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Sample records for constituent benzyl isothiocyanate

  1. Insights into the Mode of Action of Benzyl Isothiocyanate on Campylobacter jejuni

    PubMed Central

    Dufour, Virginie; Stahl, Martin; Rosenfeld, Eric; Stintzi, Alain

    2013-01-01

    Campylobacter jejuni is a widespread pathogen responsible for most of the food-borne gastrointestinal diseases in Europe. The use of natural antimicrobial molecules is a promising alternative to antibiotic treatments for pathogen control in the food industry. Isothiocyanates are natural antimicrobial compounds, which also display anticancer activity. Several studies described the chemoprotective effect of isothiocyanates on eukaryotic cells, but the antimicrobial mechanism is still poorly understood. We investigated the early cellular response of C. jejuni to benzyl isothiocyanate by both transcriptomic and physiological approaches. The transcriptomic response of C. jejuni to benzyl isothiocyanate showed upregulation of heat shock response genes and an impact on energy metabolism. Oxygen consumption was progressively impaired by benzyl isothiocyanate treatment, as revealed by high-resolution respirometry, while the ATP content increased soon after benzyl isothiocyanate exposition, which suggests a shift in the energy metabolism balance. Finally, benzyl isothiocyanate induced intracellular protein aggregation. These results indicate that benzyl isothiocyanate affects C. jejuni by targeting proteins, resulting in the disruption of major metabolic processes and eventually leading to cell death. PMID:24014524

  2. Effects of benzyl isothiocyanate on the reproduction of Meloidogyne incognita on Glycine max and Capsicum annuum

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Reproduction of Meloidogyne incognita on Capsicum annuum or Glycine max was suppressed when infective juveniles (J2) were exposed to 0.03 millimolar benzyl isothiocyanate (BITC) for 2hr prior to inoculation of the host. Infectivity assessed by gall index was significantly reduced on both G. max (co...

  3. Benzyl isothiocyanate affects development, hatching and reproduction of the soybean cyst nematode Heterodera glycines

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Benzyl isothiocyanate (BITC) applied at micromolar doses decreased Heterodera glycines J2 movement, H. glycines hatching, and reproduction of H. glycines on soybean, Glycine max. Direct exposure of J2 to 30 microM BITC caused an immediate decrease (17%; P < 0.05) in J2 movement relative to 1% methan...

  4. Behavioral Response of Meloidogyne incognita to Benzyl Isothiocyanate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    One reported mechanism of plant-parasitic nematode suppression by brassicaceous cover crops is the production of isothiocyanates (ITC) in soil after biomass incorporation. While plant-parasitic nematode mortality is the objective when using these cover crops for biofumigation, very little is known ...

  5. Selective cytotoxicity of benzyl isothiocyanate in the proliferating fibroblastoid cells.

    PubMed

    Miyoshi, Noriyuki; Uchida, Koji; Osawa, Toshihiko; Nakamura, Yoshimasa

    2007-02-01

    In the present study, experiments using presynchronization culture cells demonstrated that benzyl ITC (BITC), previously isolated from a tropical papaya fruit extract, induced the cytotoxic effect preferentially in the proliferating human colon CCD-18Co cells to the quiescent ones. Quiescent CCD-18Co cells were virtually unaffected by BITC and marginal cytotoxicity was observed at 15 microM. We observed that BITC dramatically induced the p53 phosphorylation and stabilization only in the quiescent (G(0)/G(1) phase-arrested) cells, but not significantly in the proliferating human colon CCD-18Co cells when compared with quiescent ones. We also observed ataxia telangiectasia-mutated (ATM) phosphorylation in the quiescent cells. The BITC-induced p53 phosphorylation was counteracted by caffeine treatment, implying the involvement of an ATM/ataxia telangiectasia and Rad3-related kinase signaling pathway. Moreover, downregulation of p53 by a siRNA resulted in the enhancement of susceptibility to undergo apoptosis by BITC. We also showed here that depletion of p53 abrogated G(0)/G(1) arrest accompanied by the declined expression of p21(waf1/cip1) and p27(kip1) in CCD-18Co cells. In conclusion, we identified p53 as a potential negative regulator of the apoptosis induction by BITC in the normal colon CCD-18Co cells through the inhibition of cell-cycle progression at the G(0)/G(1) phase. PMID:17096346

  6. Dietary chemopreventative benzyl isothiocyanate inhibits breast cancer stem cells in vitro and in vivo.

    PubMed

    Kim, Su-Hyeong; Sehrawat, Anuradha; Singh, Shivendra V

    2013-08-01

    A small subset of mammary tumor-initiating cells (also known as breast cancer stem cells; bCSC), characterized by expression of different markers [CD44(high)/CD24(low)/epithelial-specific antigen (ESA)+], aldehyde dehydrogenase-1 (ALDH1) activity, and ability to form mammospheres under ultra-low attachment culture conditions, are suspected to evade conventional therapies leading to disease recurrence. Elimination of both therapy-sensitive epithelial tumor cells and therapy-resistant bCSC is therefore necessary for prevention of breast cancer. We have shown previously that a nontoxic small-molecule constituent of edible cruciferous vegetables (benzyl isothiocyanate; BITC) inhibits mammary cancer development in mouse mammary tumor virus-neu (MMTV-neu) transgenic mice by causing epithelial tumor cell apoptosis. The present study shows efficacy of BITC against bCSC in vitro and in vivo. Mammosphere formation frequency and CD44(high)/CD24(low)/ESA+ and/or ALDH1+ populations in cultured MCF-7 (estrogen receptor-positive) and SUM159 (triple-negative) human breast cancer cells were decreased significantly in the presence of plasma achievable concentrations of BITC. BITC administration in the diet (3 μmol BITC/g diet for 29 weeks) resulted in a marked decrease in bCSCs in the MMTV-neu mice tumors in vivo. Overexpression of full-length Ron as well as its truncated form (sfRon), but not urokinase-type plasminogen activator receptor, conferred near complete protection against BITC-mediated inhibition of bCSCs in MCF-7 cells. The BITC treatment downregulated protein levels of Ron and sfRon in cultured breast cancer cells and in tumor xenografts. Ron overexpression resulted in upregulation of bCSC-associated genes Oct-4, SOX-2, and Nanog. In conclusion, the present study indicates that BITC treatment eliminates bCSCs in vitro and in vivo. PMID:23661606

  7. Evaluation of antibacterial activity of 3-butenyl, 4-pentenyl, 2-phenylethyl, and benzyl isothiocyanate in Brassica vegetables.

    PubMed

    Jang, Miran; Hong, Eunyoung; Kim, Gun-Hee

    2010-09-01

    This study investigated antibacterial activities of 4 isothiocyanates (3-butenyl, 4-phentenyl, 2-phenylethyl, and benzyl isothiocyanate) against 4 Gram-positive bacteria (Bacillus cereus, Bacillus subtilis, Listeria monocytogenes, and Staphylococcus aureus) and 7 Gram-negative bacteria (Aeromonas hydrophila, Pseudomonas aeruginosa, Salmonella choleaesuis, Salmonella enterica, Serratia marcescens, Shigella sonnei, and Vibrio parahaemolyticus) by an agar disc diffusion assay. Benzyl isothiocyanate (> 90.00 mm inhibition zone diameter at 0.1 μL/mL) and 2-phenylethyl isothiocyanate (58.33 mm at 0.2 μL/mL) showed large inhibition zones especially against B. cereus. Also, 3-butenyl isothiocyanate (21.67 mm at 1.0 μL/mL) and 4-pentenyl isothiocyanate (19.67 mm at 1.0 μL/mL) displayed potent antibacterial activity against A. hydrophila. Benzyl and 2-phenylethyl isothiocyanate indicated higher activity against most of the pathogenic bacteria than 3-butenyl and 4-pentenyl isothiocyanate, and were more effective against Gram-positive bacteria than Gram-negative bacteria. PMID:21535549

  8. Short-form RON overexpression augments benzyl isothiocyanate-induced apoptosis in human breast cancer cells.

    PubMed

    Sehrawat, Anuradha; Singh, Shivendra V

    2016-05-01

    Chemoprevention of breast cancer is feasible with the use of non-toxic phytochemicals from edible and medicinal plants. Benzyl isothiocyanate (BITC) is one such plant compound that prevents mammary cancer development in a transgenic mouse model in association with tumor cell apoptosis. Prior studies from our laboratory have demonstrated a role for reactive oxygen species (ROS)-dependent Bax activation through the intermediary of c-Jun N-terminal kinases in BITC-induced apoptosis in human breast cancer cells. The present study demonstrates that truncated Recepteur d'Origine Nantais (sfRON) is a novel regulator of BITC-induced apoptosis in breast cancer cells. Overexpression of sfRON in MCF-7 and MDA-MB-361 cells resulted in augmentation of BITC-induced apoptosis when the apoptotic fraction was normalized against vehicle control for each cell type (untransfected and sfRON overexpressing cells). ROS generation and G2 /M phase cell cycle arrest resulting from BITC treatment were significantly attenuated in sfRON overexpressing cells after normalization with vehicle control for each cell type. Increased BITC-induced apoptosis by sfRON overexpression was independent of c-Jun N-terminal kinase or p38 mitogen-activated protein kinase hyperphosphorylation. On the other hand, activation of Bax and Bak following BITC exposure was markedly more pronounced in sfRON overexpressing cells than in controls. sfRON overexpression also augmented apoptosis induction by structurally diverse cancer chemopreventive phytochemicals including withaferin A, phenethyl isothiocyanate, and D,L-sulforaphane. In conclusion, the present study provides novel mechanistic insights into the role of sfRON in apoptosis regulation by BITC and other electrophilic phytochemicals. © 2015 Wiley Periodicals, Inc. PMID:25857724

  9. Benzyl isothiocyanate inhibits inflammasome activation in E. coli LPS-stimulated BV2 cells.

    PubMed

    Lee, Chang-Min; Lee, Dae-Sung; Jung, Won-Kyo; Yoo, Jong Su; Yim, Mi-Jin; Choi, Yung Hyun; Park, Saegwang; Seo, Su-Kil; Choi, Jung Sik; Lee, Young-Min; Park, Won Sun; Choi, Il-Whan

    2016-09-01

    Inflammasomes are multi-protein complexes that play a crucial role in innate immune responses. Benzyl isothiocyanate (BITC) is a naturally occurring compound found in cruciferous vegetables, and BITC exhibits potential as a chemopreventive agent. However, whether BITC exerts inflammasome-mediated regulatory effects on neuroinflammation is unknown. In this study, we examined the effects of BITC on inflammasome-mediated interleukin-1β (IL-1β) production in E. coli lipopolysaccharide (LPS)-stimulated BV2 microglial cells. IL-1β production is tightly regulated at the post-translational level through the inflammasoume. We measured the levels of IL-1β produced from the LPS-exposed BV2 microglial cells using enzyme-linked immunosorbent assays (ELISAs). The BITC regulatory mechanisms in inflammasome-mediated cellular signaling pathways were examined by RT-PCR, western blot analysis and electrophoretic mobility shift assays. BITC inhibited the secretion of IL-1β induced by LPS in the BV2 microglial cells. BITC inhibited inflammasome activation and NLR family, pyrin domain containing 3 (NLRP3)-mediated caspase-1 activation, and decreased the levels of inflammasome activation pro-inflammatory mediators, including mitochondrial reactive oxygen species (ROS) and adenosine triphosphate (ATP) secretion in the LPS-stimulated BV2 microglial cells. Furthermore, we demonstrated that nuclear factor-κB (NF-κB) activation induced by LPS was inhibited by BITC, which may contribute to the attenuated secretion of IL-1β. These BITC-mediated inhibitory effects on IL-1β expression may thus regulate neuroinflammation through the inflammasome-mediated signaling pathway. PMID:27430883

  10. Nuclear factor-kappaB sensitizes to benzyl isothiocyanate-induced antiproliferation in p53-deficient colorectal cancer cells.

    PubMed

    Abe, N; Hou, D-X; Munemasa, S; Murata, Y; Nakamura, Y

    2014-01-01

    Benzyl isothiocyanate (BITC), a dietary isothiocyanate derived from cruciferous vegetables, inhibits the proliferation of colorectal cancer cells, most of which overexpress β-catenin as a result of mutations in the genes for adenomatous polyposis coli or mutations in β-catenin itself. Because nuclear factor-κB (NF-κB) is a plausible target of BITC signaling in inflammatory cell models, we hypothesized that it is also involved in BITC-inhibited proliferation of colorectal cancer cells. siRNA-mediated knockdown of the NF-κB p65 subunit significantly decreased the BITC sensitivity of human colorectal cancer HT-29 cells with mutated p53 tumor suppressor protein. Treating HT-29 cells with BITC induced the phosphorylation of IκB kinase, IκB-α and p65, the degradation of IκB-α, the translocation of p65 to the nucleus and the upregulation of NF-κB transcriptional activity. BITC also decreased β-catenin binding to a positive cis element of the cyclin D1 promoter and thus inhibited β-catenin-dependent cyclin D1 transcription, possibly through a direct interaction between p65 and β-catenin. siRNA-mediated knockdown of p65 confirmed that p65 negatively affects cyclin D1 expression. On the other hand, when human colorectal cancer HCT-116 cells with wild-type p53 were treated with BITC, translocation of p65 to the nucleus was inhibited rather than enhanced. p53 knockout increased the BITC sensitivity of HCT-116 cells in a p65-dependent manner, suggesting that p53 negatively regulates p65-dependent effects. Together, these results identify BITC as a novel type of antiproliferative agent that regulates the NF-κB pathway in p53-deficient colorectal cancer cells. PMID:25412312

  11. Nuclear factor-kappaB sensitizes to benzyl isothiocyanate-induced antiproliferation in p53-deficient colorectal cancer cells

    PubMed Central

    Abe, N; Hou, D-X; Munemasa, S; Murata, Y; Nakamura, Y

    2014-01-01

    Benzyl isothiocyanate (BITC), a dietary isothiocyanate derived from cruciferous vegetables, inhibits the proliferation of colorectal cancer cells, most of which overexpress β-catenin as a result of mutations in the genes for adenomatous polyposis coli or mutations in β-catenin itself. Because nuclear factor-κB (NF-κB) is a plausible target of BITC signaling in inflammatory cell models, we hypothesized that it is also involved in BITC-inhibited proliferation of colorectal cancer cells. siRNA-mediated knockdown of the NF-κB p65 subunit significantly decreased the BITC sensitivity of human colorectal cancer HT-29 cells with mutated p53 tumor suppressor protein. Treating HT-29 cells with BITC induced the phosphorylation of IκB kinase, IκB-α and p65, the degradation of IκB-α, the translocation of p65 to the nucleus and the upregulation of NF-κB transcriptional activity. BITC also decreased β-catenin binding to a positive cis element of the cyclin D1 promoter and thus inhibited β-catenin-dependent cyclin D1 transcription, possibly through a direct interaction between p65 and β-catenin. siRNA-mediated knockdown of p65 confirmed that p65 negatively affects cyclin D1 expression. On the other hand, when human colorectal cancer HCT-116 cells with wild-type p53 were treated with BITC, translocation of p65 to the nucleus was inhibited rather than enhanced. p53 knockout increased the BITC sensitivity of HCT-116 cells in a p65-dependent manner, suggesting that p53 negatively regulates p65-dependent effects. Together, these results identify BITC as a novel type of antiproliferative agent that regulates the NF-κB pathway in p53-deficient colorectal cancer cells. PMID:25412312

  12. Preparation and characterization of inclusion complex of benzyl isothiocyanate extracted from papaya seed with β-cyclodextrin.

    PubMed

    Li, Wenzhao; Liu, Xiaoyu; Yang, Qingfeng; Zhang, Ning; Du, Yideng; Zhu, Huaping

    2015-10-01

    The inclusion complex of benzyl isothiocyanate (BITC), extracted from papaya seed with β-cyclodextrin (β-CD), was prepared. Different analytical techniques, such as Fourier transform infrared spectroscopy, thermal analysis, X-ray diffractometry, particle size distribution analysis and (1)H Nuclear magnetic resonance analysis, were used to investigate the characterization of the inclusion complex (BITC-β-CD). All these approaches indicated that the inclusion complex was capable of being formed. The inclusion complex exhibited different spectroscopic and thermodynamic features and properties from BITC, and we deduced the possible inclusion modes for BITC-β-CD. The calculated apparent stability constant of the BITC-β-CD was 600.8l/mol, and the aqueous solubility of BITC was indistinctively improved by phase solubility studies. The results illustrated that β-CD was a proper excipient for increasing the stability and controlled release of BITC. Thus, β-CD complexation technology would be a promising approach, in expanding the application of BITC as a food antibacterial agent. PMID:25872431

  13. Benzyl isothiocyanate alters the gene expression with cell cycle regulation and cell death in human brain glioblastoma GBM 8401 cells.

    PubMed

    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

  14. Expression of the platelet-activating factor receptor enhances benzyl isothiocyanate-induced apoptosis in murine and human melanoma cells.

    PubMed

    Sahu, Ravi Prakash

    2015-07-01

    Melanoma cells often express platelet-activating factor receptor (PAF-R), which has been demonstrated to increase metastatic behavior. However, the effect of PAF-R on the responsiveness of melanoma to naturally occurring cytotoxic agents remains to be elucidated. The present study aimed to determine the relative cytotoxicity and mechanism of benzyl isothiocyanate (BITC), a component of cruciferous vegetables, in melanoma cells expressing PAF-R. To evaluate the importance of PAF-R signaling in melanoma cell growth, PAF-R-negative murine B16F10 cells were transduced with a retrovirus containing the cDNA for PAF-R to generate cells stably expressing PAF-R (B16-PAF-R) or an empty vector (MSCV) to generate PAF-R-deficient B16-MSCV control cells. Activation of PAF-R, using the PAF-R agonist, 1-hexadecyl-2-N-methylcarbamoyl-3-glycerophosphocholine, induced an increase in the proliferation of B16-PAF-R cells compared with the B16-MSCV cells. Reverse transcription quantitative polymerase chain reaction revealed the presence of functional PAF-R in human melanoma SK23MEL cells, but not in SK5MEL cells. The present study investigated the effect of BITC treatments on the survival of murine and human melanoma cells, in the presence or absence of functional PAF-R. The results revealed that treatment with BITC decreased the survival rate of the PAF-R-positive and negative murine and human melanoma cells. However, the expression of PAF-R substantially augmented BITC-mediated cytotoxicity in the PAF-R-positive cells at lower concentrations compared with the PAF-R-negative cells. In order to determine the underlying mechanism, flow cytometric analysis was used, which demonstrated a significant increase in the generation of reactive oxygen species (ROS) in the B16-PAF-R cells compared with the B16-MSCV cells, which enhanced apoptosis by BITC, as measured by increased caspase-3/7 luminescence. Notably, the BITC-mediated decreased cell survival rate, increased ROS and increased

  15. 4(α-L-RHAMNOSYLOXY)-BENZYL ISOTHIOCYANATE, A BIOACTIVE PHYTOCHEMICAL THAT DEFENDS CEREBRAL TISSUE AND PREVENTS SEVERE DAMAGE INDUCED BY FOCAL ISCHEMIA/REPERFUSION.

    PubMed

    Galuppo, M; Giacoppo, S; Iori, R; De Nicola, G R; Milardi, D; Bramanti, P; Mazzon, E

    2015-01-01

    Natural compounds are a promising source to treat several pathologies. The present study shows the in vivo pharmacological beneficial effect of 4(α-L-rhamnosyloxy)-benzyl isothiocyanate (glucomoringin isothiocyanate; GMG-ITC) obtained from glucomoringin (GMG; 4(α;-L-rhamnosyloxy)- benzyl glucosinolate), purified from Moringa oleifera seeds and hydrolyzed by myrosinase enzyme (β-thioglucoside glucohydrolase; E.C. 3.2.1.147). Cerebral ischemia/reperfusion (CIR) was induced in rats according to a classic model of carotid artery occlusion for a time period of 1 h and the reperfusion time was prolonged for seven days. GMG-ITC (3.5 mg GMG/ml plus 30 μl enzyme/rat; one ml i.p./rat) was administered 15 min after the beginning of ischemia and daily. The results clearly show that GMG-ITC possesses the capability to counteract the CIR-induced damage reducing TNF-alpha release, IκB-alpha cytosolic degradation/NFκBp65 nuclear translocation, as well as several other direct or indirect markers of inflammation (phospho-ERK p42/44, p-selectin) and oxidative stress (inducible Nitric Oxide Synthase (iNOS), MMP-9). GMG-ITC was shown to exert neuroprotective properties in preventing CIR-induced damage and the related cascade of inflammatory and oxidative mediators that exacerbate the progression of this disease in an experimental rat model. Our results clearly show that the tested phytochemical GMG-ITC possesses the capability to counteract CIR-induced damage. PMID:26122222

  16. Administration of 4-(α-L-rhamnosyloxy)-benzyl isothiocyanate delays disease phenotype in SOD1(G93A) rats: a transgenic model of amyotrophic lateral sclerosis.

    PubMed

    Galuppo, Maria; Giacoppo, Sabrina; Iori, Renato; De Nicola, Gina Rosalinda; Bramanti, Placido; Mazzon, Emanuela

    2015-01-01

    4-(α-L-Rhamnosyloxy)-benzyl glucosinolate (glucomoringin, GMG) is a compound found in Moringa oleifera seeds. Myrosinase-catalyzed hydrolysis at neutral pH of GMG releases the biologically active compound 4-(α-L-rhamnosyloxy)-benzyl isothiocyanate (GMG-ITC). The present study was designed to test the potential therapeutic effectiveness of GMG-ITC to counteract the amyotrophic lateral sclerosis (ALS) using SOD1tg rats, which physiologically develops SOD1(G93A) at about 16 weeks of life, and can be considered a genetic model of disease. Rats were treated once a day with GMG (10 mg/Kg) bioactivated with myrosinase (20 µL/rat) via intraperitoneal (i.p.) injection for two weeks before disease onset and the treatment was prolonged for further two weeks before the sacrifice. Immune-inflammatory markers as well as apoptotic pathway were investigated to establish whether GMG-ITC could represent a new promising tool in clinical practice to prevent ALS. Achieved data display clear differences in molecular and biological profiles between treated and untreated SOD1tg rats leading to guessing that GMG-ITC can interfere with the pathophysiological mechanisms at the basis of ALS development. Therefore, GMG-ITC produced from myrosinase-catalyzed hydrolysis of pure GMG could be a candidate for further studies aimed to assess its possible use in clinical practice for the prevention or to slow down this disease. PMID:26075221

  17. Administration of 4-(α-L-Rhamnosyloxy)-benzyl Isothiocyanate Delays Disease Phenotype in SOD1G93A Rats: A Transgenic Model of Amyotrophic Lateral Sclerosis

    PubMed Central

    De Nicola, Gina Rosalinda; Mazzon, Emanuela

    2015-01-01

    4-(α-L-Rhamnosyloxy)-benzyl glucosinolate (glucomoringin, GMG) is a compound found in Moringa oleifera seeds. Myrosinase-catalyzed hydrolysis at neutral pH of GMG releases the biologically active compound 4-(α-L-rhamnosyloxy)-benzyl isothiocyanate (GMG-ITC). The present study was designed to test the potential therapeutic effectiveness of GMG-ITC to counteract the amyotrophic lateral sclerosis (ALS) using SOD1tg rats, which physiologically develops SOD1G93A at about 16 weeks of life, and can be considered a genetic model of disease. Rats were treated once a day with GMG (10 mg/Kg) bioactivated with myrosinase (20 µL/rat) via intraperitoneal (i.p.) injection for two weeks before disease onset and the treatment was prolonged for further two weeks before the sacrifice. Immune-inflammatory markers as well as apoptotic pathway were investigated to establish whether GMG-ITC could represent a new promising tool in clinical practice to prevent ALS. Achieved data display clear differences in molecular and biological profiles between treated and untreated SOD1tg rats leading to guessing that GMG-ITC can interfere with the pathophysiological mechanisms at the basis of ALS development. Therefore, GMG-ITC produced from myrosinase-catalyzed hydrolysis of pure GMG could be a candidate for further studies aimed to assess its possible use in clinical practice for the prevention or to slow down this disease. PMID:26075221

  18. 4(α-l-rhamnosyloxy)-benzyl isothiocyanate, a bioactive phytochemical that attenuates secondary damage in an experimental model of spinal cord injury.

    PubMed

    Giacoppo, Sabrina; Galuppo, Maria; De Nicola, Gina Rosalinda; Iori, Renato; Bramanti, Placido; Mazzon, Emanuela

    2015-01-01

    4(α-l-Rhamnosyloxy)-benzyl isothiocyanate (glucomoringin isothiocyanate; GMG-ITC) is released from the precursor 4(α-l-rhamnosyloxy)-benzyl glucosinolate (glucomoringin; GMG) by myrosinase (β-thioglucoside glucohydrolase; E.C. 3.2.1.147) catalyzed hydrolysis. GMG is an uncommon member of the glucosinolate group as it presents a unique characteristic consisting in a second glycosidic residue within the side chain. It is a typical glucosinolate found in large amounts in the seeds of Moringa oleifera Lam., the most widely distributed plant of the Moringaceae family. GMG was purified from seed-cake of M. oleifera and was hydrolyzed by myrosinase at neutral pH in order to form the corresponding GMG-ITC. This bioactive phytochemical can play a key role in counteracting the inflammatory response connected to the oxidative-related mechanisms as well as in the control of the neuronal cell death process, preserving spinal cord tissues after injury in mice. Spinal cord trauma was induced in mice by the application of vascular clips (force of 24g) for 1 min., via four-level T5-T8 after laminectomy. In particular, the purpose of this study was to investigate the dynamic changes occurring in the spinal cord after ip treatment with bioactive GMG-ITC produced 15 min before use from myrosinase-catalyzed hydrolysis of GMG (10mg/kg body weight+5 μl Myr mouse/day). The following parameters, such as histological damage, distribution of reticular fibers in connective tissue, nuclear factor (NF)-κB translocation and nuclear factor of kappa light polypeptide gene enhancer in B-cells inhibitor, alpha (IκB-α) degradation, expression of inducible Nitric Oxide Synthases (iNOS), as well as apoptosis, were evaluated. In conclusion, our results show a protective effect of bioactive GMG-ITC on the secondary damage, following spinal cord injury, through an antioxidant mechanism of neuroprotection. Therefore, the bioactive phytochemical GMG-ITC freshly produced before use by myrosinase

  19. Benzyl Isothiocyanate Inhibits Prostate Cancer Development in the Transgenic Adenocarcinoma Mouse Prostate (TRAMP) Model, Which Is Associated with the Induction of Cell Cycle G1 Arrest

    PubMed Central

    Cho, Han Jin; Lim, Do Young; Kwon, Gyoo Taik; Kim, Ji Hee; Huang, Zunnan; Song, Hyerim; Oh, Yoon Sin; Kang, Young-Hee; Lee, Ki Won; Dong, Zigang; Park, Jung Han Yoon

    2016-01-01

    Benzyl isothiocyanate (BITC) is a hydrolysis product of glucotropaeolin, a compound found in cruciferous vegetables, and has been shown to have anti-tumor properties. In the present study, we investigated whether BITC inhibits the development of prostate cancer in the transgenic adenocarcinoma mouse prostate (TRAMP) mice. Five-week old, male TRAMP mice and their nontransgenic littermates were gavage-fed with 0, 5, or 10 mg/kg of BITC every day for 19 weeks. The weight of the genitourinary tract increased markedly in TRAMP mice and this increase was suppressed significantly by BITC feeding. H and E staining of the dorsolateral lobes of the prostate demonstrated that well-differentiated carcinoma (WDC) was a predominant feature in the TRAMP mice. The number of lobes with WDC was reduced by BITC feeding while that of lobes with prostatic intraepithelial neoplasia was increased. BITC feeding reduced the number of cells expressing Ki67 (a proliferation marker), cyclin A, cyclin D1, and cyclin-dependent kinase (CDK)2 in the prostatic tissue. In vitro cell culture results revealed that BITC decreased DNA synthesis, as well as CDK2 and CDK4 activity in TRAMP-C2 mouse prostate cancer cells. These results indicate that inhibition of cell cycle progression contributes to the inhibition of prostate cancer development in TRAMP mice treated with BITC. PMID:26907265

  20. Raman Imaging Spectroscopy as a Tool To Investigate the Cell Damage on Aspergillus ochraceus Caused by an Antimicrobial Packaging Containing Benzyl Isothiocyanate.

    PubMed

    Clemente, Isabel; Aznar, Margarita; Nerín, Cristina

    2016-05-01

    Raman imaging spectroscopy is a nondestructive analytical method that can be a useful tool to obtain detailed information about the molecular composition and morphology of biological samples. Its high spatial resolution was used to collect spectra of Aspergillus ochraceus, a mold producer of ochratoxin A (OTA), in order to investigate the cell damage caused on it by the action of the antimicrobial benzyl isothiocyanate (BITC). The study was performed in both direct contact and vapor phase, in order to check the use of BITC as active agent in food packaging material. The results showed that there were morphologic alteration and a characteristic Raman spectrum on spore and hyphae exposed to BITC. BITC was accumulated in the mold cells where it caused an enormous amount of alterations in cellular components (lipids, proteins, saccharides, amino acids...) and cellular functions (cell cycle, respiration, metabolism, transcription of genes, fluidity of the cellular wall). All these structural, composition, and metabolic changes will affect the production of OTA. Pattern recognition with chemometrics using principal component analysis (PCA) demonstrated an excellent separation between control and BITC treated samples, both in spores and hyphae. PCA results also showed two different affection levels when samples were exposed to BITC in the vapor phase. PMID:27032001

  1. Benzyl Isothiocyanate Inhibits Prostate Cancer Development in the Transgenic Adenocarcinoma Mouse Prostate (TRAMP) Model, Which Is Associated with the Induction of Cell Cycle G1 Arrest.

    PubMed

    Cho, Han Jin; Lim, Do Young; Kwon, Gyoo Taik; Kim, Ji Hee; Huang, Zunnan; Song, Hyerim; Oh, Yoon Sin; Kang, Young-Hee; Lee, Ki Won; Dong, Zigang; Park, Jung Han Yoon

    2016-01-01

    Benzyl isothiocyanate (BITC) is a hydrolysis product of glucotropaeolin, a compound found in cruciferous vegetables, and has been shown to have anti-tumor properties. In the present study, we investigated whether BITC inhibits the development of prostate cancer in the transgenic adenocarcinoma mouse prostate (TRAMP) mice. Five-week old, male TRAMP mice and their nontransgenic littermates were gavage-fed with 0, 5, or 10 mg/kg of BITC every day for 19 weeks. The weight of the genitourinary tract increased markedly in TRAMP mice and this increase was suppressed significantly by BITC feeding. H and E staining of the dorsolateral lobes of the prostate demonstrated that well-differentiated carcinoma (WDC) was a predominant feature in the TRAMP mice. The number of lobes with WDC was reduced by BITC feeding while that of lobes with prostatic intraepithelial neoplasia was increased. BITC feeding reduced the number of cells expressing Ki67 (a proliferation marker), cyclin A, cyclin D1, and cyclin-dependent kinase (CDK)2 in the prostatic tissue. In vitro cell culture results revealed that BITC decreased DNA synthesis, as well as CDK2 and CDK4 activity in TRAMP-C2 mouse prostate cancer cells. These results indicate that inhibition of cell cycle progression contributes to the inhibition of prostate cancer development in TRAMP mice treated with BITC. PMID:26907265

  2. Cytotoxicity, Antioxidant and Apoptosis Studies of Quercetin-3-O Glucoside and 4-(β-D-Glucopyranosyl-1→4-α-L-Rhamnopyranosyloxy)-Benzyl Isothiocyanate from Moringa oleifera.

    PubMed

    Maiyo, Fiona C; Moodley, Roshila; Singh, Moganavelli

    2016-01-01

    Moringa oleifera, from the family Moringaceae, is used as a source of vegetable and herbal medicine and in the treatment of various cancers in many African countries, including Kenya. The present study involved the phytochemical analyses of the crude extracts of M.oleifera and biological activities (antioxidant, cytotoxicity and induction of apoptosis in-vitro) of selected isolated compounds. The compounds isolated from the leaves and seeds of the plant were quercetin-3-O-glucoside (1), 4-(β-D-glucopyranosyl-1→4-α-L-rhamnopyranosyloxy)-benzyl isothiocyanate (2), lutein (3), and sitosterol (4). Antioxidant activity of compound 1 was significant when compared to that of the control, while compound 2 showed moderate activity. The cytotoxicity of compounds 1 and 2 were tested in three cell lines, viz. liver hepatocellular carcinoma (HepG2), colon carcinoma (Caco-2) and a non-cancer cell line Human Embryonic Kidney (HEK293), using the MTT cell viability assay and compared against a standard anticancer drug, 5-fluorouracil. Apoptosis studies were carried out using the acridine orange/ethidium bromide dual staining method. The isolated compounds showed selective in vitro cytotoxic and apoptotic activity against human cancer and non-cancer cell lines, respectively. Compound 1 showed significant cytotoxicity against the Caco-2 cell line with an IC50 of 79 μg mL(-1) and moderate cytotoxicity against the HepG2 cell line with an IC50 of 150 μg mL(-1), while compound 2 showed significant cytotoxicity against the Caco- 2 and HepG2 cell lines with an IC50 of 45 μg mL(-1) and 60 μg mL(-1), respectively. Comparatively both compounds showed much lower cytotoxicity against the HEK293 cell line with IC50 values of 186 μg mL(-1) and 224 μg mL(-1), respectively. PMID:26428271

  3. Benzyl isothiocyanate disturbs lipid metabolism in rats in a way independent of its thyroid impact following in vivo long-term treatment and in vitro adipocytes studies.

    PubMed

    Okulicz, Monika; Hertig, Iwona

    2013-03-01

    During recent decades, benzyl isothiocyanate (BITC) was examined mainly in terms of its cancer chemopreventive action. Although some research has been conducted on goitrogenic activity of many glucosinolate derivatives, little attention has been paid to the BITC impact on the thyroid gland and lipid metabolism strictly associated with it. Therefore, this research project aimed at expanding our knowledge about how non-physiological doses of BITC (widely used in chemotherapy) influence some hormonal and metabolic (lipid) parameters in in vivo and in vitro experiments. The trial was focused on BITC action on thyroid tissue, liver, as well as white adipocyte tissue, at doses which were previously proved to exert a strong anticancer effect (10 mg/kg body weight in vivo and 1, 10 and 100 μmol/L in in vitro trials, respectively). Two-week oral administration of BITC in in vivo trial affected thyroid gland by decreasing total thyroxine and triiodothyronine. However, the obtained lipid profile was not specific for thyroid hormone deficiency because no lipid changes in the blood serum and liver steatosis were observed. BITC per se evoked elevation of basal lipolysis at 1 and 100 μmol/L and limitation of basal lipogenesis at 100 μmol/L in adipocyte tissues in in vitro experiment. BITC did not remain indifferent to liver metabolism by its possible influence on hepatic cholesterol 7α-hydroxylase and 5-deiodinase as well as on adipocytes by its enhanced basal lipolysis and limited lipogenesis independently of epinephrine and insulin action steps, respectively. Additionally, BITC was probably involved in bile flow obstruction. PMID:22798227

  4. Determination of benzyl isothiocyanate metabolites in human plasma and urine by LC-ESI-MS/MS after ingestion of nasturtium (Tropaeolum majus L.).

    PubMed

    Platz, Stefanie; Kühn, Carla; Schiess, Sonja; Schreiner, Monika; Mewis, Inga; Kemper, Margrit; Pfeiffer, Andreas; Rohn, Sascha

    2013-09-01

    A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed and validated to determine the concentration of benzyl isothiocyanate (BITC) metabolites in human plasma and urine. In this study, the following BITC metabolites have been considered: BITC-glutathione, BITC-cysteinylglycine, BITC-cysteine, and BITC-N-acetyl-L-cysteine. The assay development included: (1) synthesis of BITC conjugates acting as reference substances; (2) sample preparation based on protein precipitation and solid-phase extraction; (3) development of a quantitative LC-MS/MS method working in the multiple-reaction monitoring mode; (4) validation of the assay; (5) investigation of the stability and the reactivity of BITC conjugates in vitro; (6) application of the method to samples from a human intervention study. The lower limits of quantification were in the range of 21-183 nM depending on analyte and matrix, whereas the average recovery rates from spiked plasma and urine were approximately 85 and 75 %, respectively. BITC conjugates were found to be not stable in alkaline buffered solutions. After consumption of nasturtium, containing 1,000 μM glucotropaeolin, the primary source of BITC, quantifiable levels of BITC-NAC, BITC-Cys, and BITC-CysGly were found in human urine samples. Maximum levels in urine were determined 4 h after the ingestion of nasturtium. With regard to the human plasma samples, all metabolites were determined including individual distributions. The work presented provides a validated LC-MS/MS method for the determination of BITC metabolites and its successful application for the analysis of samples collected in a human intervention study. PMID:23852079

  5. Unexpected side products in the conjugation of an amine-derivatized morpholino oligomer with p-isothiocyanate benzyl DTPA and their removal.

    PubMed

    Liu, Guozheng; Dou, Shuping; Liu, Yuxia; Liang, Minmin; Chen, Ling; Cheng, Dengfeng; Greiner, Dale; Rusckowski, Mary; Hnatowich, Donald J

    2011-02-01

    In connection with pretargeting, an amine-derivatized morpholino phosphorodiamidate oligomer (NH(2)-cMORF) was conjugated conventionally with p-isothiocyanate benzyl-DTPA (p-SCN-Bn-DTPA). However, after (111)In radiolabeling, unexpected label instability was observed. To understand this instability, the NH(2)-cMORF and, as control, the native cMORF without the amine were conjugated in the conventional manner. Surprisingly, the (111)In labeling of the native cMORF conjugate was equally effective as that of the NH(2)-cMORF conjugate (>95%) despite the absence of the amine group. Furthermore, heating the radiolabeled NH(2)-cMORF and native cMORF conjugates resulted in a 35% loss and a complete loss of the label, respectively. Since the (111)In labeled DTPA is known to be stable, the instability in both cases must be due to some unstable association of DTPA to the cMORF, presumably unstable association to some endogenous sites in cMORF. Based on this assumption, a postconjugation-prepurification heating step was introduced, and labeling efficiency and stability were again investigated. By introducing the heating step, the side products were dissociated, and after purification and labeling, the NH(2)-cMORF conjugate provided a stable label and high labeling efficiency with no need for postlabeling purification. The biodistribution of this radiolabeled conjugate in normal mice showed significantly lower backgrounds compared with the labeled unstable native cMORF conjugate. In conclusion, the conventional conjugation procedure to attach the p-SCN-Bn-DTPA to NH(2)-cMORF resulted in side product(s) that were responsible for the (111)In label instability. Adding a postconjugation-prepurification heating step dissociated the side products, improved the label stability and lowered tissue backgrounds in mice. PMID:21315270

  6. Inhibition of lipopolysaccharide-induced cyclooxygenase-2 expression and inducible nitric oxide synthase by 4-[(2′-O-acetyl-α-l-rhamnosyloxy)benzyl]isothiocyanate from Moringa oleifera

    PubMed Central

    Park, Eun-Jung; Cheenpracha, Sarot; Chang, Leng Chee; Kondratyuk, Tamara P.; Pezzuto, John M.

    2011-01-01

    Moringa oleifera Lamarack is commonly consumed for nutritional or medicinal properties. We recently reported the isolation and structure elucidation of novel bioactive phenolic glycosides, including 4-[(2′-O-acetyl-α-l-rhamnosyloxy)benzyl]isothiocyanate (RBITC), which was found to suppress inducible nitric oxide synthase (iNOS) expression and nitric oxide production in lipopolysaccharide-stimulated RAW 264.7 mouse macrophage cells. Inhibitors of proteins such as cyclooxygenase-2 (COX-2) and iNOS are potential anti-inflammatory and cancer chemopreventive agents. The inhibitory activity of RBITC on NO production (IC50 = 0.96 ± 0.23 µM) was greater than that mediated by other well-known isothiocyanates such as sulforaphane (IC50 = 2.86 ± 0.39 µM) and benzyl isothiocyanate (IC50 = 2.08 ± 0.28 µM). RBITC inhibited expression of COX-2 and iNOS at both the protein and mRNA levels. Major upstream signaling pathways involved mitogen-activated protein kinases and nuclear factor-κB (NF-κB). RBITC inhibited phosphorylation of extracellular signal regulated kinase and stress-activated protein kinase, as well as ubiquitin-dependent degradation of inhibitor κBα (IκBα). In accordance with IκBα degradation, nuclear accumulation of NF-κB, and subsequent binding to NF-κB cis-acting element, was attenuated by treatment with RBITC. These data suggest RBITC should be included in the dietary armamentarium of isothiocyanates potentially capable of mediating anti-inflammatory or cancer chemopreventive activity. PMID:21774591

  7. Effects of benzyl isothiocyanate and its N-acetylcysteine conjugate on induction of detoxification enzymes in hepa1c1c7 mouse hepatoma cells.

    PubMed

    Hwang, Eun-Sun

    2014-12-01

    The induction of detoxification enzymes by benzyl isothiocyanate (BITC) and its synthetic N-acetyl-L-cysteine (NAC) conjugate (NAC-BITC) was examined in Hepa1c1c7 murine hepatoma cells. BITC and NAC-BITC inhibited Hepa1c1c7 cell growth in a dose-dependent manner. Cell growth was 4.5~57.2% lower in Hepa1c1c7 cells treated with 0.1~10 μM BITC than in control-treated Hepa1c1c7 cells. The NAC-BITC treatment had a similar inhibitory pattern on Hepa1c1c7 cell growth; 0.5 μM and 10 μM NAC-BITC decreased cell growth by 13.6% and 47.4%, respectively. Treatment of Hepa1c1c7 cells with 0.1~2.0 μM BITC also elicited a dose-response effect on the induction of quinone reductase quinone reductase (QR) activity and QR mRNA expression. Treatment with 1 μM and 2 μM BITC caused 1.8- and 2.8-fold inductions of QR mRNA, respectively. By comparison, treatment with 1 μM and 2 μM NAC-BITC caused 1.6- and 1.9-fold inductions of QR mRNA, respectively. Cytochrome P450 (CYP) 1A1 and CYP2E1 induction were lower in 0.1~2 μM BITC-treated cells than in control-treated cells. CYP2E1 activity was 1.2-fold greater in 0.1 μM NAC-BITC-treated cells than in control-treated cells. However, the CYP2E1 activity of cells treated with higher concentrations (i.e., 1~2 μM) of NAC-BITC was similar to the activity of control-treated cells. Considering the potential of isothiocyanatesto prevent cancer, these results provide support for the use of BITC and NAC-BITC conjugates as chemopreventive agents. PMID:25580390

  8. Effects of Benzyl Isothiocyanate and Its N-Acetylcysteine Conjugate on Induction of Detoxification Enzymes in Hepa1c1c7 Mouse Hepatoma Cells

    PubMed Central

    Hwang, Eun-Sun

    2014-01-01

    The induction of detoxification enzymes by benzyl isothiocyanate (BITC) and its synthetic N-acetyl-L-cysteine (NAC) conjugate (NAC-BITC) was examined in Hepa1c1c7 murine hepatoma cells. BITC and NAC-BITC inhibited Hepa1c1c7 cell growth in a dose-dependent manner. Cell growth was 4.5~57.2% lower in Hepa1c1c7 cells treated with 0.1~10 μM BITC than in control-treated Hepa1c1c7 cells. The NAC-BITC treatment had a similar inhibitory pattern on Hepa1c1c7 cell growth; 0.5 μM and 10 μM NAC-BITC decreased cell growth by 13.6% and 47.4%, respectively. Treatment of Hepa1c1c7 cells with 0.1~2.0 μM BITC also elicited a dose-response effect on the induction of quinone reductase quinone reductase (QR) activity and QR mRNA expression. Treatment with 1 μM and 2 μM BITC caused 1.8- and 2.8-fold inductions of QR mRNA, respectively. By comparison, treatment with 1 μM and 2 μM NAC-BITC caused 1.6- and 1.9-fold inductions of QR mRNA, respectively. Cytochrome P450 (CYP) 1A1 and CYP2E1 induction were lower in 0.1~2 μM BITC-treated cells than in control-treated cells. CYP2E1 activity was 1.2-fold greater in 0.1 μM NAC-BITC-treated cells than in control-treated cells. However, the CYP2E1 activity of cells treated with higher concentrations (i.e., 1~2 μM) of NAC-BITC was similar to the activity of control-treated cells. Considering the potential of isothiocyanatesto prevent cancer, these results provide support for the use of BITC and NAC-BITC conjugates as chemopreventive agents. PMID:25580390

  9. Derivatization of isothiocyanates and their reactive adducts for chromatographic analysis.

    PubMed

    Agerbirk, Niels; De Nicola, Gina Rosalinda; Olsen, Carl Erik; Müller, Caroline; Iori, Renato

    2015-10-01

    Isothiocyanates form adducts with a multitude of biomolecules, and these adducts need analytical methods. Likewise, analytical methods for hydrophilic isothiocyanates are needed. We considered reaction with ammonia to form thiourea derivatives. The hydrophilic, glycosylated isothiocyanate moringin, 4-(α-L-rhamnopyranosyloxy)benzyl isothiocyanate, was efficiently derivatized to the thiourea derivative by incubation with ammonia. The hydrophobic benzyl isothiocyanate was also efficiently derivatized to the thiourea derivative. The thiourea group provided a UV absorbing chromophore, and the derivatives showed expectable sodium and hydrogen adducts in ion trap mass spectrometry and were suitable for liquid chromatography analysis. Reactive dithiocarbamate adducts constitute the major type of reactive ITC adduct expected in biological matrices. Incubation of a model dithiocarbamate with ammonia likewise resulted in conversion to the corresponding thiourea derivative, suggesting that a variety of matrix-bound reactive isothiocyanate adducts can be determined using this strategy. As an example of the application of the method, recovery of moringin and benzyl isothiocyanate applied to cabbage leaf discs was studied in simulated insect feeding assays. The majority of moringin was recovered as native isothiocyanate, but a major part of benzyl isothiocyanate was converted to reactive adducts. PMID:26342619

  10. Beyond Benzyl Grignards: Facile Generation of Benzyl Carbanions from Styrenes

    PubMed Central

    Grigg, R. David; Rigoli, Jared W.; Van Hoveln, Ryan; Neale, Samuel

    2015-01-01

    The facile generation of benzyl anion equivalents from styrenes has been achieved. A Cu-catalyzed hydroboration is used in conjunction with sterically-induced cleavage of the C-B bond with tBuOK. Quenching this reactive intermediate with heterocumulene electrophiles, including CO2, CS2, isocyanates and isothiocyanates, yields benzylic C-C bond formation. The utility of this methodology was demonstrated in a synthesis of the non-steroidal anti-inflammatory drug (+)-flurbiprofen. PMID:22718528

  11. Naturally Occurring Isothiocyanates Exert Anticancer Effects by Inhibiting Deubiquitinating Enzymes.

    PubMed

    Lawson, Ann P; Long, Marcus J C; Coffey, Rory T; Qian, Yu; Weerapana, Eranthie; El Oualid, Farid; Hedstrom, Lizbeth

    2015-12-01

    The anticancer properties of cruciferous vegetables are well known and attributed to an abundance of isothiocyanates such as benzyl isothiocyanate (BITC) and phenethyl isothiocyanate (PEITC). While many potential targets of isothiocyanates have been proposed, a full understanding of the mechanisms underlying their anticancer activity has remained elusive. Here we report that BITC and PEITC effectively inhibit deubiquitinating enzymes (DUB), including the enzymes USP9x and UCH37, which are associated with tumorigenesis, at physiologically relevant concentrations and time scales. USP9x protects the antiapoptotic protein Mcl-1 from degradation, and cells dependent on Mcl-1 were especially sensitive to BITC and PEITC. These isothiocyanates increased Mcl-1 ubiquitination and either isothiocyanate treatment, or RNAi-mediated silencing of USP9x decreased Mcl-1 levels, consistent with the notion that USP9x is a primary target of isothiocyanate activity. These isothiocyanates also increased ubiquitination of the oncogenic fusion protein Bcr-Abl, resulting in degradation under low isothiocyanate concentrations and aggregation under high isothiocyanate concentrations. USP9x inhibition paralleled the decrease in Bcr-Abl levels induced by isothiocyanate treatment, and USP9x silencing was sufficient to decrease Bcr-Abl levels, further suggesting that Bcr-Abl is a USP9x substrate. Overall, our findings suggest that USP9x targeting is critical to the mechanism underpinning the well-established anticancer activity of isothiocyanate. We propose that the isothiocyanate-induced inhibition of DUBs may also explain how isothiocyanates affect inflammatory and DNA repair processes, thus offering a unifying theme in understanding the function and useful application of isothiocyanates to treat cancer as well as a variety of other pathologic conditions. PMID:26542215

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

    PubMed

    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. PMID:24731259

  13. CXCR4 is a novel target of cancer chemopreventative isothiocyanates in prostate cancer cells.

    PubMed

    Sakao, Kozue; Vyas, Avani R; Chinni, Sreenivasa R; Amjad, Ali I; Parikh, Rahul; Singh, Shivendra V

    2015-05-01

    Isothiocyanates (ITCs) derived from cruciferous vegetables, including phenethyl isothiocyanate (PEITC) and sulforaphane (SFN), exhibit in vivo activity against prostate cancer in a xenograft and transgenic mouse model, and thus are appealing for chemoprevention of this disease. Watercress constituent PEITC and SFN-rich broccoli sprout extract are under clinical investigations but the molecular mechanisms underlying their cancer chemopreventive effects are not fully understood. The present study demonstrates that chemokine receptor CXCR4 is a novel target of ITCs in prostate cancer cells. Exposure of prostate cancer cells (LNCaP, 22Rv1, C4-2, and PC-3) to pharmacologically applicable concentrations of PEITC, benzyl isothiocyanate (BITC), and SFN (2.5 and 5 μmol/L) resulted in downregulation of CXCR4 expression. None of the ITCs affected secretion of CXCR4 ligand (stromal-derived factor-1). In vivo inhibition of PC-3 xenograft growth upon PEITC treatment was associated with a significant decrease in CXCR4 protein level. A similar trend was discernible in the tumors from SFN-treated TRAMP mice compared with those of control mice, but the difference was not significant. Stable overexpression of CXCR4 in PC-3 cells conferred significant protection against wound healing, cell migration, and cell viability inhibition by ITCs. Inhibition of cell migration resulting from PEITC and BITC exposure was significantly augmented by RNAi of CXCR4. This study demonstrates, for the first time, that cancer chemopreventive ITCs suppress CXCR4 expression in prostate cancer cells in vitro as well as in vivo. These results suggest that CXCR4 downregulation may be an important pharmacodynamic biomarker of cancer chemopreventative ITCs in prostate adenocarcinoma. PMID:25712054

  14. Benzyl chloride

    Integrated Risk Information System (IRIS)

    Benzyl chloride ; CASRN 100 - 44 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

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

    PubMed Central

    Dias, Carla; Aires, Alfredo; Saavedra, Maria José

    2014-01-01

    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. PMID:25353177

  16. Tetraalkylammonium uranyl isothiocyanates.

    PubMed

    Rowland, Clare E; Kanatzidis, Mercouri G; Soderholm, L

    2012-11-01

    Three tetraalkylammonium uranyl isothiocyanates, [(CH(3))(4)N](3)UO(2)(NCS)(5) (1), [(C(2)H(5))(4)N](3)UO(2)(NCS)(5) (2), and [(C(3)H(7))(4)N](3)UO(2)(NCS)(5) (3), have been synthesized from aqueous solution and their structures determined by single-crystal X-ray diffraction. All of the compounds consist of the uranyl cation equatorially coordinated to five N-bound thiocyanate ligands, UO(2)(NCS)(5)(3-), and charge-balanced by three tetraalkylammonium cations. Raman spectroscopy data have been collected on compounds 1-3, as well as on solutions of uranyl nitrate with increasing levels of sodium thiocyanate. By tracking the Raman signatures of thiocyanate, the presence of both free and bound thiocyanate is confirmed in solution. The shift in the Raman signal of the uranyl symmetric stretching mode suggests the formation of higher-order uranyl thiocyanate complexes in solution, while the solid-state Raman data support homoleptic isothiocyanate coordination about the uranyl cation. Presented here are the syntheses and crystal structures of 1-3, pertinent Raman spectra, and a discussion regarding the relationship of these isothiocyanates to previously described uranyl halide phases, UO(2)X(4)(2-). PMID:23072277

  17. Benzyl isothiocyanate sensitizes human pancreatic cancer cells to radiation therapy.

    PubMed

    Sahu, Ravi Prakash; Epperly, Michael Wayne; Srivastava, Sanjay Kumar

    2009-01-01

    Increase in systemic toxicity and resistance are the major drawbacks of radiation therapy in the treatment of pancreatic cancer. We have shown previously that BITC inhibits the growth of human pancreatic cancer cells and induces apoptosis. Here we determined whether BITC could sensitize BxPC-3 cells and increase the therapeutic potential of gamma-irradiation. Cells were pretreated with 2.5 microM BITC for 24h followed by exposure to 5 Gy of gamma-irradiation and were allowed to grow for another 24 or 48 h before being analyzed. Combination of BITC and gamma-irradiation significantly reduced survival of cells and caused significantly enhanced arrest of cells in G2/M phase as compared to cells exposed to gamma-irradiation alone. G2/M arrest was associated with DNA damage leading to the phosphorylation of ATR (Ser-428), Chk2 (Thr-68), Cdc25C (Ser-216), Cdk-1 (Tyr-15) and induction of p21Waf1/Cip1. However, combination treatment after 48 h caused 2.8-fold increase in apoptosis in BxPC-3 cells. Apoptosis at 48 h was associated with NF-kappa B inhibition and p38 activation. Taken together, results of the present study suggest that the apoptosis-inducing effect of gamma-irradiation can be increased by BITC. PMID:19482673

  18. Peptide Reactivity of Isothiocyanates - Implications for Skin Allergy.

    PubMed

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

    2016-01-01

    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. PMID:26883070

  19. Peptide Reactivity of Isothiocyanates – Implications for Skin Allergy

    PubMed Central

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

    2016-01-01

    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. PMID:26883070

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

    PubMed Central

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

    2014-01-01

    Moringa (Moringa oleifera Lam.) is an edible plant used as 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 (1–4) into moringa isothiocyanates (5–8). Optimum conditions maximizing MC yield, compound 5 (4-[(α-L-rhamnosyloxy)benzyl]isothiocyanate), and compound 8 (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. Compound 8 exhibited 80% stability at 37 °C for 30 days. MC, 5, and 8 significantly decreased gene expression and production of inflammatory markers in RAW macrophages. Specifically, 5 and 8 attenuated expression of iNOS and IL-1β and production of nitric oxide and TNFβ at 1 and 5 µM. Our results suggest a potential for stable and concentrated moringa isothiocyanates (5–8), delivered in MC as a food-grade product, to alleviate low-grade inflammation associated with chronic diseases. PMID:24731259

  1. Benzyl Alcohol Topical

    MedlinePlus

    Benzyl alcohol lotion is used to treat head lice (small insects that attach themselves to the skin) in adults and children ... It works by killing the lice. Benzyl alcohol lotion will not kill lice eggs, so the medication ...

