10-01

    Nowadays an increasing application of nanotechnology in different fields has arisen an extensive debate about the effect of the engineered nanoparticles on environment . Phytotoxicity of nanoparticles has come into limelight in the last few years. However, very few studies have been done so far on the beneficial aspects of nanoparticles on plants. In this article, we report the beneficial effect of multi-walled carbon nanotubes (MWCNTs) having diameter of 30 nm on Brassica juncea (mustard) seeds. Measurements of germination rate, T 50 (time taken for 50% germination), shoot and root growth have shown encouraging results using low concentration of oxidized MWCNT (OMWCNT) treated seeds as compared to non-oxidized as well as high concentration OMWCNT treated seeds. For toxicity study we measured the germination index and relative root elongation, while conductivity test and infra-red spectra were also performed to study the overall effect of oxidized and non-oxidized nanotubes on mustard seeds and seedlings.

  15. A mediational model of PTSD in World War II veterans exposed to mustard gas.

    Science.gov (United States)

    Jankowski, M Kay; Schnurr, Paula P; Adams, Gary A; Green, Bonnie L; Ford, Julian D; Friedman, Matthew J

    2004-08-01

    Structural equation modeling (SEM) was used to examine associations among trauma-related contextual factors, initial psychological reactions, social support, and subsequent disclosure on posttraumatic stress disorder (PTSD) symptoms in a sample of World War II (WWII) veterans exposed to mustard gas (N = 305). A structural model suggested that initial psychological reaction mediated the relationship between variables related to the context of mustard gas exposure and severity of PTSD symptoms 50 years later. Unexpectedly, social support appeared to be positively related to PTSD symptoms, and not related to the contextual variables or initial psychological reactions. These findings contribute to our understanding of PTSD in older veterans, and have relevance for early intervention services to prevent PTSD among those at risk for exposure to toxic agents.

  16. Diversity of Pollinator Insects in Relation to Seed Set of Mustard (Brassica rapa L.: Cruciferae

    Directory of Open Access Journals (Sweden)

    TRI ATMOWIDI

    2007-12-01

    Full Text Available Pollinators provide key services to both natural and agricultural ecosystems. Agricultural productivity depends, in part, on pollinator populations from adjacent seminatural habitats. Here we analysed the diversity of pollinator insects and its effect to seed set of mustard (Brassica rapa planted in agricultural ecosystem near the Gunung Halimun-Salak National Park, West Java. At least 19 species of insects pollinated the mustard, and three species, i.e. Apis cerana, Ceratina sp., and Apis dorsata showed a high abundance. The higher abundance and species richness of pollinators occurred at 08.30-10.30 am and the diversity was related to the number of flowering plants. Insect pollinations increased the number of pods, seeds per pod, seed weights per plant, and seed germination.

  17. SELECTED YIELD COMPONENTS IN WHITE MUSTARD (SINAPIS ALBA VERSUS SULFUR FERTILIZATION

    Directory of Open Access Journals (Sweden)

    Bożena BARCZAK

    2011-10-01

    Full Text Available As shown by the research made based on the four-year field experiment, sulfur fertilization, in general, significantly differentiated the white mustard yield components. Of all the factors (sulfur application method, its form and dose, the greatest effect on the yield structure components was demonstrated for the sulfur dose. The use of 40 kg S·ha-1, regardless of the form applied and the sulfur application method, resulted in significant increases in most of the characters, as compared with the control. The application of sulfur into soil showed a significantly more favorable effect on the seed weigh and number per silique and on the weight of seeds of the entire plant than the foliar application of this nutrient. The white mustard seed yield size was most correlated with the number of siliques per plant, and successively less with the thousand seed weight.

  18. Beneficial role of carbon nanotubes on mustard plant growth: an agricultural prospect

    International Nuclear Information System (INIS)

    Mondal, Anindita; Basu, Ruma; Das, Sukhen; Nandy, Papiya

    2011-01-01

    Nowadays an increasing application of nanotechnology in different fields has arisen an extensive debate about the effect of the engineered nanoparticles on environment. Phytotoxicity of nanoparticles has come into limelight in the last few years. However, very few studies have been done so far on the beneficial aspects of nanoparticles on plants. In this article, we report the beneficial effect of multi-walled carbon nanotubes (MWCNTs) having diameter of ∼30 nm on Brassica juncea (mustard) seeds. Measurements of germination rate, T 50 (time taken for 50% germination), shoot and root growth have shown encouraging results using low concentration of oxidized MWCNT (OMWCNT) treated seeds as compared to non-oxidized as well as high concentration OMWCNT treated seeds. For toxicity study we measured the germination index and relative root elongation, while conductivity test and infra-red spectra were also performed to study the overall effect of oxidized and non-oxidized nanotubes on mustard seeds and seedlings.

  19. Laser effects on the growth and photosynthesis process in mustard plants (Sinapis Alba)

    Science.gov (United States)

    Anghel, Sorin; Stanescu, Constantin S.; Giosanu, Dana; Flenacu, Monica; Iorga-Siman, Ion

    2001-06-01

    In this paper we present the results of our experiments concerning the influence of the low energy laser (LEL) radiation on the germination, growth and photosyntheses processes in mustard plants (sinapis alba). We used a He-Ne laser ((lambda) equals 632.8 nm, P equals 6 mW) to irradiate the mustard seeds with different exposure times. The seeds were sowed and some determinations (the germination and growth intensity, chlorophyll quantity, and respiration intensity) were made on the plant culture. We ascertained that the germination and growth of the plants are influenced by the irradiation. Also, the chlorophyll quantity is the same for both plants from irradiated and non-irradiated seeds but the respiration and photosynthesis processes are influenced by the irradiation.

  20. Prevalence of Skin Cancers Among Iranian Veterans, 18-23 Years Following Exposure to Sulfur Mustard

    International Nuclear Information System (INIS)

    Emadi, S. N.; Soroush, R.; Khateri, S.

    2007-01-01

    In this historical Cohort, in a population of 800 veterans with documented history of exposure to Sulfur Mustard during the period of 1984-88 (all have been under the close health monitoring program) 25 cases are found to have developed skin cancer over the past years. The most common cancer among these cases has been Basal Cell Carcinoma -BCC- with 9 cases and then Squamous Cell Carcinoma -SCC- , mycosis fungoides-MF-, Bowen disease and Dermatofibrosarcoma protuberans-DFSP- (5, 5, 4 and 2 cases respectively). Considering the number of diagnosed skin cancers among the subjects of this study and new cases even 2 decades after exposure, more in depth studies are necessary to investigate the possible casual relationship between the exposure to mustard gas and the skin cancers. (author)

  1. Treatment for Sulfur Mustard Lung Injuries; New Therapeutic Approaches from Acute to Chronic Phase

    Directory of Open Access Journals (Sweden)

    Zohreh Poursaleh

    2012-09-01

    Full Text Available Objective: Sulfur mustard (SM is one of the major potent chemical warfare and attractive weapons for terrorists. It has caused deaths to hundreds of thousands of victims in World War I and more recently during the Iran-Iraq war (1980-1988. It has ability to develop severe acute and chronic damage to the respiratory tract, eyes and skin. Understanding the acute and chronic biologic consequences of SM exposure may be quite essential for developing efficient prophylactic/therapeutic measures. One of the systems majorly affected by SM is the respiratory tract that numerous clinical studies have detailed processes of injury, diagnosis and treatments of lung. The low mortality rate has been contributed to high prevalence of victims and high lifetime morbidity burden. However, there are no curative modalities available in such patients. In this review, we collected and discussed the related articles on the preventive and therapeutic approaches to SM-induced respiratory injury and summarized what is currently known about the management and therapeutic strategies of acute and long-term consequences of SM lung injuries.Method:This review was done by reviewing all papers found by searching following key words sulfur mustard; lung; chronic; acute; COPD; treatment.Results:Mustard lung has an ongoing pathological process and is active disorder even years after exposure to SM. Different drug classes have been studied, nevertheless there are no curative modalities for mustard lung. Conclusion:Complementary studies on one hand regarding pharmacokinetic of drugs and molecular investigations are mandatory to obtain more effective treatments.

  2. Treatment for sulfur mustard lung injuries; new therapeutic approaches from acute to chronic phase

    Directory of Open Access Journals (Sweden)

    Poursaleh Zohreh

    2012-09-01

    Full Text Available Abstract Objective Sulfur mustard (SM is one of the major potent chemical warfare and attractive weapons for terrorists. It has caused deaths to hundreds of thousands of victims in World War I and more recently during the Iran-Iraq war (1980–1988. It has ability to develop severe acute and chronic damage to the respiratory tract, eyes and skin. Understanding the acute and chronic biologic consequences of SM exposure may be quite essential for developing efficient prophylactic/therapeutic measures. One of the systems majorly affected by SM is the respiratory tract that numerous clinical studies have detailed processes of injury, diagnosis and treatments of lung. The low mortality rate has been contributed to high prevalence of victims and high lifetime morbidity burden. However, there are no curative modalities available in such patients. In this review, we collected and discussed the related articles on the preventive and therapeutic approaches to SM-induced respiratory injury and summarized what is currently known about the management and therapeutic strategies of acute and long-term consequences of SM lung injuries. Method This review was done by reviewing all papers found by searching following key words sulfur mustard; lung; chronic; acute; COPD; treatment. Results Mustard lung has an ongoing pathological process and is active disorder even years after exposure to SM. Different drug classes have been studied, nevertheless there are no curative modalities for mustard lung. Conclusion Complementary studies on one hand regarding pharmacokinetic of drugs and molecular investigations are mandatory to obtain more effective treatments.

  3. Veterans at Risk: The Health Effects of Mustard Gas and Lewisite

    Science.gov (United States)

    1993-01-01

    in Abyssinia and the Japanese in China . In the beginning of World War II (WWII), the specter of chemical warfare was again raised by reports of the use...Annales Medicinae Militaris Belgicae 3:S1-61. World Health Organization. 1970. Health Aspects of Chemical and Biological Weapons: Report of a WHO Group...Clinical management of mustard gas casualties. Annales Medicinae Militaris Belgicae 3:51-61. Winternitz MC. 1919. Anatomical changes in the

  4. A Literature Review on the Mechanism of Action of Sulphur and Nitrogen Mustard

    Science.gov (United States)

    1989-07-01

    for years is also poeqible (Aasted et al, 1987; Colardyn et al, 1986). Severely poisoned individuals exhibit bone marrow depression and may die from...MMS does not produce the enhanced depression of DNA synthesis in sensitive cells, compared to resistant cells, produced by sulphur mustard and...Compound MATD 1 Protection (mg/mouse) index 2 WR-3689 15 159 WR-2721 15 44 Aminoethylcysteine 80 27 N- acetylcysteine 8 26 Glutathione 60 22 Cysteine 8

  5. [Isolation and partial characterization of DNA topoisomerase I from the nucleoids of white mustard chloroplasts].

    Science.gov (United States)

    Belkina, G G; Pogul'skaia, E V; Iurina, N P

    2004-01-01

    DNA topoisomerase was isolated for the first time from nucleoids of white mustard (Sinapis alba L.) chloroplasts. The enzyme had a molecular weight of 70 kDa; it was ATP-independent, required the presence of mono- (K+) and bivalent (Mg2+) cations, and was capable of relaxing both negatively and positively supercoiled DNA. These results suggest that the enzyme isolated belongs to type IB DNA topoisomerases.

  6. Effect of gamma rays on growth and survival of three mustard varieties in M1 generation

    International Nuclear Information System (INIS)

    Kamala, T.; Rao, R.N.B.

    1982-01-01

    Effects of gamma radiation on germination, survival percentage, seedling height, leaf length and breadth, and growth rate in three mustard varieties were studied in M 1 generation. Seeds were exposed to 15, 30, 45, 60 and 80 Kr doses for the study. Germinations and survival percentages and seedling height showed dose-dependent decrease, while growth rate, leaf length and breadth increased at 60, 45 and 30 Kr and decreased at 80 Kr, though varietal differences were observed. (M.G.B.)

  7. Cytokinetic Analysis of Slowly Renewing Bone-Marrow Cells after Administration of Nitrogen Mustard

    Energy Technology Data Exchange (ETDEWEB)

    Haas, R.; Fliedner, T. M.; Stehle, H. [Abteilung fuer Klinische Physiologie der Universitaet Ulm, Ulm/Donau, Federal Republic of Germany (Germany)

    1968-08-15

    The continuous or repeated administration of tritiated thymidine into pregnant rats during organogenesis provides a method for the complete labelling of newborn rats. If these are continuously injected with tritiated thymidine for the first four weeks after birth, the fraction of labelled cells of all organs and cell-renewal systems is still 100% If completely labelled animals are sacrificed at regular intervals after the discontinuance of thymidine administration, one can distinguish two groups of cells with distinct differences in their cell renewal. While the reticular cells A and B, the endothelial cells and the bone-marrow lymphocytes belong to a slowly proliferating group of cells, the differentiated myelopoietic and erythropoietic cells of the bone marrow proliferate rapidly. That labelled erythropoietic or myelopoietic cells are not found later than 6-10 days after discontinuance of tritated thymidine injection in these animals argues strongly against the hypothesis that under normal steady-state conditions a G{sub 0} fraction exists in the bone-marrow, from which stem cells are deviated into the differentiated cell pools by adequate stimuli. The administration of nitrogen mustard in a dose sufficient to cause bone-marrow aplasia neither destroys nor stimulates the reticular cells and endothelial cells of the bone-marrow matrix. These cells retain their label and remain present in normal numbers throughout the period of observation after nitrogen mustard treatment: The only cell type in the marrow that changes its labelling intensity after nitrogen mustard administration is the marrow lymphocyte. The decrease in the fraction and intensity of labelled bone-marrow lymphocytes precedes the rapid regeneration of nitrogen mustard aplastic bone-marrow. This cell type, in our opinion, would be the only cell to qualify as a stem cell, although positive evidence is still lacking. (author)

  8. Thermal studies on unirradiated and γ-irradiated polymer of allyl diglycol carbonate

    International Nuclear Information System (INIS)

    Kalsi, P.C.; Pandey, A.K.; Iyer, R.H.; Singh Mudher, K.D.

    1995-01-01

    The thermal decomposition of unirradiated and γ-irradiated (5.93-15.5 MRad dose range) allyl diglycol carbonate polymer (trade name, CR-39) was studied by thermogravimetry (TG) and differential thermal analysis (DTA). These studies indicate four main decomposition steps in CR-39 polymer in air. Assessment of the influence of radiation dose on the above range shows that while the 5.93 MRad γ-irradiated polymer CR-39 degrades in three steps, the 15.5 MRad γ-irradiated polymer degrades in only two steps. The kinetics of the different stages of degradation were also evaluated from the TG curves. Irradiation enhances the decomposition rate and the effect increases further with increasing radiation dose. The activation energy values calculated for all the decomposition stages decrease on irradiation

  9. Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

    KAUST Repository

    Behenna, Douglas C.

    2011-12-18

    The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

  10. Trifluoroethylation of Alkynes: Synthesis of Allylic-CF3 Compounds by Visible-Light Photocatalysis

    Institute of Scientific and Technical Information of China (English)

    Geum-bee Roh; Naeem Iqbal; Eun Jin Cho

    2016-01-01

    Two types of allylic trifluoromethylated compounds were synthesized by reacting alkynes with CF3CH2I using visible-light photocatalysis.Subtle differences in the catalytic system controlled the selectivity of iodotrifluoroethylation and hydrotrifluoroethylation.The iodotrifluoroethylated products were obtained in the presence of [Ru(bpy)3]C12 and TMEDA in CH3CN under visible-light irradiation,whereas hydrotrifluoroethylated products were synthesized usingfac-[Ir(ppy)3] and a mixture of DBU and K2CO3 in DMF.The iodotrifluoroethylation reaction worked particularly well,even at gram-scale,and the synthetic utility of iodotrifluoroethylated products was proved by their coupling reactions,providing complex CF3-containing products.