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

    SciTech Connect

    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.

  3. Antimicrobial Activities of Isothiocyanates Against Campylobacter jejuni Isolates

    PubMed Central

    Dufour, Virginie; Alazzam, Bachar; Ermel, Gwennola; Thepaut, Marion; Rossero, Albert; Tresse, Odile; Baysse, Christine

    2012-01-01

    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. AITC and BITC displayed a potent antibacterial activity against C. jejuni. BITC showed a higher overall antibacterial effect (MIC of 1.25–5 μg mL−1) compared to AITC (MIC of 50–200 μg mL−1). Both compounds are bactericidal rather than bacteriostatic. The sensitivity levels of C. jejuni isolates against isothiocyanates were neither correlated with the presence of a GGT (γ-Glutamyl Transpeptidase) encoding gene in the genome, with antibiotic resistance nor with the origin of the biological sample. However the ggt mutant of C. jejuni 81-176 displayed a decreased survival rate compared to wild-type when exposed to ITC. This work determined the MIC of two ITC against a panel of C. jejuni isolates, showed that both compounds are bactericidal rather than bacteriostatic, and highlighted the role of GGT enzyme in the survival rate of C. jejuni exposed to ITC. PMID:22919644

  4. Anticancer activity of glucomoringin isothiocyanate in human malignant astrocytoma cells.

    PubMed

    Rajan, Thangavelu Soundara; De Nicola, Gina Rosalinda; Iori, Renato; Rollin, Patrick; Bramanti, Placido; Mazzon, Emanuela

    2016-04-01

    Isothiocyanates (ITCs) released from their glucosinolate precursors have been shown to inhibit tumorigenesis and they have received significant attention as potential chemotherapeutic agents against cancer. Astrocytoma grade IV is the most frequent and most malignant primary brain tumor in adults without any curative treatment. New therapeutic drugs are therefore urgently required. In the present study, we investigated the in vitro antitumor activity of the glycosylated isothiocyanate moringin [4-(α-l-rhamnopyranosyloxy)benzyl isothiocyanate] produced from quantitative myrosinase-induced hydrolysis of glucomoringin (GMG) under neutral pH value. We have evaluated the potency of moringin on apoptosis induction and cell death in human astrocytoma grade IV CCF-STTG1 cells. Moringin showed to be effective in inducing apoptosis through p53 and Bax activation and Bcl-2 inhibition. In addition, oxidative stress related Nrf2 transcription factor and its upstream regulator CK2 alpha expressions were modulated at higher doses, which indicated the involvement of oxidative stress-mediated apoptosis induced by moringin. Moreover, significant reduction in 5S rRNA was noticed with moringin treatment. Our in vitro results demonstrated the antitumor efficacy of moringin derived from myrosinase-hydrolysis of GMG in human malignant astrocytoma cells. PMID:26882972

  5. Mechanisms of the Anticancer Effects of Isothiocyanates.

    PubMed

    Fofaria, Neel M; Ranjan, Alok; Kim, Sung-Hoon; Srivastava, Sanjay K

    2015-01-01

    Cancer results from aberrant signaling pathways that result in uncontrolled cellular proliferation. The epidemiological studies have shown a strong inverse correlation between dietary consumption of cruciferous vegetables and incidences of cancer. Isothiocyanates (ITCs) are present in cruciferous vegetables like broccoli, cabbage, watercress, etc. and are identified as the major active constituents. Several mechanistic studies have demonstrated chemopreventive and chemotherapeutic activity of ITCs against various tumor types. ITCs exert anticancer activity by suppressing various critical hallmarks of cancer like cellular proliferation, angiogenesis, apoptosis, metastasis, etc., in vitro as well as in preclinical animal model. ITCs also generate reactive oxygen species to induce apoptosis in cancer cells. Due to promising preclinical results, few ITCs have also advanced to clinical trials. This chapter provides a candid review on the chemopreventive and chemotherapeutic activity of various major ITCs. PMID:26298458

  6. [Determination of benzyl glucosinolate in Lepidium meyenii from different regions by HPLC].

    PubMed

    Tang, Lin; Yin, Hong-jun; Si, Cong-cong; Hu, Xiao-yan; Long, Zheng-hai

    2015-12-01

    The content of benzyl isothiocyanate (BITC) which as the enzymatic hydrolysis product of benzyl glucosinolate through thioglucosidase was determined by HPLC. The content of benzyl isothiocyanate (BITC) which as the enzymatic hydrolysis product of benzyl glucosinolate through thioglucosidase was determined by HPLC. The chromatography condition was as follows: Kaseisorb LC ODS 2000 (4.6 mm x 150 mm, 5 min) column with the mobile phase of acetonitrile(A)-water( B) under gradient elution (0-5 min, 3%-8% A; 5-9 min, 8%-48% A; 9-23 min, 48%-62% A; 23-28 min, 62%-99% A); the flow rate was 1.0 mL x min(-1) with 10 microL injection volume; detection wavelength was 246 nm and temperature of column was 40 degrees C. The content of benzyl glucosinolate was in the range of 10.76-17.91 g x L(-1). The method is simple, accurate and good reproducibility which can be used for the determination of benzyl glucosinolate in Lepidium meyenii, effectively. PMID:27141661

  7. Direct and Indirect Antioxidant Activity of Polyphenol- and Isothiocyanate-Enriched Fractions from Moringa oleifera

    PubMed Central

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

    2016-01-01

    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. PMID:25605589

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

    PubMed

    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. PMID:25605589

  9. Isothiocyanates as effective agents against enterohemorrhagic Escherichia coli: insight to the mode of action

    PubMed Central

    Nowicki, Dariusz; Rodzik, Olga; Herman-Antosiewicz, Anna; Szalewska-Pałasz, Agnieszka

    2016-01-01

    Production of Shiga toxins by enterohemorrhagic Escherichia coli (EHEC) which is responsible for the pathogenicity of these strains, is strictly correlated with induction of lambdoid bacteriophages present in the host’s genome, replication of phage DNA and expression of stx genes. Antibiotic treatment of EHEC infection may lead to induction of prophage into a lytic development, thus increasing the risk of severe complications. This, together with the spread of multi-drug resistance, increases the need for novel antimicrobial agents. We report here that isothiocyanates (ITC), plant secondary metabolites, such as sulforaphane (SFN), allyl isothiocyanate (AITC), benzyl isothiocynanate (BITC), phenyl isothiocyanate (PITC) and isopropyl isothiocyanate (IPRITC), inhibit bacterial growth and lytic development of stx-harboring prophages. The mechanism underlying the antimicrobial effect of ITCs involves the induction of global bacterial stress regulatory system, the stringent response. Its alarmone, guanosine penta/tetraphosphate ((p)ppGpp) affects major cellular processes, including nucleic acids synthesis, which leads to the efficient inhibition of both, prophage induction and toxin synthesis, abolishing in this way EHEC virulence for human and simian cells. Thus, ITCs could be considered as potential therapeutic agents in EHEC infections. PMID:26922906

  10. Benzyl Alcohol Topical

    MedlinePlus

    ... lice. Benzyl alcohol lotion will not kill lice eggs, so the medication must be used a second ... kill the lice that may hatch from these eggs. ... to remove the dead lice and nits (empty egg shells) after this treatment. You may also need ...

  11. Butyl benzyl phthalate

    Integrated Risk Information System (IRIS)

    Butyl benzyl phthalate ; CASRN 85 - 68 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinog

  12. A glutathione S-transferase inducer from papaya: rapid screening, identification and structure-activity relationship of isothiocyanates.

    PubMed

    Nakamura, Y; Morimitsu, Y; Uzu, T; Ohigashi, H; Murakami, A; Naito, Y; Nakagawa, Y; Osawa, T; Uchida, K

    2000-09-01

    We have developed a simple system for rapid detection and measurement of glutathione S-transferase placental form (GSTP1) that detoxify polycyclic aromatic hydrocarbons using the cultured rat normal liver epithelial cell line, (RL34) cells. Survey of fruit extracts for GST inducing ability identified both papaya and avocado as significant sources. Benzyl isothiocyanate (BITC) was isolated from papaya methanol extract as a principal inducer of GST activity. Further, the GST inducing ability of a total of 20 isothiocyanates (ITCs) and their derivatives was investigated. Some ITCs showed significant induction, and BITC was one of the most potent inducers among all compounds tested in the present study. The modification of isothiocyanate group (-NCS) or introduction of substituent group to the alpha-carbon modifies GST induction. Moreover, a significant correlation (P<0.01, r=0.913) between the GST activity enrichment and GSTP1 protein induction by ITCs was observed. We also indicated that phenethyl ITC and nitrophenyl ITC, potently inducing GST activity, but not inactive benzyl isocyanate, are potential inducers of intracellular reactive oxygen intermediates (ROIs). Our system of GSTP1 induction is appropriate for the chemical research such as screening and identification of novel type of inducers as well as the structure-activity relationship studies, providing mechanistic insight into essential structural elements for GSTP1 induction. PMID:10936680

  13. The anti-oxidant properties of isothiocyanates: a review.

    PubMed

    de Figueiredo, Sônia M; Filho, Sidney A V; Nogueira-Machado, José A; Caligiorne, Rachel B

    2013-09-01

    Cruciferous vegetables, such as broccoli and watercress, have been studied extensively aiming to evaluate their chemopreventive properties. Some of them have already been established using animal models. The ITCs induce Phase II enzymes related to detoxification processes of chemical carcinogens to prevent the start of carcinogenesis. They also exhibit antitumor activity at post-initiation phase, suggesting their additional role(s) in cancer prevention. Sulforaphane is the most extensively studied isothiocyanate, focused in its anti-tumoral activity and it is mainly found in great amounts in broccoli and other cruciferous. In a dose dependent manner, ITCs inhibit the cell viability of human cervical cancer cells, human pancreatic cancer cells, human hepatocellular carcinoma cells, human ovarian cancer cells, and have antiinflammatory properties in the treatment of human T-cell leukemia cells. This protective effect may be due to improved antioxidant status. Although the health effects of diet in humans are generally considered promising, there are definite challenges and limitations of the current data in better understanding of the molecular mechanisms responsible for this effect, together with the possible interactions between different dietary constituents. The survey of relevant patents on the use of isothiocyanates such as sulforaphane for cancer and cardiovascular diseases treatments is also included in this review. PMID:23978168

  14. Phenethyl Isothiocyanate: A comprehensive review of anti-cancer mechanisms

    PubMed Central

    Gupta, Parul; Wright, Stephen E.; Kim, Sung-Hoon; Srivastava, Sanjay K.

    2014-01-01

    The epidemiological evidence suggests a strong inverse relationship between dietary intake of cruciferous vegetables and the incidence of cancer. Among other constituents of cruciferous vegetables, isothiocyanates (ITC) are the main bioactive chemicals present. Phenethyl isothiocyanate (PEITC) is present as gluconasturtiin in many cruciferous vegetables with remarkable anti-cancer effects. PEITC is known to not only prevent the initiation phase of carcinogenesis process but also to inhibit the progression of tumorigenesis. PEITC targets multiple proteins to suppress various cancer-promoting mechanisms such as cell proliferation, progression and metastasis. Pre-clinical evidence suggests that combination of PEITC with conventional anti-cancer agents is also highly effective in improving overall efficacy. Based on accumulating evidence, PEITC appears to be a promising agent for cancer therapy and is already under clinical trials for leukemia and lung cancer. This is the first review which provides a comprehensive analysis of known targets and mechanisms along with a critical evaluation of PEITC as a future anti-cancer agent. PMID:25152445

  15. Isothiocyanates: a class of bioactive metabolites with chemopreventive potential.

    PubMed

    Kumar, Gaurav; Tuli, Hardeep Singh; Mittal, Sonam; Shandilya, Jitendra Kumar; Tiwari, Anil; Sandhu, Sardul Singh

    2015-06-01

    In recent years, growing interest has been focused on the field of chemoprevention using natural therapies. The reason to turn toward "natural" remedies is associated with diverse beneficial pharmacological properties of natural compounds. Isothiocyanates (ITCs), the major pharmacological active constituents of cruciferous vegetables, are derived from the enzymatic hydrolysis of glucosinolates (GSLs). ITCs govern many intracellular targets including cytochrome P 450 (CYP) enzymes, proteins involved in antioxidant response, tumorigenesis, apoptosis, cell cycle, and metastasis. Investigation of the mechanisms of anti-cancer drugs has given important information regarding the use of natural chemopreventive compounds. This extensive review covers various molecular aspects of the interactions of ITCs with their recognized cellular targets involved in cancer treatment in order to enhance anti-tumor outcome with decreased toxicity to patients. PMID:25835976

  16. Health and environmental effects profile for benzyl chloride

    SciTech Connect

    Not Available

    1986-06-01

    The Health and Environmental Effects Profile for Benzyl Chloride was prepared to support listings of hazardous constituents of a wide range of waste streams under Section 3001 of the Resource Conservation and Recovery Act (RCRA) and to provide health-related limits for emergency actions under Section 101 of the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Both published literature and information obtained from Agency program office files were evaluated as they pertained to potential human health, aquatic life and environmental effects of hazardous-waste constituents. Quantitative estimates are presented provided sufficient data are available. Benzyl chloride has been evaluated as a carcinogen. The human carcinogen potency factor for benzyl chloride is 0.0171 (mg/kg/day) for oral exposure. The Reportable Quantity (RQ) value of 1, 10, 100, 1000 or 5000 pounds is used to determine the quantity of a hazardous substance for which notification is required in the event of a release as specified by CERCLA based on chronic toxicity. The RQ value for benzyl chloride is 1000.

  17. A principal mechanism for the cancer chemopreventive activity of phenethyl isothiocyanate is modulation of carcinogen metabolism.

    PubMed

    Ioannides, Costas; Konsue, Nattaya

    2015-08-01

    Isothiocyanates are small molecules characterized by high chemical reactivity that allows them to interact readily with cellular constituents eliciting a plethora of biological activities. They are present exclusively in cruciferous vegetables, as glucosinolates, the intake of which has been associated with cancer chemoprevention. When the physical structure of these vegetables is disturbed, e.g. during mastication, the enzyme myrosinase is released and converts the glucosinolates to isothiocyanates (R-N=C=S), where R can be aliphatic or aromatic. Although sulforaphane, an aliphatic isothiocyanate, has received most attention worldwide, the most extensively studied aromatic isothiocyanate is phenethyl isothiocyanate (PEITC), and there are substantial differences in biological activity between the two sub-classes. In animal cancer models, PEITC effectively antagonized the carcinogenicity of chemicals, especially nitrosocompounds. A principal mechanism of their action is to protect the integrity of DNA by decreasing the levels of the genotoxic metabolites of chemical carcinogens. Extensive studies established that PEITC modulates the metabolism of the tobacco-specific carcinogenic nitrosamine 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) by inhibiting its cytochrome P450-mediated bioactivation. Moreover, PEITC is a potent inducer of detoxification enzymes such as quinone reductase, glutathione S-transferase and glucuronosyl transferase. PEITC is rapidly absorbed and is characterized by a large bioavailability; Cmax concentrations achieved in plasma after dietary intake are sufficient to modulate carcinogen metabolism. PEITC is primarily metabolized by glutathione conjugation and is excreted in the urine and bile as the mercapturate. The ability of PEITC to perturb carcinogen metabolism through modulation of cytochrome P450 and phase II detoxification enzymes is comprehensively and critically reviewed. PMID:26119477

  18. Peculiar Reactivity of Isothiocyanates with Pentaphenylborole.

    PubMed

    Huang, Kexuan; Martin, Caleb D

    2016-01-01

    The reactions of isothiocyanates with the antiaromatic pentaphenylborole were investigated, revealing significantly different outcomes than the analogous reactions with isocyanates. The 1:1 stoichiometric reaction products isolated include a seven-membered BNC5 heterocycle and a fused bicyclic 4/5-ring system. Studies suggest that the seven-membered ring undergoes an intramolecular [2 + 2] electrocyclic ring closure to produce the bicyclic system. The only derivative for which stoichiometry influenced the reaction outcome was 4-methoxyphenylisothiocyanate. The reaction of borole with an excess of 4-methoxyphenylisothiocyanate resulted in the formation of a fused tetracyclic species with two equivalents of isothiocyanate incorporated into the product. Rational pathways for these unusual transformations are presented. PMID:26682496

  19. Broad spectrum antibacterial activity of a mixture of isothiocyanates from nasturtium (Tropaeoli majoris herba) and horseradish (Armoraciae rusticanae radix).

    PubMed

    Conrad, A; Biehler, D; Nobis, T; Richter, H; Engels, I; Biehler, K; Frank, U

    2013-02-01

    Isothiocyanates have been reported to exert antimicrobial activity. These compounds are found in a licensed native preparation of nasturtium (Tropaeoli majoris herba) and horseradish (Armoraciae rusticanae radix) which is used for treatment of upper respiratory and urinary tract infections. The aim of our investigation was to assess the antimicrobial activity of a mixture of the contained benzyl-, allyl-, and phenylethyl- isothiocyanates against clinically important bacterial and fungal pathogens including antimicrobial resistant isolates. Susceptibility testing was performed by agar-dilution technique. Isothiocyanates were mixed in proportions identical to the licensed drug. Minimum inhibitory- and minimum bactericidal concentrations were assessed. The Minimum inhibitory concentration90 was defined as the concentration which inhibited 90% of the microbial species tested. H. influenzae, M. catarrhalis, S. marcescens, P. vulgaris, and Candida spp. were found to be highly susceptible, with minimum inhibitory concentration90 -values ranging between ≤0.0005% and 0.004% (v/v) of total ITC. Intermediate susceptibilities were observed for S. aureus, S. pyogenes, S. pneumoniae, K. pneumoniae, E. coli and P. aeruginosa, with Minimum inhibitory concentration90 -values ranging between 0.004% and 0.125% (v/v), but with elevated Minimum bactericidal concentrations90-values (2-7 dilution steps above Minimum inhibitory concentration90). Low susceptibilities were determined for viridans streptococci and enterococci. Interestingly, both resistant and non-resistant bacteria were similarly susceptible to the test preparation. PMID:23447075

  20. Lacosamide Isothiocyanate-based Agents: Novel Agents to Target and Identify Lacosamide Receptors

    PubMed Central

    Park, Ki Duk; Morieux, Pierre; Salomé, Christophe; Cotten, Steven W.; Reamtong, Onrapak; Eyers, Claire; Gaskell, Simon J.; Stables, James P.; Liu, Rihe; Kohn, Harold

    2009-01-01

    (R)-Lacosamide ((R)-2, (R)-N-benzyl 2-acetamido-3-methoxypropionamide), has recently gained regulatory approval for the treatment of partial-onset seizures in adults. Whole animal pharmacological studies have documented that (R)-2 function is unique. A robust strategy is advanced for the discovery of interacting proteins associated with function and toxicity of (R)-2 through the use of (R)-2 analogs, 3, that contain “affinity bait (AB)” and “chemical reporter (CR)” functional groups. In 3, covalent modification of the interacting proteins proceeds at the AB moiety, and detection or isolation of the selectively captured protein occurs through the bioorthogonal CR group upon reaction with an appropriate probe. We report the synthesis, pharmacological evaluation, and interrogation of the mouse soluble brain proteome using 3 where the AB group is an isothiocyanate moiety. One compound, (R)-N-(4-isothiocyanato)benzyl 2-acetamido-3-(prop-2-ynyloxy)propionamide ((R)-9), exhibited excellent seizure protection in mice and, like (R)-2, anticonvulsant activity principally resided in the (R)-stereoisomer. Several proteins were preferentially labeled by (R)-9 compared with (S)-9, including collapsin response mediator protein 2. PMID:19795888

  1. Monitoring of isothiocyanates emanating from Arabidopsis thaliana upon paraquat spraying.

    PubMed

    Vercammen, J; Pham-Tuan, H; Arickx, I; Van der Straeten, D; Sandra, P

    2001-03-30

    Arabidopsis thaliana plants were sprayed with the superoxide-generating herbicide paraquat. The headspace of sprayed plants was characterized by a number of compounds, which were absent in the headspace of untreated plants. They were identified as isothiocyanates (ITCs) with 4-methylthiobutyl isothiocyanate as main compound. After identification, a GC-system, based on PDMS sorption, was used to continuously monitor the ITC emissions. The specificity of isothiocyanate emission was also determined by subjecting the Arabidopsis thaliana plants to in vitro mechanical wounding. Again, 4-methylthiobutyl isothiocyanate was the main component, but the emission profile was completely different since the compound was emitted immediately, i.e., during wounding itself. PMID:11307975

  2. Molecular Targets of Isothiocyanates in Cancer: Recent Advances

    PubMed Central

    Gupta, Parul; Kim, Bonglee; Kim, Sung-Hoon; Srivastava, Sanjay K.

    2014-01-01

    Cancer is a multistep process resulting in uncontrolled cell division. It results from aberrant signaling pathways that lead to uninhibited cell division and growth. Various recent epidemiological studies have indicated that consumption of cruciferous vegetables such as garden cress, broccoli, etc., reduces the risk of cancer. Isothiocyanates (ITC) have been identified as major active constituents of cruciferous vegetables. ITCs occur in plants as glucosinolate and can readily be derived by hydrolysis. Numerous mechanistic studies have demonstrated the anti-cancer effects of ITCs in various cancer types. ITCs suppress tumor growth by generating reactive oxygen species or by inducing cycle arrest leading to apoptosis. Based on the exciting outcomes of pre-clinical studies, few ITCs have advanced to the clinical phase. Available data from pre-clinical as well as available clinical studies suggests ITCs to be one of the promising anti-cancer agents available from natural sources. This is an up-to-date exhaustive review on the preventive and therapeutic effects of ITCs in cancer. PMID:24510468

  3. SaxA-Mediated Isothiocyanate Metabolism in Phytopathogenic Pectobacteria.

    PubMed

    Welte, Cornelia U; Rosengarten, Jamila F; de Graaf, Rob M; Jetten, Mike S M

    2016-04-01

    Pectobacteria are devastating plant pathogens that infect a large variety of crops, including members of the family Brassicaceae. To infect cabbage crops, these plant pathogens need to overcome the plant's antibacterial defense mechanisms, where isothiocyanates are liberated by hydrolysis of glucosinolates. Here, we found that a Pectobacterium isolate from the gut of cabbage root fly larvae was particularly resistant to isothiocyanate and even seemed to benefit from the abundant Brassica root metabolite 2-phenylethyl isothiocyanate as a nitrogen source in an ecosystem where nitrogen is scarce. The Pectobacterium isolate harbored a naturally occurring mobile plasmid that contained a sax operon. We hypothesized that SaxA was the enzyme responsible for the breakdown of 2-phenylethyl isothiocyanate. Subsequently, we heterologously produced and purified the SaxA protein and characterized the recombinant enzyme. It hydrolyzed 2-phenylethyl isothiocyanate to yield the products carbonyl sulfide and phenylethylamine. It was also active toward another aromatic isothiocyanate but hardly toward aliphatic isothiocyanates. It belongs to the class B metal-dependent beta-lactamase fold protein family but was not, however, able to hydrolyze beta-lactam antibiotics. We discovered that several copies of the saxA gene are widespread in full and draft Pectobacterium genomes and therefore hypothesize that SaxA might be a new pathogenicity factor of the genus Pectobacterium, possibly compromising food preservation strategies using isothiocyanates. PMID:26873319

  4. The first naturally occurring aromatic isothiocyanates, rapalexins A and B, are cruciferous phytoalexins.

    PubMed

    Pedras, M Soledade C; Zheng, Qing-An; Gadagi, Ravi S

    2007-01-28

    The discovery of the first naturally occurring aromatic isothiocyanates, indole-3-isothiocyanates, their first synthesis, antimicrobial activity and proposed biogenetic origin in canola plants are reported. PMID:17220973

  5. Jet spectroscopy of benzyl and benzyl-α-d2

    NASA Astrophysics Data System (ADS)

    Fukushima, Masaru; Obi, Kinichi

    1992-03-01

    Benzyl and benzyl-α-d2 radicals are produced by the ArF laser (193 nm) photolysis of benzylchloride and benzylchloride-α-d2, respectively, in a supersonic free jet. The spectroscopy of the D1 1 2A2-D0 1 2B1 transition of these radicals is studied by means of the laser induced fluorescence (LIF) method. LIF excitation spectra show well resolved but unusual vibrational structure. The assignments of vibronic bands have been carried out on the basis of dispersed spectra from the single vibronic level (SVL) and transition band types derived from rotational analysis of high resolution LIF excitation spectra. The intensity anomaly of the vibronic bands in the excitation spectra is interpreted as the breakdown of the accidental forbidden character of the D1-D0 and D2-D0 electronic transitions, whose mechanism will be discussed in terms of vibronic coupling.

  6. A new class of isothiocyanate-based irreversible inhibitors of Macrophage Migration Inhibitory Factor (MIF)

    PubMed Central

    Ouertatani-Sakouhi, Hajer; El-Turk, Farah; Fauvet, Bruno; Roger, Thierry; Le Roy, Didier; Karpinar, Damla Pinar; Leng, Lin; Bucala, Richard; Zweckstetter, Markus; Calandra, Thierry; Lashuel, Hilal A.

    2013-01-01

    Macrophage migration inhibitory factor (MIF) is a homotrimeric multifunctional proinflammatory cytokine that has been implicated in the pathogenesis of several inflammatory and autoimmune diseases. Current therapeutic strategies for targeting MIF focus on developing inhibitors of its tautomerase activity or modulating its biological activities using anti-MIF neutralizing antibodies. Herein we report a new class of isothiocyanate (ITC)-based irreversible inhibitors of MIF. Modification by benzyl isothiocyanate (BITC) and related analogues occurred at the N-terminal catalytic proline residue without affecting the oligomerization state of MIF. Different alkyl and arylalkyl ITCs-modified MIF with nearly the same efficiency as BITC. To elucidate the mechanism of action, we performed detailed biochemical, biophysical, and structural studies to determine the effect of BITC and its analogues on the conformational state, quaternary structure, catalytic activity, receptor binding and biological activity of MIF. Light scattering, analytical ultracentrifugation and NMR studies on unmodified and ITC-modified MIF demonstrated that modification of Pro1 alters the tertiary, but not the secondary or quaternary, structure of the trimer without affecting its thermodynamic stability. BITC induced drastic effects on the tertiary structure of MIF, in particular residues that cluster around Pro1 and constitute the tautomerase active site. These changes in tertiary structure and loss of catalytic activity translated into reduction in MIF receptor binding activity, MIF-mediated glucocorticoid overriding and MIF-induced Akt phosphorylation. Together, these findings highlight the role of tertiary structure in modulating the biochemical and biological activities of MIF and present new opportunities for modulating MIF biological activities in vivo. PMID:19737008

  7. Benzylglucosinolate Derived Isothiocyanate from Tropaeolum majus Reduces Gluconeogenic Gene and Protein Expression in Human Cells.

    PubMed

    Guzmán-Pérez, Valentina; Bumke-Vogt, Christiane; Schreiner, Monika; Mewis, Inga; Borchert, Andrea; Pfeiffer, Andreas F H

    2016-01-01

    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. PMID:27622707

  8. Effects of Brassicaceae Isothiocyanates on Prostate Cancer.

    PubMed

    Novío, Silvia; Cartea, María Elena; Soengas, Pilar; Freire-Garabal, Manuel; Núñez-Iglesias, María Jesús

    2016-01-01

    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. PMID:27187332

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

    PubMed Central

    Hu, Ping; Hollister, Emily B.; Somenahally, Anilkumar C.; Hons, Frank M.; Gentry, Terry J.

    2015-01-01

    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 a transient 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. PMID:25709600

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

    PubMed

    Hu, Ping; Hollister, Emily B; Somenahally, Anilkumar C; Hons, Frank M; Gentry, Terry J

    2014-01-01

    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 a transient 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. PMID:25709600

  11. Pd-catalyzed benzylic C-H amidation with benzyl alcohols in water: a strategy to construct quinazolinones.

    PubMed

    Hikawa, Hidemasa; Ino, Yukari; Suzuki, Hideharu; Yokoyama, Yuusaku

    2012-08-17

    A novel method for the synthesis of 4-phenylquinazolinones via a palladium-catalyzed domino reaction of o-aminobenzamides with benzyl alcohols is developed. This protocol involves N-benzylation, benzylic C-H amidation, and dehydrogenation in water, which may play an important role in the smooth generation of the (η(3)-benzyl)palladium species by activation of the hydroxyl group of the benzyl alcohol. PMID:22852777

  12. [Determination of volatile constituents in guanxin suhe wan by gas chromatography-mass spectrometry].

    PubMed

    Sun, Xiu-yan; Wu, Jian-bing; Wang, Su-juan

    2002-07-01

    The volatile constituents of Guanxin Suhe Wan and its ingredient drugs were analyzed by gas chromatography-mass spectrometry. Two compounds, borneol and benzyl benzoate were determined by selected ion monitoring with methyl salicylate as the internal standard. The recoveries of borneol and benzyl benzoate were 91.7% and 89.7% with the RSDs of 5.6% and 2.3%, respectively. PMID:12541931

  13. Isothiocyanates of Phosphorus Acids, N-Phosphorylated Thiocarbamates and Thioureas

    NASA Astrophysics Data System (ADS)

    Kamalov, R. M.; Zimin, M. G.; Pudovik, A. N.

    1985-12-01

    Current data on the synthesis, structures, the activities, and practical applications of the isothiocyanates of tricoordinate, tetracoordinate, pentacoordinate, and hexacoordinate phosphorus acids and N-phosphorylated and N-thiophosphorylated thiocarbamates, dithiocarbamates, and thioureas are examined and surveyed. The bibliography includes 223 references.

  14. Water and methyl isothiocyanate distribution in soil after drip fumigation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl isothiocyanate (MITC) generators, such as metam sodium (Met-Na), are used for soil fumigation of agricultural land. The ban on the fumigant methyl bromide (MBr) has resulted in greater use of MITC generators. In order to understand the efficacy of MITC, it is necessary to assess its generat...

  15. Novel Route to Transition Metal Isothiocyanate Complexes Using Metal Powders and Thiourea

    NASA Technical Reports Server (NTRS)

    Harris, Jerry D.; Eckles, William E.; Hepp, Aloysius F.; Duraj, Stan A.; Hehemann, David G.; Fanwick, Phillip E.; Richardson, John

    2003-01-01

    A new synthetic route to isothiocyanate-containing materials is presented. Eight isothiocyanate- 4-methylpyridine (y-picoline) compounds were prepared by refluxing metal powders (Mn, Fe, Co, Ni, and Cu) with thiourea in y-picoline. With the exception of compound 5,prepared with Co, the isothiocyanate ligand was generated in situ by the isomerization of thiourea to NH4+SCN- at reflux temperatures. The complexes were characterized by x-ray crystallography. Compounds 1,2, and 8 are the first isothiocyanate- 4-methylpyridine anionic compounds ever prepared and structurally characterized. Compounds 1 and 2 are isostructural with four equatorially bound isothiocyanate ligands and two axially bound y-picoline molecules. Compound 8 is a five-coordinate copper(II) molecule with a distorted square-pyramidal geometry. Coordinated picoline and two isothiocyanates form the basal plane and the remaining isothiocyanate is bound at the apex. Structural data are presented for all compounds.

  16. Glycosidic constituents from in vitro Anoectochilus formosanus.

    PubMed

    Du, X M; Sun, N Y; Irino, N; Shoyama, Y

    2000-11-01

    The glycosidic constituents of whole plants of Anoectochilus formosanus propagated by tissue culture were investigated. A new compound, 2-(beta-D-glucopyranosyloxymethyl)-5-hydroxymethylfuran, along with the known compounds, 3-(R)-3-beta-D-glucopyranosyloxybutanolide (kinsenoside), 3-(R)-3-beta-D-glucopyranosyloxy-4-hydroxybutanoic acid, 1-O-isopropyl-beta-D-glucopyranoside, (R)-(+)-3,4-dihydroxy-butanoic acid y-lactone, 4-(beta-D-glucopyranosyloxy)benzyl alcohol, (6R,9S)-9-hydroxy-megastigma-4,7-dien-3-one-9-O-beta-glucopy ranoside, and corchoionoside C were isolated. PMID:11086921

  17. Isothiocyanates Ameliorate the Symptom of Heart Dysfunction and Mortality in a Murine AIDS Model by Inhibiting Apoptosis in the Left Ventricle

    PubMed Central

    Ho, Jin-Nyoung; Yoon, Ho-Geun; Park, Chang-Soo; Kim, Sunoh; Jun, Woojin; Choue, Ryowon

    2012-01-01

    Abstract Cardiac involvement has been reported in as many as 45–55% of patients with human immunodeficiency virus (HIV) infection and acquired immune deficiency syndrome (AIDS), and significant cardiac morbidity is reported in 6–7% of HIV patients. We investigated the inhibitory effects of isothiocyanates (ITCs) on heart dysfunction and mortality by regulating apoptosis in the left ventricle of the heart in a murine AIDS model. Mice were divided into six groups: an uninfected group, an untreated LP-BM5 retrovirus-infected group, and four LP-BM5 retrovirus-infected groups treated with one of four ITCs (sulforaphane [SUL], indolo[3,2-b]carbazole, benzyl isothiocyanate [BITC], or phenethyl isothiocyanate [PEITC]). After 16 weeks, the median survival time of the LP-BM5 retrovirus-infected mice was 87 days, whereas that of the uninfected control group and all ITC treatment groups was over 112 days. SUL, PEITC, and BITC significantly inhibited apoptosis in the left ventricle by increasing the Bcl-2/Bax ratio compared with LP-BM5-infected mice. In addition, SUL and PEITC suppressed inducible nitric oxide synthase (iNOS) expression at both the mRNA and protein levels in the left ventricle of heart tissue infected with the LP-BM5 retrovirus by inactivating cytoplasmic nuclear factor κB (NF-κB). In conclusion, LP-BM5 retrovirus infection was related to survival of murine AIDS mice, and NF-κB-mediated iNOS expression may be an important mediator of left ventricle dysfunction of the heart. Furthermore, certain ITCs may have the potential to improve AIDS-related heart dysfunction due to their inhibition of apoptosis by decreasing iNOS and Bax expression through suppression of NF-κB. PMID:22925072

  18. Phytochemical profiling of five medicinally active constituents across 14 Eutrema species.

    PubMed

    Hao, Guoqian; Wang, Qian; Liu, Bingbing; Liu, Jianquan

    2016-04-01

    Wasabi or Japanese horseradish (Eutrema japonicum) is both a traditional condiment and a medicinally important plant with diverse uses. Its medicinally active constituents appear to include five isothiocyanates, but their spatial variations in naturally occurring congeners are unknown. Thus, in this study we measured concentrations of these five active constituents in 20 populations of 14 species of Eutrema and one related species, Yinshania sinuata. Three to five of these constituents were detected in each of the examined species, at concentrations that varied greatly between sampled species and populations of the same species. However, two species, Eutrema tenue and Eutrema deltoideum, had higher total concentrations of the five isothiocyanates and substantially higher concentrations of one or two, than the widely cultivated E. japonicum. Thus, both of these species could be important wild resources for artificial cultivation, in addition to the currently widely cultivated E. japonicum. PMID:26946379

  19. Volatile Constituents of Three Piper Species from Vietnam.

    PubMed

    Hieua, Le D; Hoic, Tran M; Thangda, Tran D; Ogunwande, Isiaka A

    2015-11-01

    The chemical compositions of the essential oils obtained by hydrodistillation of three Piper plants grown in Vietnam are reported. The analysis was achieved by means of gas chromatography with flame ionization detection (GC-FID) and gas chromatography coupled with mass spectrometry (GC-MS). The main constituents of the leaf oil of Piper majusculum Blume were β-caryophyllene (20.7%), germacrene D (18.6%) and β-elemene (11.3%). The quantitatively significant compounds of the volatile oils of P. harmandii C. DC were sabinene (leaves, 14.5%; stems, 16.2%), benzyl benzoate (leaves, 20.0%; stems, 29.40%) and benzyl salicylate (leaves, 14.1%; stems, 24.3%). Also, α-cadinol (17.0%) was identified in large proportion in the leaf oil. However, sabinene (leaves, 17.9%; stems, 13.5%), benzyl benzoate (leaves, 20.5%; stems, 32.5%) and β-eudesmol (leaves, 13.8%; stems, 8.4%) were the main constituents of P. brevicaule C. DC. This is the first report on the volatile constituents of both P. harmandii and P. brevicaule. PMID:26749846

  20. Modulation of Histone Deacetylase Activity by Dietary Isothiocyanates and Allyl Sulfides: Studies with Sulforaphane and Garlic Organosulfur Compounds

    PubMed Central

    Nian, Hui; Delage, Barbara; Ho, Emily; Dashwood, Roderick H.

    2009-01-01

    Histone deacetylase (HDAC) inhibitors reactivate epigenetically-silenced genes in cancer cells, triggering cell cycle arrest and apoptosis. Recent evidence suggests that dietary constituents can act as HDAC inhibitors, such as the isothiocyanates found in cruciferous vegetables and the allyl compounds present in garlic. Broccoli sprouts are a rich source of sulforaphane (SFN), an isothiocyanate that is metabolized via the mercapturic acid pathway and inhibits HDAC activity in human colon, prostate, and breast cancer cells. In mouse preclinical models, SFN inhibited HDAC activity and induced histone hyperacetylation coincident with tumor suppression. Inhibition of HDAC activity also was observed in circulating peripheral blood mononuclear cells obtained from people who consumed a single serving of broccoli sprouts. Garlic organosulfur compounds can be metabolized to allyl mercaptan (AM), a competitive HDAC inhibitor that induced rapid and sustained histone hyperacetylation in human colon cancer cells. Inhibition of HDAC activity by AM was associated with increased histone acetylation and Sp3 transcription factor binding to the promoter region of the P21WAF1 gene, resulting in elevated p21 protein expression and cell cycle arrest. Collectively, the results from these studies, and others reviewed herein, provide new insights into the relationships between reversible histone modifications, diet, and cancer chemoprevention. PMID:19197985

  1. Allyl isothiocyanate induces replication-associated DNA damage response in NSCLC cells and sensitizes to ionizing radiation

    PubMed Central

    Barnett, Reagan; Bachaboina, Lavanya; Scalici, Jennifer; Rocconi, Rodney P.; Owen, Laurie B.; Piazza, Gary A.

    2015-01-01

    Allyl isothiocyanate (AITC), a constituent of many cruciferous vegetables exhibits significant anticancer activities in many cancer models. Our studies provide novel insights into AITC-induced anticancer mechanisms in human A549 and H1299 non-small cell lung cancer (NSCLC) cells. AITC exposure induced replication stress in NSCLC cells as evidenced by γH2AX and FANCD2 foci, ATM/ATR-mediated checkpoint responses and S and G2/M cell cycle arrest. Furthermore, AITC-induced FANCD2 foci displayed co-localization with BrdU foci, indicating stalled or collapsed replication forks in these cells. Although PITC (phenyl isothiocyanate) exhibited concentration-dependent cytotoxic effects, treatment was less effective compared to AITC. Previously, agents that induce cell cycle arrest in S and G2/M phases were shown to sensitize tumor cells to radiation. Similar to these observations, combination therapy involving AITC followed by radiation treatment exhibited increased DDR and cell killing in NSCLC cells compared to single agent treatment. Combination index (CI) analysis revealed synergistic effects at multiple doses of AITC and radiation, resulting in CI values of less than 0.7 at Fa of 0.5 (50% reduction in survival). Collectively, these studies identify an important anticancer mechanism displayed by AITC, and suggest that the combination of AITC and radiation could be an effective therapy for NSCLC. PMID:25742788

  2. Benzyl salicylate: a survey of consumer patch-test sensitization.

    PubMed

    Kohrman, K A; Booman, K A; Dorsky, J; Rothenstein, A S; Sedlak, R I; Steltenkamp, R J; Thompson, G R

    1983-12-01

    The potential of benzyl salicylate, an important fragrance and flavour ingredient, to induce hypersensitivity or to elicit reactions to pre-existing hypersensitivity in the general population was evaluated by analysing patch-test data. Results obtained from fragrance and formulator companies for a total of 10,538 patch tests on benzyl salicylate alone, on a variety of household and personal care consumer products and on fragrance blends containing benzyl salicylate were analysed as part of this survey. No induced or elicited responses directly attributable to benzyl salicylate were observed in the 35 patch tests on benzyl salicylate alone, or in the 10,503 patch tests on consumer products or fragrance blends containing benzyl salicylate. The highest concentration of benzyl salicylate tested in the consumer-product tests was 2 X 10(-1)%, and benzyl salicylate alone was tested at 10% in ethanol. This study indicates that benzyl salicylate has a very low potential to induce hypersensitivity ('induced' reactions) or to elicit reactions presumably attributable to pre-existing sensitization ('elicited' reactions) and thus supports the safe use of benzyl salicylate in consumer products and fragrance blends. PMID:6686578

  3. Pharmacodynamics of benzyl chloride in rats.

    PubMed

    Saxena, S; Abdel-Rahman, M S

    1989-09-01

    In today's world of high industrialization, toxicity and pollution have become common terms of references. Both laymen and experts are becoming increasingly concerned about various health hazards created by occupational and industrial wastes dumped in and around public places. Benzyl chloride (BCl) was one of the chemicals dumped by Hooker Chemicals in Love Canal, N.Y. Benzyl chloride (BCl) is extensively used in industry in the manufacture of dyes, perfumes, resins, and synthetic tannins. It has been found at various dump sites and industrial wastes, which has led to potential hazards to health. This study was conducted to investigate the pharmacodynamics of BCl in rats. Rats were given 14C-BCl in corn oil by gavage. The peak plasma level was reached at 30 min and began to decline. BCl elimination pattern follows a two compartment model. The distribution half-life (alpha-phase) was 1.3 hr while the half-life of elimination (beta-phase) was 58.53 hr. Distribution studies after 48 hr of BCl administration revealed that the concentration of radioisotopes was highest in the stomach, gastric content, ileum, and duodenum followed by liver, adrenal, bone marrow, whole blood, pancreas, lung, esophagus, skin, kidney, heart, thymus, fat, testes, spleen, brain, and carcass. Approximately 76% of the initial dose was excreted by kidney during the 72 hr studies. About 7% was detected in expired air as 14CO2, while less than 1.3% was present as 14C-BCl or 14C-BCl metabolites in expired air during 72 hr. Metabolism studies revealed that S-benzyl-N-acetyl cysteine, benzyl alcohol, and benzaldehyde were the metabolites present in the urine.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2802671

  4. A one-pot approach to pyridyl isothiocyanates from amines.

    PubMed

    Zhang, Hao; Liu, Rui-Quan; Liu, Ke-Chang; Li, Qi-Bo; Li, Qing-Yang; Liu, Shang-Zhong

    2014-01-01

    A one-pot preparation of pyridyl isothiocyanates (ITCs) from their corresponding amines has been developed. This method involves aqueous iron(III) chloride-mediated desulfurization of a dithiocarbamate salt that is generated in situ by treatment of an amine with carbon disulfide in the present of DABCO or sodium hydride. The choice of base is of decisive importance for the formation of the dithiocarbamate salts. This one-pot process works well for a wide range of pyridyl ITCs. Utilizing this protocol, some highly electron-deficient pyridyl and aryl ITCs are obtained in moderate to good yields. PMID:25185069

  5. Fragrance material review on benzyl alcohol.

    PubMed

    Scognamiglio, J; Jones, L; Vitale, D; Letizia, C S; Api, A M

    2012-09-01

    A toxicologic and dermatologic review of benzyl alcohol when used as a fragrance ingredient is presented. Benzyl alcohol is a member of the fragrance structural group Aryl Alkyl Alcohols and is a primary alcohol. The AAAs are a structurally diverse class of fragrance ingredients that includes primary, secondary, and tertiary alkyl alcohols covalently bonded to an aryl (Ar) group, which may be either a substituted or unsubstituted benzene ring. The common structural element for the AAA fragrance ingredients is an alcohol group -C-(R1)(R2)OH and generically the AAA fragrances can be represented as an Ar-C-(R1)(R2)OH or Ar-Alkyl-C-(R1)(R2)OH group. This review contains a detailed summary of all available toxicology and dermatology papers related to this individual fragrance ingredient and is not intended as a stand-alone document. Available data for benzyl alcohol were evaluated then summarized and includes physical properties, acute toxicity, skin irritation, mucous membrane (eye) irritation, skin sensitization, elicitation, phototoxicity, photoallergy, toxicokinetics, repeated dose, reproductive toxicity, genotoxicity, and carcinogenicity data. A safety assessment of the entire Aryl Alkyl Alcohols will be published simultaneously with this document; please refer to Belsito et al. (2012) for an overall assessment of the safe use of this material and all Aryl Alkyl Alcohols in fragrances. PMID:22036973

  6. Effects of hyperthermia, irradiation, and cytotoxic drugs on fluorescein isothiocyanate staining intensity for flow cytofluorometry

    SciTech Connect

    Dyson, J.E.; McLaughlin, J.B.; Surrey, C.R.; Simmons, D.M.; Daniel, J.

    1987-01-01

    Measurement of fluorescein isothiocyanate (FITC) staining intensity of cultured lymphoblastoid cells following hyperthermia showed large increases without concomitant increases in nuclear protein. Similar measurements of cells following incubation with cytotoxic drugs showed fluorescent intensity increases that exceeded the increases in nuclear protein that were due to the cell cycle blocking action of the drug. The reverse, however, was true for cells following irradiation. In contrast, FITC staining intensity and nuclear protein measurements of cells proceeding through the cell cycle after removal of the cycle blocking agent showed nearly parallel changes, although there were reproducible minor differences, especially following blocking with hydroxyurea. These results suggest that FITC staining intensity is a function not only of nuclear protein content but also of stain access to the reaction sites of the protein constituents of the chromatin. Thus, it is possible that FITC staining may be used as a probe of changes in chromatin structure following experimental manipulation of cells in vitro or treatment of tumors in vivo.