  11. An Efficient Amide-Aldehyde-Alkene Condensation: Synthesis for the N-Allyl Amides.

    Science.gov (United States)

    Quan, Zheng-Jun; Wang, Xi-Cun

    2016-02-01

    The allylamine skeleton represents a significant class of biologically active nitrogen compounds that are found in various natural products and drugs with well-recognized pharmacological properties. In this personal account, we will briefly discuss the synthesis of allylamine skeletons. We will focus on showing a general protocol for Lewis acid-catalyzed N-allylation of electron-poor N-heterocyclic amides and sulfonamide via an amide-aldehyde-alkene condensation reaction. The substrate scope with respect to N-heterocyclic amides, aldehydes, and alkenes will be discussed. This method is also capable of preparing the Naftifine motif from N-methyl-1-naphthamide or methyl (naphthalene-1-ylmethyl)carbamate, with paraformaldehyde and styrene in a one-pot manner. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Asymmetric Benzylic Allylic Alkylation Reaction of 3-Furfural Derivatives by Dearomatizative Dienamine Activation.

    Science.gov (United States)

    He, Xiao-Long; Zhao, Hui-Ru; Duan, Chuan-Qi; Han, Xu; Du, Wei; Chen, Ying-Chun

    2018-04-20

    The dearomatizative dienamine-type ortho-quinodimethane species are smoothly generated between 2-alkyl-3-furfurals and chiral secondary amine catalysts, which undergo asymmetric benzylic allylic alkylation reactions with 2-nitroallylic acetates efficiently. A spectrum of densely functionalized 3-furfural derivatives are delivered in moderate to high yields with good to excellent diastereo- and enantioselectivity (up to 98 % yield, >19:1 d.r., >99 % ee). The latent transformations allow the facile production of some enantioenriched architectures, such as 1,1,2,2-tetraarylethanes and triarylmethanes, which are not easily available from other protocols. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Cutting thin sheets of allyl diglycol carbonate (CR-39) with a CW CO2, laser

    International Nuclear Information System (INIS)

    Kukreja, L.M.; Bhawalkar, D.D.; Basu, C.; Goswami, J.N.

    1984-01-01

    Recent studies have shown that Allyl Diglycol Carbonate, commercially known as CR-39 (the most sensitive among etch track detectors) can detect relativistic oxygen and other heavier nuclei. We are using large sheets of special grade CR-39 (DOP) in our experiment in Space Shuttle-Spacelab-3. As CR-39 is a highly brittle substance, special care is required to cut CR-39 shetts, especially in case of large sheets and circular cuts. A study of cutting of CR-39 sheets using laser light is described in this paper. It has been found that this method is sufficiently fast to handle large number of sheets and also equally safe for big sheets. A maximum speed up to 200 cm/min with a 5 x 10 4 W/cm 2 laser is obtained during the present study. This study also shows that laser cutting does not affect the track properties of CR-39. (orig.)

  14. Highly Diastereoselective Indium-Mediated Allylation of Proline-Derived Hydrazones

    International Nuclear Information System (INIS)

    Satyender, Apuri; Jang, Doo Ok

    2013-01-01

    A highly diastereoselective indium-mediated addition reaction to L-proline-derived hydrazones has been developed. The method affords an efficient and general synthesis of homoallylic amines of high optically purity in high yields and diastereomeric ratios up to 98:2. It is well known that (S)-1-amino-2-methoxymethylpyrro-lidine and (S)-4-isopropyl- or (S)-4-phenylmethyl-oxa-zolidin-2-one-derived hydrazones have been used for metal-mediated diastereoselective allylation additions to produce chiral homoallylic amines. However, the optically pure hydrazine precursors are either commercially expensive and/or involve laborious synthetic procedures employing toxic reagents for their preparation. Thus, the design of novel classes of chiral hydrazines that would further broaden the scope of asymmetric synthesis to access optically pure homoallylic amines is highly desirable

  15. Mesoporous iron–manganese oxides for sulphur mustard and soman degradation

    Energy Technology Data Exchange (ETDEWEB)

    Štengl, Václav, E-mail: stengl@iic.cas.cz [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 Řež (Czech Republic); J.E. Purkyně University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem (Czech Republic); Grygar, Tomáš Matys [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 Řež (Czech Republic); J.E. Purkyně University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem (Czech Republic); Bludská, Jana [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 Řež (Czech Republic); Opluštil, František; Němec, Tomáš [Military Technical Institute of Protection Brno, Veslařská 230, 628 00 Brno (Czech Republic)

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ► New nanodispersive materials based on Fe and Mn oxides for degradations of warfare agents. ► The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min). ► One pot synthesis with friendly transformed to industrial conditions. -- Abstract: Substituted iron(III)–manganese(III, IV) oxides, ammonio-jarosite and birnessite, were prepared by a homogeneous hydrolysis of potassium permanganate and iron(III) sulphate with 2-chloroacetamide and urea, respectively. Synthesised oxides were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy and scanning electron microscopy (SEM). The oxides were taken for an experimental evaluation of their reactivity against sulphur mustard (HD) and soman (GD). When ammonio-jarosite formation is suppressed by adding urea to the reaction mixture, the reaction products are mixtures of goethite, schwertmannite and ferrihydrite, and their degradation activity against soman considerably increases. The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min) were observed for FeMn{sub 7}5 with 32.6 wt.% Fe (36.8 wt.% Mn) and FeMn{sub 3}7U with 60.8 wt.% Fe (10.1 wt.% Mn) samples, respectively.

  16. Overexpressing both ATP sulfurylase and selenocysteine methyltransferase enhances selenium phytoremediation traits in Indian mustard

    International Nuclear Information System (INIS)

    LeDuc, Danika L.; AbdelSamie, Manal; Montes-Bayon, Maria; Wu, Carol P.; Reisinger, Sarah J.; Terry, Norman

    2006-01-01

    A major goal of our selenium (Se) phytoremediation research is to use genetic engineering to develop fast-growing plants with an increased ability to tolerate, accumulate, and volatilize Se. To this end we incorporated a gene (encoding selenocysteine methyltransferase, SMT) from the Se hyperaccumulator, Astragalus bisulcatus, into Indian mustard (LeDuc, D.L., Tarun, A.S., Montes-Bayon, M., Meija, J., Malit, M.F., Wu, C.P., AbdelSamie, M., Chiang, C.-Y., Tagmount, A., deSouza, M., Neuhierl, B., Boeck, A., Caruso, J., Terry, N., 2004. Overexpression of selenocysteine methyltransferase in Arabidopsis and Indian mustard increases selenium tolerance and accumulation Plant Physiol. 135, 377-383.). The resulting transgenic plants successfully enhanced Se phytoremediation in that the plants tolerated and accumulated Se from selenite significantly better than wild type. However, the advantage conferred by the SMT enzyme was much less when Se was supplied as selenate. In order to enhance the phytoremediation of selenate, we developed double transgenic plants that overexpressed the gene encoding ATP sulfurylase (APS) in addition to SMT, i.e., APS x SMT. The results showed that there was a substantial improvement in Se accumulation from selenate (4 to 9 times increase) in transgenic plants overexpressing both APS and SMT. - Simultaneous overexpression of APS and SMT genes in Indian mustard greatly increases ability to accumulate selenate

  17. Solid-Phase Extraction of Sulfur Mustard Metabolites Using an Activated Carbon Fiber Sorbent.

    Science.gov (United States)

    Lee, Jin Young; Lee, Yong Han

    2016-01-01

    A novel solid-phase extraction method using activated carbon fiber (ACF) was developed and validated. ACF has a vast network of pores of varying sizes and microporous structures that result in rapid adsorption and selective extraction of sulfur mustard metabolites according to the pH of eluting solvents. ACF could not only selectively extract thiodiglycol and 1-methylsulfinyl-2-[2-(methylthio)-ethylsulfonyl]ethane eluting a 9:1 ratio of dichloromethane to acetone, and 1,1'-sulfonylbis[2-(methylsulfinyl)ethane] and 1,1'-sulfonylbis- [2-S-(N-acetylcysteinyl)ethane] eluting 3% hydrogen chloride in methanol, but could also eliminate most interference without loss of analytes during the loading and washing steps. A sample preparation method has been optimized for the extraction of sulfur mustard metabolites from human urine using an ACF sorbent. The newly developed extraction method was applied to the trace analysis of metabolites of sulfur mustard in human urine matrices in a confidence-building exercise for the analysis of biomedical samples provided by the Organisation for the Prohibition of Chemical Weapons. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

  18. Effect of mustard gas hydrolysis products on the development of water-bloom forming cyanobacteria

    Directory of Open Access Journals (Sweden)

    Zaytseva Tatyana

    2017-03-01

    Full Text Available Mustard gas and its hydrolysis products (MGHP belong to stable organochlorine compounds with high toxicity and broad spectrum of activity. Since the Second World War many aquatic ecosystems including the Baltic and the Adriatic Sea as well as the coastal waters of Japan, the USA, the UK, Australia have been contaminated with mustard gas due to the dumping of chemical weapon. Mustard gas and its hydrolysis products have a negative impact on aquatic life including microbiota. The aim of this work was to define the effect of MGHP on the growth, photosynthetic activity and synthesis of secondary metabolites by water-bloom forming cyanobacteria Trichormus variabilis, Aphanizomenon flos-aquae, Microcystis aeruginosa, Nodularia spumigena. Microbiological, chromatographic, spectrophotometric methods were used. The growth inhibition test with MGHP on cyanobacteria showed influence on the concentration EC50 within the range of 5.5 – 11.2 mg of organochlorine compounds (ОCC per liter. The synthesis of chlorophyll a was also decreased. It was shown that the chlorophyll synthesis was more sensitive to MGHP than the growth of cyanobacteria. NGHP induced enhanced excretion of exopolysaccharides. Low concentration of MGHP – 0.3 mg OCC/l - promoted the growth of toxigenic cyanobacterium Microcystis aeruginosa and increased microcystin-LR concentration in the environment. enhanced excretion of such metabolites as polysaccharides and cyanotoxins has a serious negative impact on water pollution due to MGHP.

  19. Remediation Of Cadmium And Lead Contamination In Mustard-Maize Cropping System

    Directory of Open Access Journals (Sweden)

    Amrit Kumar Jha

    2017-10-01

    Full Text Available Farmers field trial was conducted at Patratu Ramgarh to study the effect of lime compost plant growth promoting rhizobacteria and arbuscular mycorrhizal fungi for remediation of high trace metal levels in mustard-maize cropping system. Results reveal that microbial inoculants with or without vermicompost increased the trace metal removal however vermicompost alone decreased the removal. Vermicompost lime and lime vermicompost significantly reduced the total Cd uptake by mustard and maize. Inoculation with Glomus mossae resulted in elevated level of Cd in mustard and maize plants. Total trace metal content in soil was significantly reduced by microbial inoculation alone or that in combination with vermicompost. However DTPA-extractable trace metals decreased with addition of amendments as well as inoculation of microbes. Glomus mossae was most effective in remediating the trace metals. under this study the total metal content reduced effectively by their inoculation alone while inoculation along with vermicompost resulted in reducing the DTPA-extractable fraction more effectively. The extent of reduction in total Cd and Pb after harvest of both crops was 6 to 26 and 5 to 12 per cent respectively over control. However the corresponding values observed for DTPA extractable Cd and Pb was 53 to 65 and 20 to 32 per cent over control in microbial inoculation and 46 to 47 and 14 to 17 per cent in case of amendments.

  20. In-situ degradation of sulphur mustard using (1R)-(-)-(camphorylsulphonyl) oxaziridine impregnated adsorbents

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Abha, E-mail: abha_052002@yahoo.co.in [Industrial Toxicology Research Centre, Mahatam Gandhi Marg, Lucknow, UP (India); Saxena, Amit; Singh, Beer [Defence Research and Development Establishment, Jhansi Road, Gwalior, MP (India)

    2009-12-30

    Bis-2-chloroethyl sulphide (sulphur mustard or HD) is an extremely toxic and persistent chemical warfare agent. For in-situ degradation of HD and its analogues (simulants), i.e., dibutyl sulphide (DBS) and ethyl 2-hydroxyethyl sulphide (HEES), different adsorbents systems loaded with (1R)-(-)-(camphorylsulphonyl) oxaziridine were prepared. Solution of sulphur mustard and its simulants was prepared in carbon tetrachloride and taken for uniform adsorption on the impregnated systems using incipient volume. Degradation kinetics monitored by GC/FID were found to be first-order. The half-life of degradation reactions for simulants was obtained in less than 30 and for HD in 120 min. From the studied kinetics it was observed that reaction was very rapid with simulants and decreased rate was found for HD. The order of reactivity of MgO/Oxa system for HD and simulants was found to be DBS > HEES > HD. Reaction products of the oxidation reaction of simulants and HD on adsorbents were extracted in dichloromethane and analysed by GC-MS. The products were found to be non-toxic sulphoxide. The objective of the study is to develop a reactive adsorbent for in-situ degradation of sulphur mustard which could be used in nuclear biological and chemical (NBC) filtration systems.

  1. Temporal and spatial features of the formation of DNA adducts in sulfur mustard-exposed skin

    Energy Technology Data Exchange (ETDEWEB)

    Batal, Mohamed [Laboratoire «Lésions des Acides Nucléiques», Université Joseph Fourier – Grenoble 1, CEA/Institut Nanoscience et Cryogénie/SCIB, UMR-E3, Grenoble (France); Département de Toxicologie et Risques Chimiques, Unité de Brûlure Chimique, Institut de Recherche Biomédicale des Armées, Antenne de La Tronche (France); Boudry, Isabelle; Mouret, Stéphane; Wartelle, Julien; Emorine, Sandy; Bertoni, Marine [Département de Toxicologie et Risques Chimiques, Unité de Brûlure Chimique, Institut de Recherche Biomédicale des Armées, Antenne de La Tronche (France); Bérard, Izabel [Laboratoire «Lésions des Acides Nucléiques», Université Joseph Fourier – Grenoble 1, CEA/Institut Nanoscience et Cryogénie/SCIB, UMR-E3, Grenoble (France); Cléry-Barraud, Cécile [Département de Toxicologie et Risques Chimiques, Unité de Brûlure Chimique, Institut de Recherche Biomédicale des Armées, Antenne de La Tronche (France); and others

    2013-12-15

    Sulfur mustard (SM) is a chemical warfare agent that targets skin where it induces large blisters. DNA alkylation is a critical step to explain SM-induced cutaneous symptoms. We determined the kinetics of formation of main SM–DNA adducts and compare it with the development of the SM-induced pathogenesis in skin. SKH-1 mice were exposed to 2, 6 and 60 mg/kg of SM and treated skin was biopsied between 6 h and 21 days. Formation of SM DNA adducts was dose-dependent with a maximum immediately after exposure. However, adducts were persistent and still detectable 21 days post-exposure. The time-dependent formation of DNA adducts was also found to be correlated with the appearance of apoptotic cells. This temporal correlation suggests that these two early events are responsible for the severity of the damage to the skin. Besides, SM–DNA adducts were also detected in areas located next to contaminated zone, thus suggesting that SM diffuses in skin. Altogether, this work provides for the first time a clear picture of SM-induced genotoxicity using DNA adducts as a marker. - Highlights: • Sulfur mustard adducts are formed in DNA after skin exposure. • DNA damage formation is an early event in the pathological process of skin burn. • The amount of SM–DNA adducts is maximal at the earliest time point investigated. • Adducts are still detected 3 weeks after exposure. • Sulfur mustard diffuses in skin especially when large doses are applied.