  7. Allyl isothiocyanate induces stomatal closure in Vicia faba.

    PubMed

    Sobahan, Muhammad Abdus; Akter, Nasima; Okuma, Eiji; Uraji, Misugi; Ye, Wenxiu; Mori, Izumi C; Nakamura, Yoshimasa; Murata, Yoshiyuki

    2015-01-01

    Isothiocyanates are enzymatically produced from glucosinolates in plants, and allyl isothiocyanate (AITC) induces stomatal closure in Arabidopsis thaliana. In this study, we investigated stomatal responses to AITC in Vicia faba. AITC-induced stomatal closure accompanied by reactive oxygen species (ROS) and NO production, cytosolic alkalization and glutathione (GSH) depletion in V. faba. GSH monoethyl ester induced stomatal reopening and suppressed AITC-induced GSH depletion in guard cells. Exogenous catalase and a peroxidase inhibitor, salicylhydroxamic acid, inhibited AITC-induced stomatal closure, unlike an NAD(P)H oxidase inhibitor, diphenylene iodonium chloride. The peroxidase inhibitor also abolished the AITC-induced ROS production, NO production, and cytosolic alkalization. AITC-induced stomatal closure was suppressed by an NO scavenger, 2-(4-carboxyphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, and an agent to acidify cytosol, butyrate. These results indicate that AITC-induced stomatal closure in V. faba as well as in A. thaliana and suggest that AITC signaling in guard cells is conserved in both plants. PMID:26027691

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

    PubMed Central

    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

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

    PubMed

    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

  10. Reactivity, SCE induction and mutagenicity of benzyl chloride derivatives.

    PubMed

    Hemminki, K; Falck, K; Linnainmaa, K

    1983-08-01

    Benzyl chloride, benzyl bromide, p-methylbenzyl chloride, and p-nitrobenzyl chloride were used to study chemical reactivity with 4-(p-nitrobenzyl)-pyridine (NBP), and with guanosine in vitro, in relation to mutagenic potency in S. typhimurium and sister chromatid exchange (SCE) induction in CHO cells. Benzyl bromide was found to be the most reactive compound, followed by p-methylbenzyl chloride, benzyl chloride and p-nitrobenzyl chloride. The order of mutagenicity was p-nitrobenzyl chloride much greater than benzyl bromide greater than benzyl chloride approximately equal to p-methylbenzyl chloride. The compounds tested caused base-pair mutations only. The order of SCE-inducing ability decreased as follows: benzyl bromide greater than benzyl chloride approximately equal to p-nitrobenzyl chloride approximately equal to p-methylbenzyl chloride. The particularly high mutagenicity of p-nitrobenzyl chloride in bacteria may be due to reactions other than direct aralkylation, or it may react particularly actively with DNA. Among the other compounds, benzyl bromide was the most active aralkylating compound, mutagen and SCE inducer. The results suggested that reaction of N2 of guanine, as compared with N-7 of guanine, failed to show any remarkable mutagenicity or SCE induction, since p-methylbenzyl chloride, reacting preferentially at N2 of guanosine, failed to show unexceptional potency. PMID:6358331

  11. Myrosinase-dependent and –independent formation and control of isothiocyanate products of glucosinolate hydrolysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Brassicales contain a myrosinase enzyme that hydrolyzes glucosinolates to form toxic isothiocyanates, as a defense against bacteria, fungi, insects and herbivores including man. Low levels of isothiocyanates trigger a host defense system in mammals that protects them against chronic diseases. Becaus...

  12. Isothiocyanate exposure, glutathione S-transferase polymorphisms, and colorectal cancer risk1234

    PubMed Central

    Gao, Yu-Tang; Shu, Xiao-Ou; Cai, Qiuyin; Li, Guo-Liang; Li, Hong-Lan; Ji, Bu-Tian; Rothman, Nathaniel; Dyba, Marcin; Xiang, Yong-Bing; Chung, Fung-Lung; Chow, Wong-Ho; Zheng, Wei

    2010-01-01

    Background: Isothiocyanates, compounds found primarily in cruciferous vegetables, have been shown in laboratory studies to possess anticarcinogenic activity. Glutathione S-transferases (GSTs) are involved in the metabolism and elimination of isothiocyanates; thus, genetic variations in these enzymes may affect in vivo bioavailability and the activity of isothiocyanates. Objective: The objective was to prospectively evaluate the association between urinary isothiocyanate concentrations and colorectal cancer risk as well as the potential modifying effect of GST genotypes on the association. Design: A nested case-control study of 322 cases and 1251 controls identified from the Shanghai Women's Health Study was conducted. Results: Urinary isothiocyanate concentrations were inversely associated with colorectal cancer risk; the inverse association was statistically significant or nearly significant in the GSTM1-null (P for trend = 0.04) and the GSTT1-null (P for trend = 0.07) genotype groups. The strongest inverse association was found among individuals with both the GSTM1-null and the GSTT1-null genotypes, with an adjusted odds ratio of 0.51 (95% CI: 0.27, 0.95), in a comparison of the highest with the lowest tertile of urinary isothiocyanates. No apparent associations between isothiocyanate concentration and colorectal cancer risk were found among individuals who carried either the GSTM1 or GSTT1 gene (P for interaction < 0.05). Conclusion: This study suggests that isothiocyanate exposure may reduce the risk of colorectal cancer, and this protective effect may be modified by the GSTM1 and GSTT1 genes. PMID:20042523

  13. Trypanocidal and antileukaemic effects of the essential oils of Hagenia abyssinica, Leonotis ocymifolia, Moringa stenopetala, and their main individual constituents.

    PubMed

    Nibret, E; Wink, M

    2010-10-01

    Essential oils from three Ethiopian medicinal plants; Hagenia abyssinica (Rosaceae), Leonotis ocymifolia (Lamiaceae), and Moringa stenopetala (Moringaceae) were investigated for their chemical composition, trypanocidal, and cytotoxic activities. Twenty components were identified from the essential oil of H. abyssinica female flowers, ledol (58.57%) being the principal volatile oil component. Sixty-eight components were identified from the essential oil of L. ocymifolia aerial part, caryophyllene oxide (12.06%) being the major component. The essential oil of M. stenopetala seeds was dominated by isothiocyanates; benzyl isothiocyanate (54.30%) and isobutyl isothiocyanate (16.37%) were the major components. The trypanocidal (Trypanosoma b. brucei) and antileukaemic (HL-60) effects of the three essential oils were studied. The oil of M. stenopetala seeds and its main compound, benzyl isothiocyanate showed the most potent trypanocidal activities with IC(50) values of 5.03 μg/ml and 1.20 μg/ml, respectively. The oils of H. abyssinica and L. ocymifolia exhibited trypanocidal activities with IC(50) values of 42.30 μg/ml and 15.41 μg/ml, respectively. Individual components (28 compounds) of the essential oils bearing different functional groups were also studied for their structure-activity relationships using trypanosomes and human leukaemia cells. Cinnamaldehyde (IC(50)=2.93 μg/ml) (a representative for aldehydes), nerolidol (IC(50)=15.78 μg/ml) (an alcohol), cedrene (IC(50)=4.07 μg/ml) (a hydrocarbon), benzyl isothiocyanate (IC(50)=1.20 μg/ml) (a representative for mustard oils), 1,8-cineole (IC(50)=83.15 μg/ml) (an ether), safrole (IC(50)=18.40 μg/ml) (aromatics with allyl and/or methoxy side chains), carvone (IC(50)=12.94μg/ml) (a ketone), styrene oxide (IC(50)=3.76 μg/ml) (an epoxide) and carvacrol (IC(50)=11.25 μg/ml) (a phenol) showed the most potent trypanocidal activities from their respective groups. Of all essential oil components tested, carvone

  14. Isolation and identification of 4-α-rhamnosyloxy benzyl glucosinolate in Noccaea caerulescens showing intraspecific variation.

    PubMed

    de Graaf, Rob M; Krosse, Sebastian; Swolfs, Ad E M; te Brinke, Esra; Prill, Nadine; Leimu, Roosa; van Galen, Peter M; Wang, Yanli; Aarts, Mark G M; van Dam, Nicole M

    2015-02-01

    Glucosinolates are secondary plant compounds typically found in members of the Brassicaceae and a few other plant families. Usually each plant species contains a specific subset of the ∼ 130 different glucosinolates identified to date. However, intraspecific variation in glucosinolate profiles is commonly found. Sinalbin (4-hydroxybenzyl glucosinolate) so far has been identified as the main glucosinolate of the heavy metal accumulating plant species Noccaea caerulescens (Brassicaceae). However, a screening of 13 N. caerulescens populations revealed that in 10 populations a structurally related glucosinolate was found as the major component. Based on nuclear magnetic resonance (NMR) and mass spectrometry analyses of the intact glucosinolate as well as of the products formed after enzymatic conversion by sulfatase or myrosinase, this compound was identified as 4-α-rhamnosyloxy benzyl glucosinolate (glucomoringin). So far, glucomoringin had only been reported as the main glucosinolate of Moringa spp. (Moringaceae) which are tropical tree species. There was no apparent relation between the level of soil pollution at the location of origin, and the presence of glucomoringin. The isothiocyanate that is formed after conversion of glucomoringin is a potent antimicrobial and antitumor agent. It has yet to be established whether glucomoringin or its breakdown product have an added benefit to the plant in its natural habitat. PMID:25482220

  15. Transcriptomic alterations in human prostate cancer cell LNCaP tumor xenograft modulated by dietary phenethyl isothiocyanate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Temporal growth of tumor xenografts in mice on a control diet was compared to mice supplemented daily with 3 µmol/g of the cancer preventive compound phenethyl isothiocyanate. Phenethyl isothiocyanate decreased the rate of tumor growth. The effects of phenethyl isothiocyanate on tumor growth were ex...

  16. Chemoselective C-benzylation of unprotected anilines with benzyl alcohols using Re2O7 catalyst.

    PubMed

    Nallagonda, Rajender; Rehan, Mohammad; Ghorai, Prasanta

    2014-04-01

    An unprecedented dehydrative C-C bond formation between unprotected anilines with benzyl alcohols is disclosed. Re2O7 catalyst (5 mol %) at elevated reaction temperature (80 °C) provided C-benzylanilines with high to excellent yields and with good chemoselectivities (over N-alkylation). A probable mechanism has been proposed based on mechanistic studies. PMID:24601671

  17. Genetic Incorporation of a Reactive Isothiocyanate Group into Proteins.

    PubMed

    Xuan, Weimin; Li, Jack; Luo, Xiaozhou; Schultz, Peter G

    2016-08-16

    Methods for the site-specific modification of proteins are useful for introducing biological probes into proteins and engineering proteins with novel activities. Herein, we genetically encode a novel noncanonical amino acid (ncAA) that contains an aryl isothiocyanate group which can form stable thiourea crosslinks with amines under mild conditions. We show that this ncAA (pNCSF) allows the selective conjugation of proteins to amine-containing molecular probes through formation of a thiourea bridge. pNCSF was also used to replace a native salt bridge in myoglobin with an intramolecular crosslink to a proximal Lys residue, leading to increased thermal stability. Finally, we show that pNCSF can form stable intermolecular crosslinks between two interacting proteins. PMID:27418387

  18. Cruciferous vegetables, isothiocyanates, and prevention of bladder cancer

    PubMed Central

    Veeranki, Omkara L.; Bhattacharya, Arup; Tang, Li; Marshall, James R.; Zhang, Yuesheng

    2015-01-01

    Approximately 80% of human bladder cancers (BC) are non-muscle invasive when first diagnosed and are usually treated by transurethral tumor resection. But 50–80% of patients experience cancer recurrence. Agents for prevention of primary BC have yet to be identified. Existing prophylactics against BC recurrence, e.g., Bacillus Calmette-Guerin (BCG), have limited efficacy and utility; they engender significant side effects and require urethral catheterization. Many cruciferous vegetables, rich sources of isothiocyanates (ITCs), are commonly consumed by humans. Many ITCs possess promising chemopreventive activities against BC and its recurrence. Moreover, orally ingested ITCs are selectively delivered to bladder via urinary excretion. This review is focused on urinary delivery of ITCs to the bladder, their cellular uptake, their chemopreventive activities in preclinical and epidemiological studies that are particularly relevant to prevention of BC recurrence and progression, and their chemopreventive mechanisms in BC cells and tissues. PMID:26273545

  19. Antimicrobial activities of phenethyl isothiocyanate isolated from horseradish.

    PubMed

    Chen, Hongxia; Wang, Chengzhang; Ye, Jianzhong; Zhou, Hao; Chen, Xijuan

    2012-01-01

    Phenethyl isothiocyanate (PEITC) was obtained from horseradish. The preparation procedure was as follows: the horseradish powder was hydrolysed in the water first, and then, after filtration, the residue was extracted by petroleum ether; finally, PEITC was isolated by silica gel column. The structure of PEITC was identified by IR, MS, ¹H-NMR and ¹³C-NMR chromatography methods. The inhibitory activities of PEITC against Gibberella zeae, Xanthomonas axonopodis pv . citri, Cytospora sp . and Phytophthora capsisi showed that PEITC had good inhibition effects. The EC₅₀ values of G. zeae, X. axonopodis pv . citri, Cytospora sp . and P. capsisi were 13.92, 1.20, 0.73 and 3.69 µg mL⁻¹, respectively. PMID:21815843

  20. Whole cells in enantioselective reduction of benzyl acetoacetate

    PubMed Central

    Ribeiro, Joyce Benzaquem; Ramos, Aline de Souza; Lopes, Raquel de Oliveira; da Silva, Gabriela Veloso Vieira; de Souza, Rodrigo Octavio Mendonça Alves

    2014-01-01

    The β-ketoester benzyl acetoacetate was enantioselectively reduced to benzyl (S)-3-hydroxybutanoate by seven microorganism species. The best result using free cells was obtained with the yeast Hansenula sp., which furnished 97% ee and 85% of conversion within 24 h. After immobilization in calcium alginate spheres, K.marxianus showed to be more stable after 2 cycles of reaction. PMID:25477927

  1. Suzuki Coupling of Potassium Cyclopropyl- and Alkoxymethyltrifluoroborates with Benzyl Chlorides

    PubMed Central

    Colombel, Virginie; Rombouts, Frederik; Oehlrich, Daniel; Molander, Gary A.

    2012-01-01

    Efficient Csp3-Csp3 Suzuki couplings have been developed with both potassium cyclopropyl- and alkoxymethyltrifluoroborates. Moderate to good yields have been achieved in the cross-coupling of potassium cyclopropyltrifluoroborate with benzyl chlorides possessing electron-donating or electron-withdrawing substituents. Benzyl chloride was also successfully cross-coupled to potassium alkoxymethyltrifluoroborates derived from primary, secondary, and tertiary alcohols. PMID:22390789

  2. Palladium-Catalyzed α-Arylation of Benzylic Phosphonates

    PubMed Central

    2015-01-01

    A new synthetic route to access diarylmethyl phosphonates is presented. The transformation enables the introduction of aromatic groups on benzylic phosphonates via a deprotonative cross-coupling process (DCCP). The Pd(OAc)2/CataCXium A-based catalyst afforded a reaction between benzyl diisopropyl phosphonate derivatives and aryl bromides in good to excellent isolated yields (64–92%). PMID:24520897

  3. Suzuki coupling of potassium cyclopropyl- and alkoxymethyltrifluoroborates with benzyl chlorides.

    PubMed

    Colombel, Virginie; Rombouts, Frederik; Oehlrich, Daniel; Molander, Gary A

    2012-03-16

    Efficient Csp(3)-Csp(3) Suzuki couplings have been developed with both potassium cyclopropyl- and alkoxymethyltrifluoroborates. Moderate to good yields have been achieved in the cross-coupling of potassium cyclopropyltrifluoroborate with benzyl chlorides possessing electron-donating or electron-withdrawing substituents. Benzyl chloride was also successfully cross-coupled to potassium alkoxymethyltrifluoroborates derived from primary, secondary, and tertiary alcohols. PMID:22390789

  4. Palladium Catalysis Enables Benzylation of α,α-Difluoroketone Enolates.

    PubMed

    Yang, Ming-Hsiu; Hunt, Jordan R; Sharifi, Niusha; Altman, Ryan A

    2016-07-25

    A palladium-catalyzed decarboxylative benzylation reaction of α,α-difluoroketone enolates is reported, in which the key C(α)-C(sp(3) ) bond is generated by reductive elimination from a palladium intermediate. The transformation provides convergent access to α-benzyl-α,α-difluoroketone-based products, and should be useful for accessing biological probes. PMID:27312868

  5. Association between consumption of cruciferous vegetables and condiments and excretion in urine of isothiocyanate mercapturic acids.

    PubMed

    Vermeulen, Martijn; van den Berg, Robin; Freidig, Andreas P; van Bladeren, Peter J; Vaes, Wouter H J

    2006-07-26

    A high intake of cruciferous vegetables is associated with a reduced risk of cancer and cardiovascular diseases. This protective effect has been linked to isothiocyanates, enzymatic hydrolysis products of glucosinolates. In this study, the metabolic fate of glucosinolates and isothiocyanates after ingestion of 19 different cruciferous vegetables was studied in three male subjects. After the consumption of 13 cruciferous vegetables (glucosinolate content, 0.01-0.94 mmol/kg) and six condiments (isothiocyanate content, 0.06-49.3 mmol/kg), eight different isothiocyanate mercapturic acids were determined in urine samples. Excretion levels after the consumption of raw vegetables and condiments were higher (bioavailability, 8.2-113%) as compared to cooked vegetables (bioavailability, 1.8-43%), but the excretion rate was similar (t1/2=2.1-3.9 h). Isothiocyanates in urine remain longer at a nonzero level after the consumption of glucosinolates from cooked vegetables, as compared to raw vegetables and condiments, and maximal levels in urine were reached about 4 h later. Isothiocyanate mercapturic acids can be used as a biomarker to reflect the active dose of isothiocyanates absorbed. PMID:16848516

  6. Total isothiocyanate yield from raw cruciferous vegetables commonly consumed in the United States

    PubMed Central

    Tang, Li; Paonessa, Joseph D.; Zhang, Yuesheng; Ambrosone, Christine B.; McCann, Susan E.

    2013-01-01

    Dietary isothiocyanates are a group of promising chemopreventive agents obtained primarily from cruciferous vegetables. Due to their potent chemopreventive and/or anti-cancer activities, there is a growing interest in assessing dietary isothiocyanate exposure and its impact on human health. Using the HPLC-based cyclocondensation assay, the current study measured total isothiocyanate yield from raw cruciferous vegetables. A total of 73 samples comprising nine types of cruciferous vegetables were analyzed. We observed a wide range of isothiocyanate content across the individual vegetables with an average level of 16.2 μmol/100g wet weight, ranging from 1.5 μmol in raw cauliflower to 61.3 μmol in raw mustard greens. The data represent the maximum amount of isothiocyanates released from the intake of raw cruciferous vegetables. Given that the vegetables assayed in this study include the most commonly consumed cruciferous vegetables in western diets, the data may be particularly useful in estimation of dietary isothiocyanate exposure in these populations. However, due to the variation observed within each vegetable, biomarkers such as urinary isothiocyanate level may be necessary for accurate estimation of individual exposure. PMID:24443655

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

    PubMed

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

    2015-10-01

    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 enter the gas phase and all ITCs may react with matrix components. Deterrence to herbivores resulting from topically applied volatile ITCs in artificial feeding assays may hence lead to ambiguous conclusions. In the present study, the non-volatile ITC moringin (4-(α-L-rhamnopyranosyloxy)benzyl ITC) and its glucosinolate precursor glucomoringin were examined for effects on behaviour and taste physiology of specialist insect herbivores of Brassicales. In feeding bioassays, glucomoringin was not deterrent to larvae of Pieris napi (Lepidoptera: Pieridae) and Athalia rosae (Hymenoptera: Tenthredinidae), which are adapted to glucosinolates. Glucomoringin stimulated feeding of larvae of the related Pieris brassicae (Lepidoptera: Pieridae) and also elicited electrophysiological activity from a glucosinolate-sensitive gustatory neuron in the lateral maxillary taste sensilla. In contrast, the ITC moringin was deterrent to P. napi and P. brassicae at high levels and to A. rosae at both high and low levels when topically applied to cabbage leaf discs (either 12, 120 or 1200 nmol moringin per leaf disc of 1cm diameter). Survival of A. rosae was also significantly reduced when larvae were kept on leaves treated with moringin for several days. Furthermore, moringin elicited electrophysiological activity in a deterrent-sensitive neuron in the medial maxillary taste sensillum of P. brassicae, providing a sensory mechanism for the deterrence and the first known ITC taste response of an insect. In simulated feeding assays, recovery of moringin was high, in accordance with its non-volatile nature. Our results demonstrate taste-mediated deterrence of a non-volatile, natural ITC to glucosinolate

  8. Bim contributes to phenethyl isothiocyanate-induced apoptosis in breast cancer cells.

    PubMed

    Hahm, Eun-Ryeong; Singh, Shivendra V

    2012-06-01

    Phenethyl isothiocyanate (PEITC) is a highly promising cancer chemopreventive constituent of cruciferous vegetables (e.g., watercress) with in vivo efficacy in experimental rodent cancer models. Research thus far implicates apoptosis induction in cancer chemopreventive response to PEITC, but the mechanism of proapoptotic effect is not fully understood. The present study demonstrates that p53 upregulated modulator of apoptosis (PUMA)-independent apoptosis by PEITC is mediated by B-cell lymphoma 2 interacting mediator of cell death (Bim). Exposure of a cell line (BRI-JM04) derived from spontaneously developing mammary tumor of a MMTV-neu transgenic mouse to pharmacological concentrations of PEITC resulted in decreased cell viability coupled with apoptosis induction, characterized by release of histone-associated DNA fragments into the cytosol and cleavage of poly-(ADP-ribose)-polymerase and procaspase-3. The PEITC-induced apoptosis in BRI-JM04 cells was associated with up-regulation of Bak, PUMA, and Bim (long and short forms of Bim), increased S65 phosphorylation of BimEL (extra-long form), and down-regulation of Bcl-xL and Bcl-2. On the other hand, a non-tumorigenic human mammary epithelial cell line (MCF-10A) was significantly more resistant to PEITC-induced apoptosis compared with BRI-JM04 despite induction of Bax and PUMA due to concomitant overexpression of anti-apoptotic proteins, including Bcl-xL, Bcl-2, and Mcl-1. Wild-type HCT-116 cells and its isogenic PUMA knockout variant exhibited comparable sensitivity to PEITC-induced apoptosis. On the other hand, small interfering RNA knockdown of Bim protein imparted partial but statistically significant protection against PEITC-induced apoptosis in BRI-JM04, MCF-7, and MDA-MB-231 cells. In conclusion, the present study provides novel insight into the mechanism of PEITC-induced apoptosis involving Bim. PMID:21739479

  9. Effect of Allyl Isothiocyanate on developmental toxicity in exposed Xenopus laevis embryos

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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 re...

  10. Degradation Kinetics of Benzyl Nicotinate in Aqueous Solution

    PubMed Central

    Mbah, C. J.

    2010-01-01

    The degradation of benzyl nicotinate in aqueous solution over a pH range of 2.0-10.0 at 50±0.2° was studied. The degradation was determined by high performance liquid chromatography. The degradation was observed to follow apparent first-order rate kinetics and the rate constant for the decomposition at 25° was estimated by extrapolation. The reaction was shown to be hydroxide ion catalyzed and the Arrhenius plots showed the temperature dependence of benzyl nicotinate degradation. A significant increase in the stability of benzyl nicotinate was observed when glycerol or polyethylene glycol 400 was incorporated into the aqueous solution. PMID:20582189

  11. Release of allyl isothiocyanate from mustard seed meal powder.

    PubMed

    Dai, Ruyan; Lim, Loong-Tak

    2014-01-01

    Allyl isothiocyanate (AITC) is a wide-spectrum antimicrobial compound found in mustard seeds, produced when their tissues are disrupted. The formation of AITC in mustard seed is mediated by the myrosinase enzyme which catalyzes the release of volatile AITC from a glucosinolate-sinigrin. Since water is a substrate in the reaction, humidity from the air can be used to activate the release of AITC from mustard seed. In this study, defatted and partially defatted mustard seed meals were ground into powders with particle size ranging from 5 to 300 μm. The mustard seed meal powder (MSMP) samples were enclosed within hermetically sealed glass jars wherein the headspace air was adjusted to 85% or 100% relative humidity at 5, 20, or 35 °C. Data from gas chromatography analysis showed that AITC release rate and amount increased with increasing relative humidity and temperature. Moreover, the release rate can be manipulated by particle size and lipid content of the MSMP samples. The amount of AITC released ranged from 2 to 17 mg/g MSMP within 24 h under the experimental conditions tested. In view of the antimicrobial properties of AITC, the mustard meal powder may be used as a natural antimicrobial material for extending the shelf life of food products. PMID:24313968

  12. Proteins as binding targets of isothiocyanates in cancer prevention

    PubMed Central

    Mi, Lixin; Di Pasqua, Anthony J.

    2011-01-01

    Isothiocyanates are versatile cancer-preventive compounds. Evidence from animal studies indicates that the anticarcinogenic activities of ITCs involve all the major stages of tumor growth: initiation, promotion and progression. Epidemiological studies have also shown that dietary intake of ITCs is associated with reduced risk of certain human cancers. A number of mechanisms have been proposed for the chemopreventive activities of ITCs. To identify the molecular targets of ITCs is a first step to understand the molecular mechanisms of ITCs. Studies in recent years have shown that the covalent binding to certain protein targets by ITCs seems to play an important role in ITC-induced apoptosis and cell growth inhibition and other cellular effects. The knowledge gained from these studies may be used to guide future design and screen of better and more efficacious compounds. In this review, we intend to cover all potential protein targets of ITCs so far studied and summarize what are known about their binding sites and the potential biological consequences. In the end, we also offer discussions to shed light onto the relationship between protein binding and reactive oxygen species generation by ITCs. PMID:21665889

  13. Allyl isothiocyanate affects the cell cycle of Arabidopsis thaliana

    PubMed Central

    Åsberg, Signe E.; Bones, Atle M.; Øverby, Anders

    2015-01-01

    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. PMID:26042144

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

    PubMed

    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. PMID:25863635

  15. Oxidative conversion of isothiocyanates to isocyanates by rat liver.

    PubMed Central

    Lee, M S

    1994-01-01

    This report describes the oxidative metabolism of isothiocyanates to isocyanates catalyzed by rat liver microsomes. Incubation of 2-naphthylisothiocyanate, microsomes, and NADPH yielded either N,N'-di-naphthylurea or, on inclusion of 2-aminofluorene in the incubations, N-2-naphthyl-N'-2-fluorenylurea. These ureas were formed by the production of the known genotoxicant, 2-naphthylisocyanate, which reacted with its hydrolysis product, 2-aminonaphthalene, to yield the symmetrical urea, or with 2-aminofluorene to form the mixed urea. Formation of N,N'-di-2-naphthylthiourea was also observed because 2-aminonaphthalene reacted with the substrate. Urea formation was dependent on the microsomes, NADPH, and oxygen. Use of microsomes from rats previously treated with Aroclor 1254 increased urea formation greater than 10-fold. The enzyme activity was inhibited by alpha-napthoflavone, flavone, or CO, and slightly inhibited by metyrapone, 7-ethoxycoumarin, or SKF-525A. It was not inhibited by methimazole or paraoxon, suggesting that neither flavin-containing monooxygenase nor hydrolytic enzyme was involved. These data are consistent with a cytochrome P450-dependent, oxidative desulfuration of 2-naphthylisothiocyanate to yield 2-naphthylisocyanate. Further studies with the isomeric 1-naphthylisothiocyanate and the dietary benzylisothiocyanate showed that they can also be metabolized to their isocyanates, as evidenced by the trapping of isocyanates with 2-aminofluorene to form the mixed ureas. PMID:7889832

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

    PubMed

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

    2013-05-24

    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 260-320 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

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

    PubMed Central

    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

  18. Cosolvent-Promoted O-Benzylation with Silver(I) Oxide: Synthesis of 1'-Benzylated Sucrose Derivatives, Mechanistic Studies, and Scope Investigation.

    PubMed

    Wang, Lei; Hashidoko, Yasuyuki; Hashimoto, Makoto

    2016-06-01

    A cosolvent-promoted O-benzylation strategy with Ag2O was developed. The cosolvent consisting of CH2Cl2 and n-hexane can not only improve the reaction solubility for carbohydrates but also increase the benzylation efficiency. The formation of byproducts is greatly inhibited in the developed method. This method is simple, mild, and highly effective, and numerous 1'-benzylated sucrose derivatives were prepared including a photoreactive (trifluoromethyl)phenyldiazirine-based sucrose. The mechanisms of benzylation with primary and secondary benzyl bromides were also elaborated. Furthermore, the application scope with alcohols, glucose, and ribose derivatives was investigated. PMID:27149197

  19. In vitro studies of phenethyl isothiocyanate against the growth of LN229 human glioma cells.

    PubMed

    Su, Ji-Chun; Lin, Kai; Wang, Yan; Sui, Shao-Hua; Gao, Zhi-Yu; Wang, Zhi-Gang

    2015-01-01

    Phenethyl isothiocyanate (PEITC) is one of the best studied members of isothiocyanates (ITC), a variety of edible cruciferous vegetables including broccoli, watercress, and cabbage, and have generated particular interest because of its remarkable chemopreventive activity. Many literature reports proved that phenethyl isothiocyanate exhibited significant anti-cancer chemopreventive effects including lung, glioma and leukemia cancer. In this study, we explored the inhibitory effects as well as mechanisms of PEITC on human glioma LN229 cells. Results demonstrated that PEITC possesses the potential ability to inhibit proliferation, induce apoptosis and arrest cell cycling against LN229 human glioma cells. Moreover, investigated results showed that PEITC inhibited the expression of superoxide dismutase (SOD) and glutathione (GSH), and caused oxidative stress to tumor cells. Collective results suggested us to believe that PEITC can inhibit the growth of LN229 cells and its mechanism can be related to the fact that PEITC can cause oxidative stress to tumor cells. PMID:26097624

  20. In vitro studies of phenethyl isothiocyanate against the growth of LN229 human glioma cells

    PubMed Central

    Su, Ji-Chun; Lin, Kai; Wang, Yan; Sui, Shao-Hua; Gao, Zhi-Yu; Wang, Zhi-Gang

    2015-01-01

    Phenethyl isothiocyanate (PEITC) is one of the best studied members of isothiocyanates (ITC), a variety of edible cruciferous vegetables including broccoli, watercress, and cabbage, and have generated particular interest because of its remarkable chemopreventive activity. Many literature reports proved that phenethyl isothiocyanate exhibited significant anti-cancer chemopreventive effects including lung, glioma and leukemia cancer. In this study, we explored the inhibitory effects as well as mechanisms of PEITC on human glioma LN229 cells. Results demonstrated that PEITC possesses the potential ability to inhibit proliferation, induce apoptosis and arrest cell cycling against LN229 human glioma cells. Moreover, investigated results showed that PEITC inhibited the expression of superoxide dismutase (SOD) and glutathione (GSH), and caused oxidative stress to tumor cells. Collective results suggested us to believe that PEITC can inhibit the growth of LN229 cells and its mechanism can be related to the fact that PEITC can cause oxidative stress to tumor cells. PMID:26097624

  1. Phenethyl isothiocyanate inhibits growth of human chronic myeloid leukemia K562 cells via reactive oxygen species generation and caspases.

    PubMed

    Wang, Yating; Wei, Sixi; Wang, Jishi; Fang, Qin; Chai, Qixiang

    2014-07-01

    Phenethyl isothiocyanate (PEITC), a potential cancer chemopreventive constituent of cruciferous vegetables, including watercress, has been reported to inhibit cancer cell growth by arresting the cell cycle and inducing apoptosis in various human cancer cell models. However, the role of PEITC in the inhibition of human chronic myeloid leukemia (CML) K562 cell growth and its underlying mechanisms have yet to be elucidated. In the present study, PEITC was found to induce cell death through the induction of reactive oxygen species (ROS) stress and oxidative damage. Heme oxygenase‑1 (HO‑1), which participates in the development of numerous tumors and the sensitivity of these tumors to chemotherapeutic drugs, plays a protective role by modulating oxidative injury. Therefore, the present study assessed the inhibitory effect of PEITC on K562 cells and whether HO‑1 facilitated cell apoptosis and ROS generation. PEITC was found to suppress cell growth and cause apoptosis by promoting Fas and Fas ligand expression, increasing ROS generation and by the successive release of cytochrome c as well as the activation of caspase‑9 and caspase‑3. PEITC was also combined with the HO‑1 inhibitor zinc protoporphyrin IX and the inducer hemin to assess whether HO‑1 determines cell survival and ROS generation. The results of the present study suggest that PEITC may be a potential anti‑tumor compound for CML therapy, and that HO‑1 has a critical function in PEITC‑induced apoptosis and ROS generation. PMID:24788892

  2. Isocyanates and isothiocyanates as versatile platforms for accessing (thio)amide-type compounds.

    PubMed

    Pace, Vittorio; Monticelli, Serena; de la Vega-Hernández, Karen; Castoldi, Laura

    2016-08-16

    The addition of carbon (Grignard and organolithium reagents) and hydride nucleophiles (Schwartz reagent) to isocyanates and isothiocyanates constitutes a versatile, direct and high yielding approach to the synthesis of functionalized (thio)amide derivatives including haloamides and formamides. The chemoselective delivery of a nucleophilic (eventually configurationally stable) organometallic species to a given iso(thio)cyanate is the crucial parameter for the success of the strategy. Thus, the influence of the factors governing classical methodologies (e.g. dehydrative condensation) such as steric hindrance and electronic properties of the reactants become practically negligible. PMID:27461156

  3. Comparison of ivermectin and benzyl benzoate for treatment of scabies.

    PubMed

    Glaziou, P; Cartel, J L; Alzieu, P; Briot, C; Moulia-Pelat, J P; Martin, P M

    1993-12-01

    A randomized investigator-blinded trial of oral ivermectin 100 micrograms/kg single dose vs. benzyl benzoate 10% application in the treatment of scabies, was conducted in 1992 in French Polynesia. In total, 44 patients aged 5-56 years were included in the study: 23 in the group ivermectin (IVER) and 21 in the group benzyl benzoate (BB). At day 30 after treatment, the cumulative recovery rates were 70% (16/23) in the group IVER, and 48% (10/21) in the group BB, 95% confidence intervals 51-87% and 29-70% respectively. The rates of recovery were greater in the group IVER at day 7, 14 and 30, but the difference was not statistically significant. Our results show that oral ivermectin is a valuable alternative to benzyl benzoate local treatment. PMID:8134777

  4. Growth and characterization of organic single crystal benzyl carbamate

    NASA Astrophysics Data System (ADS)

    Bala Solanki, S. Siva; Perumal, Rajesh Narayana; Suthan, T.; Bhagavannarayana, G.

    2015-10-01

    Benzyl carbamate single crystal is grown by a solution and vertical Bridgman technique for the first time. The cell parameters and morphologies are assessed from single crystal X-ray diffraction analysis. High resolution X-ray diffraction analysis indicates the crystalline perfection of the grown benzyl carbamate crystal. Fourier Transforms Infrared spectroscopy study has been applied to arrive at the different functional groups. Thermo gravimetric analysis and differential scanning calorimetry are used to study its thermal behavior. The microhardness test is carried out and the load dependent hardness is measured.

  5. Couplings of benzylic halides mediated by titanocene chloride: synthesis of bibenzyl derivatives.

    PubMed

    Barrero, Alejandro F; Herrador, M Mar; del Moral, José F Quílez; Arteaga, Pilar; Akssira, Mohammed; El Hanbali, Fadwa; Arteaga, Jesús F; Diéguez, Horacio R; Sánchez, Elena M

    2007-03-16

    Titanocene monochloride catalyzes the homocoupling of benzylic halides and benzylic gem-dibromides to give the corresponding bibenzyl and stilbenyl systems. Exposure of benzylic bromides to Ti(III) in the presence of aldehydes gave rise to the Barbier-type products. Examples of the utility of the herein described processes are included. PMID:17309310

  6. Oestrogenic activity of benzyl salicylate, benzyl benzoate and butylphenylmethylpropional (Lilial) in MCF7 human breast cancer cells in vitro.

    PubMed

    Charles, A K; Darbre, P D

    2009-07-01

    Benzyl salicylate, benzyl benzoate and butylphenylmethylpropional (Lilial) are added to bodycare cosmetics used around the human breast. We report here that all three compounds possess oestrogenic activity in assays using the oestrogen-responsive MCF7 human breast cancer cell line. At 3 000 000-fold molar excess, they were able to partially displace [(3)H]oestradiol from recombinant human oestrogen receptors ERalpha and ERbeta, and from cytosolic ER of MCF7 cells. At concentrations in the range of 5 x 10(-5) to 5 x 10(-4 )m, they were able to increase the expression of a stably integrated oestrogen-responsive reporter gene (ERE-CAT) and of the endogenous oestrogen-responsive pS2 gene in MCF7 cells, albeit to a lesser extent than with 10(-8 )m 17beta-oestradiol. They increased the proliferation of oestrogen-dependent MCF7 cells over 7 days, which could be inhibited by the antioestrogen fulvestrant, suggesting an ER-mediated mechanism. Although the extent of stimulation of proliferation over 7 days was lower with these compounds than with 10(-8 )m 17beta-oestradiol, given a longer time period of 35 days the extent of proliferation with 10(-4 )m benzyl salicylate, benzyl benzoate or butylphenylmethylpropional increased to the same magnitude as observed with 10(-8 )m 17beta-oestradiol over 14 days. This demonstrates that benzyl salicylate, benzyl benzoate and butylphenylmethylpropional are further chemical components of cosmetic products which give oestrogenic responses in a human breast cancer cell line in culture. Further research is now needed to investigate whether oestrogenic responses are detectable using in vivo models and the extent to which these compounds might be absorbed through human skin and might enter human breast tissues. PMID:19338011

  7. Assessment of DNA damage and repair in adults consuming allyl isothiocyanate or Brassica vegetables

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Allyl isothiocyanate (AITC) is a dietary component with potentially important anti-cancer effects, though much of the information about AITC and cancer processes has been obtained from cell studies. To investigate the effect of AITC on DNA integrity and repair in vivo, a human feeding study was con...

  8. Effect of allyl isothiocyanate on antioxidants and fruit decay of blueberries

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effect of allyl isothiocyanate (AITC) on flavonoids, radical scavenging capacity, fruit decay and quality of blueberries (Vaccinium corymbosum L. cv. Duke) was evaluated. Results from this study showed that AITC was effective in retarding blueberry decay during storage at 10 'C. AITC treatment r...

  9. DIETARY ISOTHIOCYANATE IBERIN INHIBITS GROWTH AND INDUCES APOPTOSIS IN HUMAN GLIOBLASTOMA CELLS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this study, we evaluated the antiproliferative and proapoptotic effects of the isothiocyanate iberin, a bioactive agent in Brassicaceae species, in human glioblastoma cells. The human glioblastoma cell cultures were treated with different concentrations of iberin and tested for growth inhibition...

  10. Spectroscopic and structural investigations of iron(III) isothiocyanates. A comparative theoretical and experimental study.

    PubMed

    Elijošiutė, Erika; Eicher-Lorka, Olegas; Griškonis, Egidijus; Kuodis, Zenonas; Jankūnaitė, Dalia; Denafas, Gintaras

    2014-08-14

    A combined experimental and theoretical study on the molecular structure and vibrational spectra of [Fe(NCS)](2+) complex in the aqueous solution at the pH∼2 ± 0.1 have been performed. Experimental Raman spectra of the iron(III) isothiocyanate with higher coordination number in the acidic aqueous solution have been analyzed. Molecular modeling of the iron(III) monoisothiocyanate complex was accomplished by the density functional theory (DFT) method using B3LYP and PBE1PBE functionals. Theoretical vibrational spectra of the iron(III) monoisothiocyanate were interpreted by means of the potential energy distributions (PEDs). The influence of different solvation models and position of SO4(2)(-) ligand vs. NCS(-) ligand upon its geometry and vibrational frequencies have been evaluated. The effect of H2O/D2O isotopic substitution on the experimental and calculated Raman spectra of iron(III) isothiocyanates has been examined. Procedures of Raman spectra subtraction have been applied for the extractions of weak and/or obscured Raman signals. As a result, the presence of bound SO4(2)(-) ion and water molecules in the first coordination sphere in the acidic aqueous iron(III) isothiocyanate solution was confirmed. The vibrational assignments for the investigated iron(III) isothiocyanates were proposed here for the first time. PMID:24721282

  11. Water and Methyl-Isothiocyanate Distribution in Soil Following Drip Fumigation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methyl isothiocyanate (MITC) generators, such as metam sodium (Met-Na), are used for soil fumigation of agricultural land. The ban on the fumigant methyl bromide (MBr) has resulted in greater use of MITC generators. In order to understand the efficacy of MITC, it is necessary to assess its generat...

  12. Evaluating surface seals in soil columns to mitigate methy isothiocyanate volatilization

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The banning of methyl bromide (MeBr) as a pre-plant soil fumigant due to its implication as an ozone depleting substance, has led to increased interest in finding alternative soil fumigants to replace MeBr. One of the promising alternatives for certain crops is methyl isothiocyanate (MITC) generati...

  13. A Quick and Simple Conversion of Carboxylic Acids into Their Anilides of Heating with Phenyl Isothiocyanate.

    ERIC Educational Resources Information Center

    Ram, Ram N.; And Others

    1983-01-01

    Converting carboxylic acids into their anilides, which usually involves preparation of acid chloride or mixed anhydride followed by treatment with aniline, is tedious and/or time-consuming. A quick and easier procedure, using phenyl isothiocyanate, is provided. Reactions involved and a summary table of results are included. (JN)

  14. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... halogenated benzyl ester acrylate (PMN P-90-1527) is subject to reporting under this section for the... processors of this substance as specified in § 721.125 (a), (b), (c), (d), (f), (g), (h), and (i). (2... substance may cause internal organ effects (kidney and blood). The requirements of this section do not...

  15. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.329 Halogenated benzyl ester acrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically...

  16. 40 CFR 721.329 - Halogenated benzyl ester acrylate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.329 Halogenated benzyl ester acrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically...

  17. Study of Benzyl Salicylate/beta-Cyclodextrin Inclusion Complex Formation by Positron Annihilation

    NASA Astrophysics Data System (ADS)

    Bellitto, V. J.; Hsu Hadley, F. H., Jr.; Trinh, T.

    1996-11-01

    Results of positron annihilation lifetime spectra of beta-cyclodextrin and beta-cyclodextrin complexed with benzyl salicylate,benzyl acetate, or ethyl salicylate in air and vacuum were used to determine the fraction of beta-cyclodextrin which remains uncomplexed in the benzyl salicylate/beta-cyclodextrin 1:2 molar ratio inclusion complex. The intensity of the longest-lived component in vacuum was shown to decrease when the beta-cyclodextrin cavity was filled with benzyl salicylate, benzyl acetate, or ethyl salicylate guest molecules. Comparison of the intensity for beta-cyclodextrin, benzyl salicylate/beta-cyclodextrin 1:2 molar ratio, and 1:1 molar ratio indicated that the benzyl and salicylate moieties each formed an inclusion complex with a molecule of beta-cyclodextrin in the benzyl salicylate/beta-cyclodextrin 1:2 complex. It was determined that the benzyl moiety of the benzyl salicylate molecule is preferred by the beta-cyclodextrin "host" and that only 34of the salicylate moieties are complexed in the benzyl salicylate/beta-cyclodextrin 1:2 sample.

  18. The CIDNP-detected laser-flash photolysis of benzyl ketones

    NASA Astrophysics Data System (ADS)

    Läufer, Martina; Dreeskamp, Herbert

    The near UV photolysis of benzyl ketones leads to acyl and benzyl radicals via Norrish type I cleavage. A minor reaction pathway for these radicals is the formation of semibenzenes. Several not previously recognized polarizations of semibenzene products in the CIDNP spectra of methyl benzyl, isopropyl benzyl, benzyl phenyl, and dibenzyl ketone were found using a 308 nm pulsed excimer laser and a 250 MHz 1H NMR spectrometer. The chemical shifts of the semibenzenes formed as recombination products are given and the spectrum of benzyl semibenzene, stable under the experimental conditions, is analyzed. The evolution of main and minor diamagnetic products on a microsecond time scale is presented. From these data the rate of the diffusion-controlled termination reaction of benzyl radicals to bibenzyl was found to be 7 × 10 9M-1 s -1 in benzene solution at room temperature.

  19. Identification of cancer chemopreventive isothiocyanates as direct inhibitors of the arylamine N-acetyltransferase-dependent acetylation and bioactivation of aromatic amine carcinogens

    PubMed Central

    Duval, Romain; Xu, Ximing; Bui, Linh-Chi; Mathieu, Cécile; Petit, Emile; Cariou, Kevin; Dodd, Robert H.; Dupret, Jean-Marie; Rodrigues-Lima, Fernando

    2016-01-01

    Aromatic amines (AAs) are chemicals of industrial, pharmacological and environmental relevance. Certain AAs, such as 4-aminobiphenyl (4-ABP), are human carcinogens that require enzymatic metabolic activation to reactive chemicals to form genotoxic DNA adducts. Arylamine N-acetyltransferases (NAT) are xenobiotic metabolizing enzymes (XME) that play a major role in this carcinogenic bioactivation process. Isothiocyanates (ITCs), including benzyl-ITC (BITC) and phenethyl-ITC (PEITC), are phytochemicals known to have chemopreventive activity against several aromatic carcinogens. In particular, ITCs have been shown to modify the bioactivation and subsequent mutagenicity of carcinogenic AA chemicals such as 4-ABP. However, the molecular and biochemical mechanisms by which these phytochemicals may modulate AA carcinogens bioactivation and AA-DNA damage remains poorly understood. This manuscript provides evidence indicating that ITCs can decrease the metabolic activation of carcinogenic AAs via the irreversible inhibition of NAT enzymes and subsequent alteration of the acetylation of AAs. We demonstrate that BITC and PEITC react with NAT1 and inhibit readily its acetyltransferase activity (ki = 200 M−1.s−1 and 66 M−1.s−1 for BITC and PEITC, respectively). Chemical labeling, docking approaches and substrate protection assays indicated that inhibition of the acetylation of AAs by NAT1 was due to the chemical modification of the enzyme active site cysteine. Moreover, analyses of AAs acetylation and DNA adducts in cells showed that BITC was able to modulate the endogenous acetylation and bioactivation of 4-ABP. In conclusion, we show that direct inhibition of NAT enzymes may be an important mechanism by which ITCs exert their chemopreventive activity towards AA chemicals. PMID:26840026

  20. Identification of cancer chemopreventive isothiocyanates as direct inhibitors of the arylamine N-acetyltransferase-dependent acetylation and bioactivation of aromatic amine carcinogens.

    PubMed

    Duval, Romain; Xu, Ximing; Bui, Linh-Chi; Mathieu, Cécile; Petit, Emile; Cariou, Kevin; Dodd, Robert H; Dupret, Jean-Marie; Rodrigues-Lima, Fernando

    2016-02-23

    Aromatic amines (AAs) are chemicals of industrial, pharmacological and environmental relevance. Certain AAs, such as 4-aminobiphenyl (4-ABP), are human carcinogens that require enzymatic metabolic activation to reactive chemicals to form genotoxic DNA adducts. Arylamine N-acetyltransferases (NAT) are xenobiotic metabolizing enzymes (XME) that play a major role in this carcinogenic bioactivation process. Isothiocyanates (ITCs), including benzyl-ITC (BITC) and phenethyl-ITC (PEITC), are phytochemicals known to have chemopreventive activity against several aromatic carcinogens. In particular, ITCs have been shown to modify the bioactivation and subsequent mutagenicity of carcinogenic AA chemicals such as 4-ABP. However, the molecular and biochemical mechanisms by which these phytochemicals may modulate AA carcinogens bioactivation and AA-DNA damage remains poorly understood.This manuscript provides evidence indicating that ITCs can decrease the metabolic activation of carcinogenic AAs via the irreversible inhibition of NAT enzymes and subsequent alteration of the acetylation of AAs. We demonstrate that BITC and PEITC react with NAT1 and inhibit readily its acetyltransferase activity (ki = 200 M-1.s-1 and 66 M-1.s-1 for BITC and PEITC, respectively). Chemical labeling, docking approaches and substrate protection assays indicated that inhibition of the acetylation of AAs by NAT1 was due to the chemical modification of the enzyme active site cysteine. Moreover, analyses of AAs acetylation and DNA adducts in cells showed that BITC was able to modulate the endogenous acetylation and bioactivation of 4-ABP. In conclusion, we show that direct inhibition of NAT enzymes may be an important mechanism by which ITCs exert their chemopreventive activity towards AA chemicals. PMID:26840026

  1. DETERMINATION OF ALIPHATIC AMINES IN WATER USING DERIVATIZATION WITH FLUORESCEIN ISOTHIOCYANATE AND CAPILLARY ELECTROPHORESIS/LASER-INDUCED FLUORESCENCE DETECTION.

    EPA Science Inventory

    Detection-oriented derivatization of aliphatic amines and amine functional groups in coumpounds of environmental interest was studied using fluorescein isothiocyanate (FITC) with separation/determination by capillary electrophoresis/laser-induced fluorescence. Determinative level...

  2. 3-Benzyl-5-methyl-1,2-benzoxazole 2-oxide

    PubMed Central

    Anuradha, G.; Gopalsamy, Vasuki; Veera Reddy, A.; Laxminarasimhulu, G.

    2012-01-01

    In the title compound, C15H13NO2, the isoxazole unit and the attached benzene ring are almost coplanar, making a dihedral angle of 1.42 (8)°. The benzyl ring is inclined to the isoxazole ring by 74.19 (8)° and is in a +sc conformation with respect to the benzisoxazole unit. In the crystal, C—H⋯O hydrogen bonds link the mol­ecules, forming zigzag chains propagating along the b axis. There are also π–π inter­actions present involving the isoxazole and benzyl rings [centroid–centroid distance = 3.5209 (10) Å], and C—H⋯π inter­actions involving the benzene ring of the benzoisoxazole unit and the methyl­ene bridging group. PMID:23125740

  3. Reaction of /alpha/,/beta/-unsaturated acyl isothiocyanates with salts of dithiocarbamic acids

    SciTech Connect

    Krus, K.; Masias, A.; Beletskaya, I.P.

    1989-01-10

    The reaction of unsaturated isothiocyanates with the sodium and calcium salts of N-alkyl- and N,N-dialkyldithiocarbamic acids was studied. Depending on the structure of the dithiocarbamate, the reaction products are thiazines or acyl dithiocarbamates. For the salts of methyldithiocarbamic acid the effect of the concentration and the nature of the metal on the relative yields of 6-phenyl-3-methylpropiorhodanine and 6-phenylpropiorhodanine was studied. A method is proposed for the synthesis of 3-substituted propiorhodanines.