  2. Mesoporous iron–manganese oxides for sulphur mustard and soman degradation

    International Nuclear Information System (INIS)

    Štengl, Václav; Grygar, Tomáš Matys; Bludská, Jana; Opluštil, František; Němec, Tomáš

    2012-01-01

    Graphical abstract: Display Omitted Highlights: ► New nanodispersive materials based on Fe and Mn oxides for degradations of warfare agents. ► The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min). ► One pot synthesis with friendly transformed to industrial conditions. -- Abstract: Substituted iron(III)–manganese(III, IV) oxides, ammonio-jarosite and birnessite, were prepared by a homogeneous hydrolysis of potassium permanganate and iron(III) sulphate with 2-chloroacetamide and urea, respectively. Synthesised oxides were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy and scanning electron microscopy (SEM). The oxides were taken for an experimental evaluation of their reactivity against sulphur mustard (HD) and soman (GD). When ammonio-jarosite formation is suppressed by adding urea to the reaction mixture, the reaction products are mixtures of goethite, schwertmannite and ferrihydrite, and their degradation activity against soman considerably increases. The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min) were observed for FeMn 7 5 with 32.6 wt.% Fe (36.8 wt.% Mn) and FeMn 3 7U with 60.8 wt.% Fe (10.1 wt.% Mn) samples, respectively.

  3. Modification of Bisphenol-A Based Bismaleimide Resin (BPA-BMI) with an Allyl-Terminated Hyperbranched Polyimide (AT-PAEKI)

    National Research Council Canada - National Science Library

    Qin, Haihu; Mather, Patrick T; Baek, Jong-Beom; Tan, Loon-Seng

    2006-01-01

    As a continuation of previous work involving synthesis of an allyl-functionalized hyperbranched polyimide, AT-PAEKI, we have studied the use of this reactive polymer as a modifier of bisphenol-A based...

  4. Enantioselective allylations of selected alpha, beta, gamma, delta-unsaturated aldehydes by axially chiral N,N'-dioxides. Synthesis of the left-hand part of papulacandin D

    Czech Academy of Sciences Publication Activity Database

    Vlašaná, K.; Betík, R.; Valterová, Irena; Nečas, D.; Kotora, M.

    2016-01-01

    Roč. 3, č. 3 (2016), s. 301-305 ISSN 2213-3372 Institutional support: RVO:61388963 Keywords : allylation * aldehyde * Lewis base * asymmetric synthesis * organocatalysis * homoallylic alcohol s Subject RIV: CC - Organic Chemistry

  5. Living catalyzed-chain-growth polymerization and block copolymerization of isoprene by rare-earth metal allyl precursors bearing a constrained-geometry-conformation ligand.

    Science.gov (United States)

    Jian, Zhongbao; Cui, Dongmei; Hou, Zhaomin; Li, Xiaofang

    2010-05-07

    Aminophenyl functionalized cyclopentadienyl ligated rare-earth metal allyl mediated cationic systems display high cis-1,4 selectivity for the polymerization of isoprene, and living reversible and rapid chain transfer to aluminium additives.

  6. Oxidation reaction of 4-allyl-4-hydroperoxy-2-methoxycyclohexa-2,5-dienone in the presence of potassium permanganate without a co-oxidant

    Directory of Open Access Journals (Sweden)

    Mehmet Serdar Gültekin

    2016-12-01

    Full Text Available 4-Allyl-4-hydroperoxy-2-methoxycyclohexa-2,5-dienone (5 was synthesized by photooxygenation of commercially available Eugenol in the presence of tetraphenylporphyrin (TPP as a singlet oxygen sensitizer. The brief and one-pot syntheses of some natural product skeletons were conducted using the corresponding allylic hydroperoxide at different temperatures (0 oC and room temperature with potassium permanganate (KMnO 4 in mild condition at N 2(g atm.

  7. Asymmetric allylation of α-ketoester-derived N-benzoylhydrazones promoted by chiral sulfoxides/N-oxides Lewis bases: highly enantioselective synthesis of quaternary α-substituted α-allyl-α-amino acids.

    Science.gov (United States)

    Reyes-Rangel, Gloria; Bandala, Yamir; García-Flores, Fred; Juaristi, Eusebio

    2013-09-01

    Chiral sulfoxides/N-oxides (R)-1 and (R,R)-2 are effective chiral promoters in the enantioselective allylation of α-keto ester N-benzoylhydrazone derivatives 3a-g to generate the corresponding N-benzoylhydrazine derivatives 4a-g, with enantiomeric excesses as high as 98%. Representative hydrazine derivatives 4a-b were subsequently treated with SmI2, and the resulting amino esters 5a-b with LiOH to obtain quaternary α-substituted α-allyl α-amino acids 6a-b, whose absolute configuration was assigned as (S), with fundament on chemical correlation and electronic circular dichroism (ECD) data. © 2013 Wiley Periodicals, Inc.

  8. Determination of mustard and lewisite related compounds in abandoned chemical weapons (Yellow shells) from sources in China and Japan.

    Science.gov (United States)

    Hanaoka, Shigeyuki; Nomura, Koji; Wada, Takeharu

    2006-01-06

    Knowledge of the states of the contents in chemical munitions that Japanese Imperial Forces abandoned at the end of World War II in Japan and China is gravely lacking. To unearth and recover these chemical weapons and detoxify the contents safely, it is essential to establish analytical procedures to definitely determine the CWA contents. We established such a procedure and applied it to the analysis of chemicals in the abandoned shells. Yellow shells are known to contain sulfur mustard, lewisite, or a mixture of both. Lewisite was analyzed without thiol derivatization, because it and its decomposition products yield the same substances in the derivatization. Analysis using our new procedure showed that both mustard and lewisite remained as the major components after the long abandonment of nearly 60 years. The content of mustard was 43% and that of lewisite 55%. The viscous material found was suggested to be mostly oligomers of mustard. Comparison of the components in the Yellow agents with mustard recovered in both Japan and China showed a difference in the impurities between the CWAs produced by the former Imperial navy and those by the former Imperial army.

  9. DNA-directed alkylating ligands as potential antitumor agents: sequence specificity of alkylation by intercalating aniline mustards.

    Science.gov (United States)

    Prakash, A S; Denny, W A; Gourdie, T A; Valu, K K; Woodgate, P D; Wakelin, L P

    1990-10-23

    The sequence preferences for alkylation of a series of novel parasubstituted aniline mustards linked to the DNA-intercalating chromophore 9-aminoacridine by an alkyl chain of variable length were studied by using procedures analogous to Maxam-Gilbert reactions. The compounds alkylate DNA at both guanine and adenine sites. For mustards linked to the acridine by a short alkyl chain through a para O- or S-link group, 5'-GT sequences are the most preferred sites at which N7-guanine alkylation occurs. For analogues with longer chain lengths, the preference of 5'-GT sequences diminishes in favor of N7-adenine alkylation at the complementary 5'-AC sequence. Magnesium ions are shown to selectively inhibit alkylation at the N7 of adenine (in the major groove) by these compounds but not the alkylation at the N3 of adenine (in the minor groove) by the antitumor antibiotic CC-1065. Effects of chromophore variation were also studied by using aniline mustards linked to quinazoline and sterically hindered tert-butyl-9-aminoacridine chromophores. The results demonstrate that in this series of DNA-directed mustards the noncovalent interactions of the carrier chromophores with DNA significantly modify the sequence selectivity of alkylation by the mustard. Relationships between the DNA alkylation patterns of these compounds and their biological activities are discussed.

  10. Childhood physical abnormalities following paternal exposure to sulfur mustard gas in Iran: a case-control study

    Directory of Open Access Journals (Sweden)

    Khademolhosseini Seyyed M

    2010-07-01

    Full Text Available Abstract Background Mustard gas, a known chemical weapon, was used during the Iran-Iraq war of 1980-1988. We aimed to determine if exposure to mustard gas among men was significantly associated with abnormalities and disorders among progenies. Methods Using a case-control design, we identified all progenies of Sardasht men (exposed group, n = 498, who were born at least nine months after the exposure, compared to age-matched controls in Rabat, a nearby city (non-exposed group, n = 689. We conducted a thorough medical history, physical examination, and appropriate paraclinical studies to detect any physical abnormality and/or disorder. Given the presence of correlated data, we applied Generalized Estimating Equation (GEE multivariable models to determine associations. Results The overall frequency of detected physical abnormalities and disorders was significantly higher in the exposed group (19% vs. 11%, Odds Ratio [OR] 1.93, 95% Confidence Interval [CI], 1.37-2.72, P = 0.0002. This was consistent across sexes. Congenital anomalies (OR 3.54, 95% CI, 1.58-7.93, P = 0.002 and asthma (OR, 3.12, 95% CI, 1.43-6.80, P = 0.004 were most commonly associated with exposure. No single abnormality was associated with paternal exposure to mustard gas. Conclusion Our study demonstrates a generational effect of exposure to mustard gas. The lasting effects of mustard gas exposure in parents effects fertility and may impact child health and development in the long-term.

  11. Endogenous Phenolics in Hulls and Cotyledons of Mustard and Canola: A Comparative Study on Its Sinapates and Antioxidant Capacity

    Directory of Open Access Journals (Sweden)

    Shyamchand Mayengbam

    2014-08-01

    Full Text Available Endogenous sinapic acid (SA, sinapine (SP, sinapoyl glucose (SG and canolol (CAN of canola and mustard seeds are the potent antioxidants in various lipid-containing systems. The study investigated these phenolic antioxidants using different fractions of canola and mustard seeds. Phenolic compounds were extracted from whole seeds and their fractions: hulls and cotyledons, using 70% methanol by the ultrasonication method and quantified using HPLC-DAD. The major phenolics from both hulls and cotyledons extracts were SP, with small amounts of SG, and SA with a significant difference of phenolic contents between the two seed fractions. Cotyledons showed relatively high content of SP, SA, SG and total phenolics in comparison to hulls (p < 0.001. The concentration of SP in different fractions ranged from 1.15 ± 0.07 to 12.20 ± 1.16 mg/g and followed a decreasing trend- canola cotyledons > mustard cotyledons > mustard seeds > canola seeds > mustard hulls > canola hulls. UPLC-tandem Mass Spectrometry confirmed the presence of sinapates and its fragmentation in these extracts. Further, a high degree of correlation (r = 0.93 was noted between DPPH scavenging activity and total phenolic content.

  12. One-pot synthesis of enantiomerically pure N-protected allylic amines from N-protected α-amino esters

    Directory of Open Access Journals (Sweden)

    Gastón Silveira-Dorta

    2016-05-01

    Full Text Available An improved protocol for the synthesis of enantiomerically pure allylic amines is reported. N-Protected α-amino esters derived from natural amino acids were submitted to a one-pot tandem reduction–olefination process. The sequential reduction with DIBAL-H at −78 °C and subsequent in situ addition of organophosphorus reagents yielded the corresponding allylic amines without the need to isolate the intermediate aldehyde. This circumvents the problem of instability of the aldehydes. The method tolerates well both Wittig and Horner–Wadsworth–Emmons organophosphorus reagents. A better Z-(diastereoselectivity was observed when compared to the previous one-pot method. The (diastereoselectivity of the process was affected neither by the reaction solvent nor by the amount of DIBAL-H employed. The method is compatible with the presence of free hydroxy groups as shown with serine and threonine derivatives.

  13. Concentration- and Time-Dependent Effects of Isothiocyanates Produced from Brassicaceae Shoot Tissues on the Pea Root Rot Pathogen Aphanomyces euteiches

    NARCIS (Netherlands)

    Hossain, S.; Bergkvist, G.; Berglund, K.; Glinwood, R.; Kabouw, P.; Martensson, A.; Persson, P.

    2014-01-01

    Isothiocyanates (ITCs) hydrolyzed from glucosinolates (GSLs) in Brassicaceae tissue are toxic to soil organisms. In this study, the effect of aliphatic and aromatic ITCs from hydrated dry Brassicaceae shoot tissues on the mycelium and oospores of the pea root rot pathogen Aphanomyces euteiches was

  14. Optimizing isothiocyanate formation during enzymatic glucosinolate breakdown by adjusting pH value, temperature and dilution in Brassica vegetables and Arabidopsis thaliana

    NARCIS (Netherlands)

    Hanschen, F.; Klopsch, R.; Oliviero, T.; Schreiner, M.; Verkerk, R.; Dekker, M.

    2017-01-01

    Consumption of glucosinolate-rich Brassicales vegetables is associated with a decreased risk of cancer with enzymatic hydrolysis of glucosinolates playing a key role. However, formation of health-promoting isothiocyanates is inhibited by the epithiospecifier protein in favour of nitriles and

  15. Evaluation of Growth Indices and Estimation Seed Yield Loss Threshold of Canola in Response to Various Densities of Crop and Wild Mustard

    Directory of Open Access Journals (Sweden)

    Z Anafjeh

    2012-02-01

    Full Text Available ABSTRACT In order to study the effect of various densities of wild mustard (Sinapis arvensis L. on growth indices of Canola (Brassica napus L. in climate of Molathani, Ahvaz, an experiment was conducted in the experimental field of Ramin Agricultural and Natural Resources University, in 2006-2007. The split-plot set of treatments was arranged within randomized complete block design with four replications. Treatments included of wild mustard at five levels (0, 7, 14, 21 and 35 plants m2 and Canola at three densities (60, 80 and 100 plants m2. The results showed that the increase in mustard density rates lead to decreasing total dry matter, leaf area index, crop growth rate, relative growth rate and mean pod dry matter in three canola densities (60, 80 and 100 plants m2. Somewhat the lowest growth indices was obtained in 35 plants mustard (that is the highest mustard density. In addition damage rate of mustard decreased canola seed yield for 7, 14, 21 and 35 plants mustard up to 61, 71, 76 and 91%, respectively. Keywords: Plant density, Competition, Yield loss threshold, Growth indices, Canola, Mustard

  16. Diagnosis and dosimetry of exposure to sulfur mustard: Development of a standard operating procedure for hemoglobin adducts: Exploratory research on albumin and keratin adducts

    NARCIS (Netherlands)

    Noort, D.; Fidder, A.; Jong, L.P.A. de; Schans, G.P. van der; Benschop, H.P.

    2000-01-01

    A standard operating procedure (SOP) for determination of the sulfur mustard adduct to the N-terminal valine in hemoglobin was developed. By using this SOP, it was found that the Nterminal valine adduct in globin of hairless guinea pigs and marmosets which had been exposed to sulfur mustard (0.5

  17. Alkylation of human serum albumin by sulfur mustard in vitro and in vivo : Mass spectrometric analysis of a cysteine adduct as a sensitive biomarker of exposure

    NARCIS (Netherlands)

    Noort, D.; Hulst, A.G.; Jong, L.P.A. de; Benschop, H.P.

    1999-01-01

    To develop a mass spectrometric assay for the detection of sulfur mustard adducts with human serum albumin, the following steps were performed: quantitation of the binding of the agent to the protein by using [14C] sulfur mustard and analysis of acidic and tryptic digests of albumin from blood after

  18. Clinical practice guidelines for prevention, diagnosis and management of early and delayed-onset ocular injuries due to mustard gas exposure

    Directory of Open Access Journals (Sweden)

    Zhale Rajavi

    2017-01-01

    Conclusion: Considering the lack of CPGs for the prevention, diagnosis, and management of mustard gas-induced keratitis, these recommendations would be useful to prevent the serious ocular complications of mustard gas and standardize eye care services to the affected individuals.

  19. Formation of Ketenimines via the Palladium-Catalyzed Decarboxylative π-Allylic Rearrangement of N-Alloc Ynamides.

    Science.gov (United States)

    Alexander, Juliana R; Cook, Matthew J

    2017-11-03

    A new approach for the formation of ketenimines via a decarboxylative allylic rearrangement pathway that does not require strong stabilizing or protecting groups has been developed. The products can be readily hydrolyzed into their corresponding secondary amides or reacted with sulfur ylides to perform an additional [2,3]-Wittig process. Mechanistic studies suggest an outer-sphere process in which reductive alkylation is rate-limiting.

  20. Eosin Y-catalyzed, visible-light-promoted carbophosphinylation of allylic alcohols via a radical neophyl rearrangement.

    Science.gov (United States)

    Yin, Yao; Weng, Wei-Zhi; Sun, Jian-Guo; Zhang, Bo

    2018-03-28

    A visible-light-promoted phosphinylation of allylic alcohols with concomitant 1,2-aryl migration is described. This transformation proceeds smoothly under metal-free and mild conditions by using an inexpensive organic dye, eosin Y, as the photocatalyst, affording various β-aryl-γ-ketophosphine oxides in moderate to good yields. Mechanistic studies suggested that the 1,2-aryl migration proceeded through a radical (neophyl) rearrangement.

  1. Low-temperature synthesis of allyl dimethylamine by selective heating under microwave irradiation used for water treatment

    International Nuclear Information System (INIS)

    Tian Binghui; Luan Zhaokun; Li Mingming

    2005-01-01

    Low-temperature synthesis of allyl dimethylamine (ADA) by selective heating under microwave irradiation (MI) used for water treatment is investigated. The effect of MI, ultrasound irradiation (UI) and conventional heating on yield of ADA, reaction time and the flocculation efficiency of polydiallyl dimethylammunion chloride (PDADMAC) prepared form ADA were studied. The results show that by selective heating at low temperature, MI not only increases yield of ADA and reduces reaction time, but also greatly enhances the flocculation efficiency of PDADMAC

  2. Oxidant-free Rh(III)-catalyzed direct C-H olefination of arenes with allyl acetates.

    Science.gov (United States)

    Feng, Chao; Feng, Daming; Loh, Teck-Peng

    2013-07-19

    Rh(III)-catalyzed direct olefination of arenes with allyl acetate via C-H bond activation is described using N,N-disubstituted aminocarbonyl as the directing group. The catalyst undergoes a redox neutral process, and high to excellent yields of trans-products are obtained. This protocol exhibits a wide spectrum of functionality compatibility because of the simple reaction conditions employed and provides a highly effective synthetic method in the realm of C-H olefination.

  3. Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study.

    Science.gov (United States)

    Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan

    2015-09-21

    Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au-allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

  4. Fluorescein isothiocyanate and rhodamine B dye encapsulated mesoporous SiO2 for applications of blue LED excited white LED

    Science.gov (United States)

    Das, Sourav; Manam, J.

    2018-05-01

    In this work, the fluorescein isothiocyanate (FITC) and rhodamine B (RhB) dyes were encapsulated in mesoporous silica nanoparticles (MSNp). The MSNp-FITC-RhB nanohybrids phosphor showed a dichromatic PL emission at green region and orange region when excited at 460 nm. A Forster Resonance Energy Transfer (FRET) was observed from FITC to RhB. The materials were further characterized by XRD, FTIR, TEM, and temperature dependent photoluminescence. The CIE coordinates were tuned from greenish yellow to the orange region and quantum yield was reached 52.04% based on FRET. So by combining the MSNp-FITC-RhB nanohybrids phosphor with the blue LED chip, the white light emission with flexible Color Correlated Temperature and improved Color Rendering Index can be obtained.

  5. Long-Term Outcome of Mustard/Senning Correction for Transposition of the Great Arteries in Sweden and Denmark

    DEFF Research Database (Denmark)

    Vejlstrup, Niels; Sørensen, Keld; Mattsson, Eva

    2015-01-01

    and leaves the right ventricle as the systemic ventricle. The Mustard and Senning cohort is now well into adulthood and we begin to see the long-term outcome. METHODS AND RESULTS: All the 6 surgical centers that performed Mustard and Senning operations in Sweden and Denmark identified all operated TGA...... patients. Information about death was obtained in late 2007 and early 2008 from the Danish and Swedish Centralised Civil Register by using the patients' unique national Civil Registration Numbers. Four hundred sixty-eight patients undergoing the atrial switch operation were identified. Perioperative 30-day...... of long-term outcome (hazard ratio, 1.90; 95% confidence interval, 1.05-3.46, P=0.04), once the TGA patient has survived the perioperative period. The risk of reoperation was correlated to the presence of associated defects and where the first Mustard/Senning operation was performed. CONCLUSIONS: The long...

  6. The stibian mustard gold from the Kriván¿ Au deposit,Tatry Mts., Slovak Republic

    DEFF Research Database (Denmark)

    Makovicky, Emil; Martin, Chovan; František, Bakos

    2007-01-01

    The Kriván Au-Sb mineralization is hosted in several subhorizontal variscan mylonite zones located in granitoid rocks. Ore minerals occur in thin lens-shaped quartz veinlets. Albite, chlorite, calcite, muscovite and tourmaline are minor gangue minerals. Four mineral assemblages have been recognized...... - (1) pyrite-arsenopyrite-gold, (2) stibnite-sulfosalts-sphalerite, (3) tetrahedrite- chalcopyrite-electrum, (4) supergene minerals. Isometric and irregular grains of mustard gold are 0.X mm in size. In refl ected light it is isotropic with low refl ectivity and orange-red or brown-yellow color...... with pores more or less fi lled by oxidation products of Sb and Fe. Compositionally it does not conform with stibian mustard gold from Yakutia and Bolivia, approximately AuSb1.4O2.1, derived from decomposition of aurostibite, but it conforms with mustard gold from Krásná Hora, Czech Republic. For this type...

  7. Study on remediation for uranium contaminated soils enhanced by chelator using brassica mustard

    International Nuclear Information System (INIS)

    Wan Qinfang; Pan Ning; Jin Yongdong; Xia Chuanqin

    2012-01-01

    Screening of perfect hyperaccumulators is the key to the application of this technology. Through the previous stage study, mustard was found to be good at absorption and accumulation of uranium among 51 species, the plant grows fast with wide adaptability and large biomass. Researches will focus on the following two aspects: 1. Simulating U- contaminated soils was prepared by two different ways to add uranium. (1). UO 2 (NO 3 ) 2 . 6H 2 O solution was sprayed into soil when the plant was grown in the soil; (2). Above U-contaminated soils after planting and placed for a year. Study on whether the way of adding uranium can effect mustard accumulate uranium. Results found: in the first Phytoremediation, U-contaminated concentration at 100 mg/kg, U concentration in shoots reaches 1103.42 mg/kg, roots reach 1909.49 mg/kg, annual removal rate is 7.81%; in the second Phytoremediation, U-contaminated concentration at 100 mg/kg, U concentration in shoots reach 295.83 mg/kg, roots reach 268.42 mg/kg, annual removal rate is 2.52%. Led to the difference between the twice remediation is the speciation of uranium m soils has changed, respectively, Tessier-five step continuous extraction method for determination of uranium speciation in soils and found available uranium (exchangeable uranium, uranium carbonate) in the soil of the first phytoremediation was 52% higher than the second phytoremediation. 2. Study on chelators (Citric acids, Malic acids) and soil amendments (Organic fertilizer, microbe fertilizer. Humic acid organic fertilizer, Urea) whether effect mustard accumulate uranium, found organic fertilizer can reduce shoots accumulate uranium, Citric acid and microbe fertilizer increase shoots enrichment of uranium. (authors)

  8. Nitrogen mustard (Chlorambucil) has a negative influence on early vascular development

    International Nuclear Information System (INIS)

    Schmidt, Annette; Boelck, Birgit; Jedig, Maria; Steinritz, Dirk; Balszuweit, Frank; Kehe, Kai; Bloch, Wilhelm

    2009-01-01

    The sulphur and nitrogen mustards are strong alkylating agents, which induces inflammations of the skin including blistering right up to ulcerations. Depending on the severity, the wounds may need weeks to heal. In the past it was shown that sulphur mustard has a destructive effect on endothelial precursor cells, which have been shown to play a pivotal role in the wound healing reaction by inducing neovascularisation. However, for these alkylating agents as well as for sulphur mustard nothing is known about their effects on endothelial precursors. Therefore, we investigated and compared the influence of Chlorambucil on proliferation, apoptosis and differentiation of endothelial cells in intact mouse embryoid bodies (EB). EBs were treated at different developmental stages and with different periods of Chlorambucil treatment. It was found that in each developmental stage and under each treatment period's Chlorambucil has an extremely negative effect on the vascularisation with a vessel reduction of around 99%. Of particular importance was the negative effect of treatment around day 3 of the development. On this day we found 377 vessels under control conditions but only 1.6 vessels under 24 h treatment of Chlorambucil. At this point in time many endothelial precursors can be found in the EB. Moreover, a negative effect on all stem cells was evident at this point in time, shown by an extreme reduction in EB size with 17.9 mm 2 for the control and only 1.55 mm 2 under Chlorambucil treatment. This negative effect on the vascularisation, on endothelial precursors but also on stem cells in general is of possible importance for impaired wound healing.

  9. DNA damage in internal organs after cutaneous exposure to sulphur mustard

    International Nuclear Information System (INIS)

    Batal, Mohamed; Boudry, Isabelle; Mouret, Stéphane; Cléry-Barraud, Cécile; Wartelle, Julien; Bérard, Izabel; Douki, Thierry

    2014-01-01

    Sulphur mustard (SM) is a chemical warfare agent that attacks mainly skin, eye and lungs. Due to its lipophilic properties, SM is also able to diffuse through the skin and reach internal organs. DNA represents one of the most critical molecular targets of this powerful alkylating agent which modifies DNA structure by forming monoadducts and biadducts. These DNA lesions are involved in the acute toxicity of SM as well as its long-term carcinogenicity. In the present work we studied the formation and persistence of guanine and adenine monoadducts and guanine biadducts in the DNA of brain, lungs, kidneys, spleen, and liver of SKH-1 mice cutaneously exposed to 2, 6 and 60 mg/kg of SM. SM-DNA adducts were detected in all studied organs, except in liver at the two lowest doses. Brain and lungs were the organs with the highest level of SM-DNA adducts, followed by kidney, spleen and liver. Monitoring the level of adducts for three weeks after cutaneous exposure showed that the lifetime of adducts were not the same in all organs, lungs being the organ with the longest persistence. Diffusion from skin to internal organs was much more efficient at the highest compared to the lowest dose investigated as the result of the loss of the skin barrier function. These data provide novel information on the distribution of SM in tissues following cutaneous exposures and indicate that brain is an important target. - Highlights: • Sulphur mustard reaches internal organs after skin exposure • Adducts are detected in the DNA of internal organs • Brain is the organ with the highest level of DNA damage • The barrier function of skin is lost at high dose of sulphur mustard • DNA adducts persist in organs for 2 or 3 weeks

  10. DNA damage in internal organs after cutaneous exposure to sulphur mustard

    Energy Technology Data Exchange (ETDEWEB)

    Batal, Mohamed [Laboratoire « Lésions des Acides Nucléiques », Université Joseph Fourier – Grenoble 1/CEA/Institut Nanoscience et Cryogénie/SCIB, UMR-E3, Grenoble (France); Département de Toxicologie et Risques Chimiques, Unité de Brûlure Chimique, Institut de Recherche Biomédicale des Armées, Antenne de La Tronche, BP87, F-38702 La Tronche Cedex (France); Boudry, Isabelle; Mouret, Stéphane; Cléry-Barraud, Cécile; Wartelle, Julien [Département de Toxicologie et Risques Chimiques, Unité de Brûlure Chimique, Institut de Recherche Biomédicale des Armées, Antenne de La Tronche, BP87, F-38702 La Tronche Cedex (France); Bérard, Izabel [Laboratoire « Lésions des Acides Nucléiques », Université Joseph Fourier – Grenoble 1/CEA/Institut Nanoscience et Cryogénie/SCIB, UMR-E3, Grenoble (France); Douki, Thierry, E-mail: thierry.douki@cea.fr [Laboratoire « Lésions des Acides Nucléiques », Université Joseph Fourier – Grenoble 1/CEA/Institut Nanoscience et Cryogénie/SCIB, UMR-E3, Grenoble (France)

    2014-07-01

    Sulphur mustard (SM) is a chemical warfare agent that attacks mainly skin, eye and lungs. Due to its lipophilic properties, SM is also able to diffuse through the skin and reach internal organs. DNA represents one of the most critical molecular targets of this powerful alkylating agent which modifies DNA structure by forming monoadducts and biadducts. These DNA lesions are involved in the acute toxicity of SM as well as its long-term carcinogenicity. In the present work we studied the formation and persistence of guanine and adenine monoadducts and guanine biadducts in the DNA of brain, lungs, kidneys, spleen, and liver of SKH-1 mice cutaneously exposed to 2, 6 and 60 mg/kg of SM. SM-DNA adducts were detected in all studied organs, except in liver at the two lowest doses. Brain and lungs were the organs with the highest level of SM-DNA adducts, followed by kidney, spleen and liver. Monitoring the level of adducts for three weeks after cutaneous exposure showed that the lifetime of adducts were not the same in all organs, lungs being the organ with the longest persistence. Diffusion from skin to internal organs was much more efficient at the highest compared to the lowest dose investigated as the result of the loss of the skin barrier function. These data provide novel information on the distribution of SM in tissues following cutaneous exposures and indicate that brain is an important target. - Highlights: • Sulphur mustard reaches internal organs after skin exposure • Adducts are detected in the DNA of internal organs • Brain is the organ with the highest level of DNA damage • The barrier function of skin is lost at high dose of sulphur mustard • DNA adducts persist in organs for 2 or 3 weeks.

  11. Flavanone silibinin treatment attenuates nitrogen mustard-induced toxic effects in mouse skin

    Energy Technology Data Exchange (ETDEWEB)

    Jain, Anil K.; Tewari-Singh, Neera; Inturi, Swetha; Kumar, Dileep [Department of Pharmaceutical Sciences, University of Colorado Anschutz Medical Campus, Aurora, CO 80045 (United States); Orlicky, David J. [Department of Pathology, University of Colorado Anschutz Medical Campus, Aurora, CO 80045 (United States); Agarwal, Chapla [Department of Pharmaceutical Sciences, University of Colorado Anschutz Medical Campus, Aurora, CO 80045 (United States); White, Carl W. [Department of Pediatrics, University of Colorado Anschutz Medical Campus, Aurora, CO 80045USA (United States); Agarwal, Rajesh, E-mail: Rajesh.Agarwal@UCDenver.edu [Department of Pharmaceutical Sciences, University of Colorado Anschutz Medical Campus, Aurora, CO 80045 (United States)

    2015-05-15

    Currently, there is no effective antidote to prevent skin injuries by sulfur mustard (SM) and nitrogen mustard (NM), which are vesicating agents with potential relevance to chemical warfare, terrorist attacks, or industrial/laboratory accidents. Our earlier report has demonstrated the therapeutic efficacy of silibinin, a natural flavanone, in reversing monofunctional alkylating SM analog 2-chloroethyl ethyl sulfide-induced toxic effects in mouse skin. To translate this effect to a bifunctional alkylating vesicant, herein, efficacy studies were carried out with NM. Topical application of silibinin (1 or 2 mg) 30 min after NM exposure on the dorsal skin of male SKH-1 hairless mice significantly decreased NM-induced toxic lesions at 24, 72 or 120 h post-exposure. Specifically, silibinin treatment resulted in dose-dependent reduction of NM-induced increase in epidermal thickness, dead and denuded epidermis, parakeratosis and microvesication. Higher silibinin dose also caused a 79% and 51%reversal in NM-induced increases in myeloperoxidase activity and COX-2 levels, respectively. Furthermore, silibinin completely prevented NM-induced H2A.X phosphorylation, indicating reversal of DNA damage which could be an oxidative DNA damage as evidenced by high levels of 8-oxodG in NM-exposed mouse skin that was significantly reversed by silibinin. Together, these findings suggest that attenuation of NM-induced skin injury by silibinin is due to its effects on the pathways associated with DNA damage, inflammation, vesication and oxidative stress. In conclusion, results presented here support the optimization of silibinin as an effective treatment of skin injury by vesicants. - Highlights: • Silibinin treatment attenuated nitrogen mustard (NM)-induced skin injury. • Silibinin affects pathways associated with DNA damage, inflammation and vesication. • The efficacy of silibinin could also be associated with oxidative stress. • These results support testing and optimization of

  12. Tracer studies on P use efficiency by mustard (Brassica juncea L.), safflower (Carthamus tinctorius L.) and chickpea (Cicer arietinum L.)

    International Nuclear Information System (INIS)

    Singh, S.; Kamath, M.B.