  4. Inhibition of Bladder Cancer by Broccoli Isothiocyanates Sulforaphane and Erucin: Characterization, Metabolism and Interconversion

    PubMed Central

    Abbaoui, Besma; Riedl, Kenneth M; Ralston, Robin A; Thomas-Ahner, Jennifer M; Schwartz, Steven J; Clinton, Steven K; Mortazavi, Amir

    2013-01-01

    Epidemiologic evidence suggests diets rich in cruciferous vegetables, particularly broccoli, are associated with lower bladder cancer risk. Our objectives are to investigate these observations and determine the role of isothiocyanates in primary or secondary bladder cancer prevention. We initially investigate the mechanisms whereby broccoli and broccoli sprout extracts and pure isothiocyanates inhibit normal, non-invasive (RT4) and invasive (J82, UMUC3) human urothelial cell viability. Sulforaphane (IC50= 5.66±1.2μM) and erucin (IC50= 8.79±1.3μM) are found to be the most potent inhibitors and normal cells are least sensitive. This observation is associated with downregulation of survivin, EGFR and HER2/neu, G2/M cell cycle accumulation and apoptosis. In a murine UMUC3 xenograft model, we fed semipurified diets containing 4% broccoli sprouts, or 2% broccoli sprout isothiocyanate extract; or gavaged pure sulforaphane or erucin (each at 295 μmol/kg, similar to dietary exposure); and report tumor weight reduction of 42% (p=0.02), 42% (p=0.04), 33% (p=0.04) and 58% (p<0.0001), respectively. Sulforaphane and erucin metabolites are present in mouse plasma (micromolar range) and tumor tissue, with N-acetyl cysteine conjugates as the most abundant. Interconversion of sulforaphane and erucin metabolites was observed. This work supports development of fully characterized, novel food products for phase I/II human studies targeting bladder cancer prevention. PMID:23038615

  5. Induction of epoxide hydrolase, glucuronosyl transferase, and sulfotransferase by phenethyl isothiocyanate in male Wistar albino rats.

    PubMed

    Abdull Razis, Ahmad Faizal; Mohd Noor, Noramaliza; Konsue, Nattaya

    2014-01-01

    Phenethyl isothiocyanate (PEITC) is an isothiocyanate found in watercress as the glucosinolate (gluconasturtiin). The isothiocyanate is converted from the glucosinolate by intestinal microflora or when contacted with myrosinase during the chopping and mastication of the vegetable. PEITC manifested protection against chemically-induced cancers in various tissues. A potential mechanism of chemoprevention is by modulating the metabolism of carcinogens so as to promote deactivation. The principal objective of this study was to investigate in rats the effect of PEITC on carcinogen-metabolising enzyme systems such as sulfotransferase (SULT), N-acetyltransferase (NAT), glucuronosyl transferase (UDP), and epoxide hydrolase (EH) following exposure to low doses that simulate human dietary intake. Rats were fed for 2 weeks diets supplemented with PEITC at 0.06 µmol/g (low dose, i.e., dietary intake), 0.6 µmol/g (medium dose), and 6.0 µmol/g (high dose), and the enzymes were monitored in rat liver. At the Low dose, no induction of the SULT, NAT, and EH was noted, whereas UDP level was elevated. At the Medium dose, only SULT level was increased, whereas at the High dose marked increase in EH level was observed. It is concluded that PEITC modulates carcinogen-metabolising enzyme systems at doses reflecting human intake thus elucidating the mechanism of its chemoprevention. PMID:24592387

  6. Induction of Epoxide Hydrolase, Glucuronosyl Transferase, and Sulfotransferase by Phenethyl Isothiocyanate in Male Wistar Albino Rats

    PubMed Central

    Mohd Noor, Noramaliza; Konsue, Nattaya

    2014-01-01

    Phenethyl isothiocyanate (PEITC) is an isothiocyanate found in watercress as the glucosinolate (gluconasturtiin). The isothiocyanate is converted from the glucosinolate by intestinal microflora or when contacted with myrosinase during the chopping and mastication of the vegetable. PEITC manifested protection against chemically-induced cancers in various tissues. A potential mechanism of chemoprevention is by modulating the metabolism of carcinogens so as to promote deactivation. The principal objective of this study was to investigate in rats the effect of PEITC on carcinogen-metabolising enzyme systems such as sulfotransferase (SULT), N-acetyltransferase (NAT), glucuronosyl transferase (UDP), and epoxide hydrolase (EH) following exposure to low doses that simulate human dietary intake. Rats were fed for 2 weeks diets supplemented with PEITC at 0.06 µmol/g (low dose, i.e., dietary intake), 0.6 µmol/g (medium dose), and 6.0 µmol/g (high dose), and the enzymes were monitored in rat liver. At the Low dose, no induction of the SULT, NAT, and EH was noted, whereas UDP level was elevated. At the Medium dose, only SULT level was increased, whereas at the High dose marked increase in EH level was observed. It is concluded that PEITC modulates carcinogen-metabolising enzyme systems at doses reflecting human intake thus elucidating the mechanism of its chemoprevention. PMID:24592387

  7. Sulfation of benzyl alcohol by the human cytosolic sulfotransferases (SULTs): a systematic analysis.

    PubMed

    Zhang, Lingtian; Kurogi, Katsuhisa; Liu, Ming-Yih; Schnapp, Alaina M; Williams, Frederick E; Sakakibara, Yoichi; Suiko, Masahito; Liu, Ming-Cheh

    2016-09-01

    The aim of the present study was to identify human cytosolic sulfotransferases (SULTs) that are capable of sulfating benzyl alcohol and to examine whether benzyl alcohol sulfation may occur in cultured human cells as well as in human organ homogenates. A systematic analysis revealed that of the 13 known human SULTs, SULT1A1 SULT1A2, SULTA3, and SULT1B1 are capable of mediating the sulfation of benzyl alcohol. The kinetic parameters of SULT1A1 that showed the strongest benzyl alcohol-sulfating activity were determined. HepG2 human hepatoma cells were used to demonstrate the generation and release of sulfated benzyl alcohol under the metabolic settings. Moreover, the cytosol or S9 fractions of human liver, lung, kidney and small intestine were examined to verify the presence of benzyl alcohol sulfating activity in vivo. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26663444

  8. Friction behavior of 304 stainless steel of varying hardness lubricated with benzene and some benzyl structures

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1974-01-01

    The lubricating properties of some benzyl and benzene structures were determined by using 304 stainless steel surfaces strained to various hardness. Friction coefficients and wear track widths were measured with a Bowden-Leben type friction apparatus by using a pin-on-disk specimen configuration. Results obtained indicate that benzyl monosulfide, dibenzyl disulfide, and benzyl alcohol resulted in the lowest friction coefficients for 304 stainless steel, while benzyl ether provided the least surface protection and gave the highest friction. Strainhardening of the 304 stainless steel prior to sliding resulted in reduced friction in dry sliding. With benzyl monosulfide, dibenzyl disulfide, and benzyl alcohol changes in 304 stainless steel hardness had no effect upon friction behavior.

  9. Effect of strain hardening on friction behavior of iron lubricated with benzyl structures

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.; Brainard, W. A.

    1974-01-01

    Sliding friction experiments were conducted with iron, copper, and aluminum in contact with iron in various states of strain. The surfaces were examined in dry sliding and with various benzyl compounds applied as lubricants. Friction experiments were conducted with a hemispherical rider contacting a flat disk at loads of from 50 to 600 grams with a sliding speed of 0.15 cm/min. Results indicate that straining increases friction for dry sliding and for surfaces lubricated with certain benzyl structures such as dibenzyl disulfide. With other benzyl compounds (e.g., benzyl formate), friction coefficients are lower for strained than for annealed iron.

  10. Metal-mediated reaction modeled on nature: the activation of isothiocyanates initiated by zinc thiolate complexes.

    PubMed

    Eger, Wilhelm A; Presselt, Martin; Jahn, Burkhard O; Schmitt, Michael; Popp, Jürgen; Anders, Ernst

    2011-04-18

    On the basis of detailed theoretical studies of the mode of action of carbonic anhydrase (CA) and models resembling only its reactive core, a complete computational pathway analysis of the reaction between several isothiocyanates and methyl mercaptan activated by a thiolate-bearing model complex [Zn(NH(3))(3)SMe](+) was performed at a high level of density functional theory (DFT). Furthermore, model reactions have been studied in the experiment using relatively stable zinc complexes and have been investigated by gas chromatography/mass spectrometry and Raman spectroscopy. The model complexes used in the experiment are based upon the well-known azamacrocyclic ligand family ([12]aneN(4), [14]aneN(4), i-[14]aneN(4), and [15]aneN(4)) and are commonly formulated as ([Zn([X]aneN(4))(SBn)]ClO(4). As predicted by our DFT calculations, all of these complexes are capable of insertion into the heterocumulene system. Raman spectroscopic investigations indicate that aryl-substituted isothiocyanates predominantly add to the C═N bond and that the size of the ring-shaped ligands of the zinc complex also has a very significant influence on the selectivity and on the reactivity as well. Unfortunately, the activated isothiocyanate is not able to add to the thiolate-corresponding mercaptan to invoke a CA analogous catalytic cycle. However, more reactive compounds such as methyl iodide can be incorporated. This work gives new insight into the mode of action and reaction path variants derived from the CA principles. Further, aspects of the reliability of DFT calculations concerning the prediction of the selectivity and reactivity are discussed. In addition, the presented synthetic pathways can offer a completely new access to a variety of dithiocarbamates. PMID:21405064

  11. Repellent activity of essential oils and some of their individual constituents against Tribolium castaneum herbst.

    PubMed

    Caballero-Gallardo, Karina; Olivero-Verbel, Jesús; Stashenko, Elena E

    2011-03-01

    A tool for integrated pest management is the use of essential oils (EOs) and plant extracts. In this study, EOs from Tagetes lucida , Lepechinia betonicifolia , Lippia alba , Cananga odorata , and Rosmarinus officinalis , species grown in Colombia, were analyzed by gas chromatography-mass spectrometry. These oils as well as several of their constituents were tested for repellent activity against Tribolium castaneum , using the area preference method. The main components (>10%) found in EOs were methylchavicol, limonene/α-pinene, carvone/limonene, benzyl acetate/linalool/benzyl benzoate, and α-pinene, for T. lucida, L. betonicifolia, L. alba, C. odorata, and R. officinalis, respectively. All EOs were repellent, followed a dose-response relationship, and had bioactivity similar to or better than that of commercial compound IR3535. EOs from C. odorata and L. alba were the most active. Compounds from EOs, such benzyl benzoate, β-myrcene, and carvone, showed good repellent properties. In short, EOs from plants cultivated in Colombia are sources of repellents against T. castaneum. PMID:21291237

  12. Isothiocyanate synthetic analogs: biological activities, structure-activity relationships and synthetic strategies.

    PubMed

    Milelli, Andrea; Fimognari, Carmela; Ticchi, Nicole; Neviani, Paolo; Minarini, Anna; Tumiatti, Vincenzo

    2014-01-01

    Sulforaphane is a natural product that is constantly under biological investigation for its unique biological properties. This naturally occurring isothiocyanate (ITC) and its analogs are the main components of cruciferous vegetables, such as cauliflower, watercress, broccoli, cabbage, Brussels sprouts, widely used as chemopreventive agents. Due to their interesting biological profiles, natural ITCs have been exploited as starting point to develop new synthetic analogs. The present mini-review briefly highlights the most important biological actions of selected new synthetic ITCs focusing on their structure-activity relationships and related synthetic strategies. PMID:25373847

  13. Synthesis of Cyclic Azomethine Imines by Cycloaddition Reactions of N-Isocyanates and N-Isothiocyanates.

    PubMed

    Bongers, Amanda; Ranasinghe, Indee; Lemire, Philippe; Perozzo, Alyssa; Vincent-Rocan, Jean-François; Beauchemin, André M

    2016-08-01

    Various nitrogen-substituted iso(thio)cyanates engage in [3 + 2]-cycloaddition reactions to form azomethine imines containing triazolone, triazole-thione, and pyrazole-thione cores. First, iminoisothiocyanates are shown to undergo aminothiocarbonylation reactions with strained alkenes, and a comparison with recently reported reactions of iminoisocyanates highlights their reduced reactivity. In contrast, amino(thio)carbonylation reactions of imines with iminoisocyanates and iminoisothiocyanates proved more efficient, providing access to triazolone and triazole-thione cores. The dipole products can be converted to valuable heterocyclic cores through simple derivatization reactions. PMID:27458786

  14. Studies on the interaction of fluorescein isothiocyanate and its sugar analogues with cetyltrimethylammonium bromide

    NASA Astrophysics Data System (ADS)

    Ghosh, Sujit Kumar; Ali, Mohammed; Chatterjee, Hirak

    2013-03-01

    The interaction of fluorescein isothiocyanate (FITC) and its two sugar analogues (viz., FITC-Dextran 40S and FITC-Dextran 2000S) with cetyltrimethylammonium bromide has been elucidated by absorption, fluorescence, Fourier transform infrared spectroscopy and fluorescence microscopic studies. It is seen that the emission of the probe molecules is uniquely sensitive to the changes in surfactant concentrations at a particular regime due to the formation of dye-surfactant supramolecular assembly. The formation of supramolecular assembly becomes effective at a lower surfactant concentration with increasing dextran size as a consequence of definite dye-surfactant interaction and could pave a facile strategy for designing hierarchical superstructures.

  15. An unexpected rearrangement of pent-4-enofuranosides to cyclopentanones upon hydrogenolysis of the anomeric benzyl group.

    PubMed

    Nie, Shenyou; Chen, Xiaoping; Ma, Yuyong; Li, Wei; Yu, Biao

    2016-09-01

    During our synthesis toward the unique nucleoside antibiotic A201A, we were surprised to find that a benzyl arabino-pent-4-enofuranoside underwent a Ferrier II-like rearrangement readily to provide the corresponding cyclopentanone derivative in high yield and stereoselectivity upon hydrogenolysis of the anomeric benzyl group. PMID:27366975

  16. Depolymerization of lignin by microwave-assisted methylation of benzylic alcohols.

    PubMed

    Zhu, Guodian; Qiu, Xueqing; Zhao, Ying; Qian, Yong; Pang, Yuxia; Ouyang, Xinping

    2016-10-01

    A new two-step lignin depolymerization strategy was developed, in which the benzylic alcohols in lignin was methylated under microwave irradiation, followed by a hydrogenolysis for the cleavage of βO4 bond with Pd/C as the catalyst. The results showed that an efficient and selective catalytic methylation of benzylic alcohols was achieved with various lignin model compounds, and the acidic environment promoted the methylation of benzylic alcohol. Methylation of benzylic alcohol increased the βO4 bond cleavage rate by 55.9%, and improved products selectivity. Preliminary study of lignin depolymerization illustrated that methylation pretreatment of benzylic alcohols facilitated lignin depolymerization to produce aromatic monomers and reduced the oxygen content of aromatic monomers. PMID:27420159

  17. Benzyl Viologen-Mediated Counteraction of Diquat and Paraquat Phytotoxicities 1

    PubMed Central

    Lewinsohn, Efraim; Gressel, Jonathan

    1984-01-01

    There was reason from bacterial and algal systems to expect that pretreatments with a paraquat analog might confer tolerance against a subsequent paraquat treatment. Thus, a series of compounds were tested for protective activity against bipyridinium herbicides. These included other bipyridinium compounds and derivatives, as well as compounds having similar or more positive redox potentials than paraquat and compounds known to increase or maintain high superoxide dismutase activity levels in plants. Only treatments with benzyl viologen, a benzyl analog of paraquat, protected Spirodela oligorrhiza (Kurz) Hegelm. colonies from otherwise damaging levels of diquat. NADP photoreduction by isolated thylakoids was inhibited by the same concentrations of paraquat, diquat, and benzyl viologen given separately. Thus, the benzyl viologen-mediated tolerance against the bipyridinium herbicides is probably not due to a direct interaction at the thylakoid level. Superoxide dismutase activity was about 50% higher in broken plastids of benzyl viologen-treated plants compared to controls, which may partly explain the observed tolerance. PMID:16663782

  18. Arylalkylation of 4-tert-butyltoluene with substituted benzyl chlorides

    SciTech Connect

    Pozdnyakovich Y.V.; Savyak, R.P.; Shein, S.M.

    1986-08-01

    The reaction of 4-alkylbenzyl chlorides with 4-tert-butyltoluene in the presence of titanium tetrachloride and ferric chloride leads to the formation of 2-methyl-4'-alkyl-5-tert-butyldiphenylmethanes. The arylalkylation of 4-tert-butyltoluene with 2- and 4-chlorobenzyl chlorides, catalyzed by titanium tetrachloride, leads to the formation of mixtures of 2-methyl-5-tert-butyldiphenylmethane, 2-tert-butyl-5-methyldiphenylmethane, and isomeric methyldiphenylmethanes containing a chloride atom in the benzyl fragment. The products of the reaction catalyzed by ferric chloride do not contain 2-tert-butyl-5-methylchlorodiphenylmethanes. The reaction of 4-nitrobenzyl chloride with 4-tert-butyltoluence in the presence of ferric chloride leads to the formation of a mixture of 2-methyl-4'-nitro-5-tert-butyldiphenylmethane and isomeric methylnitrodiphenylmethanes. Under the influence of AlCl/sub 3/-CH/sub 3/NO/sub 2/ in benzene 2,4'-dimethyl-5-tert-butyldiphenylmethane eliminates both the 4-methylbenzyl group and the tert-butyl group. Under analogous conditions 2-methyl-5-tert-butyldiphenylmethanes containing a chlorine atom or a nitro group in the benzyl fragment are dealkylated with the elimination of only the tert-butyl group.

  19. Thermal Decomposition of Benzyl Radical via Multiple Active Pathways

    NASA Astrophysics Data System (ADS)

    Buckingham, Grant; Robichaud, David; Ormond, Thomas; Nimlos, Mark R.; Daily, John W.; Ellison, Barney

    2014-06-01

    The thermal decomposition of benzyl radical (C6H5CH2) has been investigated using a combination infrared absorption spectroscopy in a neon matrix and 118.2 (10.487 eV) photoionization mass spectrometry. Both techniques are coupled with a heated tubular reactor to allow temperature control over the decomposition to indicate relative barrier heights of fragmentation pathways. Three possible chemical mechanisms have been considered. 1) Ring expansion to cycloheptatrienyl radical (C7H7) with subsequent breakdown to HCCH and C5H5, 2) isomerization to the substituted five-membered ring fulvenallene (C5H4=C=CH2), which is of interest to kinetic theorists and finally 3) hydrogen shift to form methyl-substituted phenyl radical, which can then form ortho-benzyne, diacetylene and other fragments. Benzyl radical is generated from two precursors, C6H5CH2CH3 and C6H5CH2Br, and both lead to the appearance of HCCH and C5H5. At slightly hotter temperatures peaks are observed at m/z 90, presumed to be C5H4=C=CH2, and 89, potentially the substituted propargyl C5H4=C=CH. Additionally, decomposition of isotopically substituted parent molecules C6H5CD2CD3 and C6D5CH2CH3 indicates C7H7 as an intermediate due to H/D ratios in fragment molecules.

  20. Phenethyl isothiocyanate-induced apoptosis in PC-3 human prostate cancer cells is mediated by reactive oxygen species-dependent disruption of the mitochondrial membrane potential.

    PubMed

    Xiao, Dong; Lew, Karen L; Zeng, Yan; Xiao, Hui; Marynowski, Stanley W; Dhir, Rajiv; Singh, Shivendra V

    2006-11-01

    The present study was undertaken to gain insights into the molecular mechanism of apoptosis induction by phenethyl isothiocyanate (PEITC), which is a cancer chemopreventive constituent of cruciferous vegetables, using PC-3 human prostate cancer cells as a model. The PEITC-induced cell death in PC-3 cells was associated with disruption of the mitochondrial membrane potential, release of apoptogenic molecules (cytochrome c and Smac/DIABLO) from mitochondria to the cytosol and generation of reactive oxygen species (ROS), which were blocked in the presence of a combined mimetic of superoxide dismutase and catalase (Euk134). Ectopic expression of Bcl-xL, whose protein level is reduced markedly on treatment of PC-3 cells with PEITC, conferred partial protection against PEITC-induced apoptosis only at higher drug concentrations (>10 microM). Administration of 12 micromol PEITC/day (Monday through Friday) by oral gavage significantly retarded growth of PC-3 xenografts in athymic mice. For instance, 31 days after the initiation of PEITC administration, the average tumor volume in control mice (721 +/- 153 mm3) was approximately 2-fold higher compared with mice receiving 12 micromol PEITC/day. The PEITC-mediated inhibition of PC-3 xenograft growth was associated with induction of Bax and Bid proteins. In conclusion, the present study indicates that the PEITC-induced apoptosis in PC-3 cells is mediated by ROS-dependent disruption of the mitochondrial membrane potential and regulated by Bax and Bid. PMID:16774948

  1. Antimicrobial, antioxidant, cytotoxic and molecular docking properties of N-benzyl-2,2,2-trifluoroacetamide

    NASA Astrophysics Data System (ADS)

    Balachandran, C.; Kumar, P. Saravana; Arun, Y.; Duraipandiyan, V.; Sundaram, R. Lakshmi; Vijayakumar, A.; Balakrishna, K.; Ignacimuthu, S.; Al-Dhabi, N. A.; Perumal, P. T.

    2015-02-01

    N-Benzyl-2,2,2-trifluoroacetamide was obtained by acylation of benzylamine with trifluoroacetic anhydride using Friedel-Crafts acylation method. The synthesised compound was confirmed by spectroscopic and crystallographic techniques. N-Benzyl-2,2,2 -trifluoroacetamide was assessed for its antimicrobial, antioxidant, cytotoxic and molecular docking properties. It showed good antifungal activity against tested fungi and moderate antibacterial activity. The minimum inhibitory concentration values of N-benzyl-2,2,2 -trifluoroacetamide against fungi were 15.62 μg/mL against A. flavus, 31.25 μg/mL against B. Cinerea and 62.5 μg/mL against T. mentagrophytes, Scopulariopsis sp., C. albicans and M. pachydermatis. N-Benzyl-2,2,2-trifluoroacetamide showed 78.97 ± 2.24 of antioxidant activity at 1,000 μg/mL. Cupric ion reducing antioxidant capacity of N-benzyl-2,2,2-trifluoroacetamide was dependent on the concentration. Ferric reducing antioxidant power assay of N-benzyl-2,2,2-trifluoroacetamide showed (1.352 ± 0.04 mM Fe(II)/g) twofold higher value compared to the standard. N-Benzyl-2,2,2-trifluoroacetamide showed 75.3 % cytotoxic activity at the dose of 200 μg/mL with IC50 (54.7 %) value of 100 μg/mL. N-Benzyl-2,2,2-trifluoroacetamide was subjected to molecular docking studies for the inhibition AmpC beta-lactamase, Glucosamine-6-Phosphate Synthase and lanosterol 14 alpha-demethylase (CYP51) enzymes which are targets for antibacterial and antifungal drugs. Docking studies of N-benzyl-2,2,2-trifluoroacetamide showed low docking energy. N-Benzyl-2,2,2-trifluoroacetamide can be evaluated further for drug development.

  2. Comparative study between extraction techniques and column separation for the quantification of sinigrin and total isothiocyanates in mustard seed.

    PubMed

    Cools, Katherine; Terry, Leon A

    2012-07-15

    Glucosinolates are β-thioglycosides which are found naturally in Cruciferae including the genus Brassica. When enzymatically hydrolysed, glucosinolates yield isothiocyanates and give a pungent taste. Both glucosinolates and isothiocyanates have been linked with anticancer activity as well as antifungal and antibacterial properties and therefore the quantification of these compounds is scientifically important. A wide range of literature exists on glucosinolates, however the extraction and quantification procedures differ greatly resulting in discrepancies between studies. The aim of this study was therefore to compare the most popular extraction procedures to identify the most efficacious method and whether each extraction can also be used for the quantification of total isothiocyanates. Four extraction techniques were compared for the quantification of sinigrin from mustard cv. Centennial (Brassica juncea L.) seed; boiling water, boiling 50% (v/v) aqueous acetonitrile, boiling 100% methanol and 70% (v/v) aqueous methanol at 70 °C. Prior to injection into the HPLC, the extractions which involved solvents (acetonitrile or methanol) were freeze-dried and resuspended in water. To identify whether the same extract could be used to measure total isothiocyanates, a dichloromethane extraction was carried out on the sinigrin extracts. For the quantification of sinigrin alone, boiling 50% (v/v) acetonitrile was found to be the most efficacious extraction solvent of the four tested yielding 15% more sinigrin than the water extraction. However, the removal of the acetonitrile by freeze-drying had a negative impact on the isothiocyanate content. Quantification of both sinigrin and total isothiocyanates was possible when the sinigrin was extracted using boiling water. Two columns were compared for the quantification of sinigrin revealing the Zorbax Eclipse to be the best column using this particular method. PMID:22743340

  3. Effect of Indole Ethyl Isothiocyanates on Proliferation, Apoptosis and MAPK Signaling in Neuroblastoma Cell Lines

    PubMed Central

    Singh, Rakesh K.; Lange, Thilo S.; Kim, Kyu Kwang; Zou, Yongping; Lieb, Casey; Sholler, Giselle L.; Brard, Laurent

    2007-01-01

    Several indole ethyl isothiocyanate (IEITC) analogs were designed, synthesized and screened to evaluate their cytotoxicity against neuroblastoma (NB) cells in-vitro. In NB, predominantly a tumor of early childhood, survival remains low despite aggressive treatments. Therefore, novel treatment strategies are greatly needed. The objective of the present study was to study the therapeutic potential of IEITC by analyzing the cytotoxic, anti-proliferative and apoptotic effects on NB cell lines. 7-methyl-indole-3-ethyl isothiocyanate (7Me-IEITC) proved to be cytotoxic to various NB cell lines (SMS-KCNR, SK-N-SH, SH-SY5Y, IMR-32) with an IC50 at 2.5-5.0 μM, while primary control cells (lung fibroblasts) were not affected. 7Me-IEITC led to the activation of apoptotic markers caspase-3, - 8 and -9, caused activation of pro-apoptotic p38 MAPK and SAP/JNK, and down-regulated pro-survival factor AKT in SMS-KCNR cells. Moreover, 7Me-IEITC displayed anti-proliferative effects (IC50 at 600 nM) and caused an arrest in cell cycle progression. This wide effect of 7Me-IEITC on NB cell signaling and survival suggests that it could be developed as a therapeutic agent against neuroblastoma. PMID:17855093

  4. Blockade of ATP binding site of P2 purinoceptors in rat parotid acinar cells by isothiocyanate compounds.

    PubMed

    Soltoff, S P; McMillian, M K; Talamo, B R; Cantley, L C

    1993-05-01

    Extracellular ATP activates a P2Z-type purinergic receptor (purinoceptor) in rat parotid acinar cells that increases the intracellular free Ca2+ concentration via the entry of extracellular Ca2+ through an ATP-sensitive cation channel (Soltoff et al., Am J Physiol 262: C934-C940, 1992). To learn more about the ATP binding site of the purinoceptor, we examined the effects of several stilbene isothiocyanate analogs of DIDS (4,4'-diisothiocyanatostilbene-2,2'-disulfonic acid), which block the binding of [32P]ATP to intact parotid cells (McMillian et al., Biochem J 255:291-300, 1988) and blocked the activation of the P2Z purinoceptor. The ATP-stimulated 45Ca2+ uptake was blocked by DIDS, H2DIDS (dihydro-DIDS; 4,4'-diisothiocyanatodihydrostilbene-2,2'-disulfonic acid), and SITS (4-acetamido-4'-isothiocyanatostilbene-2,2'-disulfonic acid), but not by DNDS (4,4'-dinitrostilbene-2,2'-disulfonic acid), a stilbene disulfonate compound lacking isothiocyanate (SCN-) groups, or by KSCN. The potency of the stilbene disulfonates was related to the number of isothiocyanate groups on each compound. Under the experimental conditions, the IC50 value of DIDS (approximately 35 microM), which has two SCN-groups, was much lower than that of SITS (approximately 125 microM), which has only one SCN-group. The inhibitory effects of DIDS appeared to be much more potent than those of SITS due to the kinetics of their binding to the purinoceptors. Eosin-5-isothiocyanate (EITC) and fluorescein-5-isothiocyanate (FITC), non-stilbene isothiocyanate compounds with single SCN-groups, also blocked the response to ATP and were less potent than DIDS. Trinitrophenyl-ATP (TNP-ATP), an ATP derivative that is not an effective agonist of the parotid P2Z receptor, blocked the covalent binding of DIDS to the plasma membrane, suggesting that ATP and DIDS bind to the same site. Reactive Blue 2 (Cibacron Blue 3GA), an anthraquinone-sulfonic acid derivative that is a noncovalent purinergic antagonist, also blocked

  5. Fumigation of wheat using liquid ethyl formate plus methyl isothiocyanate in 50-tonne farm bins.

    PubMed

    Ren, Yonglin; Lee, Byungho; Mahon, Daphne; Xin, Ni; Head, Matthew; Reid, Robin

    2008-04-01

    Australian Standard White wheat, Triticum aestivum L. (a marketing grade with mixed grain hardness),with a moisture content of 12.5% was fumigated with a new ethyl formate formulation (95% ethyl formate plus 5% methyl isothiocyanate) identified and developed by Commonwealth Scientific and Industrial Research Organization Entomology, Canberra, Australia. Wheat was fumigated with the formulation at a calculated application rate of 80 g/m3 in two 50-tonne sealed metal vertical silos located at Fisherman Islands, Queensland, Australia. Access was gained through the top of the silo where the application of the formulation was completed within a few minutes by pouring it onto the top of the wheat. After 2 h of recirculation, using a 0.5-kW fan, the in-bin concentrations of ethyl formate achieved equilibrium with a concentration variation < 7%. The ethyl formate concentration, in both silos 1 and 2, during the first day's exposure period remained above 10 g/m3. The concentration of ethyl formate by time product achieved was 790 and 650 g h/m3 in silos 1 and 2, respectively. In silo 1, the formulation was sufficient to kill all life stages of mixed age cultures of Sitophilus oryzae (L.), Rhyzopertha dominica (F.), and Tribolium castaneum (Herbst). In silo 2, control was 100% for R. dominica and T. castaneum and 99.4% for S. oryzae. After 5 d fumigation, the silo top-hatch was opened but no forced aeration was initiated. The in-bin concentration of ethyl formate was lower than the Australian experimental threshold limit value of 100 ppm. The ethyl formate and methyl isothiocyanate residues in the grain had declined to below the Australian experimental maximum residue limit of 0.2 and 0.1 mg/kg, respectively. The workspace and environmental levels of ethyl formate and methyl isothiocyanate were less than the detection limit of 0.1 ppm. The treatment with ethyl formate formulation had no affect on the wheat germination and seed color compared with untreated controls. PMID

  6. Orthogonal aerobic conversion of N-benzyl amidoximes to 1,2,4-oxadiazoles or quinazolinones.

    PubMed

    Zhang, Feng-Lian; Wang, Yi-Feng; Chiba, Shunsuke

    2013-09-28

    Concise synthesis of 1,2,4-oxadiazoles was achieved by heating N-benzyl amidoximes with K3PO4 in DMF at 60 °C under an O2 atmosphere via benzylic C-H oxygenation. On the other hand, aerobic treatment of N-benzyl amidoximes with Cs2CO3 in DMSO at 100 °C could result in oxidative skeletal rearrangement to deliver quinazolinones as a major product. This orthogonal product selectivity could be realized by difference of the reaction temperature as well as selection of the solvents and inorganic bases. PMID:23939248

  7. Search for soliton modes in helical poly-γ-benzyl-l-glutamate

    NASA Astrophysics Data System (ADS)

    Renthal, Robert; Taboada, J.

    1989-07-01

    Solid α-helical poly(γ-benzyl-L-glutamate) was examined at low temperature for evidence of the unusual temperature-dependent vibrational mode found by Careri and co-workers in solid acetanilide and attributed to a soliton wave trapped in protein-like hydrogen bonds. We have confirmed the anomaly in acetanilide, however, a similar temperature-dependent mode was not observed in poly(γ-benzyl-L-glutamate). These results indicate that anharmonic amide modes may only be present in certain α-helical structures. Two new low frequency modes (180 and 90 cm -1) are observed for poly(γ-benzyl-L-glutamate).

  8. Selective methylation of kaempferol via benzylation and deacetylation of kaempferol acetates.

    PubMed

    Mei, Qinggang; Wang, Chun; Yuan, Weicheng; Zhang, Guolin

    2015-01-01

    A strategy for selective mono-, di- and tri-O-methylation of kaempferol, predominantly on the basis of selective benzylation and controllable deacetylation of kaempferol acetates, was developed. From the selective deacetylation and benzylation of kaempferol tetraacetate (1), 3,4',5,-tri-O-acetylkaempferol (2) and 7-O-benzyl-3,4'5,-tri-O-acetylkaempferol (8) were obtained, respectively. By controllable deacetylation and followed selective or direct methylation of these two intermediates, eight O-methylated kaempferols were prepared with 51-77% total yields from kaempferol. PMID:25815082

  9. Anaphylaxis Triggered by Benzyl Benzoate in a Preparation of Depot Testosterone Undecanoate

    PubMed Central

    Ong, Gregory S. Y.; Somerville, Colin P.; Jones, Timothy W.; Walsh, John P.

    2012-01-01

    We report the first case of an anaphylactic reaction to Reandron 1000 (depot testosterone undecanoate with a castor oil and benzyl benzoate vehicle). While considered to have a favourable safety profile, serious complications such as oil embolism and anaphylaxis can occur. In our patient, skin testing identified benzyl benzoate to be the trigger, with no reaction to castor oil or testosterone undecanoate components. As benzyl benzoate exists in multiple pharmaceuticals, foods, and cosmetics, individual components of pharmaceuticals should be tested when investigating drug allergies. Doctors should be alert to the potential for serious reactions to any of the components of Reandron 1000. PMID:22272209

  10. Carbon-Silicon Bond Formation in the Synthesis of Benzylic Silanes.

    PubMed

    Visco, Michael D; Wieting, Joshua M; Mattson, Anita E

    2016-06-17

    Sterically encumbered organosilanes can be difficult to synthesize with conventional, strongly basic reagents; the harsh reaction conditions are often low yielding and not suitable for many functional groups. As an alternative to the typical anionic strategies to construct silanes, the coupling of benzylic halides and arylhalosilanes with sonication has been identified as a high yielding and general strategy to access bulky and functionalized benzylic silanes. This new methodology provides a solution for the synthesis of families of bulky benzylic silanes for study in catalysis and other areas of chemical synthesis. PMID:27255675

  11. Effect of allyl isothiocyanate on antioxidant enzyme activities, flavonoids and fruit quality of blueberry (Vaccinium corymbosum L., cv. Duke)

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effect of allyl isothiocyanate (AITC) on antioxidant enzyme activities, flavonoid content, and fruit quality of blueberries var. Duke (Vaccinium corymbosum L.) was evaluated. Results from this study showed that AITC was effective in maintaining higher amounts of sugars and lower organic acids co...

  12. Dietary phenethyl isothiocyanate inhibition of androgen-responsive LNCaP prostate cancer cell tumor growth correlates with decreased angiogenesis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Phenethyl isothiocyanate (PEITC), found in certain cruciferous vegetables, has antitumor activity in several cancer models, including prostate cancer. In our xenograft model, dietary administration of PEITC (100-150 mg/kg/d) inhibited androgen-responsive LNCaP human prostate cancer cell tumor growth...

  13. Antimicrobial effect of allyl isothiocyanate and modified atmosphere on Pseudomonas aeruginosa in fresh catfish fillet under abuse temperatures

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Pseudomonas aeruginosa, a common spoilage microorganism on fresh catfish products, can grow rapidly at temperatures above 4 degree C during storage and transportation. Allyl isothiocyanate (AIT), an extract of horseradish oil, and modified atmosphere (MA) can be used to inhibit the growth of P. aeru...

  14. Structural Interactions Dictate the Kinetics of Macrophage Migration Inhibitory Factor Inhibition by Different Cancer-Preventive Isothiocyanates

    PubMed Central

    Crichlow, Gregg V.; Fan, Chengpeng; Keeler, Camille; Hodsdon, Michael; Lolis, Elias J.

    2012-01-01

    Regulation of cellular processes by dietary nutrients is known to affect the likelihood of cancer development. One class of cancer preventive nutrients, isothiocyanates (ITCs) derived from consumption of cruciferous vegetables, is known to have various effects on cellular biochemistry. One target of ITCs is macrophage migration inhibitory factor (MIF), a widely expressed protein with known inflammatory, pro-tumorigenic, pro-angiogenic, and anti-apoptotic properties. MIF is covalently inhibited by a variety of ITCs, which in part, may explain how they exert their cancer-preventive effects. We report the crystallographic structures of human MIF bound to phenethylisothiocyanate and to L-sulforaphane (dietary isothiocyanates derived from watercress and broccoli, respectively), and correlate structural features of these two isothiocyanates with their second-order rate constants for MIF inactivation. We also characterize changes in the MIF structure using NMR HSQC spectra of these complexes and observe many changes at the subunit interface. While a number of chemical shifts do not change, many of those that change do not have similar features in magnitude or direction for the two isothiocyanates. The difference in the binding modes of these two ITCs provides a means of using structure-activity relationships to reveal insights into MIF biological interactions. The results of this study provide a framework for the development of therapeutics that target MIF. PMID:22931430

  15. Structural interactions dictate the kinetics of macrophage migration inhibitory factor inhibition by different cancer-preventive isothiocyanates.

    PubMed

    Crichlow, Gregg V; Fan, Chengpeng; Keeler, Camille; Hodsdon, Michael; Lolis, Elias J

    2012-09-25

    Regulation of cellular processes by dietary nutrients is known to affect the likelihood of cancer development. One class of cancer-preventive nutrients, isothiocyanates (ITCs), derived from the consumption of cruciferous vegetables, is known to have various effects on cellular biochemistry. One target of ITCs is macrophage migration inhibitory factor (MIF), a widely expressed protein with known inflammatory, pro-tumorigenic, pro-angiogenic, and anti-apoptotic properties. MIF is covalently inhibited by a variety of ITCs, which in part may explain how they exert their cancer-preventive effects. We report the crystallographic structures of human MIF bound to phenethylisothiocyanate and to l-sulforaphane (dietary isothiocyanates derived from watercress and broccoli, respectively) and correlate structural features of these two isothiocyanates with their second-order rate constants for MIF inactivation. We also characterize changes in the MIF structure using nuclear magnetic resonance heteronuclear single-quantum coherence spectra of these complexes and observe many changes at the subunit interface. While a number of chemical shifts do not change, many of those that change do not have features similar in magnitude or direction for the two isothiocyanates. The difference in the binding modes of these two ITCs provides a means of using structure-activity relationships to reveal insights into MIF biological interactions. The results of this study provide a framework for the development of therapeutics that target MIF. PMID:22931430

  16. Effect of allyl isothiocyanate in headspace and modified atmosphere on Pseduomonas Aeruginosa growth in fresh catfish fillets under abuse temperatures

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Pseudomonas aeruginosa, a common spoilage microorganism on fresh catfish products, can grow rapidly at temperatures above 4 deg C during storage and transportation. Allyl isothiocyanate (AIT), an extract of horseradish oil, and modified atmosphere (MA) can be used to inhibit the growth of P. aerugin...

  17. Growth behavior prediction of fresh catfish fillet with Pseudomonas aeruginosa under stresses of allyl isothiocyanate, temperature and modified atmosphere

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Pseudomonas aeruginosa, a common spoilage microorganism in fish, grows rapidly when temperature rises above 4 degree C. The combination of allyl isothiocyanate (AIT) and modified atmosphere (MA) was applied and proved to be effective to retard the growth of P. aeruginosa. The objective of this resea...

  18. Overexpression of Glutathione Transferase E7 in Drosophila Differentially Impacts Toxicity of Organic Isothiocyanates in Males and Females

    PubMed Central

    Mannervik, Bengt; Mannervik, Mattias

    2014-01-01

    Organic isothiocyanates (ITCs) are allelochemicals produced by plants in order to combat insects and other herbivores. The compounds are toxic electrophiles that can be inactivated and conjugated with intracellular glutathione in reactions catalyzed by glutathione transferases (GSTs). The Drosophila melanogaster GSTE7 was heterologously expressed in Escherichia coli and purified for functional studies. The enzyme showed high catalytic activity with various isothiocyanates including phenethyl isothiocyanate (PEITC) and allyl isothiocyanate (AITC), which in millimolar dietary concentrations conferred toxicity to adult D. melanogaster leading to death or a shortened life-span of the flies. In situ hybridization revealed a maternal contribution of GSTE7 transcripts to embryos, and strongest zygotic expression in the digestive tract. Transgenesis involving the GSTE7 gene controlled by an actin promoter produced viable flies expressing the GSTE7 transcript ubiquitously. Transgenic females show a significantly increased survival when subjected to the same PEITC treatment as the wild-type flies. By contrast, transgenic male flies show a significantly lower survival rate. Oviposition activity was enhanced in transgenic flies. The effect was significant in transgenic females reared in the absence of ITCs as well as in the presence of 0.15 mM PEITC or 1 mM AITC. Thus the GSTE7 transgene elicits responses to exposure to ITC allelochemicals which differentially affect life-span and fecundity of male and female flies. PMID:25329882

  19. DNA Microarray Highlights Nrf2-Mediated Neuron Protection Targeted by Wasabi-Derived Isothiocyanates in IMR-32 Cells.

    PubMed

    Trio, Phoebe Zapanta; Fujisaki, Satoru; Tanigawa, Shunsuke; Hisanaga, Ayami; Sakao, Kozue; Hou, De-Xing

    2016-01-01

    6-(Methylsulfinyl)hexyl isothiocyanate (6-MSITC), 6-(methylthio)hexyl isothiocyanate (6-MTITC), and 4-(methylsulfinyl)butyl isothiocyanate (4-MSITC) are isothiocyanate (ITC) bioactive compounds from Japanese Wasabi. Previous in vivo studies highlighted the neuroprotective potential of ITCs since ITCs enhance the production of antioxidant-related enzymes. Thus, in this present study, a genome-wide DNA microarray analysis was designed to profile gene expression changes in a neuron cell line, IMR-32, stimulated by these ITCs. Among these ITCs, 6-MSITC caused the expression changes of most genes (263), of which 100 genes were upregulated and 163 genes were downregulated. Gene categorization showed that most of the differentially expressed genes are involved in oxidative stress response, and pathway analysis further revealed that Nrf2-mediated oxidative stress pathway is the top of the ITC-modulated signaling pathway. Finally, real-time polymerase chain reaction (PCR) and Western blotting confirmed the gene expression and protein products of the major targets by ITCs. Taken together, Wasabi-derived ITCs might target the Nrf2-mediated oxidative stress pathway to exert neuroprotective effects. PMID:27547033

  20. DNA Microarray Highlights Nrf2-Mediated Neuron Protection Targeted by Wasabi-Derived Isothiocyanates in IMR-32 Cells

    PubMed Central

    Trio, Phoebe Zapanta; Fujisaki, Satoru; Tanigawa, Shunsuke; Hisanaga, Ayami; Sakao, Kozue; Hou, De-Xing

    2016-01-01

    6-(Methylsulfinyl)hexyl isothiocyanate (6-MSITC), 6-(methylthio)hexyl isothiocyanate (6-MTITC), and 4-(methylsulfinyl)butyl isothiocyanate (4-MSITC) are isothiocyanate (ITC) bioactive compounds from Japanese Wasabi. Previous in vivo studies highlighted the neuroprotective potential of ITCs since ITCs enhance the production of antioxidant-related enzymes. Thus, in this present study, a genome-wide DNA microarray analysis was designed to profile gene expression changes in a neuron cell line, IMR-32, stimulated by these ITCs. Among these ITCs, 6-MSITC caused the expression changes of most genes (263), of which 100 genes were upregulated and 163 genes were downregulated. Gene categorization showed that most of the differentially expressed genes are involved in oxidative stress response, and pathway analysis further revealed that Nrf2-mediated oxidative stress pathway is the top of the ITC-modulated signaling pathway. Finally, real-time polymerase chain reaction (PCR) and Western blotting confirmed the gene expression and protein products of the major targets by ITCs. Taken together, Wasabi-derived ITCs might target the Nrf2-mediated oxidative stress pathway to exert neuroprotective effects. PMID:27547033

  1. Antimicrobial activity of allyl isothiocyanate used to coat biodegradable composite films as affected by storage and handling conditions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We evaluated the effects of storage and handling conditions on the antimicrobial activity of biodegradable composite films (polylactic acid and sugar beet pulp) coated with allyl isothiocyanate (AIT). Polylactic acid (PLA) and chitosan were incorporated with AIT and coated on one side of the film. T...

  2. Aggresome-like structure induced by isothiocyanates is novel proteasome-dependent degradation machinery

    SciTech Connect

    Mi, Lixin; Gan, Nanqin; Chung, Fung-Lung

    2009-10-16

    Unwanted or misfolded proteins are either refolded by chaperones or degraded by the ubiquitin-proteasome system (UPS). When UPS is impaired, misfolded proteins form aggregates, which are transported along microtubules by motor protein dynein towards the juxta-nuclear microtubule-organizing center to form aggresome, a single cellular garbage disposal complex. Because aggresome formation results from proteasome failure, aggresome components are degraded through the autophagy/lysosome pathway. Here we report that small molecule isothiocyanates (ITCs) can induce formation of aggresome-like structure (ALS) through covalent modification of cytoplasmic {alpha}- and {beta}-tubulin. The formation of ALS is related to neither proteasome inhibition nor oxidative stress. ITC-induced ALS is a proteasome-dependent assembly for emergent removal of misfolded proteins, suggesting that the cell may have a previously unknown strategy to cope with misfolded proteins.

  3. Myrosinase-dependent and -independent formation and control of isothiocyanate products of glucosinolate hydrolysis.

    PubMed

    Angelino, Donato; Dosz, Edward B; Sun, Jianghao; Hoeflinger, Jennifer L; Van Tassell, Maxwell L; Chen, Pei; Harnly, James M; Miller, Michael J; Jeffery, Elizabeth H

    2015-01-01

    Brassicales contain a myrosinase enzyme that hydrolyzes glucosinolates to form toxic isothiocyanates (ITC), as a defense against bacteria, fungi, insects and herbivores including man. Low levels of ITC trigger a host defense system in mammals that protects them against chronic diseases. Because humans typically cook their brassica vegetables, destroying myrosinase, there is a great interest in determining how human microbiota can hydrolyze glucosinolates and release them, to provide the health benefits of ITC. ITC are highly reactive electrophiles, binding reversibly to thiols, but accumulating and causing damage when free thiols are not available. We found that addition of excess thiols released protein-thiol-bound ITC, but that the microbiome supports only poor hydrolysis unless exposed to dietary glucosinolates for a period of days. These findings explain why 3-5 servings a week of brassica vegetables may provide health effects, even if they are cooked. PMID:26500669

  4. Combined inhibition of the EGFR/AKT pathways by a novel conjugate of quinazoline with isothiocyanate.

    PubMed

    Tarozzi, Andrea; Marchetti, Chiara; Nicolini, Benedetta; D'Amico, Massimo; Ticchi, Nicole; Pruccoli, Letizia; Tumiatti, Vincenzo; Simoni, Elena; Lodola, Alessio; Mor, Marco; Milelli, Andrea; Minarini, Anna

    2016-07-19

    Epidermal growth factor receptor inhibitors (EGFR-TKIs) represent a class of compounds widely used in anticancer therapy. An increasing number of studies reports on combination therapies in which the block of the EGFR-TK activity is associated with inhibition of its downstream pathways, as PI3K-Akt. Sulforaphane targets the PI3K-Akt pathway whose dysregulation is implicated in many functions of cancer cells. According to these considerations, a series of multitarget molecules have been designed by combining key structural features derived from an EGFR-TKI, PD168393, and the isothiocyanate sulforaphane. Among the obtained molecules 1-6, compound 6 emerges as a promising lead compound able to exert antiproliferative and proapoptotic effects in A431 epithelial cancer cell line by covalently binding to EGFR-TK, and reducing the phosphorylation of Akt without affecting the total Akt levels. PMID:27135370

  5. Myrosinase-dependent and –independent formation and control of isothiocyanate products of glucosinolate hydrolysis

    PubMed Central

    Angelino, Donato; Dosz, Edward B.; Sun, Jianghao; Hoeflinger, Jennifer L.; Van Tassell, Maxwell L.; Chen, Pei; Harnly, James M.; Miller, Michael J.; Jeffery, Elizabeth H.

    2015-01-01

    Brassicales contain a myrosinase enzyme that hydrolyzes glucosinolates to form toxic isothiocyanates (ITC), as a defense against bacteria, fungi, insects and herbivores including man. Low levels of ITC trigger a host defense system in mammals that protects them against chronic diseases. Because humans typically cook their brassica vegetables, destroying myrosinase, there is a great interest in determining how human microbiota can hydrolyze glucosinolates and release them, to provide the health benefits of ITC. ITC are highly reactive electrophiles, binding reversibly to thiols, but accumulating and causing damage when free thiols are not available. We found that addition of excess thiols released protein-thiol-bound ITC, but that the microbiome supports only poor hydrolysis unless exposed to dietary glucosinolates for a period of days. These findings explain why 3–5 servings a week of brassica vegetables may provide health effects, even if they are cooked. PMID:26500669

  6. Early events in herpes simplex virus type 1 infection: photosensitivity of fluorescein isothiocyanate-treated virions

    SciTech Connect

    DeLuca, N.; Bzik, D.; Person, S.; Snipes, W.

    1981-02-01

    Herpes simplex virus type 1 is photosensitized by treatment with fluorescein isothiocyanate (FITC). The inactivation of FITC-treated virions upon subsequent exposure to light is inhibited by the presence of sodium azide, suggesting the involvement of singlet oxygen in the process. Sodium dodecyl sulfate/polyacrylamide gel electrophoresis revealed that treatment with FITC plus light induces crosslinks in viral envelope glycoproteins. Treatment of virions with high concentrations of FITC (50 ..mu..g/ml) plus light causes a reduction in the adsorption of the virus to monolayers of human embryonic lung cells. For lower concentrations of FITC (10 ..mu..g/ml) plus light, treated virions adsorb to the host cells, but remain sensitive to light until entry occurs. The loss of light sensitivity coincides with the development of resistance to antibodies. These results are most consistent with a mechanism of entry for herpes simplex virus involving fusion of the viral membrane with the plasma membrane of the host cell.

  7. Isothiocyanates may chemically detoxify mutagenic amines formed in heat processed meat.

    PubMed

    Lewandowska, Anna; Przychodzeń, Witold; Kusznierewicz, Barbara; Kołodziejski, Dominik; Namieśnik, Jacek; Bartoszek, Agnieszka

    2014-08-15

    Meat consumption represents a dietary risk factor increasing the incidence of common cancers, probably due to carcinogenic amines (HAAs) formed upon meat heating. Interestingly, cancers whose incidence is increased by meat consumption, are decreased in populations consuming brassica vegetables regularly. This inverse correlation is attributed to brassica anticarcinogenic components, especially isothiocyanates (ITCs) that stimulate detoxification of food carcinogens. However, ITC reactivity towards amines generating stable thioureas, may also decrease mutagenicity of processed meat. We confirmed here that combining meat with cabbage (fresh or lyophilized), in proportions found in culinary recipes, limited by 17-20% formation of HAAs and significantly lowered mutagenic activity of fried burgers. Moreover, MeIQx mutagenicity was lowered in the presence of ITCs, as well as for synthetic ITC-MeIQx conjugates. This suggests that formation of thioureas could lead to chemical detoxification of food carcinogens, reducing the cancer risk associated with meat consumption. PMID:24679758

  8. Benzyl­tris­[2-(di­benzyl­amino)­eth­yl]ammonium iodide

    PubMed Central

    Bello, Mollie J.; Brady, Sarah E.; Zakharov, Lev N.; Tyler, David R.