    1991-01-01

    Mustard and chickpea derived a large fraction of their P requirement from applied phosphate compared to safflower crop at flowering. Consequently mean per cent P utilization was maximum in mustard (17.7) followed by chickpea (13.0) and safflower (9.5). However, P uptake at maturity was higher for oilseeds than for the pulse. Grain yield response per kg of applied P was higher at lower rate of P application regardless of the crop. (author). 11 refs., 4 tabs., 2 figs

  13. New high yielding mutant varieties of mustard (Brassica campestris L. var. yellow sarson)

    International Nuclear Information System (INIS)

    Rahman, A.; Das, M.L.; Pathan, A.J.

    1992-01-01

    Mutation breeding work at the Bangladesh Institute of Nuclear Agriculture has been successful with the development of a number of promising mutants and with the release of two mutant varieties of mustard (Brassica campestris L. var. Yellow Sarson), Agrani and Safal, for commercial cultivation in Bangladesh. The mutant varieties have higher seed and oil yield with higher biomass production, tolerance to Alternaria blight and aphid under field conditions. The average seed yield of the varieties is 1726 and 1754 kg/ha as compared to 1447 kg/ha of the best check Sonali. These varieties have 42-43 per cent oil in the seed. (author). 7 refs., 3 tabs

  14. The Effects of Mixed Source Fertilizer Application on Vertisol Fertility and Growth of Mustard

    Directory of Open Access Journals (Sweden)

    Jauhari Syamsiyah

    2017-09-01

    Full Text Available Soil fertility is a crucial factor determining the growth and yield of plants. The increase of nutrient content and availability in soil can be achieved by fertilization. A field experiment was conducted using a Randomized Completely Block Design (RCBD with two factors and three replications in order to study the effects of Mixed Source of Fertilizer (MSF application on the nutrient contents in Vertisol and its relationship to the growth and yield of mustard. The first factor was the three MSF formulas (F1, F2, F3 and second factor was the doses of MSF (0; 2.5; 5.0; 7.5; 10 Mg ha-1 applied to the soil. At the end of the experiment, the soil pH, CEC, organic-C, total-N, available-P and exchangeable-K contents were measured. The results show that there are no significant differences on the soil chemical characteristics, such as pH, organic-C content, available-P, exchangeable-K, -Ca and -Mg measured after application of different MSF formulas to the soil. Meanwhile, the increase of MSF doses applied to the soil significantly increases organic-C content, total-N, available-P and exchangeable-K in the soil. The significant increase of available-P (by 29.13% and total-N (by 24.1% occured after application of MSF at 5.0 Mg ha-1 and the increase of exchangeable-K (by 50% is achieved after application of 7.5 Mg ha-1, in comparison to that without MSF application. The height and fresh weight of mustard increase in accordance with the increase of MSF doses applied. The application of 10.0 Mg ha-1 MSF results in the highest height and fresh weight of the mustard up to 63.9% and 620%, respectively. The height and fresh weight of mustard are positively correlated to the total-N, available-P and exchangeable-K in the soil. The MSF is an alternative fertilizer that can be used to improve Vertisol fertility and plant growth.

  15. Cost-effectiveness of "golden mustard" for treating vitamin A deficiency in India.

    Directory of Open Access Journals (Sweden)

    Jeffrey Chow

    Full Text Available BACKGROUND: Vitamin A deficiency (VAD is an important nutritional problem in India, resulting in an increased risk of severe morbidity and mortality. Periodic, high-dose vitamin A supplementation is the WHO-recommended method to prevent VAD, since a single dose can compensate for reduced dietary intake or increased need over a period of several months. However, in India only 34 percent of targeted children currently receive the two doses per year, and new strategies are urgently needed. METHODOLOGY: Recent advancements in biotechnology permit alternative strategies for increasing the vitamin A content of common foods. Mustard (Brassica juncea, which is consumed widely in the form of oil by VAD populations, can be genetically modified to express high levels of beta-carotene, a precursor to vitamin A. Using estimates for consumption, we compare predicted costs and benefits of genetically modified (GM fortification of mustard seed with high-dose vitamin A supplementation and industrial fortification of mustard oil during processing to alleviate VAD by calculating the avertable health burden in terms of disability-adjusted life years (DALY. PRINCIPAL FINDINGS: We found that all three interventions potentially avert significant numbers of DALYs and deaths. Expanding vitamin A supplementation to all areas was the least costly intervention, at $23-$50 per DALY averted and $1,000-$6,100 per death averted, though cost-effectiveness varied with prevailing health subcenter coverage. GM fortification could avert 5 million-6 million more DALYs and 8,000-46,000 more deaths, mainly because it would benefit the entire population and not just children. However, the costs associated with GM fortification were nearly five times those of supplementation. Industrial fortification was dominated by both GM fortification and supplementation. The cost-effectiveness ratio of each intervention decreased with the prevalence of VAD and was sensitive to the efficacy rate of

  16. Effect of sulphur fertilisation on yield and quality of white mustard seeds

    Directory of Open Access Journals (Sweden)

    Pavel Ryant

    2009-01-01

    Full Text Available The objective of the present study was to estimate the effect of different forms of sulphur on yields and qualitative parameters of white mustard seeds. This topic was studied in 2004 in the form of a pot trial in a vegetation hall and linked up with an identical experiment with spring wheat conducted in 2003. Besides the control variant not fertilised with sulphur (1 we fertilised the soil with elemental sulphur (2, ammonium sulphate (3 and gypsum (4 and applied foliar dressing of elemental sulphur with bentonite (5. For all variants the nitrogen dose was 0.9 g per pot (0.15 g . kg−1 of soil and for va­riants 2 to 4 it was 1 g of sulphur per pot (0.17 g. kg−1 of soil. Foliar dressing of elemental sulphur (S0 was not applied until the stage of six true leaves in a dose of 10 kg per ha (0.032 g per pot.Significantly higher yields of white mustard seeds were achieved after foliar application of S0 which can be also due to its fungicide action. The variants where gypsum was applied showed the highest average number of branches and pods and also straw yields. After gypsum fertilisation or foliar application of S0 the oil content in the mustard seeds exceeded 25%; this is the minimal content required for the production of good quality mustard. The 1000-seed weight was significantly higher after foliar application of S0. The proportion of seeds greyish on the surface, a sign of mildew, significantly decreased after fertilisation with all forms of sulphur, but most of all after foliar application of S0.Fertilisation with ammonium sulphate reduced the exchangeable soil reaction after harvest. On the other hand gypsum alkalised the soil environment and increased the content of available calcium and water-soluble sulphur. The soil of the variant where foliar dressing of S0 was applied had a higher content of available calcium after harvest. The least amount of available sulphur and phosphorus in the soil was seen after foliar

  17. Quantum molecular modeling of the interaction between guanine and alkylating agents--1--sulfur mustard.

    Science.gov (United States)

    Broch, H; Hamza, A; Vasilescu, D

    1996-06-01

    Interaction between Guanine and the episulfonium form of Sulfur mustard (HD) was studied using the ab initio LCAO-MO method at the HF/6-31G level. The alkylation mechanism on guanine-N7 was analyzed by using a supermolecular modeling. Our stereostructural results associated with the molecular electrostatic potentials and HOMO-LUMO properties, show that in vacuum the alkylation of the N7 of guanine by HD in the aggressive episulfonium form is a direct process without transition state and of which the pathway is determined.

  18. New Methods for Evaluating Skin Injury from Sulfur Mustard in the Hairless Guinea Pig

    Science.gov (United States)

    1993-05-13

    MUSTARD IN THE HAIRLESS GUINEA PIG Ernest H. Braue, Jr., Catherine R. Bangledorf, and Robert G. Rieder "U.S. Army Medical Research Institute of Chemical...evaluating the skin hydration state. The skin of anesthetized hairless guinea pigs was exposed to saturated HD vapor (1.4mg/ml) at 4 sites for 3, 5, 7, or 9...assessment of skin damage following cutaneous exposure to HD vapor. EXPERIMENTAL METHODS Each hairless guinea pig (HGP) was exposed to saturated HD vapor

  19. Thermal neutron activation analysis of different varieties of mustard and sunflower seeds

    International Nuclear Information System (INIS)

    Rajurkar, N.S.; Bhamare, C.S.

    1991-01-01

    Neutron activation analysis (NAA) technique has been used for the estimation of Mn, Na and K in different varietes of oil seeds of mustard and sunflower in India. The samples were irradiated in a 252 Cf source with neutron flux of ∼10 9 n s -1 and the analysis was done using a multichannel analyzer (MCA) coupled to high purity germanium (HPGe) detector. Different varieties of seeds are found to have different concentrations of tracer elements when compared among themselves. (author) 5 refs.; 1 fig.; 1 tab

  20. Preliminary report into the effects of nitrogen ion bombardment treatment on mustard seeds

    International Nuclear Information System (INIS)

    Smith, C.W.; Al-Hashmi, S.A.R.; Ahmed, N.A.G.; Pollard, M.

    1988-01-01

    Mustard seeds have been subjected to nitrogen ion bombardment. A range of conditions was found within which there was an enhancement in the growth of seedlings from the ion bombardment treated seeds relative to those grown from control seeds. Scanning electron microscopy was used to examine seeds after treatment. It appeared that there had been an etching of the seed coating by the ion bombardment. This view was supported by experiments which showed that the rate of capillary water uptake by the treated seeds had been enhanced. (author)

  1. Mutagenic effectiveness and efficiency of gamma rays and ethyl methanesulhonate in Indian mustard

    International Nuclear Information System (INIS)

    Prasad, Rajendra; Singh, Basudeo

    1986-01-01

    Mutagenic effectiveness is a measure of the frequency of mutations induced by unit dose of a mutagen while mutagenic efficiency gives the proportion of mutations in relation to other associated undesirable biological effects such as gross chromosomal aberrations, lethality and sterility induced by the mutagen in question (Konzak, et al., 1965). The usefulness of any mutagen in plant breeding depends not only on its mutagenic effectiveness but also on its mutagenic efficiency. The efficiency and effectiveness of ethyl methanesulphonate (EMS) in relation to gamma rays in Indian mustard [Brassica juncea (L.) Czern and Coss] was studied. (author)

  2. Epoxy Resin Modified Quartz Crystal Microbalance Sensor for Chemical Warfare Agent Sulfur Mustard Vapor Detection

    Directory of Open Access Journals (Sweden)

    Rajendra BUNKAR

    2010-02-01

    Full Text Available An epoxy resin polymer coated quartz crystal microbalance (PC-QCM is used for detection of sulfur mustard vapor (SM. When SM vapor is exposed to PC-QCM sensor frequency shift is observed. The response of the sensor in ambient condition is 554 Hz with ±10 % variation upon exposure of 155 ppm of the SM concentration. The observed response loss is nearly 40 % over the period of 15 months. The response of the sensor is higher for SM than compare to structurally similar chloroethyl ether (CEE and other interferences.

  3. Skin manifestations in sulfur mustard exposed victims with ophthalmologic complications: Association between early and late phase

    Directory of Open Access Journals (Sweden)

    Somayeh Hejazi, MD

    Full Text Available Context: Sulfur mustard (SM was used during the Iraq-Iran war (1980–1988. Exposed veterans continue to suffer from its ocular, skin, and respiratory complications. Objective: We aimed to evaluate associations between early (at the time of acute exposure and decades later skin manifestations in individuals with severe ophthalmologic complications secondary to sulfur mustard exposure. Materials and methods: One hundred forty-nine veterans with severe ocular injuries were evaluated for acute and chronic skin complications. Logistic regression models were used to examine the associations between early and late skin manifestations. Results: Late skin complaints were observed in nearly all survivors who had early skin lesions (131 out of 137; 95.62%. Seven out of 12 patients (58.33% who did not have early skin lesions ultimately developed late skin complications. There was a significant relationship between the presence of lesions at the time of exposure and developing late skin complaints (two-sided Fisher's exact test, OR = 15.59, p < 0.001. There was an association between having at least one early skin lesion and occurrence of late skin complications. Survivors with blisters at the time of chemical exposure were more likely to complain of itching (95% CI: 3.63–25.97, p < 0.001, burning (OR = 11.16; 95% CI: 2.97–41.89, p < 0.001, pigmentation changes (OR = 10.17; 95% CI: 2.54–40.75, p = 0.001, dryness (OR = 6.71, 95% CI: 1.22–37.01, p = 0.03 or cherry angioma (OR = 2.59; 95% CI:1.21–5.55, p = 0.01 during the late phase. Using multivariate logistic models, early blisters remained significantly associated with latent skin complaints. Of note, the genitalia and great flexure areas were the most involved anatomical sites for both early and late skin lesions in SM exposed survivors. Conclusion: According to this study, the presence of blisters at the time of exposure to SM is the most important predictor of developing

  4. Allyl m-Trifluoromethyldiazirine Mephobarbital: An Unusually Potent Enantioselective and Photoreactive Barbiturate General Anesthetic

    Energy Technology Data Exchange (ETDEWEB)

    Savechenkov, Pavel Y.; Zhang, Xi; Chiara, David C.; Stewart, Deirdre S.; Ge, Rile; Zhou, Xiaojuan; Raines, Douglas E.; Cohen, Jonathan B.; Forman, Stuart A.; Miller, Keith W.; Bruzik, Karol S. (Harvard-Med); (Mass. Gen. Hosp.); (UIC)

    2012-12-10

    We synthesized 5-allyl-1-methyl-5-(m-trifluoromethyl-diazirynylphenyl)barbituric acid (14), a trifluoromethyldiazirine-containing derivative of general anesthetic mephobarbital, separated the racemic mixture into enantiomers by chiral chromatography, and determined the configuration of the (+)-enantiomer as S by X-ray crystallography. Additionally, we obtained the {sup 3}H-labeled ligand with high specific radioactivity. R-(-)-14 is an order of magnitude more potent than the most potent clinically used barbiturate, thiopental, and its general anesthetic EC{sub 50} approaches those for propofol and etomidate, whereas S-(+)-14 is 10-fold less potent. Furthermore, at concentrations close to its anesthetic potency, R-(-)-14 both potentiated GABA-induced currents and increased the affinity for the agonist muscimol in human {alpha}1{beta}2/3{gamma}2L GABA{sub A} receptors. Finally, R-(-)-14 was found to be an exceptionally efficient photolabeling reagent, incorporating into both {alpha}1 and {beta}3 subunits of human {alpha}1{beta}3 GABAA receptors. These results indicate R-(-)-14 is a functional general anesthetic that is well-suited for identifying barbiturate binding sites on Cys-loop receptors.

  5. On the X-ray reflectivity by poly allyl diglycol carbonate (PADC)

    International Nuclear Information System (INIS)

    Ghazaly, M. El

    2011-01-01

    X-ray reflectivity via the poly allyl diglycol carbonate (CR-39 polymer sheet) was investigated. X-ray reflectivity was measured for a pristine and a chemically etched CR-39 detector in 6.25N NaOH at (70 ± 0.5) .deg. C for different durations. Far from the spectral peak, the reflectivity of the CR-39 polymer sheet has a wide peak at 2θ = 20.1 .deg. , and its intensity is decreased by increasing the etching time. Moreover, the integrated counts under the peaks, C(t e ), vary linearly as a function of the etching time t e . Data are fitted using a linear function C(t e ) = A+Bt e , with fitting parameters A = (3271 ± 170) and B = (- 960 ± 84). The reflectivity deterioration is attributed to the increase of CR-39 surface's roughness due to the chemical etching. The rocking curves of X-ray reflectivity were measured for a pristine and an etched CR-39 polymer sheet. Specular reflections are observed, as well as Yoneda wings, which broaden and move away from the specular reflections due to the increase in the CR-39 surface's roughness.

  6. Biological distribution of iodo-allyl Gabapentin and iodo-Gabapentin

    International Nuclear Information System (INIS)

    Akat, H.; Yildirim, Y.; Balcan, M.; Yurt Lambrecht, F.; Yilmaz, O.; Duman, Y.

    2008-01-01

    Gabapentin (GBP) is an anticonvulsant and is widely used in the treatment of epilepsy. In this study, GBP and an allyl derivative of GBP were radioiodinated with 131 I using the iodogen method; then their radiopharmaceutical potential in rats and rabbits was investigated. The radiochemical purity of 131 I-GBP and its derivatives was determined by RTLC. The labeling yield was 95±2%. Biological evaluation was performed in normal rats and rabbits. Labeled compounds were intravenously injected into two rabbits via the ear vein after anesthetizing. The dynamic and static scintigrams were obtained using a gamma camera at different time. Then the labeled compounds were administered intravenously into the rats. The distribution was studied by counting the radioactivity in the removed organs. The results of biodistribution in the rats showed the clearance of 131 IALGBP was faster than 131 I-GBP. On the other hand, the uptake of 131 I-ALGBP in the brain was higher than 131 I-GBP at 60 minutes. (author)

  7. Immobilization/hybridization of amino-modified DNA on plasma-polymerized allyl chloride

    International Nuclear Information System (INIS)

    Zhang Zhihong; Feng Chuanliang

    2007-01-01

    The present work describes the fabrication and characterization of chloride-derivatized polymer coatings prepared by continuous wave (cw) plasma polymerization as adhesion layers in DNA immobilization/hybridization. The stability of plasma-polymerized allyl chloride (ppAC) in H 2 O was characterized by variation of the thickness of polymer films and its wettability was examined by water contact angle technique. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used to study polymer matrix properties and oligonucleotide/DNA binding interaction. With the same carrier gas rate and process pressure, plasma polymers deposited at different input powers show various comparable immobilization properties; nevertheless, low input power plasma-polymerized films gives a lower sensitivity toward DNA binding than that from high input power plasma-deposited films. The following DNA immobilization on chloride-functionalized surfaces was found dependence on the macromolecular architecture of the plasma films. The hybridization between probe DNA and total mismatch target DNA shows no non-specific adsorption between target and ppAC

  8. Sustainable and Low Viscous 1-Allyl-3-methylimidazolium Acetate + PEG Solvent for Cellulose Processing

    Directory of Open Access Journals (Sweden)

    Airong Xu

    2017-02-01

    Full Text Available Developing sustainable, low viscous and efficient solvents are always advantageous to the processing/fabricating of cellulose materials in practical applications. To this end, in this work novel solvents were developed; ([Amim][CH3COO]/PEG by dissolving polyethylene glycol 200 (PEG-200 in 1-allyl-3-methylimidazolium acetate ([Amim][CH3COO]. The solubilities of cellulose in [Amim][CH3COO]/PEG solvents were determined as a function of temperature, and the possible dissolution mechanism of cellulose in [Amim][CH3COO]/PEG solvent was investigated. The novel solvent exhibits outstanding advantages for good dissolution capacity of cellulose, such as low viscosity, negligible vapor pressure, and recycling capability. The [CH3COO]− anion and the [Amim]+ cation of [Amim][CH3COO] in [Amim][CH3COO]/PEG-10 are the driving force for cellulose dissolution verified by the 13C NMR spectra. In addition, the regenerated cellulose films from [Amim][CH3COO]/PEG solvent were characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR, and thermogravimetric analysis (TGA to estimate their morphologies and structures.

  9. Hydrolysis of cellulose catalyzed by quaternary ammonium perrhenates in 1-allyl-3-methylimidazolium chloride.

    Science.gov (United States)

    Wang, Jingyun; Zhou, Mingdong; Yuan, Yuguo; Zhang, Quan; Fang, Xiangchen; Zang, Shuliang

    2015-12-01

    Quaternary ammonium perrhenates were applied as catalyst to promote the hydrolysis of cellulose in 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The quaternary ammonium perrhenates displayed good catalytic performance for cellulose hydrolysis. Water was also proven to be effective to promote cellulose hydrolysis. Accordingly, 97% of total reduced sugar (TRS) and 42% of glucose yields could be obtained under the condition of using 5mol% of tetramethyl ammonium perrhenate as catalyst, 70μL of water, ca. 0.6mmol of microcrystalline cellulose (MCC) and 2.0g of [Amim]Cl as solvent under microwave irradiation for 30min at 150°C (optimal conditions). The influence of quaternary ammonium cation on the efficiency of cellulose hydrolysis was examined based on different cation structures of perrhenates. The mechanism on perrhenate catalyzed cellulose hydrolysis is also discussed, whereas hydrogen bonding between ReO4 anion and hydroxyl groups of cellulose is assumed to be the key step for depolymerization of cellulose. Copyright © 2015. Published by Elsevier Ltd.

  10. Preservation of beech and spruce wood by allyl alcohol-based copolymers

    International Nuclear Information System (INIS)

    Solpan, Dilek; Gueven, Olgun

    1999-01-01

    Allyl alcohol (AA), acrylonitrile (AN), methyl methacrylate (MMA), monomers and monomer mixtures AA+AN, AA+MMA were used to conserve and consolidate Beech and Spruce. After impregnation, copolymerisation and polymerisation were accomplished by gamma irradiation. The fine structure of wood+polymer(copolymer) composites was investigated by Scanning Electron Microscopy (SEM). It was observed that copolymer obtained from AA+MMA monomer mixture showed the optimum compatibility. The compressional strength and Brinell Hardness Numbers determined for untreated and treated wood samples indicated that the mechanical strength of wood+copolymer composites was increased. It was found that the mechanical strength of the wood samples containing the AA+MMA copolymer was higher than the others. In the presence of P(AA/MMA), at highest conversion, the compressive strength perpendicular to the fibres in Beech and Spruce increased approximately 100 times. The water uptake capacity of wood+copolymer composites was observed to decrease by more than 50% relative to the original samples, and biodegradation did not take place

  11. Inhibition of high affinity choline uptake by N-allyl-3-quinuclidinol

    International Nuclear Information System (INIS)

    Asermely, K.E.; O'Neill, J.J.

    1986-01-01

    The peripheral actions of N-allyl-3-quinuclidinol (N-Al-3-OHQ) on high affinity choline uptake (HAChU) on rat phrenic nerve diaphragm are described. Endplate regions (EPA) identified by the Koelle histochemical techniques for acetylcholinesterase, were dissected from adult rat hemidiaphragms and placed in cold Krebs solution (pH-7.35). All measurements of HAChU were at 37 0 C in buffers containing tritium choline (5 μM 0.124 μC/mmole) at intervals of 1, 2, 4, 8, 15 and 30 min. Tissues were washed 3x, digested in 1N NaOH and counted for tritium in Chaikoff's solution. All data are expressed as pmole Ch/g wet weight. Comparison between EPA and non-EPA tissue demonstrate HAChU and slow choline diffusion, respectively. Steady state is observed in 15 min. N-Al-3-OHQ produces 15% inhibition at 5 x 10 -5 M compared with 50% inhibition on brain synaptosomes. At 5 x 10 -4 M N-Al-3-OHQ, 30% inhibition is observed. Attempts to deplete ACh by pre-stimulation with high K + -ion (25 mM) were unsuccessful; tissue 3 H-choline uptake appeared to oscillate over a 30 min period

  12. Inhibition of high affinity choline uptake by N-allyl-3-quinuclidinol

    Energy Technology Data Exchange (ETDEWEB)

    Asermely, K.E.; O' Neill, J.J.

    1986-03-01

    The peripheral actions of N-allyl-3-quinuclidinol (N-Al-3-OHQ) on high affinity choline uptake (HAChU) on rat phrenic nerve diaphragm are described. Endplate regions (EPA) identified by the Koelle histochemical techniques for acetylcholinesterase, were dissected from adult rat hemidiaphragms and placed in cold Krebs solution (pH-7.35). All measurements of HAChU were at 37/sup 0/C in buffers containing tritium choline (5 ..mu..M 0.124 ..mu..C/mmole) at intervals of 1, 2, 4, 8, 15 and 30 min. Tissues were washed 3x, digested in 1N NaOH and counted for tritium in Chaikoff's solution. All data are expressed as pmole Ch/g wet weight. Comparison between EPA and non-EPA tissue demonstrate HAChU and slow choline diffusion, respectively. Steady state is observed in 15 min. N-Al-3-OHQ produces 15% inhibition at 5 x 10/sup -5/ M compared with 50% inhibition on brain synaptosomes. At 5 x 10/sup -4/ M N-Al-3-OHQ, 30% inhibition is observed. Attempts to deplete ACh by pre-stimulation with high K/sup +/-ion (25 mM) were unsuccessful; tissue /sup 3/H-choline uptake appeared to oscillate over a 30 min period.

  13. Effects of amount and timing of nitrogen application and weed density on wild mustard (Sinapis arvensis seed production in winter wheat

    Directory of Open Access Journals (Sweden)

    mehdi rastgoo

    2009-06-01

    Full Text Available In order to study the effects of amount and timing of nitrogen application and weed density on wild mustard (Sinapis arvensis seed production in winter wheat, an experiment was conducted in 2001 at Research station of college of agriculture, Ferdowsi University of Mashhad. A Split plot design with three replications were used with factorial combination of weed density (0, 8, 16, and 32 plant/m2 and nitrogen (low=100, optimum= 150, and high= 225 Kg/ha as main plots.The sub plot factor included nitrogen splitting pattern (P1=1/3 at planting time+2/3 at tillering, P2= 1/3 at planting time + 1/3 at tillering + 1/3 at shooting. According to the results, wild mustard seed production increased with increasing wild mustard density and nitrogen rates, due to high wild mustard biomass production. Seed production of wild mustard was 161, 311, and 488 million/ha in low, optimum and high nitrogen rates, respectively. In the other hand, density and nitrogen rates had a significant effect on wild mustard fecundity. However, nitrogen splitting pattern showed no significant effect on wild mustard seed production.

  14. HIGH-Resolution CT in Chronic Pulmonary Changes after Mustard Gas Exposure

    International Nuclear Information System (INIS)

    Bagheri, M.H.; Mostafavi, S.H.

    2003-01-01

    Purpose: To identify the findings of high-resolution CT (HRCT) of the lung in patients with previous sulfur mustard gas exposure, and to correlate these findings with clinical and chest X-ray (CXR) results. Material and Methods: 50 consecutive patients were studied prospectively. The clinical data were recorded. Standard p.a. CXR and HRCT of the lung and spirometry were performed. The findings of CXR, HRCT and clinical and spirometry results were scored between 0 and 3 according to the severity of the findings. Results: HRCT abnormality was detected in all 50 patients (100%), while CXR was abnormal in 40 patients (80%). The most common HRCT findings was airway abnormalities (bronchial wall thickening in 100% of cases). Other important findings were suggestive of interstitial lung disease (ILD) (80%), bronchiectasis (26%), and emphysema (24%). A statistically significant correlation was found between the severity of clinical presentation and that of the HCTR scores in patients with bronchiectasis, bronchitis and ILD (p< 0.05), but not with severity scores of HRCT in patients with emphysema. No significant correlation was found between severity scores of CXR findings. HRCT evidence of bronchial wall thickening and with a lower frequency ILD were present despite normal CXR in 20% of the patients. Conclusion: The results of this study suggest that bronchial wall thickening, ILD and emphysema are common chronic pulmonary sequelae of sulfur mustard injury. HRCT of the chest should be considered as the imaging modality of choice in chemical war injury

  15. HIGH-Resolution CT in Chronic Pulmonary Changes after Mustard Gas Exposure

    Energy Technology Data Exchange (ETDEWEB)

    Bagheri, M.H.; Mostafavi, S.H. [Shiraz Univ. of Medical Siences (Iran, Islamic Republic of). Dept. of Radiology; Hosseini, S.K. [Shiraz Univ. of Medical Siences (Iran, Islamic Republic of). Dept. of Internal Medicine; Alavi, S.A. [Medical Center for Chemical Warfare Victims Foundation, Shiraz (Iran, Islamic Republic of)

    2003-05-01

    Purpose: To identify the findings of high-resolution CT (HRCT) of the lung in patients with previous sulfur mustard gas exposure, and to correlate these findings with clinical and chest X-ray (CXR) results. Material and Methods: 50 consecutive patients were studied prospectively. The clinical data were recorded. Standard p.a. CXR and HRCT of the lung and spirometry were performed. The findings of CXR, HRCT and clinical and spirometry results were scored between 0 and 3 according to the severity of the findings. Results: HRCT abnormality was detected in all 50 patients (100%), while CXR was abnormal in 40 patients (80%). The most common HRCT findings was airway abnormalities (bronchial wall thickening in 100% of cases). Other important findings were suggestive of interstitial lung disease (ILD) (80%), bronchiectasis (26%), and emphysema (24%). A statistically significant correlation was found between the severity of clinical presentation and that of the HCTR scores in patients with bronchiectasis, bronchitis and ILD (p< 0.05), but not with severity scores of HRCT in patients with emphysema. No significant correlation was found between severity scores of CXR findings. HRCT evidence of bronchial wall thickening and with a lower frequency ILD were present despite normal CXR in 20% of the patients. Conclusion: The results of this study suggest that bronchial wall thickening, ILD and emphysema are common chronic pulmonary sequelae of sulfur mustard injury. HRCT of the chest should be considered as the imaging modality of choice in chemical war injury.

  16. Impact of Sowing Date Induced Temperature and Management Practices on Development Events and Yield of Mustard

    Directory of Open Access Journals (Sweden)

    MSA Khan, MA Aziz

    2015-12-01

    Full Text Available The experiment was conducted at the research field of the Agronomy Division, Bangladesh Agricultural Research Institute (BARI, Joydebpur, Gazipur, during rabi season of 2014-2015 to find out the relationship between different development events of mustard crop and sowing dates induced temperature as well as to minimize the yield reduction of the crop by adopting appropriate management practices. The mustard var. BARI Sarisha-15 was sown on 06, 25 November and 14 December 2014. Crop accumulated lower growing degree days (GDD i.e., 72.15, 521.10 and 1070 to 1154 °C were observed for the events of emergence, 50 % flowering and maturity on 14 December sowing. Late sown plants took minimum time from flowering to maturity (36 days due to increased temperature and high variability in both maximum and minimum temperature. The highest seed yield (1569 kg ha-1 was recorded from 06 November sowing with high management practices while the lowest seed yield (435 kg ha-1 from 14 December sowing with low management practices. At high management practices the crop yielded 1183 kg ha-1 at 14 December sowing. Yield reduction at late sowing condition was reduced to some extent with high management practices. The seed yield reductions at 14 December sowing as compared to high management practices at 06 November sowing were 72, 43 and 25% under low, medium and high management, respectively.

  17. Germination and seedling growth of Indian mustard exposed to cadmium and chromium

    Directory of Open Access Journals (Sweden)

    Luca Marchiol

    2006-03-01

    Full Text Available To make phytoremediation a technically viable option for large-scale applications we need plants that are able to guarantee high biomass yield as well as high accumulation of heavy metals in their aerial parts. The aim of this investigation was to study the performance of aquacultured plants of Indian mustard in the presence of different concentrations of cadmium and chromium since seed germination. The effects on germination and growth of seedlings of Indian mustard (Brassica juncea L. Czern cv. WNFP, Varuna and Barton, were investigated in/under hydroponic conditions during a 4-week experiment. Cadmium and chromium were provided since germination as cadmium nitrate Cd(NO32 and chromium bichromate K2Cr2O7 (0.5, 1 and 1.5 M. Plant biomass growth measured at the end of the experiments varied with the different metal concentrations in the nutrient solution and the accumulation of the elements in the plant fractions differed significantly among/between cultivars. Ability in the uptake of metals and their mobilization and storage in the aerial plant biomass, expressed by the bioconcentration factor (BCF and translocation factor (TF, respectively, are the most important traits of plants with phytoextraction potential. Brassica juncea was confirmed as being a highly tolerant species, but poor metal translocation values were registered, therefore the high amount of Cd and Cr concentrated in the root systems did not migrate to the aerial, harvestable, part of the plant.

  18. Relation between soil temperature and biophysical parameters in Indian mustard seeds

    Science.gov (United States)

    Adak, T.; Chakravarty, N. V. K.