    2014-01-01

    In the title quaternary ammonium salt, C55H61N4 +·I−, all three N,N-di­benzyl­ethanamine, –(CH2)2N(CH2C6H5)2, groups have different conformations. The N—C—C—N torsion angles are significantly different [89.86 (13), 162.61 (10) and 175.70 (10)°] and the dihedral angles between the phenyl rings in these groups are different as well [58.21 (4), 43.73 (4) and 76.72 (5)°]. In the crystal, the I− anions fill empty spaces between the bulky cations. The cations and anions are linked by weak C—H⋯I inter­actions, forming a chain along [110]. PMID:24526992

  9. [Chemical constituents from Chenopodium ambrosioides].

    PubMed

    Song, Kun; Wang, Hong-Qing; Liu, Chao; Kang, Jie; Li, Bao-Ming; Chen, Ruo-Yun

    2014-01-01

    Twelve compounds were isolated from the herb of Chenopodium ambrosioides, and their structures were identified by spectroscopic methods as kaempferol-7-O-alpha-L-rhamnopyranoside (1), kaempferol-3,7-di-O-alpha-L-rhamnopyranoside (2), patuletin (3), quercetin-7-O-alpha-L-rhamnopyranoside (4), grasshopper ketone (5), 4-hydroxy-4-methyl-2-cyclohexen-1-one (6), syringaresinol (7), benzyl beta-D-glucopyranoside (8), dendranthemoside B (9), N-trans-feruloyl tyramine (10), N-trans-feruloyl 4'-O-methyldopamine (11), and 4-hydroxy-N-[2-(4-hydroxyphenyl) ethyl] benzamide (12). Among them,compounds 3, 6-8,10, and 12 were isolated from the genus Chenopodium for the first time, and compounds 2-12 were isolated from this plant for the first time. PMID:24761641

  10. Pharmacokinetics and pharmacodynamics of phenethyl isothiocyanate: implications in breast cancer prevention.

    PubMed

    Morris, Marilyn E; Dave, Rutwij A

    2014-07-01

    Phenethyl isothiocyanate (PEITC)-a naturally occurring isothiocyanate in cruciferous vegetables-has been extensively studied as a chemopreventive agent in several preclinical species and in humans. Pharmacokinetic features of unchanged PEITC are (I) linear and first-order absorption, (II) high protein binding and capacity-limited tissue distribution, and (III) reversible metabolism and capacity-limited hepatic elimination. Membrane transport of PEITC is mediated by BCRP, multidrug resistance-associated protein (MRP) 1, and MRP2 transporters belonging to the ATP-binding-cassette (ABC) family. PEITC is metabolized by glutathione S-transferase (GST) in the liver, with the glutathione conjugate of PEITC undergoing further conversion to mercapturic acid by N-acetyl transferase in rats and humans. PEITC modulates the activity and expression of numerous phase I and phase II drug-metabolizing enzymes and can inhibit the metabolism of procarcinogens to form carcinogens and increase carcinogen elimination. In recent years, several in vitro and in vivo studies have elucidated molecular mechanisms underlying the pharmacodynamics of PEITC in breast cancer that include cancer cell apoptosis by upregulation of apoptotic genes, cell cycle arrest at G2/M phase by generation of reactive oxygen species and depletion of intracellular glutathione, downregulation of the estrogen receptor, decrease in sensitivity to estrogen, and inhibition of tumor metastasis. Inhibition of angiogenesis is one of the recently reported mechanisms of breast cancer prevention by PEITC. Complex pharmacokinetics and pharmacodynamics of PEITC necessitate a systems-biology approach in parallel with PK/PD modeling to develop PEITC as a therapeutic agent for treating cancers. PMID:24821055

  11. Vibronic Emission Spectroscopy of Benzyl-Type Radicals Generated by Corona Discharge

    NASA Astrophysics Data System (ADS)

    Yi, Eun Hye; Yoon, Young; Lee, Sang

    2014-06-01

    Benzyl radical is a prototypical aromatic free radical and has been the subject of numerous spectroscopic studies. On the other hand, ring-substituted benzyl radicals, benzyl-type radicals, have received less attention due to the difficulties associated with production in corona discharge and analysis of spectra. We report vibronic emission spectra of hetero halogen multi-substituted benzyl radicals generated by corona discharge of corresponding toluene derivatives using a pinhole-type glass nozzle, from which visible vibronic emission spectra were recorded using a long-path monochromator. The spectra show nice features of strongest origin band and a series of vibronic bands in the lower energies originating from the vibrationless D_1 state. From the analysis of the spectra observed, we determined the energies of the D_1 → D_0 electronic transition and vibrational mode frequencies in the ground electronic state. On the other hand, all substituted benzyl radicals show the origin bands shifted to red region with respect to the parental benzyl radical at 22002 cm-1. The shifts of multi-substituted benzyl radicals can be well estimated using the method developed from mono-substituted benzyl radicals as well as the positions of nodal point and mutual orientation of substituents, which could be useful for scientists to set a proper scanning range of their spectrometers for the spectroscopic observation of transient molecules. In this presentation, we will discuss the substituent effect on electronic transition energy and the experimental technique developed in this laboratory. Y. W. Yoon and S. K. Lee, J. Phys. Chem. A, 117, 2485 (2013). Y. W. Yoon, S. Y. Chae, and S. K. Lee, Chem. Phys. Lett., 584, 37 (2013). Y. W. Yoon and S. K. Lee, Chem. Phys. Lett., 570, 29 (2013).

  12. Ultrasound-assisted direct oxidative amidation of benzyl alcohols catalyzed by graphite oxide.

    PubMed

    Mirza-Aghayan, Maryam; Ganjbakhsh, Nahid; Molaee Tavana, Mahdieh; Boukherroub, Rabah

    2016-09-01

    Ultrasound irradiation was successfully applied for the direct oxidative amidation of benzyl alcohols with amines into the corresponding amides using graphite oxide (GO) as an oxidative and reusable solid acid catalyst in acetonitrile as solvent at 50°C under air atmosphere. The direct oxidative amidation of benzyl alcohols takes place under mild conditions yielding the corresponding amides in good to high yields (69-95%) and short reaction times under metal-free conditions. PMID:27150743

  13. 1-Benzyl-2,5-diphenyl-3-tosylimidazol­idin-4-one

    PubMed Central

    Sakthimurugesan, K.; Ranjith, S.; SubbiahPandi, A.; Namitharan, K.; Pitchumani, K.

    2011-01-01

    In the title compound, C29H26N2O3S, the central imidazolidine ring adopts an envelope conformation with the N atom bearing the benzyl ring at the flap. The S atom has distorted tetra­hedral geometry. The benzyl and tosyl rings are oriented at a dihedral angle of 52.1 (1)°. The phenyl rings connected to the imidazolidine ring form a dihedral angle of 28.7 (1)°. PMID:22058970

  14. Nickel-Catalyzed Cross Couplings of Benzylic Pivalates with Arylboroxines: Stereospecific Formation of Diarylalkanes and Triarylmethanes

    PubMed Central

    Zhou, Qi; Srinivas, Harathi D.; Dasgupta, Srimoyee; Watson, Mary P.

    2014-01-01

    We have developed a stereospecific, nickel-catalyzed cross coupling of benzylic pivalates with aryl boroxines. The success of this reaction relies on the use of Ni(cod)2 as catalyst and NaOMe as a uniquely effective base. This reaction has broad scope with respect to the aryl boroxine and benzylic pivalate, enabling the synthesis of a variety of diarylalkanes and triarylmethanes in good to excellent yields and ee's. PMID:23425080

  15. (2E,5E)-2,5-Bis(4-hy-droxy-3-meth-oxy-benzyl-idene)cyclo-penta-none ethanol monosolvate.

    PubMed

    Da'i, Muhammad; Yanuar, Arry; Meiyanto, Edy; Jenie, Umar Anggara; Supardjan, Amir Margono

    2013-04-01

    In the title structure, C21H20O5·C2H5OH, the curcumine-type mol-ecule has a double E conformation for the two benzyl-idene double bonds [C=C = 1.342 (4) and 1.349 (4) Å] and is nearly planar with respect to the non-H atoms (r.m.s. deviation from planarity = 0.069 Å). The two phenolic OH groups form bifurcated hydrogen bonds with intra-molecular branches to adjacent meth-oxy O atoms and inter-molecular branches to either a neighbouring mol-ecule or an ethanol solvent mol-ecule. The ethanol O atom donates a hydrogen bond to the keto O atom. These hydrogen bonds link the constituents into layers parallel to (101) in the crystal structure. PMID:23634071

  16. Disposition of o-benzyl-p-chlorophenol in male rats.

    PubMed

    Kao, L R; Birnbaum, L S

    1986-01-01

    The disposition and metabolism of o-benzyl-p-chlorophenol (BCP) were studied in male Fischer-344 rats. Three days after oral administration of [14C]BCP at 10, 100, or 1000 mg/kg, more than 90% of each dose was excreted in urine and feces. Comparison of disposition after intravenous, dermal, or oral administration indicated that BCP was not completely absorbed from the gastrointestinal tract or skin. Biliary excretion of BCP was dose-dependent, with proportionally less BCP-derived radioactivity being excreted in the bile as the dose was raised. The results also indicated that enterohepatic circulation was involved in BCP disposition. The major in vivo metabolites were glucuronyl conjugates of BCP and hydroxy-BCP. Glutathione conjugates were also present in urine. In vitro metabolism studies support the observation that microsomal oxidation and glutathione and glucuronyl conjugation play major roles in BCP metabolism. Spleen, kidney, and liver contained the highest tissue concentrations of BCP-derived radioactivity. The presence of more nonextractable BCP-derived radioactivity in kidney than in liver is compatible with the hypothesis that covalent binding of BCP to renal tissue may be associated with BCP-induced nephrotoxicity. PMID:3712501

  17. Pentanol and Benzyl Alcohol Attack Bacterial Surface Structures Differently

    PubMed Central

    Yano, Takehisa; Miyahara, Yoshiko; Morii, Noriyuki; Okano, Tetsuya

    2015-01-01

    The genus Methylobacterium tolerates hygiene agents like benzalkonium chloride (BAC), and infection with this organism is an important public health issue. Here, we found that the combination of BAC with particular alcohols at nonlethal concentrations in terms of their solitary uses significantly reduced bacterial viability after only 5 min of exposure. Among the alcohols, Raman spectroscopic analyses showed that pentanol (pentyl alcohol [PeA]) and benzyl alcohol (BzA) accelerated the cellular accumulation of BAC. Fluorescence spectroscopic assays and morphological assays with giant vesicles indicated that PeA rarely attacked membrane structures, while BzA increased the membrane fluidity and destabilized the structures. Other fluorescent spectroscopic assays indicated that PeA and BzA inactivate bacterial membrane proteins, including an efflux pump for BAC transportation. These findings suggested that the inactivation of membrane proteins by PeA and BzA led to the cellular accumulation but that only BzA also enhanced BAC penetration by membrane fluidization at nonlethal concentrations. PMID:26519389

  18. Toxicity of benzyl alcohol in adult and neonatal mice

    SciTech Connect

    McCloskey, S.E.

    1987-01-01

    Benzyl alcohol (BA) is an aromatic alcohol, which is used as a bacteriostat in a variety of parenteral preparations. In 1982, it was implicated as the agent responsible for precipitating The Gasping Syndrome in premature neonates. The investigate further this toxicity, BA was administered, intraperiotoneally, to adult and neonatal CD-1 male mice. Gross behavioral changes were monitored. Low doses produced minimal toxic effects within an initial 4 hour observation period. At the end of this time, the LD/sub 50/ was determined to be 1000 mg/kg for both age groups. Death was due to respiratory arrest in all cases. Rapid absorption and conversion of BA to its primary metabolite, benzaldehyde, was demonstrated by gas chromatographic analysis of plasma from both experimental groups. The conversion of BA to benzaldehyde was confirmed in in vitro by using both horse-liver and mouse liver ADH. The inhibition of alcohol dehydrogenase (ADH) by pyrazole was similarly demonstrated in both enzyme systems. /sup 14/C-labelled BA was utilized to determine the distribution of BA and its metabolites in the body, and to possibly pinpoint a target organ of toxicity.

  19. Heterogeneous catalytic isotopic exchange of benzylic compounds in solution

    SciTech Connect

    Azran, J; Shimoni, M.; Buchman, O. )

    1994-08-01

    Isotopic exchange reactions of bibenzyl and benzylic derivatives with deuterium (D[sub 2]) and tritium (T[sub 2]) gas, catalyzed by Pd/C, have been performed in solution. Catalyst pre-washed with the reacting gas showed improved H/D or H/T exchange. In aprotic solvents such as dioxane, ethyl acetate, and cyclohexane, 3.1 to 3.5 D atoms were exchanged under standard conditions in 1 h, while in benzene 1 D atom was exchanged. D atoms adsorbed on the catalyst surface were rapidly replaced by H from methanol, diluting the D[sub 2] gas phase. Compounds containing O or N atoms enhanced the rate of exchange, while S atoms inhibited the catalyst activity. The H/D exchange obeyed pseudo-first order kinetics when D[sub 2] gas was used in large excess. When T[sub 2] gas replaced D[sub 2], a substantial decrease in rate of exchange was observed, due to the slower dissociative chemisorption of T[sub 2] on the catalyst surface. The results indicated that this exchange process occurred through two simultaneous mechanisms. The breaking of the C-H bond appeared to be the rate-determining step. 22 refs., 1 fig., 5 tabs.

  20. 3 Benzyl-6-chloropyrone: a suicide inhibitor of cholesterol esterase

    SciTech Connect

    Saint, C.; Gallo, I.; Kantorow, M.; Bailey, J.M.

    1986-05-01

    Cholesterol, absorbed from the intestine, appears in lymph as the ester. Cholesterol esterase is essential for this process, since depletion of the enzyme blocks and repletion restores, absorption. Selective inhibitors of cholesterol esterase may thus prove useful in reducing cholesterol uptake. A series of potential suicide substrates were synthesized which, following cleavage by the enzyme, would attack the putative nucleophile in the active site. One of these, 3-benzyl-6-chloropyrone (3BCP), inhibited both synthesis and hydrolysis of /sup 14/C-cholesteryl oleate with an I/sub 50/ of approximately 150 ..mu..M. The inactivation was time-dependent and characteristic of a suicide mechanism. The ..cap alpha.. pyrone structure (lactone analog) is cleaved by a serine-hydroxyl in the active site. This generates an enoyl chloride which inactivates the imidazole believed to play a part in the catalytic function of the enzyme. Inhibition by 3BCP is selective for cholesterol esterase. The activity of pancreatic lipase as not affected by concentrations up to 1 mM.

  1. Sulphoraphane, a naturally occurring isothiocyanate induces apoptosis in breast cancer cells by targeting heat shock proteins

    SciTech Connect

    Sarkar, Ruma; Mukherjee, Sutapa; Biswas, Jaydip; Roy, Madhumita

    2012-10-12

    Highlights: Black-Right-Pointing-Pointer HSPs (27, 70 and 90) and HSF1 are overexpressed in MCF-7 and MDA-MB-231 cells. Black-Right-Pointing-Pointer Sulphoraphane, a natural isothiocyanate inhibited HSPs and HSF1 expressions. Black-Right-Pointing-Pointer Inhibition of HSPs and HSF1 lead to regulation of apoptotic proteins. Black-Right-Pointing-Pointer Alteration of apoptotic proteins activate of caspases particularly caspase 3 and 9 leading to induction of apoptosis. Black-Right-Pointing-Pointer Alteration of apoptotic proteins induce caspases leading to induction of apoptosis. -- Abstract: Heat shock proteins (HSPs) are involved in protein folding, aggregation, transport and/or stabilization by acting as a molecular chaperone, leading to inhibition of apoptosis by both caspase dependent and/or independent pathways. HSPs are overexpressed in a wide range of human cancers and are implicated in tumor cell proliferation, differentiation, invasion and metastasis. HSPs particularly 27, 70, 90 and the transcription factor heat shock factor1 (HSF1) play key roles in the etiology of breast cancer and can be considered as potential therapeutic target. The present study was designed to investigate the role of sulphoraphane, a natural isothiocyanate on HSPs (27, 70, 90) and HSF1 in two different breast cancer cell lines MCF-7 and MDA-MB-231 cells expressing wild type and mutated p53 respectively, vis-a-vis in normal breast epithelial cell line MCF-12F. It was furthermore investigated whether modulation of HSPs and HSF1 could induce apoptosis in these cells by altering the expressions of p53, p21 and some apoptotic proteins like Bcl-2, Bax, Bid, Bad, Apaf-1 and AIF. Sulphoraphane was found to down-regulate the expressions of HSP70, 90 and HSF1, though the effect on HSP27 was not pronounced. Consequences of HSP inhibition was upregulation of p21 irrespective of p53 status. Bax, Bad, Apaf-1, AIF were upregulated followed by down-regulation of Bcl-2 and this effect was prominent

  2. Multidirectional Time-Dependent Effect of Sinigrin and Allyl Isothiocyanate on Metabolic Parameters in Rats

    PubMed Central

    2010-01-01

    Sinigrin (SIN) and allyl isothiocyanate (AITC) are compounds found in high concentrations in Brassica family vegetables, especially in Brussels sprouts. Recently, they have been used as a nutrition supplement for their preventive and medicinal effect on some types of cancer and other diseases. In this research, nutritional significance of parent glucosinolate sinigrin 50 μmol/kg b. w./day and its degradation product allyl isothiocyanate 25 μmol/kg b. w./day and 50 μmol/kg b. w./day was studied by the evaluation of their influence on some parameters of carbohydrate and lipid metabolism in an animal rat model in vivo after their single (4 h) and 2 weeks oral administration. Additionally, the aim of this trial was to evaluate the direct action of AITC on basal and epinephrine-induced lipolysis in isolated rat adipocytes at concentration 1 μM, 10 μM and 100 μM in vitro. Sole AITC after 4 h of its ingestion caused liver triacylglycerols increment at both doses and glycaemia only at the higher dose. Multiple SIN treatment showed its putative bioconversion into AITC. It was found that SIN and AITC multiple administration in the same way strongly disturbed lipid and carbohydrate homeostasis, increasing esterified and total cholesterol, free fatty acids and lowering tracylglycerols in the blood serum. Additionally, AITC at both doses elevated insulinaemia and liver glycogen enhancement. The in vitro experiment revealed that AITC potentiated basal lipolysis process at 10 μM, and had stimulatory effect on epinephrine action at 1 μM and 10 μM. The results of this study demonstrated that the effect of SIN and AITC is multidirectional, indicating its impact on many organs like liver as well as pancreas, intestine in vivo action and rat adipocytes in vitro. Whilst consumption of cruciferous vegetables at levels currently considered “normal” seems to be beneficial to human health, this data suggest that any large increase in intake could conceivably lead

  3. Allyl isothiocyanate from mustard seed is effective in reducing the levels of volatile sulfur compounds responsible for intrinsic oral malodor.

    PubMed

    Tian, Minmin; Hanley, A Bryan; Dodds, Michael W J

    2013-06-01

    Oral malodor is a major social and psychological issue that affects general populations. Volatile sulfur compounds (VSCs), particularly hydrogen sulfide (H₂S) and methyl mercaptan (CH₃SH), are responsible for most oral malodor. The objectives for this study were to determine whether allyl isothiocyanate (AITC) at an organoleptically acceptable level can eliminate VSCs containing a free thiol moiety and further to elucidate the mechanism of action and reaction kinetics. The study revealed that gas chromatograph with a sulfur detector demonstrated a good linearity, high accuracy and sensitivity on analysis of VSCs. Zinc salts eliminate the headspace level of H₂S but not CH₃SH. AITC eliminates both H₂S and CH₃SH via a nucleophilic addition reaction. In addition, a chemical structure-activity relationship study revealed that the presence of unsaturated group on the side chain of the isothiocyanate accelerates the elimination of VSCs. PMID:23470258

  4. Preclinical Evaluation of 4-Methylthiobutyl Isothiocyanate on Liver Cancer and Cancer Stem Cells with Different p53 Status

    PubMed Central

    Lamy, Evelyn; Hertrampf, Anke; Herz, Corinna; Schüler, Julia; Erlacher, Miriam; Bertele, Daniela; Bakare, Adekunle; Wagner, Meike; Weiland, Timo; Lauer, Ulrich; Drognitz, Oliver; Huber, Roman; Rohn, Sascha; Giesemann, Torsten; Mersch-Sundermann, Volker

    2013-01-01

    Isothiocyanates from plants of the order Brassicales are considered promising cancer chemotherapeutic phytochemicals. However, their selective cytotoxicity on liver cancer has been barely researched. Therefore, in the present study, we systematically studied the chemotherapeutic potency of 4-methylthiobutyl isothiocyanate (MTBITC). Selective toxicity was investigated by comparing its effect on liver cancer cells and their chemoresistant subpopulations to normal primary hepatocytes and liver tissue slices. Additionally, in a first assessment, the in vivo tolerability of MTBITC was investigated in mice. Growth arrest at G2/M and apoptosis induction was evident in all in vitro cancer models treated with MTBITC, including populations with cancer initiating characteristics. This was found independent from TP53; however cell death was delayed in p53 compromised cells as compared to wt-p53 cells which was probably due to differential BH3 only gene regulation i. e. Noxa and its antagonist A1. In normal hepatocytes, no apoptosis or necrosis could be detected after repeated administration of up to 50 µM MTBITC. In mice, orally applied MTBITC was well tolerated over 18 days of treatment for up to 50 mg/kg/day, the highest dose tested. In conclusion, we could show here that the killing effect of MTBITC has a definite selectivity for cancer cells over normal liver cells and its cytotoxicity even applies for chemoresistant cancer initiating cells. Our study could serve for a better understanding of the chemotherapeutic properties of isothiocyanates on human liver-derived cancer cells. PMID:23936472

  5. Plasmids from the gut microbiome of cabbage root fly larvae encode SaxA that catalyses the conversion of the plant toxin 2-phenylethyl isothiocyanate.

    PubMed

    Welte, Cornelia U; de Graaf, Rob M; van den Bosch, Tijs J M; Op den Camp, Huub J M; van Dam, Nicole M; Jetten, Mike S M

    2016-05-01

    Cabbage root fly larvae (Delia radicum) cause severe crop losses (≥ 50%) of rapeseed/ canola and cabbages used in the food and biofuel industries. These losses occur despite the fact that cabbages produce insecticidal toxins such as isothiocyanates. Here we describe the cabbage root fly larval gut microbiome as a source of isothiocyanate degrading enzymes. We sequenced the microbial gut community of the larvae and analysed phylogenetic markers and functional genes. We combined this with the isolation of several microbial strains representing the phylogenetic distribution of the metagenome. Eleven of those isolates were highly resistant towards 2-phenylethyl isothiocyanate, a subset also metabolized 2-phenylethyl isothiocyanate. Several plasmids appeared to be shared between those isolates that metabolized the toxin. One of the plasmids harboured a saxA gene that upon transformation gave resistance and enabled the degradation of 2-phenylethyl isothiocyanate in Escherichia coli. Taken together, the results showed that the cabbage root fly larval gut microbiome is capable of isothiocyanate degradation, a characteristic that has not been observed before, and may help us understand and design new pest control strategies. PMID:26234684

  6. Allyl isothiocyanates and cinnamaldehyde potentiate miniature excitatory postsynaptic inputs in the supraoptic nucleus in rats.

    PubMed

    Yokoyama, Toru; Ohbuchi, Toyoaki; Saito, Takeshi; Sudo, Yuka; Fujihara, Hiroaki; Minami, Kouichiro; Nagatomo, Toshihisa; Uezono, Yasuhito; Ueta, Yoichi

    2011-03-25

    Allyl isothiocyanates (AITC) and cinnamaldehyde are pungent compounds present in mustard oil and cinnamon oil, respectively. These compounds are well known as transient receptor potential ankyrin 1 (TRPA1) agonists. TRPA1 is activated by low temperature stimuli, mechanosensation and pungent irritants such as AITC and cinnamaldehyde. TRPA1 is often co-expressed in TRPV1. Recent study showed that hypertonic solution activated TRPA1 as well as TRPV1. TRPV1 is involved in excitatory synaptic inputs to the magnocellular neurosecretory cells (MNCs) that produce vasopressin in the supraoptic nucleus (SON). However, it remains unclear whether TRPA1 may be involved in this activation. In the present study, we examined the role of TRPA1 on the synaptic inputs to the MNCs in in vitro rat brain slice preparations, using whole-cell patch-clamp recordings. In the presence of tetrodotoxin, AITC (50μM) and cinnamaldehyde (30μM) increased the frequency of miniature excitatory postsynaptic currents without affecting the amplitude. This effect was significantly attenuated by previous exposure to ruthenium red (10μM), non-specific TRP channels blocker, high concentration of menthol (300μM) and HC-030031 (10μM), which are known to antagonize the effects of TRPA1 agonists. These results suggest that TRPA1 may exist at presynaptic terminals to the MNCs and enhance glutamate release in the SON. PMID:21266172

  7. Evaluation of Fluorescein Isothiocyanate-labeled Whole Antiserum in the Immunofluorescent Identification of Microorganisms

    PubMed Central

    Sweet, George H.; Schindler, Charles A.

    1967-01-01

    Portions of a whole antiserum to Histoplasma capsulatum were reacted with amounts of fluorescein isothiocyanate (FITC) that ranged from 50 to 400 μg/mg of protein. Portions of the globulin from the same antiserum were reacted with amounts of FITC that ranged from 12.5 to 50 μg of FITC per mg of protein. The globulin conjugates (postlabeled globulins), the whole serum conjugates, and the globulins from the whole serum conjugates (prelabeled globulins) were compared with respect to their fluorescein-protein (F:P) ratios and fluorescent-antibody (FA) activities. The whole serum sample treated with 50 μg of FITC per mg of protein was least reactive in FA tests, and its globulin had the lowest F:P. All other conjugates had globulins with F:P ratios that were considered to be adequate for high FA activity. It was found, however, that the prelabeled globulins were considerably less reactive than the postlabeled globulins or the whole serum conjugates. A larger amount of brightly staining reagent per milliliter of original serum could be obtained from labeled whole serum than from postlabeled globulin. Lissamine-rhodamine conjugated to bovine serum albumin (LRBSA) was evaluated as a counterstain to be used in conjunction with FITC-labeled whole antisera. The counterstain was effective in masking nonspecific FITC fluorescence in Formalin-fixed tissues and in culture smears of fungi. Masking was incomplete in culture smears of a bacterium and in blood smears containing a protozoan. Images PMID:5337774

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

    PubMed

    Sporsheim, Bjørnar; Øverby, Anders; Bones, Atle Magnar

    2015-01-01

    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. PMID:26690132

  9. Allyl isothiocyanate depletes glutathione and upregulates expression of glutathione S-transferases in Arabidopsis thaliana

    PubMed Central

    Øverby, Anders; Stokland, Ragni A.; Åsberg, Signe E.; Sporsheim, Bjørnar; Bones, Atle M.

    2015-01-01

    Allyl isothiocyanate (AITC) is a phytochemical associated with plant defense in plants from the Brassicaceae family. AITC has long been recognized as a countermeasure against external threats, but recent reports suggest that AITC is also involved in the onset of defense-related mechanisms such as the regulation of stomatal aperture. However, the underlying cellular modes of action in plants remain scarcely investigated. Here we report evidence of an AITC-induced depletion of glutathione (GSH) and the effect on gene expression of the detoxification enzyme family glutathione S-transferases (GSTs) in Arabidopsis thaliana. Treatment of A. thaliana wild-type with AITC resulted in a time- and dose-dependent depletion of cellular GSH. AITC-exposure of mutant lines vtc1 and pad2-1 with elevated and reduced GSH-levels, displayed enhanced and decreased AITC-tolerance, respectively. AITC-exposure also led to increased ROS-levels in the roots and loss of chlorophyll which are symptoms of oxidative stress. Following exposure to AITC, we found that GSH rapidly recovered to the same level as in the control plant, suggesting an effective route for replenishment of GSH or a rapid detoxification of AITC. Transcriptional analysis of genes encoding GSTs showed an upregulation in response to AITC. These findings demonstrate cellular effects by AITC involving a reversible depletion of the GSH-pool, induced oxidative stress, and elevated expression of GST-encoding genes. PMID:25954298

  10. Involvement of the Electrophilic Isothiocyanate Sulforaphane in Arabidopsis Local Defense Responses1

    PubMed Central

    Andersson, Mats X.; Nilsson, Anders K.; Johansson, Oskar N.; Boztaş, Gülin; Adolfsson, Lisa E.; Pinosa, Francesco; Petit, Christel Garcia; Aronsson, Henrik; Mackey, David; Tör, Mahmut; Hamberg, Mats; Ellerström, Mats

    2015-01-01

    Plants defend themselves against microbial pathogens through a range of highly sophisticated and integrated molecular systems. Recognition of pathogen-secreted effector proteins often triggers the hypersensitive response (HR), a complex multicellular defense reaction where programmed cell death of cells surrounding the primary site of infection is a prominent feature. Even though the HR was described almost a century ago, cell-to-cell factors acting at the local level generating the full defense reaction have remained obscure. In this study, we sought to identify diffusible molecules produced during the HR that could induce cell death in naive tissue. We found that 4-methylsulfinylbutyl isothiocyanate (sulforaphane) is released by Arabidopsis (Arabidopsis thaliana) leaf tissue undergoing the HR and that this compound induces cell death as well as primes defense in naive tissue. Two different mutants impaired in the pathogen-induced accumulation of sulforaphane displayed attenuated programmed cell death upon bacterial and oomycete effector recognition as well as decreased resistance to several isolates of the plant pathogen Hyaloperonospora arabidopsidis. Treatment with sulforaphane provided protection against a virulent H. arabidopsidis isolate. Glucosinolate breakdown products are recognized as antifeeding compounds toward insects and recently also as intracellular signaling and bacteriostatic molecules in Arabidopsis. The data presented here indicate that these compounds also trigger local defense responses in Arabidopsis tissue. PMID:25371552

  11. Comparison of the Photobleaching and Photostability Traits of Alexa Fluor 568- and Fluorescein Isothiocyanate- conjugated Antibody

    PubMed Central

    Mahmoudian, Jafar; Hadavi, Reza; Jeddi-Tehrani, Mahmood; Mahmoudi, Ahmad Reza; Bayat, Ali Ahmad; Shaban, Elham; Vafakhah, Mohtaram; Darzi, Maryam; Tarahomi, Majid; Ghods, Roya

    2011-01-01

    Objective: Synthetic fluorescent dyes that are conjugated to antibodies are useful tools to probe molecules. Based on dye chemical structures, their photobleaching and photostability indices are quite diverse. It is generally believed that among different fluorescent dyes, Alexa Fluor family has greater photostability than traditional dyes like fluorescein isothiocyanate (FITC) and Cy5. Alexa Fluor 568 is a member of Alexa Fluor family presumed to have superior photostability and photobleahing profiles than FITC. Materials and Methods: In this experimental study, we conjugated Alexa Fluor 568 and FITC dyes to a mouse anti-human nestin monoclonal antibody (ANM) to acquire their photobleaching profiles and photostability indices. Then, the fluorophore/antibody ratios were calculated using a spectrophotometer. The photobleaching profiles and photostability indices of conjugated antibodies were subsequently studied by immunocytochemistry (ICC). Samples were continuously illuminated and digital images acquired under a fluorescent microscope. Data were processed by ImageJ software. Results: Alexa Fluor 568 has a brighter fluorescence and higher photostability than FITC. Conclusion: Alexa Fluor 568 is a capable dye to use in photostaining techniques and it has a longer photostability when compared to FITC. PMID:23508937

  12. Reduction of methyl isothiocyanate atmospheric emissions after application of metam sodium by shank injection.

    PubMed

    Ajwa, Husein A; Sullivan, David A; Holdsworth, Mark T; Sullivan, Ryan D; Nelson, Shad D

    2013-11-01

    Regulatory initiatives in the United States have created the impetus to reassess application methods for metam sodium (sodium -methyldithiocarbamate), a methyl isothiocyanate (MITC) generator, to reduce flux to the atmosphere. This paper compares flux rates in the years 1990 through 2002 with flux rates based on four studies conducted during the period 2008 through 2010 in California, Michigan, Wisconsin, and Washington using current shank-injection/compaction methods. Up to a 100-fold reduction in peak flux rates and total loss of MITC have been observed. A combination of the following factors led to these reductions in flux: soil moisture goals set at 70% of the field water holding capacity; improved design of shank-injection systems to break up the voids after injection; effective shank compaction to further reduce volatilization; and the use of water sealing, where applicable. These refinements in the application methods for metam sodium provide a means to merge environmental and agricultural goals in the United States and in other countries that use metam sodium. This paper documents the reduced atmospheric emissions of MITC under commercial production conditions when applied using good agricultural practices. This research also shows that MITC flux can be effectively managed without the use of high barrier tarp material. PMID:25602406

  13. Pharmacokinetics, Tissue Distribution, and Anti-Lipogenic/Adipogenic Effects of Allyl-Isothiocyanate Metabolites

    PubMed Central

    Ahn, Jiyun; Chung, Woo-Jae; Jang, Young Jin; Seong, Ki-Seung; Moon, Jae-Hak; Ha, Tae Youl; Jung, Chang Hwa

    2015-01-01

    Allyl-isothiocyanate (AITC) is an organosulfur phytochemical found in abundance in common cruciferous vegetables such as mustard, wasabi, and cabbage. Although AITC is metabolized primarily through the mercapturic acid pathway, its exact pharmacokinetics remains undefined and the biological function of AITC metabolites is still largely unknown. In this study, we evaluated the inhibitory effects of AITC metabolites on lipid accumulation in vitro and elucidated the pharmacokinetics and tissue distribution of AITC metabolites in rats. We found that AITC metabolites generally conjugate with glutathione (GSH) or N-acetylcysteine (NAC) and are distributed in most organs and tissues. Pharmacokinetic analysis showed a rapid uptake and complete metabolism of AITC following oral administration to rats. Although AITC has been reported to exhibit anti-tumor activity in bladder cancer, the potential bioactivity of its metabolites has not been explored. We found that GSH-AITC and NAC-AITC effectively inhibit adipogenic differentiation of 3T3-L1 preadipocytes and suppress expression of PPAR-γ, C/EBPα, and FAS, which are up-regulated during adipogenesis. GSH-AITC and NAC-AITC also suppressed oleic acid-induced lipid accumulation and lipogenesis in hepatocytes. Our findings suggest that AITC is almost completely metabolized in the liver and rapidly excreted in urine through the mercapturic acid pathway following administration in rats. AITC metabolites may exert anti-obesity effects through suppression of adipogenesis or lipogenesis. PMID:26317351

  14. Anabolic and Antiresorptive Modulation of Bone Homeostasis by the Epigenetic Modulator Sulforaphane, a Naturally Occurring Isothiocyanate.

    PubMed

    Thaler, Roman; Maurizi, Antonio; Roschger, Paul; Sturmlechner, Ines; Khani, Farzaneh; Spitzer, Silvia; Rumpler, Monika; Zwerina, Jochen; Karlic, Heidrun; Dudakovic, Amel; Klaushofer, Klaus; Teti, Anna; Rucci, Nadia; Varga, Franz; van Wijnen, Andre J

    2016-03-25

    Bone degenerative pathologies like osteoporosis may be initiated by age-related shifts in anabolic and catabolic responses that control bone homeostasis. Here we show that sulforaphane (SFN), a naturally occurring isothiocyanate, promotes osteoblast differentiation by epigenetic mechanisms. SFN enhances active DNA demethylation viaTet1andTet2and promotes preosteoblast differentiation by enhancing extracellular matrix mineralization and the expression of osteoblastic markers (Runx2,Col1a1,Bglap2,Sp7,Atf4, andAlpl). SFN decreases the expression of the osteoclast activator receptor activator of nuclear factor-κB ligand (RANKL) in osteocytes and mouse calvarial explants and preferentially induces apoptosis in preosteoclastic cells via up-regulation of theTet1/Fas/Caspase 8 and Caspase 3/7 pathway. These mechanistic effects correlate with higher bone volume (∼20%) in both normal and ovariectomized mice treated with SFN for 5 weeks compared with untreated mice as determined by microcomputed tomography. This effect is due to a higher trabecular number in these mice. Importantly, no shifts in mineral density distribution are observed upon SFN treatment as measured by quantitative backscattered electron imaging. Our data indicate that the food-derived compound SFN epigenetically stimulates osteoblast activity and diminishes osteoclast bone resorption, shifting the balance of bone homeostasis and favoring bone acquisition and/or mitigation of bone resorptionin vivo Thus, SFN is a member of a new class of epigenetic compounds that could be considered for novel strategies to counteract osteoporosis. PMID:26757819

  15. [Effect of phenylhexyl isothiocyanate on Wnt/beta-catenin signaling pathway in Jurkat cell line].

    PubMed

    Lin, Juan; Huang, Yi-Qun; Ma, Xu-Dong

    2013-04-01

    This study was purposed to investigate the effect of phenylhexyl isothiocyanate (PHI) on Wnt/β-catenin signaling pathway, histone acetylation, histone methylation and cell apoptosis in Jurkat cell line. The viability of Jurkat cells after treatment with PHI was tested by MTT. Apoptotic rate of Jurkat cells was measured by flow cytometry. The levels of Wnt/β-catenin related proteins including β-catenin, TCF, c-myc, and cyclinD1, histone acetylated H3 and H4, histone methylated H3K9 and H3K4 were detected by Western blot. The results showed that PHI inhibited the cell growth and induced apoptosis in Jurkat cells in time-and dose-dependent manners. Its IC50 at 48 h was about 20 µmol/L. Expression of histone acetylated H3, H4 and histone methylated H3k4 increased after exposure to PHI for 3 h, while histone methylated H3K9 decreased. Expression of β-catenin was not changed after exposure to PHI for 3 h, but expression of β-catenin, and its cell cycle-related genes such as TCF, c-myc and cyclinD1 decreased after exposure to PHI for 7 h. It is concluded that PHI regulates acetylation and methylation of histone, inhibits Wnt/β-catenin signal pathway, and is able to induce apoptosis and inhibits growth of Jurkat cells. PMID:23628033

  16. Isothiocyanate from the Tunisian radish (Raphanus sativus) prevents genotoxicity of Zearalenone in vivo and in vitro.

    PubMed

    Ben Salah-Abbès, Jalila; Abbès, Samir; Ouanes, Zouhour; Abdel-Wahhab, Mosaad A; Bacha, Hassen; Oueslati, Ridha

    2009-01-01

    Zearalenone (ZEN) is a naturally occurring contaminant of animal feed that has been implicated in several mycotoxicoses in farm livestock. Recently some information has become available indicating that ZEN caused cancer or at least increased its prevalence, although the mechanism of action is unknown. Many papers mentioned that exposure to ZEN results in genotoxicity and DNA damage. Therefore, we investigated the chemo-preventive role of 4-(methylthio)-3-butenyl isothiocyanate (MTBITC) extracted from Tunisian Raphanus sativus (radish) on the cytogenetic effect of ZEN in Balb/c mice and in in vitro cultures of mouse lymphocytes isolated from mouse spleen. We determined chromosome aberrations and micronuclei as well as the mitotic index and DNA fragmentation following ZEN treatment alone or in combination with MTBITC. This report is the first to provide evidence of a statistically significant decrease of structural chromosome aberrations and micronuclei associated with an augmentation of the mitotic index and prevention of DNA fragmentation in all mice treated with ZEN-MTBITC and in mouse lymphocyte cultures. The MTBITC alone was safe and succeeded in reducing the toxicity of ZEN by counteracting its deleterious effect, thus protecting against the genotoxicity and clastogenicity from ZEN. PMID:19501672

  17. Honey-Induced Protein Stabilization as Studied by Fluorescein Isothiocyanate Fluorescence

    PubMed Central

    Abdul Kadir, Habsah; Tayyab, Saad

    2013-01-01

    Protein stabilizing potential of honey was studied on a model protein, bovine serum albumin (BSA), using extrinsic fluorescence of fluorescein isothiocyanate (FITC) as the probe. BSA was labelled with FITC using chemical coupling, and urea and thermal denaturation studies were performed on FITC-labelled BSA (FITC-BSA) both in the absence and presence of 10% and 20% (w/v) honey using FITC fluorescence at 522 nm upon excitation at 495 nm. There was an increase in the FITC fluorescence intensity upon increasing urea concentration or temperature, suggesting protein denaturation. The results from urea and thermal denaturation studies showed increased stability of protein in the presence of honey as reflected from the shift in the transition curve along with the start point and the midpoint of the transition towards higher urea concentration/temperature. Furthermore, the increase in ΔGDH2O and ΔGD25°C in presence of honey also suggested protein stabilization. PMID:24222758

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

    PubMed Central

    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

    2015-01-01

    Scope 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. Methods and results 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. Conclusion 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. PMID:25620073

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

    PubMed Central

    Sporsheim, Bjørnar; Øverby, Anders; Bones, Atle Magnar

    2015-01-01

    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. PMID:26690132

  20. Phenethyl isothiocyanate induces apoptosis and inhibits cell proliferation and invasion in Hep-2 laryngeal cancer cells.

    PubMed

    Dai, Meng-Yuan; Wang, Yan; Chen, Chen; Li, Fen; Xiao, Bo-Kui; Chen, Shi-Ming; Tao, Ze-Zhang

    2016-05-01

    The dietary compound phenethyl isothiocyanate (PEITC), an important tumoricidal component found in cruciferous vegetables, exhibits strong anticancer and chemopreventive effects in a variety of tumors. However, its role in human laryngeal cancer is unclear. The aim of the present study was to investigate whether PEITC exhibits anticancer properties in human laryngeal carcinoma Hep-2 cells in vitro and to identify the potential molecular mechanisms. The results showed that treatment of Hep-2 cells with PEITC significantly inhibited cell proliferation in a dose- and time-dependent manner, promoted apoptosis with concurrent G2/M cell cycle arrest and inhibited cell invasion in a dose-dependent manner. These effects were accompanied by significant alterations in the expression levels of key proteins associated with pro-survival signaling pathways, including PI3K, Akt, ERK, NF-κB, Bcl, Bax, cyclin B, CDK4 and CDK6. Importantly, these effects were not reflected in 16HBE normal human bronchial epithelial cells, suggesting a safe range of treatment concentrations between 0 and 10 µM PEITC. In summary, PEITC exhibited significant anticancer effects against human laryngeal cancer cells in vitro with low toxicological impact on normal bronchial epithelial cells. This was achieved through dysregulation of key proteins involved in the occurrence and development of tumors, thereby offering a valuable contribution to future strategies for the treatment and screening of patients with laryngocarcinoma. PMID:26986926

  1. The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings.

    PubMed

    Buckingham, Grant T; Ormond, Thomas K; Porterfield, Jessica P; Hemberger, Patrick; Kostko, Oleg; Ahmed, Musahid; Robichaud, David J; Nimlos, Mark R; Daily, John W; Ellison, G Barney

    2015-01-28

    The pyrolysis of the benzyl radical has been studied in a set of heated micro-reactors. A combination of photoionization mass spectrometry (PIMS) and matrix isolation infrared (IR) spectroscopy has been used to identify the decomposition products. Both benzyl bromide and ethyl benzene have been used as precursors of the parent species, C6H5CH2, as well as a set of isotopically labeled radicals: C6H5CD2, C6D5CH2, and C6H5 (13)CH2. The combination of PIMS and IR spectroscopy has been used to identify the earliest pyrolysis products from benzyl radical as: C5H4=C=CH2, H atom, C5H4-C ≡ CH, C5H5, HCCCH2, and HC ≡ CH. Pyrolysis of the C6H5CD2, C6D5CH2, and C6H5 (13)CH2 benzyl radicals produces a set of methyl radicals, cyclopentadienyl radicals, and benzynes that are not predicted by a fulvenallene pathway. Explicit PIMS searches for the cycloheptatrienyl radical were unsuccessful, there is no evidence for the isomerization of benzyl and cycloheptatrienyl radicals: C6H5CH2⇋C7H7. These labeling studies suggest that there must be other thermal decomposition routes for the C6H5CH2 radical that differ from the fulvenallene pathway. PMID:25637987

  2. Benzyl-Functionalized Room Temperature Ionic Liquids for CO2/N2 Separation

    SciTech Connect

    Mahurin, Shannon Mark; Dai, Thomas N; Yeary, Joshua S; Luo, Huimin; Dai, Sheng

    2011-01-01

    In this work, three classes of room temperature ionic liquids (RTILs), including imidazolium, pyridinium, and pyrrolidinium ionic liquids with a benzyl group appended to the cation, were synthesized and tested for their performance in separating CO{sub 2} and N{sub 2}. All RTILs contained the bis(trifluoromethylsulfonyl)imide anion, permitting us to distinguish the impact of the benzyl moiety attached to the cation on gas separation performance. In general, the attachment of the benzyl group increased the viscosity of the ionic liquid compared with the unfunctionalized analogs and decreased the CO{sub 2} permeability. However, all of the benzyl-modified ionic liquids exhibited enhanced CO{sub 2}/N{sub 2} selectivities compared with alkyl-based ionic liquids, with values ranging from 22.0 to 33.1. In addition, CO{sub 2} solubilities in the form of Henry's constants were also measured and compared with unfunctionalized analogs. Results of the membrane performance tests and CO{sub 2} solubility measurements demonstrate that the benzyl-functionalized RTILs have significant potential for use in the separation of carbon dioxide from combustion products.

  3. A new approach to synthesis of benzyl cinnamate: Optimization by response surface methodology.

    PubMed

    Zhang, Dong-Hao; Zhang, Jiang-Yan; Che, Wen-Cai; Wang, Yun

    2016-09-01

    In this work, the new approach to synthesis of benzyl cinnamate by enzymatic esterification of cinnamic acid with benzyl alcohol is optimized by response surface methodology. The effects of various reaction conditions, including temperature, enzyme loading, substrate molar ratio of benzyl alcohol to cinnamic acid, and reaction time, are investigated. A 5-level-4-factor central composite design is employed to search for the optimal yield of benzyl cinnamate. A quadratic polynomial regression model is used to analyze the experimental data at a 95% confidence level (P<0.05). The coefficient of determination of this model is found to be 0.9851. Three sets of optimum reaction conditions are established, and the verified experimental trials are performed for validating the optimum points. Under the optimum conditions (40°C, 31mg/mL enzyme loading, 2.6:1 molar ratio, 27h), the yield reaches 97.7%, which provides an efficient processes for industrial production of benzyl cinnamate. PMID:27041296

  4. The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings

    NASA Astrophysics Data System (ADS)

    Buckingham, Grant T.; Ormond, Thomas K.; Porterfield, Jessica P.; Hemberger, Patrick; Kostko, Oleg; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney

    2015-01-01

    The pyrolysis of the benzyl radical has been studied in a set of heated micro-reactors. A combination of photoionization mass spectrometry (PIMS) and matrix isolation infrared (IR) spectroscopy has been used to identify the decomposition products. Both benzyl bromide and ethyl benzene have been used as precursors of the parent species, C6H5CH2, as well as a set of isotopically labeled radicals: C6H5CD2, C6D5CH2, and C6H513CH2. The combination of PIMS and IR spectroscopy has been used to identify the earliest pyrolysis products from benzyl radical as: C5H4=C=CH2, H atom, C5H4—C ≡ CH, C5H5, HCCCH2, and HC ≡ CH. Pyrolysis of the C6H5CD2, C6D5CH2, and C6H513CH2 benzyl radicals produces a set of methyl radicals, cyclopentadienyl radicals, and benzynes that are not predicted by a fulvenallene pathway. Explicit PIMS searches for the cycloheptatrienyl radical were unsuccessful, there is no evidence for the isomerization of benzyl and cycloheptatrienyl radicals: C6H5CH2⇋C7H7. These labeling studies suggest that there must be other thermal decomposition routes for the C6H5CH2 radical that differ from the fulvenallene pathway.

  5. [Chemical constituents of Desmodium sambuense].

    PubMed

    Li, Chuankuan; Zhang, Qianjun; Huang, Zhongbi; Chen, Qing; Yao, Rongjun

    2010-09-01

    The chemical constituents of Desmodium sambuense were studied. Chromatographic techniques were applied to isolate and purify the constituents, and the structures were identified on the basis of physico-chemical and spectroscopeic methods. Thirteen compounds were isolated from the 75% ethanol extract of Desmodium sambuens and elucidated as beta-amyrin(1), betulic acid(2), daucosterol(3), triacontanoic acid(4), lup-20(29)-en-3-one(5), tetracosanoic-2,3-dihydroxypropylester(6), stigmast-5-ene-3beta, 7alpha-ol (7),methyl phaeophorbidea(8), o-hydroxy benzoic acid(9),beta-sitosterol(10),d-catechin(11), luteolin (12), epigallocatechin (13). All of the compounds were isolated from this plant for the first time. PMID:21141491

  6. Chemical constituents from Abutilon indicum.

    PubMed

    Kuo, Ping-Chung; Yang, Mei-Lin; Wu, Pei-Lin; Shih, Hui-Nung; Thang, Tran Dinh; Dung, Nguyen Xuan; Wu, Tian-Shung

    2008-01-01

    The investigation on the chemical constituents of the whole plant of Abutilon indicum has resulted in the isolation of two new compounds, abutilin A (1) and (R)-N-(1'-methoxycarbonyl-2'-phenylethyl)-4-hydroxybenzamide (2), as well as 28 known compounds. The structures of the two new compounds were established on the basis of the spectroscopic analysis, and the known compounds were identified by comparison of their spectroscopic and physical data with those reported in the literature. PMID:18636384

  7. Environmentally benign Friedel-Crafts benzylation over nano-TiO2/SO4 2-

    NASA Astrophysics Data System (ADS)

    Devi, Kalathiparambil RPS; Sreeja, Puthenveetil B.; Sugunan, Sankaran

    2013-05-01

    During the past decade, much attention has been paid to the replacement of homogeneous catalysts by solid acid catalysts. Friedel-Crafts benzylation of toluene with benzyl chloride (BC) in liquid phase was carried out over highly active, nano-crystalline sulfated titania systems. These catalysts were prepared using the sol gel method. Modification was done by loading 3% of transition metal oxides over sulfated titania. Reaction parameters such as catalyst mass, molar ratio, temperature, and time have been studied. More than 80% conversion of benzyl chloride and 100% selectivity are shown by all the catalysts under optimum conditions. Catalytic activity is correlated with Lewis acidity obtained from perylene adsorption studies. The reaction appears to proceed by an electrophile, which involves the reaction of BC with the acidic titania catalyst. The catalyst was regenerated and reused up to four reaction cycles with equal efficiency as in the first run. The prepared systems are environmentally friendly and are easy to handle.

  8. Microkinetic Modeling of Benzyl Alcohol Oxidation on Carbon-Supported Palladium Nanoparticles

    DOE PAGESBeta

    Savara, Aditya; Rossetti, Ilenia; Chan-Thaw, Carine E.; Prati, Laura; Villa, Alberto

    2016-07-14

    Six products are formed from benzyl alcohol oxidation over Pd nanoparticles using O2 as the oxidant: benzaldehyde, toluene, benzyl ether, benzene, benzoic acid, and benzyl benzoate. Three experimental parameters were varied here: alcohol concentration, oxygen concentration, and temperature. Microkinetic modeling using a mechanism published recently with surface intermediates was able to produce all 18 trends observed experimentally with mostly quantitative agreement. Approximate analytical equations derived from the microkinetic model for isothermal conditions reproduced the isothermal trends and provided insight. The most important activation energies are Ea2=57.9 kJ mol₋1, Ea5=129 kJ mol₋1, and Ea6=175 kJ mol₋1, which correspond to alcohol dissociation,more » alkyl hydrogenation, and the reaction of alkyl species with alkoxy species. Upper limits for other activation energies were identified. The concepts of a sticking coefficient and steric factor in solution were applied.« less

  9. Transition-metal-free C-H oxidative activation: persulfate-promoted selective benzylic mono- and difluorination.

    PubMed

    Ma, Jing-jing; Yi, Wen-bin; Lu, Guo-ping; Cai, Chun

    2015-03-14

    An operationally simple and selective method for the direct conversion of benzylic C-H to C-F to obtain mono- and difluoromethylated arenes using Selectfluor™ as a fluorine source is developed. Persulfate can be used to selectively activate benzylic hydrogen atoms toward C-F bond formation without the aid of transition metal catalysts. PMID:25645405

  10. Intra- and Intermolecular Nickel-Catalyzed Reductive Cross-Electrophile Coupling Reactions of Benzylic Esters with Aryl Halides.

    PubMed

    Konev, Mikhail O; Hanna, Luke E; Jarvo, Elizabeth R

    2016-06-01

    Nickel-catalyzed cross-electrophile coupling reactions of benzylic esters and aryl halides have been developed. Both inter- and intramolecular variants proceed under mild reaction conditions. A range of heterocycles and functional groups are tolerated under the reaction conditions. Additionally, the first example of a stereospecific cross-electrophile coupling of a secondary benzylic ester is described. PMID:27099968

  11. Anticancer Activities of Pterostilbene-Isothiocyanate Conjugate in Breast Cancer Cells: Involvement of PPARγ

    PubMed Central

    Nikhil, Kumar; Sharan, Shruti; Singh, Abhimanyu K.; Chakraborty, Ajanta; Roy, Partha

    2014-01-01

    Trans-3,5-dimethoxy-4′-hydroxystilbene (PTER), a natural dimethylated analog of resveratrol, preferentially induces certain cancer cells to undergo apoptosis and could thus have a role in cancer chemoprevention. Peroxisome proliferator-activated receptor γ (PPARγ), a member of the nuclear receptor superfamily, is a ligand-dependent transcription factor whose activation results in growth arrest and/or apoptosis in a variety of cancer cells. Here we investigated the potential of PTER-isothiocyanate (ITC) conjugate, a novel class of hybrid compound (PTER-ITC) synthesized by appending an ITC moiety to the PTER backbone, to induce apoptotic cell death in hormone-dependent (MCF-7) and -independent (MDA-MB-231) breast cancer cell lines and to elucidate PPARγ involvement in PTER-ITC action. Our results showed that when pre-treated with PPARγ antagonists or PPARγ siRNA, both breast cancer cell lines suppressed PTER-ITC-induced apoptosis, as determined by annexin V/propidium iodide staining and cleaved caspase-9 expression. Furthermore, PTER-ITC significantly increased PPARγ mRNA and protein levels in a dose-dependent manner and modulated expression of PPARγ-related genes in both breast cancer cell lines. This increase in PPARγ activity was prevented by a PPARγ-specific inhibitor, in support of our hypothesis that PTER-ITC can act as a PPARγ activator. PTER-ITC-mediated upregulation of PPARγ was counteracted by co-incubation with p38 MAPK or JNK inhibitors, suggesting involvement of these pathways in PTER-ITC action. Molecular docking analysis further suggested that PTER-ITC interacted with 5 polar and 8 non-polar residues within the PPARγ ligand-binding pocket, which are reported to be critical for its activity. Collectively, our observations suggest potential applications for PTER-ITC in breast cancer prevention and treatment through modulation of the PPARγ activation pathway. PMID:25119466

  12. Hepatoprotective effects of allyl isothiocyanate against carbon tetrachloride-induced hepatotoxicity in rat.

    PubMed

    Ahn, Meejung; Kim, Jeongtae; Bang, Hyojin; Moon, Jihwan; Kim, Gi Ok; Shin, Taekyun

    2016-07-25

    We evaluated the hepatoprotective activity of allyl isothiocyanate (AITC) against carbon tetrachloride (CCl4)-induced liver injury in rats. Sprague Dawley rats were orally administered AITC at doses of 5 (AITC 5) and 50 (AITC 50) mg/kg body weight once daily for 3 days, with or without intraperitoneal injection of CCl4. Serum chemistry was assessed for changes in alanine aminotransferase (ALT) and aspartate aminotransferase (AST). The enzyme activities of superoxide dismutase (SOD), catalase (CAT), and malondialdehyde (MDA) were examined in liver tissues, while pro-inflammatory cytokines including tumor necrosis factor-alpha (TNF-α) and interleukin-1 beta (IL-1β) mRNA expression were analyzed using real-time polymerase chain reaction. And heme oxygenase-1 (HO-1) and ionized calcium binding protein-1 (Iba-1) immunoreactivities were evaluated by Western blot analysis and immunohistochemistry, respectively. In serum chemistry, the oral administration of AITC itself did not affect the serum levels of ALT or AST, furthermore pretreatment with AITC 5 and AITC 50 significantly reduced the ALT and AST activity levels that were elevated in CCl4-intoxicated rats. In addition, AITC significantly suppressed the reduction of SOD and CAT, and the elevation of MDA, TNF-α mRNA expression, on the other hands, induced the expression of HO-1 compared with those of the vehicle-treated CCl4 group. The histopathological evaluation and Iba-1 immunoreactivity also supported the hepatoprotective effects of AITC against CCl4-induced liver injury. These results suggest that AITC ameliorates oxidative liver injury, possibly through reducing lipid peroxidation, enhancing antioxidant enzymes, and suppressing Kupffer cells and macrophages. PMID:27241356

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

    PubMed

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

    2015-01-01

    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 92.5μM 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 the role of AITC as a potential antiproliferative compound that modulates gene expression according to the tumor cell TP53 genotype. PMID:25771977

  14. Active packaging of cheese with allyl isothiocyanate, an alternative to modified atmosphere packaging.

    PubMed

    Winther, Mette; Nielsen, Per Vaeggemose

    2006-10-01

    The natural antimicrobial compound allyl isothiocyanate (AITC), found in mustard oil, is effective against cheese-related fungi both on laboratory media and cheese. Penicillium commune, Penicillium roqueforti, and Aspergillus flavus were more sensitive to AITC when it was added just after the spores had completed 100% germination and branching had started on Czapek yeast extract agar than were spores in the dormant phase. The use of 1 AITC label (Wasaouro interior labels, LD30D, 20 by 20 mm) in combination with atmospheric air in the packaging extended the shelf life of Danish Danbo cheese from 4 1/2 to 13 weeks. Two AITC labels extended the shelf life from 4 1/2 to 28 weeks. Both 1 and 2 labels in combination with modified atmosphere packaging extended the shelf life of the cheese from 18 to 28 weeks. This study showed that AITC was absorbed in the cheese, but it was not possible to detect any volatile breakdown products from AITC in the cheese. Cheese stored for up to 12 weeks with an AITC label had an unacceptable mustard flavor. The mustard flavor decreased to an acceptable level between weeks 12 and 28. Cheese stored in atmospheric air had a fresher taste without a CO2 off-flavor than did cheese stored in modified atmosphere packaging. AITC may be a good alternative to modified atmosphere packaging for cheese. The extended shelf life of cheese in the package is very desirable: the cheese can be transported longer distances, and the packaging can be used for the final maturing of the cheese. Furthermore, AITC can address problems such as pinholes and leaking seals in cheese packaging. PMID:17066923

  15. Urinary isothiocyanate excretion, brassica consumption, and gene polymorphisms among women living in Shanghai, China.

    PubMed

    Fowke, Jay H; Shu, Xiao-Ou; Dai, Qi; Shintani, Ayumi; Conaway, C Clifford; Chung, Fung-Lung; Cai, Qiuyin; Gao, Yu-Tang; Zheng, Wei

    2003-12-01

    Alternative measures of Brassica vegetable consumption (e.g., cabbage) may clarify the association between Brassica and cancer risk. Brassica isothiocyanates (ITCs) are excreted in urine and may provide a sensitive and food-specific dietary biomarker. However, the persistence of ITCs in the body may be brief and dependent on the activity of several Phase II enzymes, raising questions about the relationship between a single ITC measure and habitual dietary patterns. This study investigates the association between urinary ITC excretion and habitual Brassica consumption, estimated by a food frequency questionnaire, among healthy Chinese women enrolled in the Shanghai Breast Cancer Study. Participants (n = 347) completed a validated food frequency questionnaire querying habitual dietary intake during the prior 5 years and provided a fasting first-morning urine specimen. Genetic deletion of glutathione S-transferases (GSTM1/GSTT1), and single nucleotide substitutions in GSTP1 (A313G) and NAD(P)H:quinone oxidoreductase 1 (NQO1: C609T), were identified from blood DNA. Urinary ITC excretion levels were marginally higher with the GSTT1-null or GSTP1-G/G genotypes (P = 0.07, P = 0.05, respectively). Mean habitual Brassica intake was 98.3 g/day, primarily as bok choy, and Brassica intake significantly increased across quartile categories of ITC levels. The association between habitual Brassica intake and urinary ITC levels was stronger among women with GSTT1-null or GSTP1-A/A genotypes, or NQO1 T-allele, and the interaction was statistically significant across GSTP1 genotype. In conclusion, a single urinary ITC measure, in conjunction with markers of Phase II enzyme activity, provides a complementary measure of habitual Brassica intake among Shanghai women. PMID:14693750

  16. Benefits and Risks of the Hormetic Effects of Dietary Isothiocyanates on Cancer Prevention

    PubMed Central

    Bao, Yongping; Wang, Wei; Zhou, Zhigang; Sun, Changhao

    2014-01-01

    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. PMID:25532034

  17. Urinary total isothiocyanates and colorectal cancer: a prospective study of men in Shanghai, China

    PubMed Central

    Moy, Kristin A.; Yuan, Jian-Min; Chung, Fung-Lung; Van Den Berg, David; Wang, Renwei; Gao, Yu-Tang; Yu, Mimi C.

    2008-01-01

    Laboratory and epidemiological evidence suggest that dietary isothiocyanates (ITCs) may have a chemopreventive effect on cancer. Humans are exposed to ITCs primarily through ingestion of cruciferous vegetables which contain glucosinolates, the precursors to ITCs. The association between urinary total ITC level and colorectal cancer risk was examined in a cohort of 18,244 men in Shanghai, China, with 16 years of follow-up. Urinary total ITCs were quantified on 225 incident cases of colorectal cancer and 1119 matched controls. Odds ratios (ORs) and their 95% confidence intervals (95% CIs) were calculated using logistic regression models. High levels of urinary total ITCs were associated with a reduced risk of colorectal cancer five years after baseline measurements of ITCs whereas a statistically nonsignificant increase in the risk of colorectal cancer was observed for cases within five years of post-enrollment (OR=1.93; 95% CI =0.85, 4.39 for the upper three quartiles of urinary ITCs versus the lowest quartile). The inverse ITC-colorectal cancer association became stronger with a longer duration of follow-up. Compared with the first quartile, ORs (95% CIs) for the second, third, and fourth quartiles of total ITCs in urine collected 10 or more years before cancer diagnosis were 0.61 (0.35, 1.05), 0.51 (0.29, 0.92), and 0.46 (0.25, 0.83), respectively, for risk of colorectal cancer (P for trend = 0.006). The present study suggests that dietary ITCs may exert tumor inhibitory effects, especially during earlier stages of the multistage process of carcinogenesis. PMID:18559550

  18. The effects and mode of action of biochar on the degradation of methyl isothiocyanate in soil.

    PubMed

    Fang, Wensheng; Wang, Qiuxia; Han, Dawei; Liu, Pengfei; Huang, Bin; Yan, Dongdong; Ouyang, Canbin; Li, Yuan; Cao, Aocheng

    2016-09-15

    Biochar is used as a new type of fertilizer in agriculture; however, its effect on the fate of fumigants in soil is not fully understood. The objective of this study was to investigate the effects of biochar on methyl isothiocyanate (MITC) degradation in soil in laboratory incubation experiments, including the effects of biochar composition, amendment rate, moisture, temperature, soil sterilization and soil type. The dissipation pathways of MITC in biochars included adsorption and chemical degradation. The adsorption of MITC by biochars was positively correlated with the specific surface area (SSA) of the biochar. Biochar with a high SSA and low H/C value (such as biochar type BC-1) reduced MITC degradation in soil substantially; following BC-1 amendment, the degradation rate was 73.9% slower than in unamended soil. The degradation of MITC was positively correlated with the H/C value of biochar, and MITC degradation in soil increased 2.2-31.1 times following amendment with biochars with higher H/C values (e.g. biochar types BC-3-6). The biochar with the lowest organic matter and low H/C value did not affect the fate of MITC in soil. Biochars affect abiotic degradation processes more than biodegradation. When soil samples had a higher water content (>10%), higher temperature (40°C), and lower organic matter, the addition of BC-1 biochar reduced MITC degradation substantially; and this did not change significantly when the amendment rate increased. However, BC-4 biochar accelerated MITC degradation with increasing amendment rate, increasing temperature, and decreasing soil water content. The differences in degradation rates due to soil type were minimized by amendment with BC-4, but significant differences in BC-1. The results showed that the rational use of biochar has the potential to reduce MITC emission by accelerated degradation and adsorption. PMID:27177140

  19. ER stress contributes to alpha-naphthyl isothiocyanate-induced liver injury with cholestasis in mice.

    PubMed

    Yao, Xiaomin; Li, Yue; Cheng, Xiaoyan; Li, Hongwei

    2016-06-01

    Endoplasmic reticulum (ER) stress is involved in the development of several liver diseases and tumors. This study investigated the underlying mechanisms of α-naphthyl isothiocyanate (ANIT)-induced liver injury with cholestasis in mice and found ER stress contributes to the injury. All animals were randomly divided into three groups. In the ANIT-intoxicated group, mice were intragastrically given 100mg/kg ANIT (dissolved in corn oil), while the other groups received an equal volume of vehicle as control. After 24 and 48h of ANIT administration, blood samples and liver tissues of all animals were collected for serum biochemistry and hepatic histopathological examinations to evaluate liver injuries with cholestasis. Hepatocellular apoptosis was assessed by the terminal deoxynucleotidyl transferase dUTP nick-end labeling (TUNEL) assay. The expression of hepatic ER stress-related markers was determined by real-time PCR, immunohistochemical assay and Western blot. ANIT was found to significantly induce liver injury with cholestasis compared with control mice as evidenced by the increase of serum transaminases and total bilirubin (TBil), and histopathological changes in mice. ANIT remarkably induced hepatocellular apoptosis, upregulated the expression of caspase-9 and cytochrome c, and inhibited the gene and protein expression of proliferating cell nuclear antigen (PCNA). The gene expression of ER stress-related markers, including glucose-regulated protein 78 (GRP78), protein kinase R-like ER kinase (PERK), eukaryotic initiation factor 2α (eIF2α), inositol requiring enzyme-1α (IRE-1α) and activating transcription factor 6 (ATF6) was upregulated by ANIT in mice. ANIT also upregulated the protein expression of GRP78 and activated the phosphorylation of IRE1. These results suggested that ANIT induced liver injury with cholestasis partly due to its ability to activate the ER stress pathway. PMID:27173049

  20. Benzyl alcohol increases voluntary ethanol drinking in rats.

    PubMed

    Etelälahti, T J; Eriksson, C J P

    2014-09-01

    The anabolic steroid nandrolone decanoate has been reported to increase voluntary ethanol intake in Wistar rats. In recent experiments we received opposite results, with decreased voluntary ethanol intake in both high drinking AA and low drinking Wistar rats after nandrolone treatment. The difference between the two studies was that we used pure nandrolone decanoate in oil, whereas in the previous study the nandrolone product Deca-Durabolin containing benzyl alcohol (BA) was used. The aims of the present study were to clarify whether the BA treatment could promote ethanol drinking and to assess the role of the hypothalamic-pituitary-adrenal-gonadal axes (HPAGA) in the potential BA effect. Male AA and Wistar rats received subcutaneously BA or vehicle oil for 14 days. Hereafter followed a 1-week washout and consecutively a 3-week voluntary alcohol consumption period. The median (± median absolute deviation) voluntary ethanol consumption during the drinking period was higher in BA-treated than in control rats (4.94 ± 1.31 g/kg/day vs. 4.17 ± 0.31 g/kg/day, p = 0.07 and 1.01 ± 0.26 g/kg/day vs. 0.38 ± 0.27 g/kg/day, p = 0.05, for AA and Wistar rats, respectively; combined effect p < 0.01). The present results can explain the previous discrepancy between the two nandrolone studies. No significant BA effects on basal and ethanol-mediated serum testosterone and corticosterone levels were observed in blood samples taken at days 1, 8 and 22. However, 2h after ethanol administration significantly (p = 0.02) higher frequency of testosterone elevations was detected in high drinking AA rats compared to low drinking Wistars, which supports our previous hypotheses of a role of testosterone elevation in promoting ethanol drinking. Skin irritation and dermatitis were shown exclusively in the BA-treated animals. Altogether, the present results indicate that earlier findings obtained with Deca-Durabolin containing BA need to be re-evaluated. PMID:24871566

  1. Base metal-catalyzed benzylic oxidation of (aryl)(heteroaryl)methanes with molecular oxygen

    PubMed Central

    Sterckx, Hans; De Houwer, Johan; Mensch, Carl; Herrebout, Wouter; Tehrani, Kourosch Abbaspour

    2016-01-01

    Summary The methylene group of various substituted 2- and 4-benzylpyridines, benzyldiazines and benzyl(iso)quinolines was successfully oxidized to the corresponding benzylic ketones using a copper or iron catalyst and molecular oxygen as the stoichiometric oxidant. Application of the protocol in API synthesis is exemplified by the alternative synthesis of a precursor to the antimalarial drug Mefloquine. The oxidation method can also be used to prepare metabolites of APIs which is illustrated for the natural product papaverine. ICP–MS analysis of the purified reaction products revealed that the base metal impurity was well below the regulatory limit. PMID:26877817

  2. Iron-Catalyzed Oxyfunctionalization of Aliphatic Amines at Remote Benzylic C-H Sites.

    PubMed

    Mbofana, Curren T; Chong, Eugene; Lawniczak, James; Sanford, Melanie S

    2016-09-01

    We report the development of an iron-catalyzed method for the selective oxyfunctionalization of benzylic C(sp(3))-H bonds in aliphatic amine substrates. This transformation is selective for benzylic C-H bonds that are remote (i.e., at least three carbons) from the amine functional group. High site selectivity is achieved by in situ protonation of the amine with trifluoroacetic acid, which deactivates more traditionally reactive C-H sites that are α to nitrogen. The scope and synthetic utility of this method are demonstrated via the synthesis and derivatization of a variety of amine-containing, biologically active molecules. PMID:27529646

  3. Catalyst system and process for benzyl ether fragmentation and coal liquefaction

    DOEpatents

    Zoeller, Joseph Robert

    1998-04-28

    Dibenzyl ether can be readily cleaved to form primarily benzaldehyde and toluene as products, along with minor amounts of bibenzyl and benzyl benzoate, in the presence of a catalyst system comprising a Group 6 metal, preferably molybdenum, a salt, and an organic halide. Although useful synthetically for the cleavage of benzyl ethers, this cleavage also represents a key model reaction for the liquefaction of coal; thus this catalyst system and process should be useful in coal liquefaction with the advantage of operating at significantly lower temperatures and pressures.

  4. [Growth-regulating activity of N-benzyl- and O-benzyl-containing compounds belonging to a new group of synthetic analogues of natural auxins].

    PubMed

    Gafurov, R G; Makhmutova, A A

    2005-01-01

    We studied the effect of benzylamine, benzyl alcohol, and their derivatives (constituting a new group of synthetic analogues of natural auxins) on rooting of leaf and stem cuttings, rhizogenesis and growth of barley plantlets and tomato seedlings, and tomato plant productivity. These compounds promoted rooting of leaf and stem bean cuttings, increased rhizogenic activity, and stimulated the development of root systems in barley and tomato seeds. The activity of the compounds studied was similar to that of standard substances (3-indoleacetic acid potassium salt and 2-naphthylacetic acid). The benzyl group attached to the oxygen or nitrogen atom was shown to be the smallest molecular structure which provided auxin activity of the compounds. Derivatives of benzyl alcohol containing the quaternary ammonium fragment possessed auxin and anti-gibberellin (retardant) properties. They were selected by chemical synthesis of low-molecular-weight bioregulators with desired properties (a combination of chemical fragments with complementary physiological activity in the molecule). Auxin and anti-gibberellin (retardant) activities produced a synergistic effect. Germination of seeds treated with these compounds was accompanied by a more significant increase in the weight and length of roots (compared to standard auxins). The rate of seedling establishment reached 100%. The development of fruits and accumulation of reserve nutrient substances were synchronized and accelerated after spraying vegetating plants with solutions of studied compounds. The synergistic effect underlay a significant increase in the amount and quality of the crop (e.g., tomatoes). PMID:15859471

  5. Fibre constituents of some foods.

    PubMed

    Rani, B; Kawatra, A

    1994-06-01

    Some plant foods viz. bottlegourd, carrot, cauliflower, cabbage, green bengalgram, pea, apple, plum, guava, karonda, blackgram husk and lentil husk were analysed for their dietary fibre components. The total dietary fibre contents of these foods varied from 14.68 to 78.21 percent on dry matter basis. As compared to fruits and vegetables, the husks had higher amount of total dietary fibre. Cellulose represented as the major fibre constituent in most of the foods whereas, husks were observed to be good sources of hemicellulose. All foods were low in pectin and lignin contents except guava. PMID:7971775

  6. In vitro antiproliferative activity of isothiocyanates and nitriles generated by myrosinase-mediated hydrolysis of glucosinolates from seeds of cruciferous vegetables.

    PubMed

    Nastruzzi, C; Cortesi, R; Esposito, E; Menegatti, E; Leoni, O; Iori, R; Palmieri, S

    2000-08-01

    A comparison of the effect of isothiocyanates and nitriles derived from some glucosinolates, namely, epi-progoitrin, sinalbin, glucotropaeolin, glucocheirolin, and glucoraphenin, on human erythroleukemic in vitro cultured cells was studied. Many studies have in fact evidenced that a consumption of vegetable containing glucosinolates could reduce the development of colorectal cancer. In the experimental conditions used, the production of isothiocyanates and nitriles from glucosinolates is almost quantitative as confirmed by HPLC or GC-MS analysis. The obtained results demonstrated that in general nitriles are considerably less potent than the corresponding isothiocyanates in inhibiting cancer cell growth. Particularly, the isothiocyanates inhibitory activity on K562 cells growth is higher in the case of products derived from epi-progoitrin, glucotropaeolin, glucoraphenin, and glucocheirolin; while for nitriles the higher activity in inhibiting K562 cells growth is showed by sinalbin-derived product. Considering the antiproliferative activity found for isothiocyanates and nitriles, further studies will be aimed to the possible application of glucosinolate-derived products as chemopreventive cancer agents for the reduction of colorectal cancer. PMID:10956152

  7. A yeast chemical genetics approach identifies the compound 3,4,5-trimethoxybenzyl isothiocyanate as a calcineurin inhibitor.

    PubMed

    Prescott, Thomas A K; Panaretou, Barry; Veitch, Nigel C; Simmonds, Monique S J

    2014-01-31

    The phosphatase enzyme calcineurin controls gene expression in a variety of biological contexts however few potent inhibitors are currently available. A screen of 360 plant extracts for inhibition of calcineurin-dependent gene expression in the model organism Saccharomyces cerevisiae identified the compound 3,4,5-trimethoxybenzyl isothiocyanate as an inhibitor. The compound was subsequently shown to inhibit human calcineurin via a mixed inhibition mechanism. To gain further mechanistic insight a yeast haploinsufficiency screen of 1152 deletion strains was carried out using a novel liquid medium screening method. The resulting haploinsufficiency profile is similar to that reported for the known calcineurin inhibitor FK506. PMID:24374339

  8. Efficient fluorescence energy transfer system between fluorescein isothiocyanate and CdTe quantum dots for the detection of silver ions.

    PubMed

    Feng, Yueshu; Liu, Liwei; Hu, Siyi; Zou, Peng; Zhang, Jiaqi; Huang, Chen; Wang, Yue; Wang, Sihan; Zhang, Xihe

    2016-03-01

    We report a fluorescence resonance energy transfer (FRET) system in which the fluorescent donor is fluorescein isothiocyanate (FITC) dye and the fluorescent acceptor is CdTe quantum dot (QDs). Based on FRET quenching theory, we designed a method to detect the concentration of silver ions (Ag(+)). The results revealed a good linear trend over Ag(+) concentrations in the range 0.01-8.96 nmol/L, a range that was larger than with other methods; the quenching coefficient is 0.442. The FRET mechanism and physical mechanisms responsible for dynamic quenching are also discussed. PMID:26277997

  9. [Chemical constituents from Bidens bipinnata].

    PubMed

    Wang, Xiao-Yu; Chen, Guan-Ru; Deng, Zi-Yun; Zhao, Jie; Ge, Jin-Fang; Li, Ning; Chen, Fei-Hu

    2014-05-01

    To investigate the chemical constituents of the whole plants of Bidens bipinnata, the separation and purification of constituents were performed by chromatography on macroporous resin, silica gel, MCI and Sephadex LH-20. Their structures were elucidated by spectroscopic data as quercetin (1), quercetin-3-0-alpha-L-rhamnoside (2), keampferol-3-O-beta-D-glucopyranoside (3), keampferol-3-O-alpha-L-rhamnoside (4), 3', 5-dyhydroxy-3, 6, 4'-trimethoxyl -7-O-beta-D-glucopyranoside flavonoid (5), 7, 8, 3', 4'-tetraflavanone(6), (2S)- and (2R)-isookanin-7-O-beta-D- glucopyranoside (7a/7b), (2S)- and (2R)-3'-methoxy-isookanin-8-O-beta-D-glucopyranoside (8a/8b), 6, 7, 3', 4'-tetrahydroxyaurone(9), maritimetin (10), esculetin (11), 3-O-caffeoyl-2-methyl-d-erythrono-1, 4-lactone (12), (7S, 8R) balanophonin-4-O-beta-D-glucopyranoside (13), eugenyl-O-beta-apiofuranosyl-( 1"-6') -O-beta-glucopyranoside (14), and (+)-syringaresinol-4'-O-beta-D-glucopyranoside (15). Compounds 8, 13, 14, and 15 were isolated from this genus for the first time. Compounds 1 and 6 were potent inhibitors against HSC-T6 cells in vitro and compounds 1, 2, 6, and 7 were capable of decreasing the inflammatory cytokine production of macrophage cells in vitro. PMID:25282892

  10. "Decarbonization" of an imino N-heterocyclic carbene via triple benzyl migration from hafnium

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An imino N-heterocyclic carbene underwent three sequential benzyl migrations upon reaction with tetrabenzylhafnium, resulting in complete removal of the carbene carbon from the ligand. The resulting eneamido-amidinato hafnium complex showed alkene polymerization activity comparable to that of a prec...

  11. Activation of Benzyl Aryl Carbonates: The Role of Cation-π Interactions.

    PubMed

    Reddy, Golipalli Ramana; Avadhani, Anusha S; Rajaram, Sridhar

    2016-05-20

    Benzyl aryl carbonates can react with a nucleophile to yield an activated electrophile and an aryloxide anion. Previously, we had utilized this in the synthesis of α-nitro esters from nitroalkanes. To further understand the process of activation of these carbonates by nucleophiles, we have performed kinetic studies on the hydrolysis of carbonates using nucleophiles. Rate constants for the hydrolysis were obtained under pseudo-first-order conditions with DABCO as the nucleophile. A comparison of rate constant for hydrolysis of isobutyl phenyl carbonate with benzyl phenyl carbonate shows that the presence of benzyl group results in a 16-fold acceleration of hydrolysis rate. This indicates that the transition state for activation of carbonate is stabilized by cation-π interactions. A comparison of the rate constant for various aromatic rings indicates that electron-donating substituents on the benzyl groups accelerate the rate of hydrolysis. Studies were also carried out with DMAP as nucleophile and the results are presented. Our studies show that stable carbonates can be activated using nucleophiles. Activated acyl groups generated from acid anhydrides have been used in several enantioselective reactions. Our studies show that carbonates can be stable alternatives to acid anhydrides. PMID:27158833

  12. Effect of cotton pectin content and bioscouring on alkyl-dimethyl-benzyl-ammonium chloride adsorption

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Our previous research has shown both the rate and the total amount of alkyl-dimethyl-benzyl-ammonium chloride (ADBAC) exhausted from a bulk solution of ADBAC are significantly greater for greige cotton nonwovens than cotton nonwovens that have been both scoured and bleached. The presence of pectin ...

  13. Allylic and benzylic sp3 C-H oxidation in water.

    PubMed

    Ang, Wei Jie; Lam, Yulin

    2015-01-28

    A copper-catalyzed method for the oxidation of allylic and benzylic sp(3) C-H by aqueous tert-butyl hydroperoxide (T-Hydro) in water using a recyclable fluorous ligand has been developed. The reaction procedure is tolerant to additional functional groups and the fluorous ligand could be reused with little loss of catalytic activity. PMID:25412371

  14. A Highly Selective Vanadium Catalyst for Benzylic C-H Oxidation.

    PubMed

    Xia, Ji-Bao; Cormier, Kevin W; Chen, Chuo

    2012-01-01

    Vanadium complexes have been used extensively to catalyze olefin and alcohol oxidation. However, their application in C-H oxidation has not been well-studied. We report herein that commercially available Cp(2)VCl(2) catalyzes benzylic C-H oxidation selectively and effectively, giving no aromatic oxidation products. PMID:22712051

  15. Polycyclic aromatic hydrocarbon (PAH) formation from benzyl radicals: a reaction kinetics study.

    PubMed

    Sinha, Sourab; Raj, Abhijeet

    2016-03-01

    The role of resonantly stabilized radicals such as propargyl, cyclopentadienyl and benzyl in the formation of aromatic hydrocarbons such as benzene and naphthalene in the high temperature environments has been long known. In this work, the possibility of benzyl recombination to form three-ring aromatics, phenanthrene and anthracene, is explored. A reaction mechanism for it is developed, where reaction energetics are calculated using density functional theory (B3LYP functional with 6-311++G(d,p) basis set) and CBS-QB3, while temperature-dependent reaction kinetics are evaluated using transition state theory. The mechanism begins with barrierless formation of bibenzyl from two benzyl radicals with the release of 283.2 kJ mol(-1) of reaction energy. The further reactions involve H-abstraction by a H atom, H-desorption, H-migration, and ring closure to gain aromaticity. Through mechanism and rate of production analyses, the important reactions leading to phenanthrene and anthracene formation are determined. Phenanthrene is found to be the major product at high temperatures. Premixed laminar flame simulations are carried out by including the proposed reactions for phenanthrene formation from benzyl radicals and compared to experimentally observed species profiles to understand their effects on species concentrations. PMID:26923612

  16. Adsorption of alkyl-dimethyl-benzyl-ammonium chloride on differently pretreated nonwoven cotton substrate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The adsorption of alkyl-dimethyl-benzyl-ammonium chloride (ADBAC), a cationic surfactant commonly employed as an antimicrobial agent, on greige, alkaline scoured, and bleached nonwoven cotton fabrics was investigated at varying surfactant concentrations and liquor ratios using UV-vis absorption spec...

  17. The Synthesis and Methanolysis of Benzyl Tosylates: An Advanced Organic Chemistry Laboratory Experiment.

    ERIC Educational Resources Information Center

    Garst, Michael E.; Gribble, Gordon W.

    1984-01-01

    Describes a series of experiments (requiring six hours/week for six to eight weeks) involving the synthesis and methanolysis of substituted benzyl tosylates. The experiments provide students with experiences in kinetic data manipulation and an introduction and firm basis for structure-activity relationships and solvent effects in organic…

  18. Urinary Isothiocyanate Levels and Lung Cancer Risk Among Non-Smoking Women: a Prospective Investigation

    PubMed Central

    Fowke, Jay H.; Gao, Yu-Tang; Chow, Wong-Ho; Cai, Qiuyin; Shu, Xiao-Ou; Li, Hong-lan; Ji, Bu-Tian; Rothman, Nat; Yang, Gong; Chung, Fung-Lung; Zheng, Wei

    2010-01-01

    Background Aside from tobacco carcinogen metabolism, isothiocyanates (ITC) from cruciferous vegetables may induce apoptosis or steroid metabolism to reduce lung cancer risk. To separate the effect of these divergent mechanisms of action, we investigated the association between urinary ITC levels and lung cancer risk among non-smoking women. Methods We conducted a nested case-control within the Shanghai Women’s Health Study. Subjects included 209 incident lung cancer cases who never used tobacco, and 787 individually matched non-smoking controls. Conditional logistic regression was used to calculate odds ratios (OR) and 95% confidence intervals (CI) summarizing the association between urinary ITC levels and lung cancer. Secondary analyses stratified the ITC-lung cancer analyses by menopausal status, exposure to environmental tobacco smoke, and GSTM1 and GSTT1 genotypes. Results Urinary ITC levels were not significantly associated with lower lung cancer risk among non-smoking women, regardless of exposure to environmental tobacco smoke or menopausal status. Furthermore, this association was not modified by GSTT1 genotype. However, an inverse association was suggested among women with a GSTM1-positive genotype (Q1: OR=1.0 (reference); Q2: OR=0.35 (0.14, 0.89); Q3: OR=0.47 (0.20, 1.10); Q4: OR=0.63 (0.35, 1.54), p-trend = 0.38)). In contrast, lung cancer risk was positively associated with urinary ITC levels among women with the GSTM1-null genotype (Q1: OR=1.0 (reference); Q2: OR=1.67 (0.80, 3.50); Q3: OR=1.54 (0.71, 3.33); Q4: OR=2.22 (1.05, 4.67), p-trend = 0.06)). Conclusion Urinary ITC levels were not associated overall with lower lung cancer risk among non-smoking women, but secondary analyses suggested an interaction between urinary ITC levels, GSTM1 genotype, and lung cancer risk. PMID:21122939

  19. Nrf2 Knockout Attenuates the Anti-Inflammatory Effects of Phenethyl Isothiocyanate and Curcumin

    PubMed Central

    2015-01-01

    The role of phytochemicals in preventive and therapeutic medicine is a major area of scientific research. Several studies have illustrated the mechanistic roles of phytochemicals in Nrf2 transcriptional activation. The present study aims to examine the importance of the transcription factor Nrf2 by treating peritoneal macrophages from Nrf2+/+ and Nrf2–/– mice ex vivo with phenethyl isothiocyanate (PEITC) and curcumin (CUR). The peritoneal macrophages were pretreated with the drugs and challenged with lipopolysaccharides (LPSs) alone and in combination with PEITC or CUR to assess their anti-inflammatory and antioxidative effects based on gene and protein expression in the treated cells. LPS treatment resulted in an increase in the expression of inflammatory markers such as cycloxygenase-2 (COX-2), inducible nitric oxide synthase (iNOS), interleukin-6 (IL-6), and tumor necrosis factor-α (TNF-α) in both Nrf2+/+ and Nrf2–/– macrophages, detected by quantitative polymerase chain reaction (qPCR). Nrf2+/+ macrophages treated with PEITC and CUR exhibited a significant decrease in the expression of these anti-inflammatory genes along with an increase in the expression of hemeoxygenase-1 (HO-1), which is an antioxidative stress gene downstream of the Nrf2 transcription factor battery. Although there was no significant decrease in the expression of the anti-inflammatory genes or an increase in HO-1 expression in Nrf2–/– macrophages treated with either PEITC or CUR, there was a significant decrease in the protein expression of COX-2 and an increase in the expression of HO-1 in Nrf2+/+ macrophages treated with PEITC compared to that with CUR treatment. No significant changes were observed in the macrophages from knockout animals. Additionally, there was a significant decrease in LPS-induced IL-6 and TNF-α production following PEITC treatment compared with that following CUR in Nrf2+/+ macrophages, whereas no change was observed in the macrophages from knockout

  20. The thermal decomposition of the benzyl radical in a heated micro-reactor. I. Experimental findings

    SciTech Connect

    Buckingham, Grant T.; Ormond, Thomas K.; Porterfield, Jessica P.; Ellison, G. Barney; Hemberger, Patrick; Kostko, Oleg; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.

    2015-01-28

    The pyrolysis of the benzyl radical has been studied in a set of heated micro-reactors. A combination of photoionization mass spectrometry (PIMS) and matrix isolation infrared (IR) spectroscopy has been used to identify the decomposition products. Both benzyl bromide and ethyl benzene have been used as precursors of the parent species, C{sub 6}H{sub 5}CH{sub 2}, as well as a set of isotopically labeled radicals: C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2}. The combination of PIMS and IR spectroscopy has been used to identify the earliest pyrolysis products from benzyl radical as: C{sub 5}H{sub 4}=C=CH{sub 2}, H atom, C{sub 5}H{sub 4}—C ≡ CH, C{sub 5}H{sub 5}, HCCCH{sub 2}, and HC ≡ CH. Pyrolysis of the C{sub 6}H{sub 5}CD{sub 2}, C{sub 6}D{sub 5}CH{sub 2}, and C{sub 6}H{sub 5}{sup 13}CH{sub 2} benzyl radicals produces a set of methyl radicals, cyclopentadienyl radicals, and benzynes that are not predicted by a fulvenallene pathway. Explicit PIMS searches for the cycloheptatrienyl radical were unsuccessful, there is no evidence for the isomerization of benzyl and cycloheptatrienyl radicals: C{sub 6}H{sub 5}CH{sub 2}⇋C{sub 7}H{sub 7}. These labeling studies suggest that there must be other thermal decomposition routes for the C{sub 6}H{sub 5}CH{sub 2} radical that differ from the fulvenallene pathway.

  1. Flavor, glucosinolates, and isothiocyanates of nau (Cook's scurvy grass, Lepidium oleraceum) and other rare New Zealand Lepidium species.

    PubMed

    Sansom, Catherine E; Jones, Veronika S; Joyce, Nigel I; Smallfield, Bruce M; Perry, Nigel B; van Klink, John W

    2015-02-18

    The traditionally consumed New Zealand native plant nau, Cook's scurvy grass, Lepidium oleraceum, has a pungent wasabi-like taste, with potential for development as a flavor ingredient. The main glucosinolate in this Brassicaceae was identified by LC-MS and NMR spectroscopy as 3-butenyl glucosinolate (gluconapin, 7-22 mg/g DM in leaves). The leaves were treated to mimic chewing, and the headspace was analyzed by solid-phase microextraction and GC-MS. This showed that 3-butenyl isothiocyanate, with a wasabi-like flavor, was produced by the endogenous myrosinase. Different postharvest treatments were used to create leaf powders as potential flavor products, which were tasted and analyzed for gluconapin and release of 3-butenyl isothiocyanate. A high drying temperature (75 °C) did not give major glucosinolate degradation, but did largely inactivate the myrosinase, resulting in no wasabi-like flavor release. Drying at 45 °C produced more pungent flavor than freeze-drying. Seven other Lepidium species endemic to New Zealand were also analyzed to determine their flavor potential and also whether glucosinolates were taxonomic markers. Six contained mostly gluconapin, but the critically endangered Lepidium banksii had a distinct composition including isopropyl glucosinolate, not detected in the other species. PMID:25625566

  2. Silica-Supported Oligomeric Benzyl Phosphate (Si-OBP) and Triazole Phosphate (Si-OTP) Alkylating Reagents.

    PubMed

    Maity, Pradip K; Faisal, Saqib; Rolfe, Alan; Stoianova, Diana; Hanson, Paul R

    2015-10-16

    The syntheses of silica-supported oligomeric benzyl phosphates (Si-OBP(n)) and triazole phosphates (Si-OTP(n)) using ring-opening metathesis polymerization (ROMP) for use as efficient alkylating reagents is reported. Ease of synthesis and grafting onto the surface of norbornenyl-tagged (Nb-tagged) silica particles has been demonstrated for benzyl phosphate and triazole phosphate monomers. It is shown that these silica polymer hybrid reagents, Si-OBP(n) and Si-OTP(n), can be used to carry out alkylation reactions with an array of different nucleophiles to afford the corresponding benzylated and (triazolyl)methylated products in good yield and high purity. PMID:26430955

  3. Final report on the safety assessment of Benzyl Alcohol, Benzoic Acid, and Sodium Benzoate.

    PubMed

    Nair, B

    2001-01-01

    Benzyl Alcohol is an aromatic alcohol used in a wide variety of cosmetic formulations as a fragrance component, preservative, solvent, and viscosity-decreasing agent. Benzoic Acid is an aromatic acid used in a wide variety of cosmetics as a pH adjuster and preservative. Sodium Benzoate is the sodium salt of Benzoic Acid used as a preservative, also in a wide range of cosmetic product types. Benzyl Alcohol is metabolized to Benzoic Acid, which reacts with glycine and excreted as hippuric acid in the human body. Acceptable daily intakes were established by the World Health Organization at 5 mg/kg for Benzyl Alcohol, Benzoic Acid, and Sodium Benzoate. Benzoic Acid and Sodium Benzoate are generally recognized as safe in foods according to the U.S. Food and Drug Administration. No adverse effects of Benzyl Alcohol were seen in chronic exposure animal studies using rats and mice. Effects of Benzoic Acid and Sodium Benzoate in chronic exposure animal studies were limited to reduced feed intake and reduced growth. Some differences between control and Benzyl Alcohol-treated populations were noted in one reproductive toxicity study using mice, but these were limited to lower maternal body weights and decreased mean litter weights. Another study also noted that fetal weight was decreased compared to controls, but a third study showed no differences between control and Benzyl Alcohol-treated groups. Benzoic Acid was associated with an increased number of resorptions and malformations in hamsters, but there were no reproductive or developmental toxicty findings in studies using mice and rats exposed to Sodium Benzoate, and, likewise, Benzoic Acid was negative in two rat studies. Genotoxicity tests for these ingredients were mostly negative, but there were some assays that were positive. Carcinogenicity studies, however, were negative. Clinical data indicated that these ingredients can produce nonimmunologic contact urticaria and nonimmunologic immediate contact reactions

  4. Apparatus and method for separating constituents

    DOEpatents

    Maronde, Carl P.; Killmeyer, Jr., Richard P.

    1992-01-01

    A centrifugal separator apparatus and method for improving the efficiency of the separation of constituents in a fluid stream. A cyclone separator includes an assembly for separately discharging both constituents through the same end of the separator housing. A rotary separator includes a rotary housing having a baffle disposed therein for minimizing the differential rotational velocities of the constituents in the housing, thereby decreasing turbulence, and increasing efficiency. The intensity of the centrifugal force and the time which the constituents reside within the housing can be independently controlled to improve efficiency of separation.

  5. Antitumor activity of phenethyl isothiocyanate in HER2-positive breast cancer models

    PubMed Central

    2012-01-01

    Background HER2 is an oncogene, expression of which leads to poor prognosis in 30% of breast cancer patients. Although trastuzumab is apparently an effective therapy against HER2-positive tumors, its systemic toxicity and resistance in the majority of patients restricts its applicability. In this study we evaluated the effects of phenethyl isothiocyanate (PEITC) in HER2-positive breast cancer cells. Methods MDA-MB-231 and MCF-7 breast cancer cells stably transfected with HER2 (high HER2 (HH)) were used in this study. The effect of PEITC was evaluated using cytotoxicity and apoptosis assay in these syngeneic cells. Western blotting was used to delineate HER2 signaling. SCID/NOD mice were implanted with MDA-MB-231 (HH) xenografts. Results Our results show that treatment of MDA-MB-231 and MCF-7 cells with varying concentrations of PEITC for 24 h extensively reduced the survival of the cells with a 50% inhibitory concentration (IC50) of 8 μM in MDA-MB-231 and 14 μM in MCF-7 cells. PEITC treatment substantially decreased the expression of HER2, epidermal growth factor receptor (EGFR) and phosphorylation of signal transducer and activator of transcription 3 (STAT3) at Tyr-705. The expression of BCL-2-associated × (BAX) and BIM proteins were increased, whereas the levels of B cell lymphoma-extra large (BCL-XL) and X-linked inhibitor of apoptosis protein (XIAP) were significantly decreased in both the cell lines in response to PEITC treatment. Substantial cleavage of caspase 3 and poly-ADP ribose polymerase (PARP) were associated with PEITC-mediated apoptosis in MDA-MB-231 and MCF-7 cells. Notably, transient silencing of HER2 decreased and overexpressing HER2 increased the effects of PEITC. Furthermore, reactive oxygen species (ROS) generation, mitochondrial depolarization and apoptosis by PEITC treatment were much higher in breast cancer cells expressing higher levels of HER2 (HH) as compared to parent cell lines. The IC50 of PEITC following 24 h of treatment was

  6. Benzyl Derivatives with in Vitro Binding Affinity for Human Opioid Receptors and Cannabinoid Receptors from the Fungus Eurotium repens

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Bioassay-guided fractionation of the fungus Eurotium repens resulted in the isolation of two benzyl derivatives, repenol A (1) and repenol B (2). Seven known secondary metabolites were also isolated including five benzaldehyde compounds, flavoglaucin (3), tetrahydroauroglaucin (4), dihydroauroglauci...

  7. A General, Simple Catalyst for Enantiospecific Cross Couplings of Benzylic Ammonium Triflates and Boronic Acids: No Phosphine Ligand Required

    PubMed Central

    Basch, Corey H.; Song, Ye-Geun; Watson, Mary P.

    2014-01-01

    Highly improved conditions for the enantiospecific cross coupling of benzylic ammonium triflates with boronic acids are reported. This method relies on the use of Ni(cod)2 without ancillary phosphine or N-heterocyclic carbene ligands as catalyst. These conditions enable the coupling of new classes of boronic acids and benzylic ammonium triflates. In particular, both heteroaromatic and vinyl boronic acids are well tolerated as coupling partners. In addition, these conditions enable the use of ammonium triflates with a variety of substituents at the benzylic stereocenter. Further, naphthyl-substitution is not required on the benzylic ammonium triflate; ammonium triflates with simple aromatic substituents also undergo this coupling. Good to high yields and levels of stereochemical fidelity are observed. This new catalyst system greatly expands the utility of enantiospecific cross couplings of these amine-derived substrates for the preparation of highly enantioenriched products. PMID:25364060

  8. [Chemical constituents of Dipsacus asper].

    PubMed

    Wang, Qiang; Liu, Er-Wei; Han, Li-Feng; Zhang, Yi

    2013-07-01

    To study the chemical constituents of Dipsacus asper, chromatographic methods such as D101 macroporous resin, silica gel, octadecylsilyl (ODS) column chromatographic techniques and preparative HPLC were used, and five compounds were isolated from 70% (v/v) ethanol extract of the plant. By using spectroscopic techniques including 1H NMR, 13C NMR, 1H-1H COSY, HSQC, HMBC and TOF-MS, the compounds were identified as 3beta-hydroxy-24-nor-urs-4 (23), 12-dien-28-oic acid (1), ursolic acid (2), oleanolic acid (3), 3-O-alpha-L-rhamnosyl(1 --> 3)-beta-D-glucopyranosyl (1 --> 3)-alpha-L-rhamnosyl (1 --> 2)-alpha-L-arabinopyranosyl hederagenin 28-O-beta-D-glucopyranosyl (1 --> 6)-beta-D-glucopyranosyl ester (4), 3-O-[beta-D-xylopyranosyl (1 --> 4)-beta-D-glucopyranosyl (1 --> 4)] [alpha-L-rhamnosyl(1 --> 3)]-beta-D-glucopyranosyl (1 --> 3)-alpha-L-rhamnosyl(1 --> 2)-alpha-L-arabinopyranosyl hederagenin (5), separately. Among them, 1 is a new compound, and 2 is isolated from this plant for the first time. PMID:24133979

  9. Chemical constituents of Saniculiphyllum guangxiense.

    PubMed

    Geng, Chang-An; Huang, Xiao-Yan; Lei, Li-Gong; Zhang, Xue-Mei; Chen, Ji-Jun

    2012-08-01

    The first phytochemical investigation on Saniculiphyllum guangxiense resulted in the isolation of two new triterpenoids, 16β-hydroxybryodulcosigenin (3) and 3α-O-feruloylolean-12-en-27-oic acid (6), together with six known compounds, menisdaurin (1), purshianin (2), oleanolic acid (4), 3β-hydroxyolean-12-en-27-oic acid (5), β-sitosterol (7), and daucosterol (8), which were characterized by extensive spectroscopic analyses and in one case by X-ray diffraction. According to this primary investigation, S. guangxiense is rich in nitrile glucosides and triterpenoids, of which menisdaurin (1; 0.06%) and purshianin (2; 0.015%) are the main constituents. Compounds 1-6 were assayed for their anti-hepatitis B virus (HBV) activities against the secretion of HBsAg and HBeAg, as well as HBV DNA replication on Hep G 2.2.15 cell line in vitro. The most active compound, menisdaurin (1), inhibits HBV DNA replication with an IC(50) value of 0.32 mM (SI>11.97). PMID:22899611

  10. [Chemical constituents of Lepidium meyenii].

    PubMed

    Liang, Wen-juan; Xu, Hong-bo; Yang, Cai-yan; Geng, Chang-an; Zhang Xue-mei; Chen, Ji-jun

    2015-12-01

    To study the chemical constituents of Lepidium meyenii, the air-dried rhizome of L. meyenii was extracted with 70% EtOH. The extract was condensed to a small amount of volume and extracted with petroleum ether, EtOAc and n-BuOH, successively. The compounds were isolated and purified by column chromatography, and identified based on spectral analyses (1H-NMR, 13C-NMR, HRESIMS). Eighteen compounds were isolated from L. meyenii, including 7 alkaloids and 4 fatty acids and 7 other compounds. They were characterized as (3-hydroxybenzyl) carbamic acid(1), phenylmethanamine(2), N-benzylformamide (3), N-benzylacetamide (4), pyridin-4-ylmethanamine(5), n-(4-methoxybenzyl) aniline(6), uracil(7), succininc acid(8), decanedioic acid(9), n-hexa- decanoic acid methyl ester(10), heptanoic acid(11), solerole(12), pyromucic acid methyl ester(13), 5-hydroxymethyl-2-furancar- boxadehyde(14), 5-(methoxymethyl)-1H-pyrrole-2-carbaldehyde(15), 1,7-dihydroxy-2,3, 4-trimethoxyxanthone (16), 1,7-di- hydroxy-3,4- dimethoxy-xanthone(17), (+)-pinoresinol(18). Meanwhile, compounds 1-18 were obtained from L. neyenii for the first time. PMID:27141659

  11. [Chemical constituents from Euphorbia lunulata].