    2013-12-01

    Temporal changes in surface soil temperature were studied in winter crop. Significant changes in bare and cropped soil temperature were revealed. Air temperature showed a statistically positive and strong relationship (R2 = 0.79** to 0.92**) with the soil temperature both at morning and afternoon hours. Linear regression analysis indicated that each unit increase in ambient temperature would lead to increase in minimum and maximum soil temperatures by 1.04 and 1.02 degree, respectively. Statistically positive correlation was revealed among biophysical variables with the cumulative surface soil temperature. Linear and non-linear regression analysis indicated 62-69, 72-86 and 72-80% variation in Leaf area index, dry matter production and heat use efficiency in Indian mustard crop as a function of soil degree days. Below 60% variation in yield in Indian mustard was revealed as a function of soil temperature. In contrast, non-significant relationship between oil content and soil temperature was found, which suggests that oil accumulation in oilseed crops was not affected significantly by the soil temperature as an independent variable.

  19. Prevention and treatment of respiratory consequences induced by sulfur mustard in Iranian casualties

    Directory of Open Access Journals (Sweden)

    Seyed M Razavi

    2013-01-01

    Full Text Available Background: About 100,000 Iranian have been exposed to chemical weapons during Iraq-Iran conflict (1980-88. After being spent of more than two decades, still about 30,000 of them are under follow-up treatment. The main aim of this study was to review various preventive and therapeutic methods for injured patients with sulfur mustard in different phases. Methods: For gathering information, we have used the electronic databases including Scopus, Medline, ISI, IranMedex, Irandoc sites. According to this search strategy, 104 published articles associated to respiratory problems and among them 50 articles related to prevention and treatment of respiratory problems were found and reviewed. Results: There is not any curative treatment for sulfur mustard induced lung injuries, but some valuable experienced measures for prevention and palliative treatments are available. Some useful measures in acute phase include: Symptomatic management, oxygen supplementation, tracheostomy in laryngospasm, use of moist air, respiratory physical therapy, mucolytic agents and bronchodilators. In the chronic phases, these measures include: Periodic clinical examinations, administration of inhaled corticosteroids alone or with long-acting beta 2 agonists, use of antioxidants, magnesium ions, long term oxygen supplement, therapeutic bronchoscopy, laser therapy, and use of respiratory tract stents. Conclusions: Most treatments are symptomatic but using preventive points immediately after exposure could improve following outcomes.

  20. Nitrogen availability regulates proline and ethylene production and alleviates salinity stress in mustard (Brassica juncea).

    Science.gov (United States)

    Iqbal, Noushina; Umar, Shahid; Khan, Nafees A

    2015-04-15

    Proline content and ethylene production have been shown to be involved in salt tolerance mechanisms in plants. To assess the role of nitrogen (N) in the protection of photosynthesis under salt stress, the effect of N (0, 5, 10, 20 mM) on proline and ethylene was studied in mustard (Brassica juncea). Sufficient N (10 mM) optimized proline production under non-saline conditions through an increase in proline-metabolizing enzymes, leading to osmotic balance and protection of photosynthesis through optimal ethylene production. Excess N (20 mM), in the absence of salt stress, inhibited photosynthesis and caused higher ethylene evolution but lower proline production compared to sufficient N. In contrast, under salt stress with an increased demand for N, excess N optimized ethylene production, which regulates the proline content resulting in recovered photosynthesis. The effect of excess N on photosynthesis under salt stress was further substantiated by the application of the ethylene biosynthesis inhibitor, 1-aminoethoxy vinylglycine (AVG), which inhibited proline production and photosynthesis. Without salt stress, AVG promoted photosynthesis in plants receiving excess N by inhibiting stress ethylene production. The results suggest that a regulatory interaction exists between ethylene, proline and N for salt tolerance. Nitrogen differentially regulates proline production and ethylene formation to alleviate the adverse effect of salinity on photosynthesis in mustard. Copyright © 2015 Elsevier GmbH. All rights reserved.

  1. Long Term Follow-Up of Sulfur Mustard Related Bronchiolitis Obliterans Treatment

    Directory of Open Access Journals (Sweden)

    Hamidreza Abtahi

    2016-10-01

    Full Text Available Bronchiolitis obliterans (BO is the most remarkable pulmonary sequels of war-related sulfur mustard inhalation. There is little if any data about long-term efficacy of associated BO treatment. Five years spirometric records of three groups of patients with obstructive pulmonary diseases (asthma, COPD, BO and documented sulfur mustard inhalation were evaluated. The BO patients were treated with inhaled Seretide 125-250/25 (2 puffs BID, azithromycin (250 mg, three times/week and N-acetylcysteine (1200-1800/day. Asthma and COPD patients were treated according to existing guidelines. Seventy-three (38 asthma, 16 COPD and 19 BO patients completed the 5 years follow-up. Basal and final FEV1 in BO patients (2.69±0.81 and 2.39±0.65 respectively were not significantly different from COPD patients (2.46±0.56 and 1.96±0.76 respectively. There was also no significant difference between the yearly FEV1 decline in BO patients compared to COPD patients (60±84 cc vs. 99±79 cc respectively, P=0.163. The non-significant difference of FEV1 decline in BO compared to COPD patients suggests the effectiveness of azithromycin, inhaled steroid and N-acetyl cysteine in BO patients. Considering safety and possible effectiveness, this treatment is recommended until more data is available from controlled clinical studies.

  2. Phytoextraction of potentially toxic elements by Indian mustard, rapeseed, and sunflower from a contaminated riparian soil.

    Science.gov (United States)

    Shaheen, Sabry M; Rinklebe, Jörg

    2015-12-01

    The objective of this study was to quantify the phytoextraction of the potentially toxic elements Al, As, Cd, Co, Cr, Cu, Mo, Ni, Pb, Se, V, and Zn by Indian mustard, rapeseed, and sunflower from a contaminated riparian soil. To achieve this goal, a greenhouse pot experiment was established using a highly contaminated grassland soil collected at the Wupper River (Germany). The impact of ethylene-diamine-tetra-acetic acid (EDTA), humate (HK), and phosphate potassium (PK) on the mobility and uptake of the elements by rapeseed also was investigated. Indian mustard showed the highest efficiency for phytoextraction of Al, Cr, Mo, Se, and V; sunflower for Cd, Ni, Pb, and Zn, and rapeseed for Cu. The bioconcentration ratios were higher than 1 for the elements (except As and Cu), indicating the suitability of the studied plants for phytoextraction. Application of EDTA to the soil increased significantly the solubility of Cd, Co, Cr, Ni, and Pb and decreased the solubility of Al, As, Se, V, and Mo. Humate potassium decreased significantly the concentrations of Al and As in rapeseed but increased the concentrations of Cu, Se, and Zn. We may conclude that HK can be used for immobilization of Al and As, while it can be used for enhancing the phytoextraction of Cu, Se, and Zn by rapeseed. Phosphate potassium immobilized Al, Cd, Pb, and Zn, but enhanced phytoextraction of As, Cr, Mo, and Se by rapeseed.

  3. Effect of method and time of application on P use efficiency by mustard (Brassica juncea L.)

    International Nuclear Information System (INIS)

    Singh, S.; Kamath, M.B.

    1990-01-01

    Radiophosphorus( 32 p) employed in a two years field study to evaluate some techniques of phosphate application in relation to P utilization by mustard as a test crop on I.A.R.I. Farm alluvial soil revealed that split application of phosphate proved superior to other methods of P fertilization as judged by significantly higher values for per cent Pdff and per cent P utilization. Band placement of plain single suprphosphate(SSP) as well as slurry blended SSP 3 to 4 cm below the seed were at par but both were superior to broadcast application of slurry blended SSP in terms of different P uptake parmeters. Fertilizer applied as a traditional practice, i.e, to broadcast it at seeding was least efficiently utilized. Moreover, alternate tagging technique conclusively indicated that mustard crop derived relatively more P from the basal dose than that of side dressed 25 days after seeding. The grain yield response per unit quantity of added P was much higher in favour of split application followed by comparable response of band placement of blended SSP and unblended fertilizer. (author). 12 refs., 2 tabs

  4. Garlic mustard and its effects on soil microbial communities in a sandy pine forest in central Illinois

    Science.gov (United States)

    Alexander B. Faulkner; Brittany E. Pham; Truc-Quynh D. Nguyen; Kenneth E. Kitchell; Daniel S. O' Keefe; Kelly D. McConnaughay; Sherri J. Morris

    2014-01-01

    This study evaluated the impacts of garlic mustard (Alliaria petiolata), an invasive species, on soil microbial community dynamics in a pine plantation on sandy soils in central Illinois. In situ soil carbon dioxide efflux was significantly greater in invaded sites. Similarly, in vitro carbon mineralization was significantly greater for soils...

  5. Inhalation and Percutaneous Toxicokinetics of Sulfur Mustard and Its adducts in Hairless Guinea Pigs and Marmosets. Efficacy of Nasal Scavengers

    National Research Council Canada - National Science Library

    Langenberg, Jan P

    2004-01-01

    As a follow-up to DAMDl7-94-V-4OO9, the inhalation toxicokinetics of sulfur mustard are studied in more detail in the hairless guinea pig as well as in a species more relevant for man, i.e., the marmoset...

  6. Study of selective metals accumulation in green mustard (Brassica rapa var. parachinesis L.) from Cameron Highlands farmlands, Pahang

    International Nuclear Information System (INIS)

    Zaini Hamzah; Marlinda Musa; Ahmad Saat; Ahmad Saat

    2011-01-01

    There are many essential and non-essential elements including metals and radionuclides present in vegetables. However, the accumulation of the several metals and radionuclides might cause the contamination to vegetables itself. Green mustard (Brasissca rapa var. Parachinesis L.) was selected to represent the vegetable in this study. Objectives of this study are to determine the concentration of metals and radionuclides in the samples and to calculate the enrichment factor (EF) and also to estimate the uptake, base on biological accumulation coefficient (BAC), for the various parts of selected vegetables. Three farmlands in the Cameron Highlands were studied namely Bharat, Kg Raja and Bertam area. The green mustard and soil samples were collected during the harvest season. Samples were dried, ground and sieved prior to analysis. Analyses for both samples were done by using X-rays Fluorescence Spectroscopy (XRF) to measure the concentration of Fe, Zn, Hg, U and Th. The concentration of all elements in the soils is lower than their concentration in the control soil, except for Zn, U and Th. The concentration of all elements in Green Mustard is lower than their concentration in the soil where it was grown. The EF values in the Brasissca rapa var. Parachinesis L are lower than 2 except for U and Th, indicating some degree of contamination due to anthropogenic activities or naturally origin. The BAC values show that Zn and Hg were accumulated in the green mustard, depending on where the plant grows. (Author)

  7. Inhalation and Percutaneous Toxicokinetics of Sulfur Mustard and Its Adducts in Hairless Guinea Pigs and Marmosets. Efficacy of Naval Scavengers

    Science.gov (United States)

    2005-08-01

    activity ca. 40 units/mg protein) from Boehringer (Mannheim, Germany); RNase A, and Tween 20 from Sigma Chemical Co. (St. Louis, MO, USA); and skimmed milk ...al. 1997). This hypothesis is still awaiting falsification . Measurement of the concentration-time course of the adduct of sulfur mustard to hemoglobin

  8. Use of Se-enriched mustard and canola seed meals as potential bioherbicides and green fertilizers in strawberry production

    Science.gov (United States)

    New plant-based products can be produced from seed harvested from Brassica species used for phytomanaging selenium (Se) in the westside of central California. We tested Se-enriched seed meals produced from canola (Brassica napus) and mustard (Sinapis alba) plants as potential bio-herbicides and as g...

  9. Sulforaphane induces phase II detoxication enzymes in mouse skin and prevents mutagenesis induced by a mustard gas analog

    Energy Technology Data Exchange (ETDEWEB)

    Abel, E.L. [Department of Molecular Carcinogenesis, The University of Texas MD Anderson Cancer Center, Science Park, Smithville, TX 78957 (United States); Boulware, S. [Division of Pharmacy and Toxicology, College of Pharmacy, The University of Texas at Austin, Dell Pediatric Research Institute, 1400 Barbara Jordan Blvd., Austin, TX 78723 (United States); Fields, T.; McIvor, E.; Powell, K.L. [Department of Molecular Carcinogenesis, The University of Texas MD Anderson Cancer Center, Science Park, Smithville, TX 78957 (United States); DiGiovanni, J.; Vasquez, K.M. [Division of Pharmacy and Toxicology, College of Pharmacy, The University of Texas at Austin, Dell Pediatric Research Institute, 1400 Barbara Jordan Blvd., Austin, TX 78723 (United States); MacLeod, M.C., E-mail: mcmacleod@mdanderson.org [Department of Molecular Carcinogenesis, The University of Texas MD Anderson Cancer Center, Science Park, Smithville, TX 78957 (United States)

    2013-02-01

    Mustard gas, used in chemical warfare since 1917, is a mutagenic and carcinogenic agent that produces severe dermal lesions for which there are no effective therapeutics; it is currently seen as a potential terrorist threat to civilian populations. Sulforaphane, found in cruciferous vegetables, is known to induce enzymes that detoxify compounds such as the sulfur mustards that react through electrophilic intermediates. Here, we observe that a single topical treatment with sulforaphane induces mouse epidermal levels of the regulatory subunit of glutamate-cysteine ligase, the rate-limiting enzyme in glutathione biosynthesis, and also increases epidermal levels of reduced glutathione. Furthermore, a glutathione S-transferase, GSTA4, is also induced in mouse skin by sulforaphane. In an in vivo model in which mice are given a single mutagenic application of the sulfur mustard analog 2-(chloroethyl) ethyl sulfide (CEES), we now show that therapeutic treatment with sulforaphane abolishes the CEES-induced increase in mutation frequency in the skin, measured four days after exposure. Sulforaphane, a natural product currently in clinical trials, shows promise as an effective therapeutic against mustard gas. -- Highlights: ► Sulforaphane induces increased levels of glutathione in mouse skin. ► Sulforaphane induces increased levels of GSTA4 in mouse skin. ► Sulforaphane, applied after CEES-treatment, completely abolishes CEES-mutagenesis. ► The therapeutic effect may suggest a long biological half-life for CEES in vivo.

  10. A comparison of decontamination effects of commercially available detergents in rats pre-exposed to topical sulphur mustard.

    Science.gov (United States)

    Misik, Jan; Jost, Petr; Pavlikova, Ruzena; Vodakova, Eva; Cabal, Jiri; Kuca, Kamil

    2013-06-01

    The genotoxic vesicant sulphur mustard [bis-2-(chloroethyl)sulphide] is a chemical warfare agent which is easily available due to its relatively simple synthesis. Thus, sulphur mustard is a potential agent for mass contamination. In this study, we focused on sulphur mustard toxicity and decontamination in a rat model using commercially available detergent mixtures for dermal decontamination. Male Wistar rats were percutaneously treated with sulphur mustard and subjected to wet decontamination 2 min postexposure. Commercially produced detergents Neodekont™, Argos™, Dermogel™ and FloraFree™ were tested for their decontamination efficacy against an exposed group and their protective ratios determined. The results showed that all tested detergent solutions produced an increase in the median lethal dose [LD(50) = 9.83 (5.87-13.63) mg·kg(-1)] in comparison to controls, which led to increased survival of experimental animals. In general, all tested detergents provided modest decontamination efficacy (PR = 2.0-5.7). The highest protective ratio (5.7) was consistently achieved with Argos™. Accordingly, Argos™ should be considered in further investigation of mass casualty decontamination.

  11. The Global Garlic Mustard Field Survey: challenges and opportunities of a unique, large-scale collaboration for invasion biology

    Czech Academy of Sciences Publication Activity Database

    Colautti, R. I.; Franks, S. J.; Hufbauer, R. A.; Kotanen, P. M.; Torchin, M.; Byers, J. E.; Pyšek, Petr; Bossdorf, O.