    PubMed

    Zhao, Ming; Wu, Shuang; Li, Jun; Tang, Wan-Xia; Wang, Jin-Lan; Zhang, Shu-Jun

    2014-06-01

    The chemical constituents from Euphorbia lunulata was investigated in this paper. Fourteen compounds were isolated and purified by column chromatographies on silica gel and preparative HPLC. Their structures were identified by physiochemical properties and NMR data analysis as lupeol (1), euphol (2), cassipourol(3) , 24-methylenecycloartan-3beta-ol (4), 24-hydroperoxycycloart-25-en-3beta-ol (5), 25-hydroperoxycycloart-23-en-3beta-ol (6), betulin (7), uvaol (8), (23E) -25-methoxycycloart-23-en-3beta-ol (9), (23E) -cycloart-23,25-dien-3beta-ol (10), 24-methylenecycloartan-3beta, 28-diol (11), salicinolide (12), 2alpha, 3beta, 5alpha, 9alpha, 15beta-pentaacetoxy-11,12-epoxy-7beta, 8alpha-diisobutyryloxyjatropha-6 (17) -en-14-one (13) and 3beta, 5alpha, 15beta-triacetoxy-7beta-isobutyryloxy-9alpha-nicotinoyloxyjatropha-6 (17), 11(E)-dien-14-one (14). Among them, compounds 1-11 were isolated from E. lunulata for the first time. PMID:25244761

  12. [Chemical constituents from Cinnamomum cassia].

    PubMed

    He, Shan; Jiang, Yong; Tu, Peng-fei

    2015-09-01

    Various column chromatography, such as silica gel, Sephadex LH-20, ODS, and semi-preparative HPLC was used to isolate and purify the chemical constituents from Cinnamomum cassia. The structures were determined on the basis of NMR and MS spectral data analysis, together with the comparison with literature data. Fifteen compounds were isolated from the 85% aqueous ethanol extract of C. cassia, and their structures were identified as (2R, 3R)-5,7,3',4'-tetramethoxyflavan-3-ol( 1), (2R, 3R)-5,7-dimethoxy-3',4'-methylenedioxyflavan-3-ol (2), coumarin (3), cinnamic acid (4), (E)-2-hydroxy-phenylpropionic acid cinnamoyl ester (5), 3, 3', 4, 4'-tetrahydroxy biphenyl (6), methylstictic acid (7), epi-boscialin (8), (1R,2S,3S,4S)-2,3-epoxy-1, 4-dihydroxy-5-methyl-5-cyelohexene (9), 4,5-dihydroxy-3-methyl cyclohex-2-enone (10), cis-4-hydroxymellein (11), and 2-hydroxy-4-methoxyl-cinnamaldehyde (12). Compounds 5-11 were obtained from this genus plants for the first time. PMID:26983207

  13. Mechanism for benzyl alcohol-induced aggregation of recombinant human interleukin-1 receptor antagonist in aqueous solution.

    PubMed

    Zhang, Ye; Roy, Shouvik; Jones, Latoya S; Krishnan, Sampathkumar; Kerwin, Bruce A; Chang, Byeong S; Manning, Mark C; Randolph, Theodore W; Carpenter, John F

    2004-12-01

    Benzyl alcohol, an antimicrobial preservative, accelerates aggregation and precipitation of recombinant human interleukin-1 receptor antagonist (rhIL-1ra) in aqueous solution. The loss of native monomer during incubation at 37 degrees C was determined by analysis of sample aliquots with size exclusion high performance liquid chromatography (SE-HPLC). Benzyl alcohol caused minor perturbation of the tertiary structure of the protein without changing its secondary structure, documenting that the preservative caused a minor shift in the protein molecular population toward partially unfolded species. Consistent with this conclusion, in the presence of benzyl alcohol the rate of H-D exchange was accelerated and the fluorescence of 1-anilinonaphthalene-8-sulfonic acid in the presence of rhIL1ra was increased. Benzyl alcohol did not alter the free energy of unfolding based on unfolding experiments in urea or guanidine HCl. With differential scanning calorimetry it was determined that benzyl alcohol reduced the apparent Tm of rhIL-1ra, but this effect occurred because the preservative lowered the temperature at which the protein aggregated during heating. Isothermal calorimetry documented that the interaction of benzyl alcohol with rhIL-1ra is relatively weak and hydrophobically driven. Thus, benzyl alcohol accelerates protein aggregation by binding to the protein and favoring an increase in the level of partially unfolded, aggregation-competent species. Sucrose partially inhibited benzyl alcohol-induced aggregation and tertiary structural change. Sucrose is preferentially excluded from the surface of the protein, favoring most compact native state species over expanded aggregation-prone forms. PMID:15514986

  14. Palladium-Catalyzed Asymmetric Benzylic Alkylation of Active Methylene Compounds with α-Naphthylbenzyl Carbonates and Pivalates.

    PubMed

    Tabuchi, Sho; Hirano, Koji; Miura, Masahiro

    2016-06-01

    A Pd/(R)-H8 -BINAP-catalyzed asymmetric benzylic alkylation of active methylene compounds has been developed. The reaction proceeds without the use of an external base, and the starting racemic diarylmethyl carbonates are converted into the optically active coupling products which contain the benzylic chiral stereocenter by a dynamic kinetic asymmetric transformation (DYKAT). Additionally, with suitable carbonates bases, the same palladium catalysis allows the corresponding pivalates to be adopted in the same DYKAT process. PMID:27120184

  15. Crystal structures of HIV-1 nonnucleoside reverse transcriptase inhibitors: N-benzyl-4-methyl-benzimidazoles

    NASA Astrophysics Data System (ADS)

    Ziółkowska, Natasza E.; Michejda, Christopher J.; Bujacz, Grzegorz D.

    2009-07-01

    HIV-1 nonnucleoside reverse transcriptase inhibitors are potentially specific and effective drugs in AIDS therapy. The presence of two aromatic systems with an angled orientation in the molecule of the inhibitor is crucial for interactions with HIV-1 RT. The inhibitor drives like a wedge into the cluster of aromatic residues of RT HIV-1 and restrains the enzyme in a conformation that blocks the chemical step of nucleotide incorporation. Structural studies provide useful information for designing new, more active inhibitors. The crystal structures of four NNRTIs are presented here. The investigated compounds are derivatives of N-benzyl-4-methyl-benzimidazole with various aliphatic and aromatic substituents at carbon 2 positions and a 2,6-dihalogeno-substituted N-benzyl moiety. Structural data reported here show that the conformation of the investigated compounds is relatively rigid. Such feature is important for the nonnucleoside inhibitor binding to HIV-1 reverse transcriptase.

  16. Spectroscopic identification of benzyl-type radicals generated by corona discharge of 2-chloro-4-fluorotoluene.

    PubMed

    Huh, Chang Soon; Yoon, Young Wook; Lee, Sang Kuk

    2012-05-01

    By means of a technique of corona excited supersonic expansion coupled with a pinhole-type glass nozzle, we generated vibronically excited but jet-cooled benzyl-type radicals from precursor 2-chloro-4-fluorotoluene seeded in a large amount of inert carrier gas He. From an analysis of the visible vibronic emission spectrum, we found evidence of the formation of the 2-chloro-4-fluorobenzyl and 4-fluorobenzyl radicals. A possible pathway for the formation of these benzyl-type radicals is herein proposed. Also, the electronic energy in the D(1) → D(0) transition and the vibrational mode frequencies of the 2-chloro-4-fluorobenzyl radical in the ground electronic state were accurately determined, for the first time, by comparison with ab initio calculations and the known vibrational data of the precursor. PMID:22583229

  17. Developmental toxicity of benzyl benzoate in rats after maternal exposure throughout pregnancy.

    PubMed

    Koçkaya, E Arzu; Kılıç, Aysun

    2014-01-01

    The maternal and fetal toxicity of benzyl benzoate, commonly used as antiparasitic insecticide, was evaluated in pregnant rats after a daily oral dose of 25 and 100 mg/kg. Biochemical, histopathological, and morphological examinations were performed. Dams were observed for maternal body weights and food and water consumption and subjected to caesarean section on (GD) 20. Maternal and fetal liver, kidney, heart, brain, and placenta were examined histopathologically under light microscope. Maternal and fetal liver and placenta were stained immunohistochemically for vascular endothelial growth factor (VEGF). Morphometric analysis of fetal body lengths, placental measurements, and fetal skeletal stainings was performed. Statistically significant alterations in biochemical parameters and placental and skeletal measurements were determined in treatment groups. In addition to histopathological changes, considerable differences were observed in the immunolocalization of VEGF in treatment groups. These results demonstrated that benzyl benzoate and its metabolites can transport to the placenta and eventually enter the fetuses. PMID:21922633

  18. Isosorbide-2-benzyl carbamate-5-salicylate, a peripheral anionic site binding subnanomolar selective butyrylcholinesterase inhibitor.

    PubMed

    Carolan, Ciaran G; Dillon, Gerald P; Khan, Denise; Ryder, Sheila A; Gaynor, Joanne M; Reidy, Sean; Marquez, Juan F; Jones, Mike; Holland, Valerie; Gilmer, John F

    2010-02-11

    Isosorbide-2-benzyl carbamate-5-benzoate is a highly potent and selective BuChE inhibitor. Meanwhile, isosorbide-2-aspirinate-5-salicylate is a highly effective aspirin prodrug that relies on the salicylate portion to interact productively with human BuChE. By integrating the salicylate group into the carbamate design, we have produced isosorbide-2-benzyl carbamate-5-salicylate, an inhibitor of high potency (150 pM) and selectivity for human BuChE over AChE (666000) and CES2 (23000). Modeling and mutant studies indicate that it achieves its exceptional potency because of an interaction with the polar D70/Y332 cluster in the PAS of BuChE in addition to pseudosubstrate interactions with the active site. PMID:20067290

  19. Cobalt co-catalysis for cross-electrophile coupling: diarylmethanes from benzyl mesylates and aryl halides†

    PubMed Central

    2014-01-01

    The nickel-catalyzed cross-coupling of aryl halides with alkyl radicals derived from alkyl halides has recently been extended to couplings with carbon radicals generated by a co-catalyst. In this study, a new co-catalyst, cobalt phthalocyanine (Co(Pc)), is introduced and demonstrated to be effective for coupling substrates not prone to homolysis. This is because Co(Pc) reacts with electrophiles by an SN2 mechanism instead of by the electron-transfer or halogen abstraction mechanisms previously explored. Studies demonstrating the orthogonal reactivity of (bpy)Ni and Co(Pc), applying this selectivity to the coupling of benzyl mesylates with aryl halides, and the adaptation of these conditions to the less reactive benzyl phosphate ester and an enantioconvergent reaction are presented. PMID:25685312

  20. Isothiocyanate-functionalized bifunctional chelates and fac-[MI(CO)3]+ (M = Re, 99mTc) complexes for targeting uPAR in prostate cancer

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Developing strategies to rapidly incorporate the fac-[MI(CO)3]+ (M = Re, 99mTc) core into biological targeting vectors is a growing realm in radiopharmaceutical development. This work presents the preparation of a novel isothiocyanate-functionalized bifunctional chelate based on 2,2´-dipicolylamine ...

  1. Development of a liquid chromatography-electrospray ionization-tandem mass spectrometry method for the simultaneous analysis of intact glucosinolates and isothiocyanates in Brassicaceae seeds and functional foods.

    PubMed

    Franco, P; Spinozzi, S; Pagnotta, E; Lazzeri, L; Ugolini, L; Camborata, C; Roda, A

    2016-01-01

    A new high pressure liquid chromatography-electrospray ionization-tandem mass spectrometry method for the simultaneous determination of glucosinolates, as glucoraphanin and glucoerucin, and the corresponding isothiocyanates, as sulforaphane and erucin, was developed and applied to quantify these compounds in Eruca sativa defatted seed meals and enriched functional foods. The method involved solvent extraction, separation was achieved in gradient mode using water with 0.5% formic acid and acetonitrile with 0.5% formic acid and using a reverse phase C18 column. The electrospray ion source operated in negative and positive mode for the detection of glucosinolates and isothiocyanates, respectively, and the multiple reaction monitoring (MRM) was selected as acquisition mode. The method was validated following the ICH guidelines. Replicate experiments demonstrated a good accuracy (bias%<10%) and precision (CV%<10%). Detection limits and quantification limits are in the range of 1-400ng/mL for each analytes. Calibration curves were validated on concentration ranges from 0.05 to 50μg/mL. The method proved to be suitable for glucosinolates and isothiocyanates determination both in biomasses and in complex matrices such as food products enriched with glucosinolates, or nutraceutical bakery products. In addition, the developed method was applied to the simultaneous determination of glucosinolates and isothiocyanates in bakery product enriched with glucosinolates, to evaluate their thermal stability after different industrial processes from cultivation phases to consumer processing. PMID:26363943

  2. 21 CFR 610.15 - Constituent materials.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 7 2014-04-01 2014-04-01 false Constituent materials. 610.15 Section 610.15 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) BIOLOGICS GENERAL BIOLOGICAL PRODUCTS STANDARDS General Provisions § 610.15 Constituent materials. (a)...

  3. 21 CFR 610.15 - Constituent materials.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 7 2013-04-01 2013-04-01 false Constituent materials. 610.15 Section 610.15 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) BIOLOGICS GENERAL BIOLOGICAL PRODUCTS STANDARDS General Provisions § 610.15 Constituent materials. (a)...

  4. Constituency Leadership: A Model for School Leaders.

    ERIC Educational Resources Information Center

    Strodl, Peter

    Principals must integrate information originating from many sectors among the schools' constituents. The degree to which constituent groups participate in school activities helps determine the quality of instruction and learning. Crucial to the role of administrator is a network of interactions between people and things, school board pressures and…

  5. C-C Coupling of Benzyl Fluorides Catalyzed by an Electrophilic Phosphonium Cation.

    PubMed

    Zhu, Jiangtao; Pérez, Manuel; Stephan, Douglas W

    2016-07-11

    The activation and cleavage of benzyl fluorides by the electrophilic organofluorophosphonium catalyst, [(C6 F5 )3 PF][B(C6 F5 )4 ], is reported and used for the preparation of 1,1-diarylalkanes (37 examples) and substituted aryl homoallylic alkenes (14 examples). This procedure involves mild conditions, avoids harmful waste, and is compatible with a range of substituted arenes and allylic silanes. PMID:27239806

  6. Inactivation of monoamine oxidase B by benzyl 1-(aminomethyl) cyclopropane-1-carboxylate.

    PubMed

    Silverman, R B; Lu, X; Blomquist, G D; Ding, C Z; Yang, S

    1997-02-01

    Monoamine oxidase (MAO) is a flavoenzyme that catalyzes the oxidation of various biogenic and xenobiotic amines. Benzyl 1-(aminomethyl)cyclopropane-1-carboxylate (1) was designed as a diactivated cyclopropane mechanism-based inactivator of MAO (Silverman, R.B.: Ding, C.Z.; Borrillo, J.L.; Chang, J.T.J. Am. Chem. Soc. 1993, 115, 2982). [1,1-2H2]-1 exhibits a deuterium isotope effect of 4.5 on inactivation, but in D2O the isotope effect is only 2.3. [1-3H]-1 and [1-14C]-1 were synthesized; upon inactivation of MAO, 1.1 and 2.0 equiv of radioactivity, respectively, are incorporated into the enzyme. Tritium as 3H2O, is released during inactivation with [1-3H]-1. The flavin absorption spectrum changes from that of oxidized to that of reduced flavin after inactivation; denaturation of the inactivated enzyme shows a reduced flavin spectrum, suggesting the formation of a modified flavin. Tryptic digestion of the enzyme labeled with [1-3H]-1 or [1-14C]-1, followed by HPLC analysis, monitoring at 310 nm [corrected] (flavin), shows that the radioactivity comigrates with the 310 nm [corrected] absorptions. The metabolites that are generated during inactivation are benzyl 1-formylcyclopropane-1-carboxylate, benzyl alcohol, and 1-formylcyclopropane-1-carboxylic acid; no ring-cleaved products were detected. The partition ratio, as determined from the ratio of nonamines to enzyme, is 110. These results are rationalized in terms of a single-electron transfer mechanism leading to the imine of benzyl 1-formylcyclopropane-1-carboxylate, which alkylates the flavin coenzyme. PMID:9061194

  7. Nickel-Catalyzed Asymmetric Reductive Cross-Coupling Between Vinyl and Benzyl Electrophiles

    PubMed Central

    2015-01-01

    A Ni-catalyzed asymmetric reductive cross-coupling between vinyl bromides and benzyl chlorides has been developed. This method provides direct access to enantioenriched products bearing aryl-substituted tertiary allylic stereogenic centers from simple, stable starting materials. A broad substrate scope is achieved under mild reaction conditions that preclude the pregeneration of organometallic reagents and the regioselectivity issues commonly associated with asymmetric allylic arylation. PMID:25245492

  8. Antifungal activities of major tea leaf volatile constituents toward Colletorichum camelliae Massea.

    PubMed

    Zhang, Zheng-Zhu; Li, Ying-Bo; Qi, Li; Wan, Xiao-Chun

    2006-05-31

    A crude glycosidic fraction was prepared from fresh tea leaves and treated with the crude tea enzyme, fractions of cis-3-hexenol, linalool oxide I (cis-furanoid), linalool oxide II (trans-furanoid), linalool, methyl salicylate, geraniol, benzyl alcohol, and 2-phenylethanol were monitored to be the major aglycone moieties by analyzing the released volatiles. The amount of the released aglycone moieties is 5.8 times higher than those in free form. For investigation of the functions of the glycosidically bound form aroma constituents in tea leaves, their antifungal activities were determined by antifungal assay. Geraniol, linalool, methyl salicylate, benzyl alcohol, and 2-phenylethanol exhibited significant antifungal activities toward Colletorichum camelliae Massea, although cis-3-hexenol and linalool oxides showed weaker activities by comparison. Among them, geraniol was shown to be the most potential antifungal substance with a MIC value of 440 microg/mL. The crude glycosidic fraction prepared from tea leaves also exhibited significant antifungal activities in a wide range of concentrations from 2 to 25 mg/mL in a PDA medium. It was deduced that the glycosidically bound volatiles are formed and stored in the intact tissue of tea leaf and hydrolyzed by the actions of both the endogenous and the exogenous glycosidases to release volatiles as antifungal substances when exposed to Colletorichum camelliae Massea. The results suggested that the higher content of the bound form geraniol in tea leaves of var. sinensis might be responsible for their stronger antipathogen properties toward tea leaf blight, as opposed to those of var. assamica. PMID:16719518

  9. Nonequilibrium hadronization and constituent quark number scaling

    SciTech Connect

    Zschocke, Sven; Horvat, Szabolcs; Mishustin, Igor N.; Csernai, Laszlo P.

    2011-04-15

    The constituent quark number scaling of elliptic flow is studied in a nonequilibrium hadronization and freeze-out model with rapid dynamical transition from ideal, deconfined, and chirally symmetric quark-gluon plasma, to final noninteracting hadrons. In this transition a bag model of constituent quarks is considered, where the quarks gain constituent quark mass while the background bag field breaks up and vanishes. The constituent quarks then recombine into simplified hadron states, while chemical, thermal, and flow equilibrium break down one after the other. In this scenario the resulting temperatures and flow velocities of baryons and mesons are different. Using a simplified few source model of the elliptic flow, we are able to reproduce the constituent quark number scaling, with assumptions on the details of the nonequilibrium processes.

  10. Thermal Decomposition of C7H7 Radicals; Benzyl, Tropyl, and Norbornadienyl

    NASA Astrophysics Data System (ADS)

    Buckingham, Grant; Ellison, Barney; Daily, John W.; Ahmed, Musahid

    2015-06-01

    Benzyl radical (C6H5CH2) and two other C7H7 radicals are commonly encountered in the combustion of substituted aromatic compounds found in biofuels and gasoline. High temperature pyrolysis of benzyl radical requires isomerization to other C7H7 radicals that may include cycloheptatrienyl (tropyl) radical (cyc-C7H7) and norbornadienyl radical. The thermal decomposition of all three radicals has now been investigated using a micro-reactor that heats dilute gas-phase samples up to 1600 K and has a residence time of about 100 μ-sec. The pyrolysis products exit the reactor into a supersonic expansion and are detected using synchrotron-based photoionization mass spectrometry and matrix-isolation IR spectroscopy. The products of the pyrolysis of benzyl radical (C6H5CH2) along with three isotopomers (C6H513CH2, C6D5CH2, and C6H5CD2) were detected and identified. The distribution of 13C atoms and D atoms indicate that multiple different decomposition pathways are active. Buckingham, G. T., Ormond, T. K., Porterfield, J. P., Hemberger, P., Kostko, O., Ahmed, M., Robichaud, D. J., Nimlos, M. R., Daily, J. W., Ellison, G. B. 2015, Journal of Chemical Physics 142 044307

  11. Synthesis and Biological Screening of 4-Benzyl-2H-phthalazine Derivatives

    PubMed Central

    El-Wahab, Ashraf H.F. Abd; Mohamed, Hany M.; El-Agrody, Ahmed M.; El-Nassag, Mohammed A.; Bedair, Ahmed H.

    2011-01-01

    Preparation of 4-benzyl-2-substituted phthalazin-1-one derivatives 2-8 is reported. Condensation of 4-benzyl-1-chlorophthalazine (9) with a series of different nucleophiles gave 4-benzylphthalazin-1-ylamino derivatives (10-13 and 16) and 4-amino-2-[N′-(4-benzylphthalazin-1-yl)-hydrazino]-6-arylpyrimidine-5-carbonitriles (14a,b). Interaction of 9 with ambident anions was also studied. 5-Benzyl-6,6a,12-triazobenzo[a]-anthracen-7-one (15) is obtained from 9 and anthranilic acid derivatives. Treatment of 16 with (EtO)3CH/Ac2O under reflux afforded the corresponding ethoxymethylene derivative 17, while aqueous ammonium hydroxide treatment afforded carboxamide derivative 18. The structures of the newly synthesized derivatives were confirmed by their elemental analysis, IR, 1H NMR, 13C NMR and mass spectral studies. Antimicrobial activities of some selected compounds were also studied and some of these were found to exhibit promising effects against Gram-positive and Gram-negative bacteria and fungi.

  12. Reversed Electron Apportionment in Mesolytic Cleavage: The Reduction of Benzyl Halides by SmI2.

    PubMed

    Yitzhaki, Offir; Hoz, Shmaryahu

    2015-06-15

    The paradigm that the cleavage of the radical anion of benzyl halides occurs in such a way that the negative charge ends up on the departing halide leaving behind a benzyl radical is well rooted in chemistry. By studying the kinetics of the reaction of substituted benzylbromides and chlorides with SmI2 in THF it was found that substrates para-substituted with electron-withdrawing groups (CN and CO2 Me), which are capable of forming hydrogen bonds with a proton donor and coordinating to samarium cation, react in a reversed electron apportionment mode. Namely, the halide departs as a radical. This conclusion is based on the found convex Hammett plots, element effects, proton donor effects, and the effect of tosylate (OTs) as a leaving group. The latter does not tend to tolerate radical character on the oxygen atom. In the presence of a proton donor, the tolyl derivatives were the sole product, whereas in its absence, the coupling dimer was obtained by a SN 2 reaction of the benzyl anion on the neutral substrate. The data also suggest that for the para-CN and CO2 Me derivatives in the presence of a proton donor, the first electron transfer is coupled with the proton transfer. PMID:25965697

  13. Electron spin resonance of transient radicals during pyrolysis and photolysis. Benzyl ether

    SciTech Connect

    Livingston, R.; Zeldes, H.

    1983-03-17

    Benzyl ether has been pyrolyzed at 452, 474, and 497/sup 0/C at a pressure of 20.7 MPa. Benzyl has been observed by ESR, and product analyses have been made. The reaction C/sub 6/H/sub 5/CHOCH/sub 2/C/sub 6/H/sub 5/ ..-->.. C/sub 6/H/sub 5/CHO + C/sub 6/H/sub 5/CH/sub 2/ is part of a proposed scheme. This reaction was separately studied photolytically by preparing the reactant radical with benzyl ether and an initiator in benzene solution. Measurements from 105 to 155/sup 0/C at 6.9 MPa gave an activation energy of 15.5 kcal/mol (+-15%) and an estimate of the Arrhenius A factor of 1 x 10/sup 12/ s/sup -1/. The various results are discussed in terms of a free-radical chain reaction. Methylcyclohexadienyl was also prepared, and ESR parameters are given.

  14. Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases

    SciTech Connect

    He, Jiayue; Lu, Lu; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

    2014-03-01

    Catalytic pathways for the cleavage of ether bonds in benzyl phenyl ether (BPE) in liquid phase using Ni- and zeolite-based catalysts are explored. In the absence of catalysts, the C-O bond is selectively cleaved in water by hydrolysis, forming phenol and benzyl alcohol as intermediates, followed by alkylation. The hydronium ions catalyzing the reactions are provided by the dissociation of water at 523 K. Upon addition of HZSM-5, rates of hydrolysis and alkylation are markedly increased in relation to proton concentrations. In the presence of Ni/SiO2, the selective hydrogenolysis dominates for cleaving the Caliphatic-O bond. Catalyzed by the dual-functional Ni/HZSM-5, hydrogenolysis occurs as the major route rather than hydrolysis (minor route). In apolar undecane, the non-catalytic thermal pyrolysis route dominates. Hydrogenolysis of BPE appears to be the major reaction pathway in undecane in the presence of Ni/SiO2 or Ni/HZSM-5, almost completely suppressing radical reactions. Density functional theory (DFT) calculations strongly support the proposed C-O bond cleavage mechanisms on BPE in aqueous and apolar phases. These calculations show that BPE is initially protonated and subsequently hydrolyzed in the aqueous phase. Finally, DFT calculations suggest that the radical reactions in non-polar solvents lead to primary benzyl and phenoxy radicals in undecane, which leads to heavier condensation products as long as metals are absent for providing dissociated hydrogen.

  15. Blood–brain barrier transport studies, aggregation, and molecular dynamics simulation of multiwalled carbon nanotube functionalized with fluorescein isothiocyanate

    PubMed Central

    Shityakov, Sergey; Salvador, Ellaine; Pastorin, Giorgia; Förster, Carola

    2015-01-01

    In this study, the ability of a multiwalled carbon nanotube functionalized with fluorescein isothiocyanate (MWCNT–FITC) was assessed as a prospective central nervous system-targeting drug delivery system to permeate the blood–brain barrier. The results indicated that the MWCNT–FITC conjugate is able to penetrate microvascular cerebral endothelial monolayers; its concentrations in the Transwell® system were fully equilibrated after 48 hours. Cell viability test, together with phase-contrast and fluorescence microscopies, did not detect any signs of MWCNT–FITC toxicity on the cerebral endothelial cells. These microscopic techniques also revealed presumably the intracellular localization of fluorescent MWCNT–FITCs apart from their massive nonfluorescent accumulation on the cellular surface due to nanotube lipophilic properties. In addition, the 1,000 ps molecular dynamics simulation in vacuo discovered the phenomenon of carbon nanotube aggregation driven by van der Waals forces via MWCNT–FITC rapid dissociation as an intermediate phase. PMID:25784800

  16. Derivatives of the triaminoguanidinium ion, 3. Multiple N-functionalization of the triaminoguanidinium ion with isocyanates and isothiocyanates

    PubMed Central

    Szabo, Jan; Karger, Kerstin; Bucher, Nicolas

    2014-01-01

    Summary 1,2,3-Triaminoguanidinium chloride was combined with benzaldehyde and hydratropic aldehyde to furnish the corresponding tris(imines), which were converted into 1,2,3-tris(benzylamino)guanidinium salts by catalytic hydrogenation in the former, and by borane reduction in the latter case. The resulting alkyl-substituted triaminoguanidinium salts underwent a threefold carbamoylation with aryl isocyanates to furnish 1,2,3-tris(ureido)guanidinium salts, while p-toluenesulfonyl isocyanate led only to a mono-ureido guanidinium salt. With aryl isothiocyanates, 3-hydrazino-1H-1,2,4-triazole-5(4H)-thione derivatives were obtained. Compounds 7a and 8 show interesting solid-state structures with intra- and intermolecular hydrogen bonds. PMID:25298792

  17. Derivatives of the triaminoguanidinium ion, 3. Multiple N-functionalization of the triaminoguanidinium ion with isocyanates and isothiocyanates.

    PubMed

    Szabo, Jan; Karger, Kerstin; Bucher, Nicolas; Maas, Gerhard

    2014-01-01

    1,2,3-Triaminoguanidinium chloride was combined with benzaldehyde and hydratropic aldehyde to furnish the corresponding tris(imines), which were converted into 1,2,3-tris(benzylamino)guanidinium salts by catalytic hydrogenation in the former, and by borane reduction in the latter case. The resulting alkyl-substituted triaminoguanidinium salts underwent a threefold carbamoylation with aryl isocyanates to furnish 1,2,3-tris(ureido)guanidinium salts, while p-toluenesulfonyl isocyanate led only to a mono-ureido guanidinium salt. With aryl isothiocyanates, 3-hydrazino-1H-1,2,4-triazole-5(4H)-thione derivatives were obtained. Compounds 7a and 8 show interesting solid-state structures with intra- and intermolecular hydrogen bonds. PMID:25298792

  18. Inhibition of mutagenicity of food-derived heterocyclic amines by sulphoraphene--an isothiocyanate isolated from radish.

    PubMed

    Shishu; Singla, A K; Kaur, I P

    2003-02-01

    The naturally derived isothiocyanate, sulphoraphene [4-isothiocyanato-(1R)-(methylsulphinyl)-1-(E)-butene], isolated from seeds of radish ( Raphanus sativus L., Cruciferae) was investigated for its antigenotoxic effects against a battery of cooked food mutagens (heterocyclic amines) in the Ames Salmonella/reversion assay using Salmonella typhimurium TA98 (frame-shift mutation sensitive) and TA100 (base -pair mutation sensitive) bacterial strains in the presence of Aroclor 1254 induced rat liver S9. Results of the present in vitro anti-mutagenicity studies using the base-pair mutation sensitive strain TA100, strongly suggest that sulphoraphene is a potent inhibitor of the S9-mediated mutagenicity of all the tested heterocyclic amines (60 - 75 % inhibition at a dose of 500 nmol/plate). PMID:12624832

  19. Fluorescein Isothiocyanate-Labeled Lectin Analysis of the Surface of the Nitrogen-Fixing Bacterium Azospirillum brasilense by Flow Cytometry

    PubMed Central

    Yagoda-Shagam, Janet; Barton, Larry L.; Reed, William P.; Chiovetti, Robert

    1988-01-01

    The cell surface of Azospirillum brasilense was probed by using fluorescein isothiocyanate (FITC)-labeled lectins, with binding determined by fluorescence-activated flow cytometry. Cells from nitrogen-fixing or ammonium-assimilating cultures reacted similarly to FITC-labeled lectins, with lectin binding in the following order: Griffonia simplicifolia II agglutinin > Griffonia simplicifolia I agglutinin > Triticum vulgaris agglutinin > Glycine max agglutinin > Canavalia ensiformis agglutinin > Limax flavus agglutinin > Lotus tetragonolobus agglutinin. The fluorescence intensity of cells labeled with FITC-labeled G. simplicifolia I, C. ensiformis, T. vulgaris, and G. max agglutinins was influenced by lectin concentration. Flow cytometry measurements of lectin binding to cells was consistent with measurements of agglutination resulting from lectin-cell interaction. Capsules surrounding nitrogen-fixing and ammonium-assimilating cells were readily demonstrated by light and transmission electron microscopies. Images PMID:16347693

  20. Dietary isothiocyanates, glutathione S-transferase -M1, -T1 polymorphisms and lung cancer risk among Chinese women in Singapore.

    PubMed

    Zhao, B; Seow, A; Lee, E J; Poh, W T; Teh, M; Eng, P; Wang, Y T; Tan, W C; Yu, M C; Lee, H P

    2001-10-01

    Chinese populations consume a diet relatively high in isothiocyanates (ITCs), a derivative of cruciferous vegetables known to have cancer-protective effects. This class of compounds is metabolized by the glutathione S-transferase family of enzymes, which are also involved in the detoxification of tobacco-related carcinogens such as polycyclic aromatic hydrocarbons and alkyl halides. We evaluated the association between dietary isothiocyanate intake, GSTM1 and GSTT1 polymorphisms, and lung cancer risk in 420 Chinese women: 233 histologically confirmed lung cancer patients and 187 hospital controls. Among these, 58.8% of cases and 90.3% of controls were lifetime nonsmokers. An allele-specific PCR method was used to detect the presence or absence of the GSTM1 and GSTT1 genes in DNA isolated from peripheral blood. Higher weekly intake of ITCs (above the control median value of 53.0 micromol) reduced the risk of lung cancer to a greater extent in smokers [adjusted odds ratio (OR), 0.31; 95% confidence interval (CI), 0.10-0.98] than nonsmokers (OR, 0.70; 95% CI, 0.45-1.11). The inverse association was stronger among subjects with homozygous deletion of GSTM1 and/or GSTT1. Among nonsmokers with GSTM1-null genotype, higher intake of ITCs significantly reduced the risk of lung cancer (OR, 0.54; 95% CI, 0.30-0.95), an effect not seen among those with detectable GSTM1 (OR, 1.07; 95% CI, 0.50-2.29). Our results, in a Chinese female population, are consistent with the hypothesis that ITC is inversely related to the risk of lung cancer, and we show that among nonsmokers this effect may be primarily confined to GST-null individuals. Conjugation and elimination of ITCs is enhanced in GST-non-null relative to -null individuals, such that the GST metabolic genotype modifies the protective effect of ITCs on lung cancer development. PMID:11588132

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

    PubMed Central

    Hanschen, Franziska S.; Yim, Bunlong; Winkelmann, Traud; Smalla, Kornelia; Schreiner, Monika

    2015-01-01

    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. PMID:26186695

  2. Iron depletion in HCT116 cells diminishes the upregulatory effect of phenethyl isothiocyanate on heme oxygenase-1.

    PubMed

    Bolloskis, Michael P; Carvalho, Fabiana P; Loo, George

    2016-04-15

    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. PMID:26945724

  3. (2E,5E)-2,5-Bis(4-hy­droxy-3-meth­oxy­benzyl­idene)cyclo­penta­none ethanol monosolvate

    PubMed Central

    Da’i, Muhammad; Yanuar, Arry; Meiyanto, Edy; Jenie, Umar Anggara; Supardjan, Amir Margono

    2013-01-01

    In the title structure, C21H20O5·C2H5OH, the curcumine-type mol­ecule has a double E conformation for the two benzyl­idene double bonds [C=C = 1.342 (4) and 1.349 (4) Å] and is nearly planar with respect to the non-H atoms (r.m.s. deviation from planarity = 0.069 Å). The two phenolic OH groups form bifurcated hydrogen bonds with intra­molecular branches to adjacent meth­oxy O atoms and inter­molecular branches to either a neighbouring mol­ecule or an ethanol solvent mol­ecule. The ethanol O atom donates a hydrogen bond to the keto O atom. These hydrogen bonds link the constituents into layers parallel to (101) in the crystal structure. PMID:23634071

  4. Nickel-Catalyzed Cross Couplings of Benzylic Ammonium Salts and Boronic Acids: Stereospecific Formation of Diarylethanes via C–N Bond Activation

    PubMed Central

    Maity, Prantik; Shacklady-McAtee, Danielle M.; Yap, Glenn P. A.; Sirianni, Eric R.; Watson, Mary P.

    2014-01-01

    We have developed a nickel-catalyzed cross coupling of benzylic ammonium triflates with aryl boronic acids to afford diarylmethanes and diarylethanes. This reaction proceeds under mild reaction conditions and with exceptional functional group tolerance. Further, it transforms branched benzylic ammonium salts to diarylethanes with excellent chirality transfer, offering a new strategy for the synthesis of highly enantioenriched diarylethanes from readily available chiral benzylic amines. PMID:23268734

  5. [Search for antidiabetic constituents of medicinal food].

    PubMed

    Nakamura, Seikou; Matsuda, Hisashi; Yoshikawa, Masayuki

    2011-01-01

    Many foods are known to have not only nutritive and taste values but also medicinal effects. In Chinese traditional medicine, the treatment using medicinal foods has been recommended highly. Recently, we examined the effects of the extract and constituents of several medicinal foods on experimental models of diabetes. In this paper, we focus on the bioactive constituents of four medicinal foods, namely the antidiabetic constituents from 1) the roots, stems and leaves of Salacia plants, 2) the male flowers of Borassus flabellifer, 3) the flower buds of Camellia sinensis, 4) the processed leaves of Hydrangea macrophylla var. thunbergii (Hydrangeae Dulcis Folium). PMID:21628977

  6. 7 CFR 930.16 - Sales constituency.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE TART CHERRIES GROWN IN THE STATES OF... consignments of cherries and does not direct where the consigned cherries are sold is not a sales constituency....

  7. 7 CFR 930.16 - Sales constituency.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... AND ORDERS; FRUITS, VEGETABLES, NUTS), DEPARTMENT OF AGRICULTURE TART CHERRIES GROWN IN THE STATES OF... consignments of cherries and does not direct where the consigned cherries are sold is not a sales constituency....

  8. 7 CFR 930.16 - Sales constituency.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... and Orders; Fruits, Vegetables, Nuts), DEPARTMENT OF AGRICULTURE TART CHERRIES GROWN IN THE STATES OF... consignments of cherries and does not direct where the consigned cherries are sold is not a sales constituency....

  9. 21 CFR 610.15 - Constituent materials.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... GENERAL BIOLOGICAL PRODUCTS STANDARDS General Provisions § 610.15 Constituent materials. (a) Ingredients... the recommended individual dose of a biological product shall not exceed: (1) 0.85 milligrams...

  10. 2-Acetamido-N-benzyl-1,4-imino-1,2,4-tride­oxy-l-xylitol (N-benzyl-l-XYLNAc)

    PubMed Central

    Jenkinson, Sarah. F.; Crabtree, Elizabeth. V.; Glawar, Andreas. F. G.; Butters, Terry D.; Fleet, George. W. J.; Watkin, David. J.

    2010-01-01

    X-ray crystallography defines the relative configuration at the three-stereogenic centres in the title compound N-benzyl-l-XYLNAc, C14H20N2O3. The five-membered pyrrolidine ring adopts an envelope conformation with the N atom lying out of the plane of the other four atoms. In the crystal structure, inter­molecular O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonds link the mol­ecules into chains along [100]. The carbonyl group O atom acts as an acceptor for a bifurcated hydrogen bond. The absolute configuration is determined by the use of l-glucuronolactone as the starting material for the synthesis. PMID:21579195

  11. Hazardous constituent source term. Revision 2

    SciTech Connect

    Not Available

    1994-11-17

    The Department of Energy (DOE) has several facilities that either generate and/or store transuranic (TRU)-waste from weapons program research and production. Much of this waste also contains hazardous waste constituents as regulated under Subtitle C of the Resource Conservation and Recovery Act (RCRA). Toxicity characteristic metals in the waste principally include lead, occurring in leaded rubber gloves and shielding. Other RCRA metals may occur as contaminants in pyrochemical salt, soil, debris, and sludge and solidified liquids, as well as in equipment resulting from decontamination and decommissioning activities. Volatile organic compounds (VOCS) contaminate many waste forms as a residue adsorbed on surfaces or occur in sludge and solidified liquids. Due to the presence of these hazardous constituents, applicable disposal regulations include land disposal restrictions established by Hazardous and Solid Waste Amendments (HSWA). The DOE plans to dispose of TRU-mixed waste from the weapons program in the Waste Isolation Pilot Plant (WIPP) by demonstrating no-migration of hazardous constituents. This paper documents the current technical basis for methodologies proposed to develop a post-closure RCRA hazardous constituent source term. For the purposes of demonstrating no-migration, the hazardous constituent source term is defined as the quantities of hazardous constituents that are available for transport after repository closure. Development of the source term is only one of several activities that will be involved in the no-migration demonstration. The demonstration will also include uncertainty and sensitivity analyses of contaminant transport.

  12. Potential confounding effects of benzyl alcohol as a formulation excipient support the elimination of the abnormal toxicity test from pharmacopoeias.

    PubMed

    Xie, Jianxun; Ottaviani, Giorgio; Sun, Kai; Lu, Mingqiu; Wu, Xiaoqin; Huang, Sunfeng; Bopst, Martin

    2015-11-01

    Benzyl alcohol is an excipient used in many drugs as a stabilizer. Depending on the amount present in drug formulations there might be confounding findings in the Abnormal Toxicity Test (ATT). The ATT is utilized as a quality control (QC) release test to detect extraneous contaminants according to national pharmacopoeias. Our study assessed the effects of benzyl alcohol as defined in ATT designs. This study - the first thorough evaluation of the confounding effects of benzyl alcohol on the ATT - was conducted in relation to particular health authority questions and was part of the root-cause analyses resulting from some transient behavioral findings observed in the test. Two strains of mice, CD-1 & Kunming, plus Hartley guinea pigs were administered intraperitoneally (ip), subcutaneously (sc), or intravenously (iv) with benzyl alcohol at dose level defined in the ATT design. In both mice and guinea pigs, only after ip administration, minimal behavioral changes were observed transiently within 2-3 min after administration. Therefore, the presence of benzyl alcohol in the product batch may confound the ATT results. This study provides further evidence to question the validity of the ATT for its intended use. PMID:26449397

  13. A Sustainable and Efficient Synthesis of Benzyl Phosphonates Using PEG/KI Catalytic System

    PubMed Central

    Disale, Shamrao; Kale, Sandip; Abraham, George; Kahandal, Sandeep; Sawarkar, Ashish N.; Gawande, Manoj B.

    2016-01-01

    An efficient and expedient protocol for the synthesis of benzyl phosphonates using KI/K2CO3 as a catalytic system and PEG-400 as benign solvent has been developed. The reaction proceeds smoothly at room temperature achieving excellent selectivity and yield of the corresponding products. The combination of PEG-400, KI, and K2CO3 in this reaction avoids the need of volatile/toxic organic solvents and reactive alkali metals or metal nanoparticles/hydrides. We believe that this benign combination (PEG-400 and KI) could be used for other related organic transformations. PMID:27579301

  14. Mild and selective vanadium-catalyzed oxidation of benzylic, allylic, and propargylic alcohols using air.

    PubMed

    Hanson, Susan K; Wu, Ruilian; Silks, L A Pete

    2011-04-15

    Transition metal-catalyzed aerobic alcohol oxidation is an attractive method for the synthesis of carbonyl compounds, but most catalytic systems feature precious metals and require pure oxygen. The vanadium complex (HQ)(2)V(V)(O)(O(i)Pr) (2 mol %, HQ = 8-quinolinate) and NEt(3) (10 mol %) catalyze the oxidation of benzylic, allylic, and propargylic alcohols with air. The catalyst can be easily prepared under air using commercially available reagents and is effective for a wide range of primary and secondary alcohols. PMID:21434606

  15. Synthesis and biological evaluation of colchicine B-ring analogues tethered with halogenated benzyl moieties.

    PubMed

    Cosentino, Laura; Redondo-Horcajo, Mariano; Zhao, Ying; Santos, Ana Rita; Chowdury, Kaniz F; Vinader, Victoria; Abdallah, Qasem M A; Abdel-Rahman, Hamdy; Fournier-Dit-Chabert, Jérémie; Shnyder, Steven D; Loadman, Paul M; Fang, Wei-shuo; Díaz, José Fernando; Barasoain, Isabel; Burns, Philip A; Pors, Klaus

    2012-12-27

    Deacetylcolchicine was reacted with substituted benzyl halides to provide a library of compounds for biological analysis. Compound 7 (3,4-difluorobenzyl-N-aminocolchicine) was shown to possess cytotoxicity in cancer cell lines in the low nanomolar range. Significantly, it showed no loss of activity in the resistant A2780AD ovarian carcinoma cell line known to overexpress the ABCB1 drug transporter and was also unaffected by overexpression of class III β-tubulin in HeLa transfected cells. PMID:23176628

  16. Excelsoside: a new benzylic diglycoside from the leaves of Milicia excelsa.

    PubMed

    Ouete, Judith L Nantchouang; Sandjo, Louis P; Kapche, Deccaux W F G; Yeboah, Samuel O; Mapitse, Renameditswe; Abegaz, Berhanu M; Opatz, Till; Ngadjui, Bonaventure T

    2014-01-01

    A new benzylic diglycoside was isolated from the leaves of Milicia excelsa and identified as 3,4-dimethoxybenzyl beta-D-xylopyranosyl (1 --> 2)-beta-D-glucopyranoside (1). It was obtained together with four known secondary metabolites including lupeol acetate (2), ursolic acid (3), triacontyl (E)-ferulate (4), and 2-(3,5-dihydroxyphenyl)benzofuran-5,6-diol (5). Their structures were determined based on their spectroscopic data and by comparison with those reported in the literature. PMID:25265846

  17. Active site diversification of P450cam with indole generates catalysts for benzylic oxidation reactions

    PubMed Central

    Herter, Susanne; Kranz, David C; Turner, Nicholas J

    2015-01-01

    Summary Cytochrome P450 monooxygenases are useful biocatalysts for C–H activation, and there is a need to expand the range of these enzymes beyond what is naturally available. A panel of 93 variants of active self-sufficient P450cam[Tyr96Phe]-RhFRed fusion enzymes with a broad diversity in active site amino acids was developed by screening a large mutant library of 16,500 clones using a simple, highly sensitive colony-based colorimetric screen against indole. These mutants showed distinct fingerprints of activity not only when screened in oxidations of substituted indoles but also for unrelated oxidations such as benzylic hydroxylations. PMID:26664590

  18. Organophosphorus compounds as coke inhibitors during naphtha pyrolysis. Effect of benzyl diethyl phosphite and triphenylphosphine sulfide

    SciTech Connect

    Das, P.; Prasad, S.; Kunztu, D.

    1992-09-01

    This paper reports that significant reduction in the rate of coke formation during naphtha pyrolysis was achieved by adding benzyl diethyl phosphite or triphenylphosphine sulfide to the feed. Although the yield of carbon oxides was reduced, there was no effect of these additives on the hydrocarbon yields. Addition of these organophosphorus compounds significantly reduced the concentration of metals, such as iron, nickel, and chromium, incorporated in the coke. A previously proposed model for coke inhibition due to the formation of a passivating metal-phosphorus complex could satisfactorily correlate the data.

  19. A Sustainable and Efficient Synthesis of Benzyl Phosphonates Using PEG/KI Catalytic System.

    PubMed

    Disale, Shamrao; Kale, Sandip; Abraham, George; Kahandal, Sandeep; Sawarkar, Ashish N; Gawande, Manoj B

    2016-01-01

    An efficient and expedient protocol for the synthesis of benzyl phosphonates using KI/K2CO3 as a catalytic system and PEG-400 as benign solvent has been developed. The reaction proceeds smoothly at room temperature achieving excellent selectivity and yield of the corresponding products. The combination of PEG-400, KI, and K2CO3 in this reaction avoids the need of volatile/toxic organic solvents and reactive alkali metals or metal nanoparticles/hydrides. We believe that this benign combination (PEG-400 and KI) could be used for other related organic transformations. PMID:27579301

  20. Crystal structure of 4-amino-1-benzyl-1,2,4-triazolin-5-one.

    PubMed

    Laus, Gerhard; Kahlenberg, Volker; Schottenberger, Herwig

    2014-10-01

    The title compound, C9H10N4O, was obtained unintentionally by hydrolysis of 4-amino-1-benzyl-5-methyl-sulfanyl-1,2,4-triazolium tetra-fluoro-borate in the presence of sodium azide. In the crystal, alternating layers of polar amino-triazolinone and apolar benzene moieties are observed. N-H⋯O hydrogen bonds between the amino and carbonyl groups form infinite chains along [010]. These infinite chains are linked by additional C-H⋯O contacts. PMID:25484684

  1. Synthesis and anticonvulsant activities of N-benzyl (2R)-2-acetamido-3-oxysubstituted propionamide derivatives

    PubMed Central

    Morieux, Pierre; Stables, James P.; Kohn, Harold

    2009-01-01

    Lacosamide has been submitted for regulatory approval in the United States and Europe for the treatment of epilepsy. Previous synthetic methods did not permit the elaboration of the structure–activity relationship (SAR) for the 3-oxy site in lacosamide. We report an expedient five-step stereospecific synthesis for N-benzyl (2R)-2-acetamido-3-oxysubstituted propionamide analogs beginning with d-serine methyl ester. The procedure incorporated alkyl (e.g. methyl, primary, secondary, and tertiary) and aryl groups at this position. The SAR for the 3-oxy site showed maximal activity in animal seizure models for small 3-alkoxy substituents. PMID:18789868

  2. Solvent-free catalytic dehydrative etherification of benzyl alcohol over graphene oxide

    NASA Astrophysics Data System (ADS)

    Yu, Huiyou; Wang, Xinde; Zhu, Yuanshuai; Zhuang, Guilin; Zhong, Xing; Wang, Jian-guo

    2013-09-01

    Graphene oxide (GO), prepared from oxidation of graphite powders using a modified Hummers method, exhibits a promising catalytic activity and a high selectivity for the solvent-free catalytic dehydrative etherification of benzyl alcohol (BA). A maximum yield (85.4%) of dibenzyl ether (DE) was achieved at 150 °C for 24 h when the BA/GO ration was 20 ml/g under solvent-free condition. This discovery provided a new insight into the development of GO as a carbocatalysts for a variety of applications in carbocatalysis.

  3. Reduced graphene oxide supported Au nanoparticles as an efficient catalyst for aerobic oxidation of benzyl alcohol

    NASA Astrophysics Data System (ADS)

    Yu, Xianqin; Huo, Yujia; Yang, Jing; Chang, Sujie; Ma, Yunsheng; Huang, Weixin

    2013-09-01

    Various Au/C catalysts were prepared by Au nanoparticels supported on different carbonaceous supports including reduced graphene oxide (RGO), activated carbon (AC) and graphite (GC) using sol-immobilization method. Au/RGO shows a much higher activity than Au/AC and Au/GC in the liquid phase aerobic oxidation of benzyl alcohol. The superior catalytic performance of Au/RGO may be related to the presence of surface O-containing functional groups and moderate graphite character of RGO supports.

  4. Preparation of halloysite nanotube-supported gold nanocomposite for solvent-free oxidation of benzyl alcohol

    PubMed Central

    2014-01-01

    Gold nanoparticles supported on halloysite nanotubes (Au/HNTs) were prepared by a homogeneous deposition-precipitation method. The specific characteristics of the catalyst were characterized in detail, in relation to their performance for solvent-free oxidation of benzyl alcohol. The particular structure of the catalyst resulted in high catalytic activity and stability compared with other supported gold catalysts. The enhanced catalytic activity of the Au/HNTs catalyst was mainly attributed to the presence of a higher amount of oxidized gold species and the tubular structure of the HNTs. PMID:24948899

  5. Bis(S-benzyl­isothio­uronium) tetra­chloridozincate(II)

    PubMed Central

    Gayathri, D.; Velmurugan, D.; Hemalatha, P.; Veeravazhuthi, V.; Ravikumar, K.