    2014-01-01

    Roč. 21, č. 1 (2014), s. 29-47 ISSN 1619-0033 Grant - others:AV ČR(CZ) AP1002 Program:Akademická prémie - Praemium Academiae Institutional support: RVO:67985939 Keywords : garlic mustard * citizen science * model system Subject RIV: EH - Ecology, Behaviour

  12. EFFECT OF REACTIVE MATERIALS ON THE CONTENT OF SELECTED ELEMENTS IN INDIAN MUSTARD GROWN IN CR(VI-CONTAMINATED SOILS

    Directory of Open Access Journals (Sweden)

    Maja Radziemska

    2016-04-01

    Full Text Available Reactive materials represent a promising agent for environmental co-remediation. The research was aimed to determine the influence of hexavalent chromium in doses of 0, 25, 50, and 150 mg Cr(VI.kg-1 of soil as well as zero valent-iron, and lignite additives on the content of macroelements in the Indian mustard (Brassica juncea L.. The average accumulation of the analysed elements in Indian mustard grown in Cr(VI contaminated soil were found to follow the decreasing order Mg>Na>P>Ca>K. Soil contamination at 150 mg Cr(VI.kg-1 of soil led to the highest increase in magnesium, calcium, sodium, and potassium content in Indian mustard. The application of zero-valent iron had a positive influence on the average Na and K content of the tested plant. The application of lignite had a positive influence on the average magnesium, sodium and calcium content in the above-ground parts of the studied plant. In the non-amended treatments (without reactive materials, the increasing rates of chromium (VI had an explicitly positive effect on the content of phosphorous and sodium in Indian mustard.

  13. The effect of nightly nasal CPAP treatment on nocturnal hypoxemia and sleep disorders in mustard gas-injured patients.

    Science.gov (United States)

    Vahedi, Ensieh; Fazeli Varzaneh, Ali Reza; Ghanei, Mostafa; Afsharpaiman, Shahla; Poursaleh, Zohre

    2014-12-01

    Sleep-related breathing disorders are associated with unusual respiratory pattern or an abnormal reduction in gas exchange during sleep that is common in sulfur mustard (SM) exposure. We compared 57 Iranian male patients injured with SM and had any complaints of sleep problems with an age-matched group of 21 Iranian male patients who had complaints of sleep problems and were not chemically injured; this group had Epworth Sleepiness Scale (ESS) above 10 and whom referred for polysomnography. Split-night studies were performed for patients with diagnostic polysomnography for obstructive sleep apnea (OSA) and respiratory events. We then studied respiratory events including episodes of OSA, apnea-hypopnea index (AHI) and respiratory disturbance index (RDI). The mean age in mustard-exposed patients was 48.14±8.04 years and in age-matched group, 48.19±8.39 years. In mustard exposed patients, there were statistical differences for the episodes of OSA (p=0.001), AHI (p=0.001), and RDI (p=0.001) between two segments of split-night studies. In the age-matched group, there were statistically differences for each parameter (episodes of OSA (p=0.001), AHI (p=0.001), and RDI (p=0.001)). There were no significant differences between two groups. This study indicated that the incidence of respiratory events and nocturnal hypoxemia during sleep in mustard-exposed patients were high and treatment with CPAP significantly reduced all these events.

  14. Benzyl isothiocyanate alters the gene expression with cell cycle regulation and cell death in human brain glioblastoma GBM 8401 cells.

    Science.gov (United States)

    Tang, Nou-Ying; Chueh, Fu-Shin; Yu, Chien-Chih; Liao, Ching-Lung; Lin, Jen-Jyh; Hsia, Te-Chun; Wu, King-Chuen; Liu, Hsin-Chung; Lu, Kung-Wen; Chung, Jing-Gung

    2016-04-01

    Glioblastoma multiforme (GBM) is a highly malignant devastating brain tumor in adults. Benzyl isothiocyanate (BITC) is one of the isothiocyanates that have been shown to induce human cancer cell apoptosis and cell cycle arrest. Herein, the effect of BITC on cell viability and apoptotic cell death and the genetic levels of human brain glioblastoma GBM 8401 cells in vitro were investigated. We found that BITC induced cell morphological changes, decreased cell viability and the induction of cell apoptosis in GBM 8401 cells was time-dependent. cDNA microarray was used to examine the effects of BITC on GBM 8401 cells and we found that numerous genes associated with cell death and cell cycle regulation in GBM 8401 cells were altered after BITC treatment. The results show that expression of 317 genes was upregulated, and two genes were associated with DNA damage, the DNA-damage-inducible transcript 3 (DDIT3) was increased 3.66-fold and the growth arrest and DNA-damage-inducible α (GADD45A) was increased 2.34-fold. We also found that expression of 182 genes was downregulated and two genes were associated with receptor for cell responses to stimuli, the EGF containing fibulin-like extracellular matrix protein 1 (EFEMP1) was inhibited 2.01-fold and the TNF receptor-associated protein 1 (TRAP1) was inhibited 2.08-fold. BITC inhibited seven mitochondria ribosomal genes, the mitochondrial ribosomal protein; tumor protein D52 (MRPS28) was inhibited 2.06-fold, the mitochondria ribosomal protein S2 (MRPS2) decreased 2.07-fold, the mitochondria ribosomal protein L23 (MRPL23) decreased 2.08-fold, the mitochondria ribosomal protein S2 (MRPS2) decreased 2.07-fold, the mitochondria ribosomal protein S12 (MRPS12) decreased 2.08-fold, the mitochondria ribosomal protein L12 (MRPL12) decreased 2.25-fold and the mitochondria ribosomal protein S34 (MRPS34) was decreased 2.30-fold in GBM 8401 cells. These changes of gene expression can provide the effects of BITC on the genetic level and are

  15. Iron depletion in HCT116 cells diminishes the upregulatory effect of phenethyl isothiocyanate on heme oxygenase-1

    International Nuclear Information System (INIS)

    Bolloskis, Michael P.; Carvalho, Fabiana P.; Loo, George

    2016-01-01

    Some of the health-promoting properties of cruciferous vegetables are thought to be partly attributed to isothiocyanates. These phytochemicals can upregulate the expression of certain cytoprotective stress genes, but it is unknown if a particular nutrient is involved. Herein, the objective was to ascertain if adequate iron is needed for enabling HCT116 cells to optimally express heme oxygenase-1 (HO-1) when induced by phenethyl isothiocyanate (PEITC). PEITC increased HO-1 expression and also nuclear translocation of Nrf2, which is a transcription factor known to activate the HO-1 gene. However, in HCT116 cells that were made iron-deficient by depleting intracellular iron with deferoxamine (DFO), PEITC was less able to increase HO-1 expression and nuclear translocation of Nrf2. These suppressive effects of DFO were overcome by replenishing the iron-deficient cells with the missing iron. To elucidate these findings, it was found that PEITC-induced HO-1 upregulation can be inhibited with thiol antioxidants (glutathione and N-acetylcysteine). Furthermore, NADPH oxidase inhibitors (diphenyleneiodonium and apocynin) and a superoxide scavenger (Tiron) each inhibited PEITC-induced HO-1 upregulation. In doing so, diphenyleneiodonium was the most potent and also inhibited nuclear translocation of redox-sensitive Nrf2. Collectively, the results imply that the HO-1 upregulation by PEITC involves an iron-dependent, oxidant signaling pathway. Therefore, it is concluded that ample iron is required to enable PEITC to fully upregulate HO-1 expression in HCT116 cells. As such, it is conceivable that iron-deficient individuals may not reap the full health benefits of eating PEITC-containing cruciferous vegetables that via HO-1 may help protect against multiple chronic diseases. - Highlights: • PEITC increased HO-1 expression in HCT116 cells. • PEITC-induced HO-1 upregulation was impaired in iron-depleted HCT116 cells. • Impairment of PEITC-induced HO-1 upregulation was

  16. Elucidation of the regio- and chemoselectivity of enzymatic allylic oxidations with Pleurotus sapidus – conversion of selected spirocyclic terpenoids and computational analysis

    Directory of Open Access Journals (Sweden)

    Verena Weidmann

    2013-10-01

    Full Text Available Allylic oxidations of olefins to enones allow the efficient synthesis of value-added products from simple olefinic precursors like terpenes or terpenoids. Biocatalytic variants have a large potential for industrial applications, particularly in the pharmaceutical and food industry. Herein we report efficient biocatalytic allylic oxidations of spirocyclic terpenoids by a lyophilisate of the edible fungus Pleurotus sapidus. This ‘’mushroom catalysis’’ is operationally simple and allows the conversion of various unsaturated spirocyclic terpenoids. A number of new spirocyclic enones have thus been obtained with good regio- and chemoselectivity and chiral separation protocols for enantiomeric mixtures have been developed. The oxidations follow a radical mechanism and the regioselectivity of the reaction is mainly determined by bond-dissociation energies of the available allylic CH-bonds and steric accessibility of the oxidation site.

  17. Mechanism of copper(I)-catalyzed allylic alkylation of phosphorothioate esters: influence of the leaving group on α regioselectivity.

    Science.gov (United States)

    Sheng, Wenhao; Wang, Mian; Lein, Matthias; Jiang, Linbin; Wei, Wanxing; Wang, Jianyi

    2013-10-11

    The mechanism of Cu(I) -catalyzed allylic alkylation and the influence of the leaving groups (OPiv, SPiv, Cl, SPO(OiPr)2 ; Piv: pivavloyl) on the regioselectivity of the reaction have been explored by using density functional theory (DFT). A comprehensive comparison of many possible reaction pathways shows that [(iPr)2 Cu](-) prefers to bind first oxidatively to the double bond of the allylic substrate at the anti position with respect to the leaving group, and this is followed by dissociation of the leaving group. If the leaving group is not taken into account, the reaction then undergoes an isomerization and a reductive elimination process to give the α- or γ-selective product. If OPiv, SPiv, Cl, or SPO(OiPr)2 groups are present, the optimal route for the formation of both α- and γ-substituted products changes from the stepwise elimination to the direct process, in which the leaving group plays a stabilizing role for the reactant and destabilizes the transition state. The differences to the energy barrier for the α- and γ-substituted products are 2.75 kcal mol(-1) with SPO(OiPr)2 , 2.44 kcal mol(-1) with SPiv, 2.33 kcal mol(-1) with OPiv, and 1.98 kcal mol(-1) with Cl, respectively; these values show that α regioselectivity in the allylic alkylation follows a SPO(OiPr)2 >SPiv>OPiv>Cl trend, which is in satisfactory agreement with the experimental findings. This trend mainly originates in the differences between the attractive electrostatic forces and the repelling steric interactions of the SPO(OiPr)2 , SPiv, OPiv, and Cl groups on the Cu group. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate.

    Science.gov (United States)

    Ding, Liyuan; Yu, Chunbing; Zhao, Zhenqiang; Li, Feifei; Zhang, Jian; Zhong, Guofu

    2017-06-21

    Direct cross-coupling between two alkenes via vinylic C-H bond activation represents an efficient strategy for the synthesis of butadienes with high atomic and step economy. However, this functionality-directed cross-coupling reaction has not been developed, as there are still limited directing groups in practical use. In particular, a stoichiometric amount of oxidant is usually required, producing a large amount of waste. Due to our interest in novel 1,3-butadiene synthesis, we describe the ruthenium-catalyzed olefination of electron-deficient alkenes using allyl acetate and without external oxidant. The reaction of 2-phenyl acrylamide and allyl acetate was chosen as a model reaction, and the desired diene product was obtained in 80% isolated yield with good stereoselectivity (Z,E/Z,Z = 88:12) under optimal conditions: [Ru(p-cymene) Cl2]2 (3 mol %) and AgSbF6 (20 mol %) in DCE at 110 ºC for 16 h. With the optimized catalytic conditions in hand, representative α- and/or β-substituted acrylamides were investigated, and all reacted smoothly, regardless of aliphatic or aromatic groups. Also, differently N-substituted acrylamides have proven to be good substrates. Moreover, we examined the reactivity of different allyl derivatives, suggesting that the chelation of acetate oxygen to the metal is crucial for the catalytic process. Deuterium-labeled experiments were also conducted to investigate the reaction mechanism. Only Z-selective H/D exchanges on acrylamide were observed, indicating a reversible cyclometalation event. In addition, a kinetic isotope effect (KIE) of 3.2 was observed in the intermolecular isotopic study, suggesting that the olefinic C-H metalation step is probably involved in the rate-determining step.

  19. Proton conductive membranes based on poly (styrene-co-allyl alcohol semi-IPN

    Directory of Open Access Journals (Sweden)

    Felipe Augusto Moro Loureiro

    2014-01-01

    Full Text Available The optimization of fuel cell materials, particularly polymer membranes, for PEMFC has driven the development of methods and alternatives to achieve systems with more adequate properties to this application. The sulfonation of poly (styrene-co-allyl alcohol (PSAA, using sulfonating agent:styrene ratios of 2:1, 1:1, 1:2, 1:4, 1:6, 1:8 and 1:10, was previously performed to obtain proton conductive polymer membranes. Most of those membranes exhibited solubility in water with increasing temperature and showed conductivity of approximately 10-5 S cm-1. In order to optimize the PSAA properties, especially decreasing its solubility, semi-IPN (SIPN membranes are proposed in the present study. These membranes were obtained from the diglycidyl ether of bisphenol A (DGEBA, curing reactions in presence of DDS (4,4-diaminodiphenyl sulfone and PSAA. Different DGEBA/PSAA weight ratios were employed, varying the PSAA concentration between 9 and 50% and keeping the mass ratio of DGEBA:DDS as 1:1. The samples were characterized by FTIR and by electrochemical impedance spectroscopy. Unperturbed bands of PSAA were observed in the FTIR spectra of membranes, suggesting that chemical integrity of the polymer is maintained during the synthesis. In particular, bands involving C-C stretching (1450 cm-1, C=C (aromatic, ~ 3030 cm-1 and C-H (2818 and 2928 cm-1 were observed, unchanged after the synthesis. The disappearance or reduction of the intensity of the band at 916 cm-1, attributed to the DGEBA epoxy ring, is evidenced for all samples, indicating the epoxy ring opening and the DGEBA crosslinking. Conductivity of H3PO4 doped membranes increases with temperature, reaching 10-4 S cm-1.

  20. Mechanism of the Suzuki–Miyaura Cross-Coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts

    KAUST Repository

    Meconi, Giulia Magi

    2017-05-24

    Density functional theory calculations have been used to investigate the activation mechanism for the precatalyst series [Pd]-X-1–4 derived from [Pd(IPr)(R-allyl)X] species by substitutions at the terminal position of the allyl moiety ([Pd] = Pd(IPr); R = H (1), Me (2), gem-Me2 (3), Ph (4), X = Cl, Br). Next, we have investigated the Suzuki–Miyaura cross-coupling reaction for the active catalyst species IPr-Pd(0) using 4-chlorotoluene and phenylboronic acid as substrates and isopropyl alcohol as a solvent. Our theoretical findings predict an upper barrier trend, corresponding to the activation mechanism for the [Pd]-Cl-1–4 series, in good agreement with the experiments. They indeed provide a quantitative explanation of the low yield (12%) displayed by [Pd]-Cl-1 species (ΔG⧧ ≈ 30.0 kcal/mol) and of the high yields (≈90%) observed in the case of [Pd]-Cl-2–4 complexes (ΔG⧧ ≈ 20.0 kcal/mol). Additionally, the studied Suzuki–Miyaura reaction involving the IPr-Pd(0) species is calculated to be thermodynamically favorable and kinetically facile. Similar investigations for the [Pd]-Br-1–4 series, derived from [Pd(IPr)(R-allyl)Br], indicate that the oxidative addition step for IPr-Pd(0)-mediated catalysis with 4-bromotoluene is kinetically more favored than that with 4-chlorotoluene. Finally, we have explored the potential of Ni-based complexes [Ni((IPr)(R-allyl)X] (X = Cl, Br) as Suzuki–Miyaura reaction catalysts. Apart from a less endergonic reaction energy profile for both precatalyst activation and catalytic cycle, a steep increase in the predicted upper energy barriers (by 2.0–15.0 kcal/mol) is calculated in the activation mechanism for the [Ni]-X-1–4 series compared to the [Pd]-X-1–4 series. Overall, these results suggest that Ni-based precatalysts are expected to be less active than the Pd-based precatalysts for the studied Suzuki–Miyaura reaction.