    2008-01-01

    The asymmetric unit of the title compound, (C8H11N2S)2[ZnCl4], contains two S-benzyl­isothio­uronium cations which differ in the C—C—S—C torsion angle [165.3 (2) and 81.9 (2)°] and a tetrahedral tetra­chloridozincate anion. The crystal structure is stabilized by N—H⋯Cl, C—H⋯Cl and C—H⋯S inter­actions. PMID:21202526

  6. Allyl isothiocyanate suppresses the proteolytic activation of sterol regulatory element-binding proteins and de novo fatty acid and cholesterol synthesis.

    PubMed

    Miyata, Shingo; Inoue, Jun; Shimizu, Makoto; Sato, Ryuichiro

    2016-05-01

    Sterol regulatory element-binding proteins (SREBPs) are a family of transcription factors that regulate lipid homeostasis by controlling the expression of genes involved in fatty acid and cholesterol synthesis. In this study, we used a stable cell line that expresses a luciferase reporter gene driven by an SRE-containing fatty acid synthase promoter to identify allyl isothiocyanate (AITC), one of the major isothiocyanates in cruciferous vegetables, as a novel SREBP inactivator. We found that AITC downregulated the proteolytic processing of SREBPs and the expression of their target genes in human hepatoma Huh-7 cells. Furthermore, AITC reduced the de novo synthesis of both fatty acids and cholesterol. Our results indicate a novel physiological function of AITC in lipid metabolism regulation. PMID:26822063

  7. GCLAS: a graphical constituent loading analysis system

    USGS Publications Warehouse

    McKallip, T.E.; Koltun, G.F.; Gray, J.R.; Glysson, G.D.

    2001-01-01

    The U. S. Geological Survey has developed a program called GCLAS (Graphical Constituent Loading Analysis System) to aid in the computation of daily constituent loads transported in stream flow. Due to the relative paucity with which most water-quality data are collected, computation of daily constituent loads is moderately to highly dependent on human interpretation of the relation between stream hydraulics and constituent transport. GCLAS provides a visual environment for evaluating the relation between hydraulic and other covariate time series and the constituent chemograph. GCLAS replaces the computer program Sedcalc, which is the most recent USGS sanctioned tool for constructing sediment chemographs and computing suspended-sediment loads. Written in a portable language, GCLAS has an interactive graphical interface that permits easy entry of estimated values and provides new tools to aid in making those estimates. The use of a portable language for program development imparts a degree of computer platform independence that was difficult to obtain in the past, making implementation more straightforward within the USGS' s diverse computing environment. Some of the improvements introduced in GCLAS include (1) the ability to directly handle periods of zero or reverse flow, (2) the ability to analyze and apply coefficient adjustments to concentrations as a function of time, streamflow, or both, (3) the ability to compute discharges of constituents other than suspended sediment, (4) the ability to easily view data related to the chemograph at different levels of detail, and (5) the ability to readily display covariate time series data to provide enhanced visual cues for drawing the constituent chemograph.

  8. Propolis specimens from different locations of central Italy: chemical profiling and gas chromatography-mass spectrometry (GC-MS) quantitative analysis of the allergenic esters benzyl cinnamate and benzyl salicylate.

    PubMed

    Aliboni, Andrea; D'Andrea, Armando; Massanisso, Paolo

    2011-01-12

    Propolis is a beehive product popular in natural medicine thanks to its noteworthy properties. Propolis is non-toxic but is responsible for allergic reactions in sensitive individuals. In this paper, we propose a new gas chromatography-mass spectrometry (GC-MS) analytical methodology for the quantitative analysis of two allergenic esters in propolis specimens, benzyl salicylate and benzyl cinnamate, and test it on specimens from different locations of central Italy. We also present the results obtained in the chemical characterization of the same specimens. The characterization showed that the resin fractions of all of the specimens are of poplar origin. PMID:21126078

  9. Synthesis of tetra-substituted imidazoles and 2-imidazolines by Ni(0)-catalyzed dehydrogenation of benzylic-type imines.

    PubMed

    Tlahuext-Aca, Adrian; Hernández-Fajardo, Oscar; Arévalo, Alma; García, Juventino J

    2014-11-14

    Ni(0)-catalyzed dehydrogenation of benzylic-type imines was performed to yield asymmetrical tetra-substituted imidazoles and 2-imidazolines. This was achieved with a single operational step while maintaining good selectivity and atom economy. The catalytic system shows low to moderate tolerance for fluoro-, trifluoromethyl-, methyl-, and methoxy-substituted benzylic-type imines. In addition, the substitution pattern at the N-heterocyclic products was easily controlled by the appropriate selection of R-groups in the starting organic substrates. Based on experimental observations, we propose a reaction mechanism in which benzylic C(sp(3))-H bond activation and insertion steps play pivotal roles in this nickel-catalyzed organic transformation. PMID:25232889

  10. Enhanced inhibition of urinary bladder cancer growth and muscle invasion by allyl isothiocyanate and celecoxib in combination.

    PubMed

    Bhattacharya, Arup; Li, Yun; Shi, Yi; Zhang, Yuesheng

    2013-11-01

    Allyl isothiocyanate (AITC) occurs in cruciferous vegetables that are commonly consumed by humans and has been shown to inhibit urinary bladder cancer growth and progression in previous preclinical studies. However, AITC does not significantly modulate cyclooxygenase-2 (Cox-2), whose oncogenic activity has been well documented in bladder cancer and other cancers. Celecoxib is a selective Cox-2 inhibitor and has been widely used for treatment of several diseases. Celecoxib has also been evaluated in bladder cancer patients, but its efficacy against bladder cancer as a single agent remains unclear. In a syngeneic rat model of orthotopic bladder cancer, treatment of the animals with the combination of AITC and celecoxib at low dose levels (AITC at 1 mg/kg and celecoxib at 10 mg/kg) led to increased or perhaps synergistic inhibition of bladder cancer growth and muscle invasion, compared with each agent used alone. The combination regime was also more effective than each single agent in inhibiting microvessel formation and stimulating microvessel maturation in the tumor tissues. The anticancer efficacy of the combination regime was associated with depletion of prostaglandin E2, a key downstream signaling molecule of Cox-2, caspase activation and downregulation of vascular endothelial growth factor in the tumor tissues. These data show that AITC and celecoxib complement each other for inhibition of bladder cancer and provide a novel combination approach for potential use for prevention or treatment of human bladder cancer. PMID:23946495

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

    PubMed Central

    Calmes, Benoit; N’Guyen, Guillaume; Dumur, Jérome; Brisach, Carlos A.; Campion, Claire; Iacomi, Béatrice; Pigné, Sandrine; Dias, Eva; Macherel, David; Guillemette, Thomas; Simoneau, Philippe

    2015-01-01

    Glucosinolates are brassicaceous secondary metabolites that have long been considered as chemical shields against pathogen invasion. Isothiocyanates (ITCs), are glucosinolate-breakdown products that have negative effects on the growth of various fungal species. We explored the mechanism by which ITCs could cause fungal cell death using Alternaria brassicicola, a specialist Brassica pathogens, as model organism. Exposure of the fungus to ICTs led to a decreased oxygen consumption rate, intracellular accumulation of reactive oxygen species (ROS) 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 ICTs. Once activated by ICT-derived ROS, 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 ICTs 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 ICT-derived oxidative stress might be a key adaptation mechanism for successful infection of host plants by Brassicaceae-specialist necrotrophs like A. brassicicola. PMID:26089832

  12. Effect of glutathione-S-transferase polymorphisms on the cancer preventive potential of isothiocyanates: an epidemiological perspective.

    PubMed

    Seow, Adeline; Vainio, Harri; Yu, Mimi C

    2005-12-30

    Isothiocyanates (ITCs) are widely distributed in cruciferous vegetables and are biologically active against chemical carcinogenesis due to their ability to induce phase II conjugating enzymes. Among these is the glutathione-S-transferase (GST) family of enzymes, which in turn catalyzes the metabolism of ITCs, for which it has high substrate specificity. A recent body of epidemiologic data on the inverse association between cruciferous vegetable/ITC intake and cancers of the colo-rectum, lung and breast, also support that this protective effect is greater among individuals who possess the GSTM1 or T1 null genotype, and who would be expected to accumulate higher levels of ITC at the target tissue level, a pre-requisite for their enzyme-inducing effects. The association between ITC and cancer, and its modification by GST status, is most consistent for lung cancer and appears to be strongest among current smokers. Within limits, a comparison between groups which have been stratified by GST genotype may be less susceptible to confounding by other variables, given the random assortment of genes in gametogenesis. While a more complete understanding of the overall effects on health will need to take into account other components such as indoles and anti-oxidants, the interaction between ITC intake and GST genotype may provide a firmer basis to support a biologically significant role for ITC in cruciferous vegetables. PMID:16019037

  13. The isothiocyanate erucin abrogates telomerase in hepatocellular carcinoma cells in vitro and in an orthotopic xenograft tumour model of HCC.

    PubMed

    Herz, Corinna; Hertrampf, Anke; Zimmermann, Stefan; Stetter, Nadine; Wagner, Meike; Kleinhans, Claudia; Erlacher, Miriam; Schüler, Julia; Platz, Stefanie; Rohn, Sascha; Mersch-Sundermann, Volker; Lamy, Evelyn

    2014-12-01

    In contrast to cancer cells, most normal human cells have no or low telomerase levels which makes it an attractive target for anti-cancer drugs. The small molecule sulforaphane from broccoli is known for its cancer therapeutic potential in vitro and in vivo. In animals and humans it was found to be quickly metabolized into 4-methylthiobutyl isothiocyanate (MTBITC, erucin) which we recently identified as strong selective apoptosis inducer in hepatocellular carcinoma (HCC) cells. Here, we investigated the relevance of telomerase abrogation for cytotoxic efficacy of MTBITC against HCC. The drug was effective against telomerase, independent from TP53 and MTBITC also blocked telomerase in chemoresistant subpopulations. By using an orthotopic human liver cancer xenograft model, we give first evidence that MTBITC at 50 mg/KG b.w./d significantly decreased telomerase activity in vivo without affecting enzyme activity of adjacent normal tissue. Upon drug exposure, telomerase decrease was consistent with a dose-dependent switch to anti-survival, cell arrest and apoptosis in our in vitro HCC models. Blocking telomerase by the specific inhibitor TMPyP4 further sensitized cancer cells to MTBITC-mediated cytotoxicity. Overexpression of hTERT, but not enzyme activity deficient DNhTERT, protected against apoptosis; neither DNA damage nor cytostasis induction by MTBITC was prevented by hTERT overexpression. These findings imply that telomerase enzyme activity does not protect against MTBITC-induced DNA damage but impacts signalling processes upstream of apoptosis execution level. PMID:25256442

  14. Phenylethyl isothiocyanate reverses cisplatin resistance in biliary tract cancer cells via glutathionylation-dependent degradation of Mcl-1.

    PubMed

    Li, Qiwei; Zhan, Ming; Chen, Wei; Zhao, Benpeng; Yang, Kai; Yang, Jie; Yi, Jing; Huang, Qihong; Mohan, Man; Hou, Zhaoyuan; Wang, Jian

    2016-03-01

    Biliary tract cancer (BTC) is a highly malignant cancer. BTC exhibits a low response rate to cisplatin (CDDP) treatment, and therefore, an understanding of the mechanism of CDDP resistance is urgently needed. Here, we show that BTC cells develop CDDP resistance due, in part, to upregulation of myeloid cell leukemia 1 (Mcl-1). Phenylethyl isothiocyanate (PEITC), a natural compound found in watercress, could enhance the efficacy of CDDP by degrading Mcl-1. PEITC-CDDP co-treatment also increased the rate of apoptosis of cancer stem-like side population (SP) cells and inhibited xenograft tumor growth without obvious toxic effects. In vitro, PEITC decreased reduced glutathione (GSH), which resulted in decreased GSH/oxidized glutathione (GSSG) ratio and increased glutathionylation of Mcl-1, leading to rapid proteasomal degradation of Mcl-1. Furthermore, we identified Cys16 and Cys286 as Mcl-1 glutathionylation sites, and mutating them resulted in PEITC-mediated degradation resistant Mcl-1 protein. In conclusion, we demonstrate for the first time that CDDP resistance is partially associated with Mcl-1 in BTC cells and we identify a novel mechanism that PEITC can enhance CDDP-induced apoptosis via glutathionylation-dependent degradation of Mcl-1. Hence, our results provide support that dietary intake of watercress may help reverse CDDP resistance in BTC patients. PMID:26848531

  15. Phenylethyl isothiocyanate reverses cisplatin resistance in biliary tract cancer cells via glutathionylation-dependent degradation of Mcl-1

    PubMed Central

    Li, Qiwei; Zhan, Ming; Chen, Wei; Zhao, Benpeng; Yang, Kai; Yang, Jie; Yi, Jing; Huang, Qihong; Mohan, Man; Hou, Zhaoyuan; Wang, Jian

    2016-01-01

    Biliary tract cancer (BTC) is a highly malignant cancer. BTC exhibits a low response rate to cisplatin (CDDP) treatment, and therefore, an understanding of the mechanism of CDDP resistance is urgently needed. Here, we show that BTC cells develop CDDP resistance due, in part, to upregulation of myeloid cell leukemia 1 (Mcl-1). Phenylethyl isothiocyanate (PEITC), a natural compound found in watercress, could enhance the efficacy of CDDP by degrading Mcl-1. PEITC-CDDP co-treatment also increased the rate of apoptosis of cancer stem-like side population (SP) cells and inhibited xenograft tumor growth without obvious toxic effects. In vitro, PEITC decreased reduced glutathione (GSH), which resulted in decreased GSH/oxidized glutathione (GSSG) ratio and increased glutathionylation of Mcl-1, leading to rapid proteasomal degradation of Mcl-1. Furthermore, we identified Cys16 and Cys286 as Mcl-1 glutathionylation sites, and mutating them resulted in PEITC-mediated degradation resistant Mcl-1 protein. In conclusion, we demonstrate for the first time that CDDP resistance is partially associated with Mcl-1 in BTC cells and we identify a novel mechanism that PEITC can enhance CDDP-induced apoptosis via glutathionylation-dependent degradation of Mcl-1. Hence, our results provide support that dietary intake of watercress may help reverse CDDP resistance in BTC patients. PMID:26848531

  16. Numbers and phenotype of lymphocytes emigrating from sheep bone marrow after in situ labelling with fluorescein isothiocyanate.

    PubMed Central

    Pabst, R; Miyasaka, M; Dudler, L

    1986-01-01

    In normal young lambs the bone marrow was selectively labelled with fluorescein isothiocyanate by a temporary perfusion of one hind-leg. One day later, the incidence of bone marrow emigrants in different lymph nodes, spleen, Peyer's patches, thymus, non-perfused bone marrow and blood was determined. The emigrants were also phenotyped by the use of monoclonal antibodies and classified into monocytes or lymphocyte subsets. Large numbers of lymphocytes left the bone marrow of the perfused leg during 1 day. Considerable numbers of cells migrated to other bone marrow compartments. Varying numbers of mononuclear emigrants were found in peripheral lymphoid organs, with labelling indices ranging from 1.06% in the blood to 0.004% in the thymus. In the spleen, comparable numbers of B- and T-lymphocyte emigrants from the bone marrow were found, whereas in the blood, lymph nodes and jejunal Peyer's patches many more emigrants were T lymphocytes than B lymphocytes. In the prescapular lymph nodes, for instance, 90.4% of emigrants were T cells but only 9.6% were B cells. Based on the large numbers of lymphocytes emigrating from the bone marrow, their phenotypes and their entry into other bone marrow compartments, it it can be concluded that the bone marrow of young lambs is an integral part of the migratory route of lymphocytes. Images Figure 2 Figure 3 PMID:3095227

  17. Transcriptional responses to exposure to the brassicaceous defence metabolites camalexin and allyl-isothiocyanate in the necrotrophic fungus Alternaria brassicicola.

    PubMed

    Sellam, Adnane; Dongo, Anita; Guillemette, Thomas; Hudhomme, Piétrick; Simoneau, Philippe

    2007-03-01

    SUMMARY Alternaria brassicicola is the causative agent of black spot disease of Brassicaceae belonging to the genera Brassica and Raphanus. During host infection, A. brassicicola is exposed to high levels of antimicrobial defence compounds such as indolic phytoalexins and glucosinolate breakdown products. To investigate the transcriptomic response of A. brassicicola when challenged with brassicaceous defence metabolites, suppression subtractive hybridization (SSH) was performed to generate two cDNA libraries from germinated conidia treated either with allyl isothiocyanate (Al-ITC) or with camalexin. Following exposure to Al-ITC, A. brassicicola displayed a response similar to that experienced during oxidative stress. Indeed, a substantial subset of differentially expressed genes was related to cell protection against oxidative damage. Treatment of A. brassicicola conidia with the phytoalexin camalexin appeared to activate a compensatory mechanism to preserve cell membrane integrity and, among the camalexin-elicited genes, several were involved in sterol and sphingolipid biosynthesis. The transcriptomic analysis suggested that protection against the two tested compounds also involved mechanisms aimed at limiting their intracellular accumulation, such as melanin biosynthesis (in the case of camalexin exposure only) and drug efflux. From the Al-ITC and the camalexin differentially expressed genes identified here, 25 were selected to perform time-course studies during interactions with brassicaceous hosts. In planta, up-regulation of all the selected genes was observed during infection of Raphanus sativus whereas only a subset were over-expressed during the incompatible interaction with Arabidopsis thaliana ecotype Columbia. PMID:20507491

  18. Isothiocyanates Are Promising Compounds against Oxidative Stress, Neuroinflammation and Cell Death that May Benefit Neurodegeneration in Parkinson's Disease.

    PubMed

    Sita, Giulia; Hrelia, Patrizia; Tarozzi, Andrea; Morroni, Fabiana

    2016-01-01

    Parkinson's disease (PD) is recognized as the second most common neurodegenerative disorder and is characterized by a slow and progressive degeneration of dopaminergic neurons in the substantia nigra. Despite intensive research, the mechanisms involved in neuronal loss are not completely understood yet; however, misfolded proteins, oxidative stress, excitotoxicity and inflammation play a pivotal role in the progression of the pathology. Neuroinflammation may have a greater function in PD pathogenesis than initially believed, taking part in the cascade of events that leads to neuronal death. To date, no efficient therapy, able to arrest or slow down PD, is available. In this context, the need to find novel strategies to counteract neurodegenerative progression by influencing diseases' pathogenesis is becoming increasingly clear. Isothiocyanates (ITCs) have already shown interesting properties in detoxification, inflammation, apoptosis and cell cycle regulation through the induction of phase I and phase II enzyme systems. Moreover, ITCs may be able to modulate several key points in oxidative and inflammatory evolution. In view of these considerations, the aim of the present review is to describe ITCs as pleiotropic compounds capable of preventing and modulating the evolution of PD. PMID:27598127

  19. Low concentrations of isothiocyanates protect mesenchymal stem cells from oxidative injuries, while high concentrations exacerbate DNA damage.

    PubMed

    Zanichelli, Fulvia; Capasso, Stefania; Di Bernardo, Giovanni; Cipollaro, Marilena; Pagnotta, Eleonora; Cartenì, Maria; Casale, Fiorina; Iori, Renato; Giordano, Antonio; Galderisi, Umberto

    2012-09-01

    Isothiocyanates (ITCs) are molecules naturally present in many cruciferous vegetables (broccoli, black radish, daikon radish, and cauliflowers). Several studies suggest that cruciferous vegetable consumption may reduce cancer risk and slow the aging process. To investigate the effect of ITCs on cellular DNA damage, we evaluated the effects of two different ITCs [sulforaphane (SFN) and raphasatin (RPS)] on the biology of human mesenchymal stem cells (MSCs), which, in addition to their ability to differentiate into mesenchymal tissues, contribute to the homeostatic maintenance of many organs. The choice of SFN and RPS relies on two considerations: they are among the most popular cruciferous vegetables in the diet of western and eastern countries, respectively, and their bioactive properties may differ since they possess specific molecular moiety. Our investigation evidenced that MSCs incubated with low doses of SFN and RPS show reduced in vitro oxidative stress. Moreover, these cells are protected from oxidative damages induced by hydrogen peroxide, while no protection was evident following treatment with the UV ray of a double strand DNA damaging drug, such as doxorubicin. High concentrations of both ITCs induced cytotoxic effects in MSC cultures and further increased DNA damage induced by peroxides. In summary, our study suggests that ITCs, at low doses, may contribute to slowing the aging process related to oxidative DNA damage. Moreover, in cancer treatment, low doses of ITCs may be used as an adjuvant to reduce chemotherapy-induced oxidative stress, while high doses may synergize with anticancer drugs to promote cell DNA damage. PMID:22684843

  20. Factors affecting the dissolution and degradation of oriental mustard-derived sinigrin and allyl isothiocyanate in aqueous media.

    PubMed

    Tsao, R; Yu, Q; Friesen, I; Potter, J; Chiba, M

    2000-05-01

    Sinigrin, the predominant glucosinolate in the oriental mustard Brassica juncea, is mainly degraded upon the enzymatic action of myrosinase under normal conditions to give allyl isothiocyanate (AITC) in an aqueous media. Because AITC is considered to be the principal nematicidal ingredient in B. juncea, its stability in aqueous media is an important issue in achieving efficient nematode control. Pure sinigrin and AITC were found to be relatively stable in buffered water in the pH range of 5.00-7.00 but less stable at pH 9.00. Both sinigrin and AITC were more stable in soil water (supernatant of a 1:1 water/air-dried soil mixture) than in buffered water at the same pH range of 5.00-9.00. Sinigrin dissolved from the mustard bran or ground seed into water very quickly and was degraded by codissolved myrosinase to AITC. The AITC that formed from the degradation of sinigrin was found to be more stable in the soil water than in the buffered water. Buffer capacity was considered to be one of the factors that contributed to the stabilization of AITC in the soil water, but other unknown factors from both bran or seed and soil may also have contributed to the stabilization. PMID:10820112

  1. Characterization of some amino acid derivatives of benzoyl isothiocyanate: Crystal structures and theoretical prediction of their reactivity

    NASA Astrophysics Data System (ADS)

    Odame, Felix; Hosten, Eric C.; Betz, Richard; Lobb, Kevin; Tshentu, Zenixole R.

    2015-11-01

    The reaction of benzoyl isothiocyanate with L-serine, L-proline, D-methionine and L-alanine gave 2-[(benzoylcarbamothioyl)amino]-3-hydroxypropanoic acid (I), 1-(benzoylcarbamothioyl)pyrrolidine-2-carboxylic acid (II), 2-[(benzoylcarbamothioyl)amino]-4-(methylsulfanyl)butanoic acid (III) and 2-[(benzoylcarbamothioyl)amino]propanoic acid (IV), respectively. The compounds have been characterized by IR, NMR, microanalyses and mass spectrometry. The crystal structures of all the compounds have also been discussed. Compound II showed rotamers in solution. DFT calculations of the frontier orbitals of the compounds have been carried out to ascertain the groups that contribute to the HOMO and LUMO, and to study their contribution to the reactivity of these compounds. The calculations indicated that the carboxylic acid group in these compounds is unreactive hence making the conversion to benzimidazoles via cyclization on the carboxylic acids impractical. This has been further confirmed by the reaction of compounds I-IV, respectively, with o-phenylene diamine which was unsuccessful but gave compound V.

  2. Isothiocyanate metabolism, distribution, and interconversion in mice following consumption of thermally processed broccoli sprouts or purified sulforaphane

    PubMed Central

    Bricker, Gregory V.; Riedl, Kenneth M.; Ralston, Robin A.; Tober, Kathleen L.; Oberyszyn, Tatiana M.; Schwartz, Steven J.

    2014-01-01

    Scope Broccoli sprouts are a rich source of glucosinolates, a group of phytochemicals that when hydrolyzed, are associated with cancer prevention. Our objectives were to investigate the metabolism, distribution, and interconversion of isothiocyanates (ITCs) in mice fed thermally processed broccoli sprout powders (BSPs) or the purified ITC sulforaphane. Methods and results For 1 wk, mice were fed a control diet (n = 20) or one of four treatment diets (n = 10 each) containing nonheated BSP, 60°C mildly heated BSP, 5-min steamed BSP, or 3 mmol purified sulforaphane. Sulforaphane and erucin metabolite concentrations in skin, liver, kidney, bladder, lung, and plasma were quantified using HPLC-MS/MS. Thermal intensity of BSP processing had disparate effects on ITC metabolite concentrations upon consumption. Mild heating generally resulted in the greatest ITC metabolite concentrations in vivo, followed by the nonheated and steamed BSP diets. We observed interconversion between sulforaphane and erucin species or metabolites, and report that erucin is the favored form in liver, kidney, and bladder, even when only sulforaphane is consumed. Conclusion ITC metabolites were distributed to all tissues analyzed, suggesting the potential for systemic benefits. We report for the first time tissue-dependent ratio of sulforaphane and erucin, though further investigation is warranted to assess biological activity of individual forms. PMID:24975513

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

    PubMed

    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. PMID:26146190

  4. The isothiocyanate erucin abrogates telomerase in hepatocellular carcinoma cells in vitro and in an orthotopic xenograft tumour model of HCC

    PubMed Central

    Herz, Corinna; Hertrampf, Anke; Zimmermann, Stefan; Stetter, Nadine; Wagner, Meike; Kleinhans, Claudia; Erlacher, Miriam; Schüler, Julia; Platz, Stefanie; Rohn, Sascha; Mersch-Sundermann, Volker; Lamy, Evelyn

    2014-01-01

    In contrast to cancer cells, most normal human cells have no or low telomerase levels which makes it an attractive target for anti-cancer drugs. The small molecule sulforaphane from broccoli is known for its cancer therapeutic potential in vitro and in vivo. In animals and humans it was found to be quickly metabolized into 4-methylthiobutyl isothiocyanate (MTBITC, erucin) which we recently identified as strong selective apoptosis inducer in hepatocellular carcinoma (HCC) cells. Here, we investigated the relevance of telomerase abrogation for cytotoxic efficacy of MTBITC against HCC. The drug was effective against telomerase, independent from TP53 and MTBITC also blocked telomerase in chemoresistant subpopulations. By using an orthotopic human liver cancer xenograft model, we give first evidence that MTBITC at 50 mg/KG b.w./d significantly decreased telomerase activity in vivo without affecting enzyme activity of adjacent normal tissue. Upon drug exposure, telomerase decrease was consistent with a dose-dependent switch to anti-survival, cell arrest and apoptosis in our in vitro HCC models. Blocking telomerase by the specific inhibitor TMPyP4 further sensitized cancer cells to MTBITC-mediated cytotoxicity. Overexpression of hTERT, but not enzyme activity deficient DNhTERT, protected against apoptosis; neither DNA damage nor cytostasis induction by MTBITC was prevented by hTERT overexpression. These findings imply that telomerase enzyme activity does not protect against MTBITC-induced DNA damage but impacts signalling processes upstream of apoptosis execution level. PMID:25256442

  5. Neuroprotection by 6-(methylsulfinyl)hexyl isothiocyanate in a 6-hydroxydopamine mouse model of Parkinson׳s disease.

    PubMed

    Morroni, Fabiana; Sita, Giulia; Tarozzi, Andrea; Cantelli-Forti, Giorgio; Hrelia, Patrizia

    2014-11-17

    A number of pathogenic factors have been implicated in the progression of Parkinson׳s disease (PD), including oxidative stress, mitochondrial dysfunction, inflammation, excitotoxicity, and signals mediating apoptosis cascade. 6-(methylsulfinyl)hexyl isothiocyanate (6-MSITC) is a major component in wasabi, a very popular spice in Japan and a member of the Brassica family of vegetables. This study was designed to investigate the neuroprotective effects of 6-MSITC in a PD mouse model. Mice were treated with 6-MSITC (5mg/kg twice a week) for four weeks after the unilateral intrastriatal injection of 6-hydroxydopamine (6-OHDA). On the 28th day, 6-OHDA-injected mice showed behavioral impairments, a significant decrease in tyrosine hydroxylase (TH) and an increase in apoptosis. In addition, lesioned mice showed reduced glutathione levels and glutathione-S-transferase and glutathione reductase activities. Notably, 6-MSITC demonstrated neuroprotective effects in our experimental model strongly related to the preservation of functional nigral dopaminergic neurons, which contributed to the reduction of motor dysfunction induced by 6-OHDA. Furthermore, this study provides evidence that the beneficial effects of 6-MSITC could be attributed to the decrease of apoptotic cell death and to the activation of glutathione-dependent antioxidant systems. These findings may render 6-MSITC as a promising molecule for further pharmacological studies on the investigation for disease-modifying treatment in PD. PMID:25257035

  6. Benzylation of Nitroalkanes Using Copper-Catalyzed Thermal Redox Catalysis: Toward the Facile C-Alkylation of Nitroalkanes

    PubMed Central

    Gildner, Peter G.; Gietter, Amber A. S.; Cui, Di; Watson, Donald A.

    2012-01-01

    The C-alkylation of nitroalkanes under mild conditions has been a significant challenge in organic synthesis for more than a century. Herein, we report a simple Cu(I) catalyst, generated in situ, that is highly effective for C-benzylation of nitroalkanes using abundant benzyl bromides and related heteroaromatic compounds. This process, which we believe proceeds via a thermal redox mechanism, allows access to a variety of complex nitroalkanes under mild reaction conditions and represents the first step towards developing a general catalytic system for the alkylation of nitroalkanes. PMID:22691127

  7. Catalytic asymmetric benzylic C-H activation by means of carbenoid-induced C-H insertions.

    PubMed

    Davies, Huw M L; Jin, Qihui; Ren, Pingda; Kovalevsky, Andrey Yu

    2002-06-14

    Tetrakis[N-[4-dodecylphenyl)sulfonyl]-(S)-prolinate]dirhodium [Rh(2)(S-DOSP)(4)]-catalyzed decomposition of methyl aryldiazoacetates in the presence of substituted ethylbenzenes results in benzylic C-H activation by means of a rhodium-carbenoid-induced C-H insertion. A Hammet study showed that positive charge buildup occurred on the benzylic carbon in the transition state of the C-H activation step. C-H activation of toluene and isopropylbenzene is possible, but a competing double cyclopropanation occurs with these substrates. The C-H activation is highly regioselective and enantioselective, and in certain cases, moderate diastereoselectivity is also possible. PMID:12054951

  8. Evaluation of Fe and Ru Pincer-Type Complexes as Catalysts for the Racemization of Secondary Benzylic Alcohols.

    PubMed

    Bornschein, Christoph; Gustafson, Karl P J; Verho, Oscar; Beller, Matthias; Bäckvall, Jan-E

    2016-08-01

    Fe and Ru pincer-type catalysts are used for the racemization of benzylic alcohols. Racemization with the Fe catalyst was achieved within 30 minutes under mild reaction conditions, with a catalyst loading as low as 2 mol %. This reaction constitutes the first example of an iron-catalyzed racemization of an alcohol. The efficiency for racemization of the Fe catalyst and its Ru analogue was evaluated for a wide range of sec-benzylic alcohols. The commercially available Ru complex proved to be highly robust and even tolerated the presence of water in the reaction mixture. PMID:27311070

  9. Convenient synthesis of 4,6-di-O-benzyl-myo-inositol and myo-inositol 1,3,5-orthoesters.

    PubMed

    Praveen, T; Shashidhar, M S

    2001-02-15

    Convenient high yielding methods for the preparation of 4,6-di-O-benzyl-myo-inositol, myo-inositol 1,3,5-orthoformate and myo-inositol 1,3,5-orthoacetate, without involving chromatography are described. Myo-inositol was converted to racemic 2,4-di-O-benzoyl-myo-inositol 1,3,5-orthoformate by successive treatment with triethyl orthoformate and benzoyl chloride. The dibenzoate obtained on benzylation with benzyl bromide and silver(I) oxide gave 2-O-benzoyl-4,6-di-O-benzyl-myo-inositol 1,3,5-orthoformate. Deprotection of the benzoate and the orthoformate with isobutylamine and aqueous trifluoroacetic acid, respectively gave 4,6-di-O-benzyl-myo-inositol in an overall yield of 67%. Myo-inositol orthoformate and orthoacetate were prepared and isolated as their tribenzoates. The free orthoesters were regenerated by deprotection of the benzoates by aminolysis with isobutylamine. PMID:11270820

  10. Gluonic structure of the constituent quark

    NASA Astrophysics Data System (ADS)

    Kochelev, Nikolai; Lee, Hee-Jung; Zhang, Baiyang; Zhang, Pengming

    2016-06-01

    Based on both the constituent quark picture and the instanton model for QCD vacuum, we calculate the unpolarized and polarized gluon distributions in the constituent quark and in the nucleon. Our approach consists of the two main steps. At the first step, we calculate the gluon distributions inside the constituent quark generated by the perturbative quark-gluon interaction, the non-perturbative quark-gluon interaction, and the non-perturbative quark-gluon-pion anomalous chromomagnetic interaction. The non-perturbative interactions are related to the existence of the instantons, strong topological fluctuations of gluon fields, in the QCD vacuum. At the second step, the convolution model is applied to derive the gluon distributions in the nucleon. A very important role of the pion field in producing the unpolarized and the polarized gluon distributions in the hadrons is discovered. We discuss a possible solution of the proton spin problem.

  11. Selective liquid phase oxidation of benzyl alcohol catalyzed by copper aluminate nanostructures

    NASA Astrophysics Data System (ADS)

    Ragupathi, C.; Judith Vijaya, J.; Thinesh Kumar, R.; John Kennedy, L.

    2015-01-01

    In this paper, a simple and economic route for the preparation of CuAl2O4 is proposed. The method was developed with the objective of obtaining a material with greater surface area, when compared to the spinel prepared by conventional combustion method (CCM). The catalytic properties of CuAl2O4 spinel prepared by CCM are compared with the one prepared microwave combustion method (MCM). Nano-sized CuAl2O4 were synthesized by both CCM and MCM using Opuntia dillenii haw as the plant extract, and were characterized by X-ray diffraction analysis (XRD), high resolution scanning electron microscopy (HR-SEM), N2 adsorption/desorption isotherms, and diffuse reflectance spectroscopy (DRS). Oxidation to their corresponding carbonyl compounds, high selectivity, and inexpensive precursors make this catalytic system a useful oxidation method for benzyl alcohol. The XRD results confirmed the formation of a cubic CuAl2O4. The formation of CuAl2O4 nanorices and nanorods structures were confirmed by HR-SEM. Through MCM method, CuAl2O4 (sample B) with a high specific surface area of was obtained. The band gap values of the (2.30 and 2.35 eV) for the obtained oxides are due to the nanometric dimensions of the nanostructures. The effect of the solvent, temperature, and oxidant on the oxidation of benzyl alcohol is reported.

  12. Preparation and characterization of phenyl-, benzyl-, and phenethyl-substituted polysilsesquioxanes

    SciTech Connect

    Schneider, D.A.; Loy, D.A.; Baugher, B.M.; Wheeler, D.R.; Assink, R.A.; Alam, T.M.; Saunders, R.

    1998-09-01

    Polysilsesquioxanes are a class of siloxane polymers commonly prepared by the hydrolysis and condensation of trialkoxysilanes or trichlorosilanes. From a trifunctional monomer one would expect the organically-modified polymers to be highly crosslinked and insoluble resins. However, while some silsesquioxane monomers with R = H, CH{sub 3}, or vinyl do form crosslinked polymers capable of forming gels, the majority react to form soluble oligosilsesquioxanes, including discrete polyhedral oligomers, and polymers. Because of their solubility, ladder structures have been proposed. However, viscosity studies by Frye indicate that the polyphenylsilsesquioxane is more likely best represented by a polymer rich in both cyclic structures and branches, but without any regular stereochemistry. In this study, the authors have examined the hydrolysis and condensation polymerizations of phenyltrialkoxysilane, benzyltrialkoxysilane, and 2-phenethyltrialkoxysilane monomers under both acidic and basic conditions. The resulting phenyl, benzyl and phenethyl-substituted polysilsesquioxanes were characterized by {sup 1}H, {sup 13}C, {sup 29}Si NMR, gel permeation chromatography, and differential scanning calorimetry. The effects of the organic substituent (phenyl, benzyl, phenethyl), alkoxide group (OMe, OEt), catalyst (HCl, NaOH), monomer concentration, and polymer processing on polymer molecular weight and glass transition temperature were determined.

  13. Contrasting retrogressive rearrangement pathways during thermolysis of silica-immobilized benzyl phenyl ether

    SciTech Connect

    Buchanan, A.C. III; Britt, P.F.; Skeen, J.T.

    1997-03-01

    Many coal model compound studies have focused on the mechanisms of bond cleavage reactions, and the means to alter reaction conditions to promote such reactions. However, there has become increasing interest in elucidating mechanisms associated with retrogressive or retrograde reactions in coal processing, which involve the formation of refractory bonds. Retrograde reactions inhibit efficient thermochemical processing of coals into liquid fuels, which has been particularly well-documented for low rank coals where abundant oxygen-containing functional groups are thought to play a key role in the chemistry. Much less is known about retrogressive reactions for ether-containing model compounds. Radical recombination through ring coupling of phenoxy radicals in benzyl phenyl ether (BPE) is known to lead to more refractory diphenylmethane linkages to a limited extent. Since this chemistry may be attributed at least in part to cage recombination, it could be promoted in a diffusionally constrained environment such as in the coal macromolecule. Using silica-immobilization to simulate restricted diffusion in coal, the authors have found that retrogressive reactions can be promoted for certain hydrocarbon model compounds. The authors have now begun an examination of the thermolysis behavior of silica-immobilized benzyl phenyl ether at 275--325 C. The initial results indicate that two retrogressive reaction pathways, radical recombination and molecular rearrangement through Si-O-C linkage to the surface of PhOCH{center_dot}Ph, are promoted by restricted diffusion. Remarkably, the retrograde products typically account for 50 mol% of the thermolysis products.

  14. Spectroscopy Identification of Benzyl-Type Radicals Generated by Corona Discharge of Precursors of Mixed Substituents

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Huh, Chang Soon; Lee, Sang Kuk

    2012-06-01

    We generated vibronically excited but jet-cooled benzyl-type radicals from corona discharge of precursor of mixed substituents using a technique of corona excited supersonic expansion coupled with a pinhole-type glass nozzle, from which the visible vibronic emission spectra were recorded with a long-path monochromator. The spectra exhibit the intensity variation of each species with discharging voltage, indicating the radical species generated in corona discharge is highly sensitive to excitation. From the analysis of the spectra, we found the Cl substituent is replaced in preference to the F substituent by the hydrogen atoms liberated from the dissociation of the C-H bond of the methyl group of the precursor, from which we proposed the possible mechanism for the elimination reaction of substituent in terms of the bond dissociation energy. Additionally, we obtained an accurate electronic energy in the D_1 → D_0 transition and the vibrational mode frequencies of newly detected benzyl-type radicals in the ground electronic state by comparison with those of ab initio calculations and the known spectroscopic data of precursors for the first time.

  15. Highly Dispersed Gold Nanoparticles Supported on SBA-15 for Vapor Phase Aerobic Oxidation of Benzyl Alcohol.

    PubMed

    Kumar, Ashish; Sreedhar, Bojja; Chary, Komandur V R

    2015-02-01

    Gold nanoparticles supported on SBA-15 are prepared by homogenous deposition-precipitation method (HDP) using urea as the precipitating agent. The structural features of the synthesized catalysts were characterized by various techniques such as X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption (BET), pore size distribution (PSD), CO chemisorption and X-ray photoelectron spectroscopy (XPS). The catalytic activity and stability of the Au/SBA-15 catalysts are investigated during the vapor phase aerobic oxidation of benzyl alcohol. The BJH pore size distribution results of SBA-15 support and Au/SBA-15 catalysts reveals that the formation of mesoporous structure in all the samples. TEM results suggest that Au nanoparticles are highly dispersed over SBA-15 and long range order of hexagonal mesopores of SBA-15 is well retained even after the deposition of Au metallic nanoparticles. XPS study reveals the formation of Au (0) after chemical reduction by NaBH4. The particle size measured from CO-chemisorption and TEM analysis are well correlated with the TOF values of the reaction. Au/SBA-1 5 catalysts are found to show higher activity compare to Au/TiO2 and Au/MgO catalysts during the vapor phase oxidation of benzyl alcohol. The catalytic functionality are well substantiated with particle size measured from TEM. The crystallite size of Au in both fresh and spent catalysts were measured from X-ray diffraction. PMID:26353720

  16. Pyrolysis of silica-immobilized benzyl phenyl ether: Competing radical rearrangement pathways under restricted diffusion

    SciTech Connect

    Buchanan, A.C. III; Britt, P.F.; Skeen, J.T.; Struss, J.A.; Elam, C.L.

    1998-12-25

    Pyrolysis studies of silica-immobilized benzyl phenyl ether ({approx}PhOCH{sub 2}Ph or {approx}BPE), a model for related ether structures in fuel resources, have been conducted at 275--325 C to examine the impact of restricted mass transport on the pyrolysis mechanism compared with previous studies in fluid phases. Significant rearrangement chemistry is observed for {approx}BPE occurring through two competitive free-radical pathways that are both promoted by the diffusional constraints. One path involves recombination of incipient benzyl and surface-bound phenoxy radicals to form benzylphenol isomers, 10. The second, previously unreported rearrangement path for {approx}BPE involves a 1,2-phenyl shift in an intermediate radical, {approx}PhOCH{center_dot}Ph, leading to formation of benzhydrol (8) and benzophenone (9) as principal products. The rearrangement products 8--10 typically account for ca. 50% of the pyrolysis products. However, the path selectivity is a sensitive function of {approx}BPE surface coverage and the presence of spacer molecules that either facilitate or hinder hydrogen atom transfer steps on the surface.

  17. Comparison of blood flow to the cutaneous temperature and redness after topical application of benzyl nicotinate

    NASA Astrophysics Data System (ADS)

    Jacobi, Ute; Kaiser, Marco; Koscielny, Jürgen; Schuetz, Rijk; Meinke, Martina C.; Sterry, Wolfram; Lademann, Jürgen

    2006-01-01

    The topical application of drugs, such as nicotinates, affects cutaneous blood flow. Such a biological response, which is dependent on the drug and the individual, can be measured noninvasively using laser Doppler flowmetry. We illustrate the kinetics of vasodilation caused by topically applied benzyl nicotinate using a new frequency-selective laser Doppler flowmeter. This flowmeter measures the blood flow in the superficial dermal plexus and the deeper lying larger capillaries simultaneously and indirectly by determining the flow velocity. Both sets of data are compared with the skin temperature and redness. Four biological parameters are measured consecutively on a skin area treated with gel containing benzyl nicotinate and on an untreated control area. A linear relationship between both blood flows is observed. However, no correlation is obtained between the microcirculation with either the cutaneous temperature or the redness. These results indicate the transport of the drug in the blood from the upper to the deeper capillaries. Cutaneous temperature and redness are unsuitable parameters to measure the kinetics of the blood flow after topical application of drugs.

  18. Catalytic hydrodechlorination of benzyl chloride promoted by Rh-N-heterocyclic carbene catalysts.

    PubMed

    Lázaro, Guillermo; Polo, Víctor; Fernández-Alvarez, Francisco J; García-Orduña, Pilar; Lahoz, Fernando J; Iglesias, Manuel; Pérez-Torrente, Jesús J; Oro, Luis A

    2015-02-01

    The rhodium(I) complexes [Rh(Cl)(COD)(R-NHC-(CH2 )3 Si(OiPr)3 )] [COD=cyclooctadiene; R=2,6-diisopropylphenyl (1 a); n-butyl (1 b)] are effective catalyst precursors for the homogeneous hydrodechlorination of benzyl chloride using HSiEt3 as hydrogen source. This reaction is selective to the formation of toluene. However, in presence of a stoichiometric amount of potassium tert-butoxide (KtBuO) the formation of mixtures containing toluene together with 17-19 mol % of the C--C homocoupling product, namely PhCH2 CH2 Ph, is observed. A mechanism proposal based on experimental insights and theoretical calculations at the DFT level that allows explanation of the experimental findings is included. Moreover, the heterogeneous catalytic system based on catalyst 1 a supported on MCM-41 has been demonstrated to be effective for the solvent-free hydrodechlorination of benzyl chloride using HSiEt3 and HSiMe(OSiMe3 )2 . PMID:25504980

  19. Visible light driven benzyl alcohol dehydrogenation in a dye-sensitized photoelectrosynthesis cell.

    PubMed

    Song, Wenjing; Vannucci, Aaron K; Farnum, Byron H; Lapides, Alexander M; Brennaman, M Kyle; Kalanyan, Berç; Alibabaei, Leila; Concepcion, Javier J; Losego, Mark D; Parsons, Gregory N; Meyer, Thomas J

    2014-07-01

    Light-driven dehydrogenation of benzyl alcohol (BnOH) to benzaldehyde and hydrogen has been shown to occur in a dye-sensitized photoelectrosynthesis cell (DSPEC). In the DSPEC, the photoanode consists of mesoporous films of TiO2 nanoparticles or of core/shell nanoparticles with tin-doped In2O3 nanoparticle (nanoITO) cores and thin layers of TiO2 deposited by atomic layer deposition (nanoITO/TiO2). Metal oxide surfaces were coderivatized with both a ruthenium polypyridyl chromophore in excess and an oxidation catalyst. Chromophore excitation and electron injection were followed by cross-surface electron-transfer activation of the catalyst to -Ru(IV)═O(2+), which then oxidizes benzyl alcohol to benzaldehyde. The injected electrons are transferred to a Pt electrode for H2 production. The nanoITO/TiO2 core/shell structure causes a decrease of up to 2 orders of magnitude in back electron-transfer rate compared to TiO2. At the optimized shell thickness, sustained absorbed photon to current efficiency of 3.7% was achieved for BnOH dehydrogenation, an enhancement of ~10 compared to TiO2. PMID:24933178

  20. Synthesis of Amaryllidaceae Constituents and Unnatural Derivatives.

    PubMed

    Ghavre, Mukund; Froese, Jordan; Pour, Milan; Hudlicky, Tomas

    2016-05-01

    This update covers the syntheses of Amaryllidaceae alkaloids since the publication of the last major review in 2008. A short summary of past syntheses and their step count is provided for the major constituents; pancratistatin, 7-deoxypancratistatin, narciclasine, lycoricidine, lycorine, and for other natural constituents, as well as for unnatural derivatives. Discussion of biological activities is provided for unnatural derivatives. Future prospects and further developments in this area are covered at the end of the review. The literature is covered to the end of August 2015. PMID:26969844

  1. Antichagasic and trichomonacidal activity of 1-substituted 2-benzyl-5-nitroindazolin-3-ones and 3-alkoxy-2-benzyl-5-nitro-2H-indazoles.

    PubMed

    Fonseca-Berzal, Cristina; Ibáñez-Escribano, Alexandra; Reviriego, Felipe; Cumella, José; Morales, Paula; Jagerovic, Nadine; Nogal-Ruiz, Juan José; Escario, José Antonio; da Silva, Patricia Bernardino; Soeiro, Maria de Nazaré C; Gómez-Barrio, Alicia; Arán, Vicente J

    2016-06-10

    Two series of new 5-nitroindazole derivatives, 1-substituted 2-benzylindazolin-3-ones (6-29, series A) and 3-alkoxy-2-benzyl-2H-indazoles (30-37, series B), containing differently functionalized chains at position 1 and 3, respectively, have been synthesized starting from 2-benzyl-5-nitroindazolin-3-one 5, and evaluated against the protozoan parasites Trypanosoma cruzi and Trichomonas vaginalis, etiological agents of Chagas disease and trichomonosis, respectively. Many indazolinones of series A were efficient against different morphological forms of T. cruzi CL Brener strain (compounds 6, 7, 9, 10 and 19-21: IC50 = 1.58-4.19 μM for epimastigotes; compounds 6, 19-21 and 24: IC50 = 0.22-0.54 μM for amastigotes) being as potent as the reference drug benznidazole. SAR analysis suggests that electron-donating groups at position 1 of indazolinone ring are associated with an improved antichagasic activity. Moreover, compounds of series A displayed low unspecific toxicities against an in vitro model of mammalian cells (fibroblasts), which were reflected in high values of the selectivity indexes (SI). Compound 20 was also very efficient against amastigotes from Tulahuen and Y strains of T. cruzi (IC50 = 0.81 and 0.60 μM, respectively), showing low toxicity towards cardiac cells (LC50 > 100 μM). In what concerns compounds of series B, some of them displayed moderate activity against trophozoites of a metronidazole-sensitive isolate of T. vaginalis (35 and 36: IC50 = 9.82 and 7.25 μM, respectively), with low unspecific toxicity towards Vero cells. Compound 36 was also active against a metronidazole-resistant isolate (IC50 = 9.11 μM) and can thus be considered a good prototype for the development of drugs directed to T. vaginalis resistant to 5-nitroimidazoles. PMID:27017556

  2. 40 CFR 264.93 - Hazardous constituents.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 264.93 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) STANDARDS FOR OWNERS AND OPERATORS OF HAZARDOUS WASTE TREATMENT, STORAGE, AND DISPOSAL FACILITIES Releases From Solid Waste Management Units § 264.93 Hazardous constituents. (a) The Regional Administrator...

  3. 40 CFR 264.93 - Hazardous constituents.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 264.93 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) SOLID WASTES (CONTINUED) STANDARDS FOR OWNERS AND OPERATORS OF HAZARDOUS WASTE TREATMENT, STORAGE, AND DISPOSAL FACILITIES Releases From Solid Waste Management Units § 264.93 Hazardous constituents. (a) The Regional Administrator...

  4. Inorganic constituents of some Turkish lignites

    SciTech Connect

    Yaman, S.; Taptik, Y.; Yavuz, R.; Kuecuekbayrak, S.

    1996-12-31

    In this study the mineral matter contents of two different Turkish lignite samples from Cayirhan and Tuncbilek regions were isolated by means of mild oxidation of organic matrix applying H{sub 2}O{sub 2}/HCOOH treatment. The isolated minerals were analyzed by XRD and FTIR techniques and constituents of the minerals were investigated qualitatively.

  5. The Constituent Quark Model: a Status Report

    SciTech Connect

    Eric S. Swanson

    2002-06-07

    A brief and biased overview of the status of the constituent quark model is presented. We concentrate on open issues and goals of hadronic phenomenology, rather than specific physics conundrums in the field. Modern attempts at addressing these issues are also presented.

  6. A Good College President: The Constituent View.

    ERIC Educational Resources Information Center

    Fujita, Eleanor

    1994-01-01

    This study explores the views of campus constituent groups about what makes a good college president. Interviews with 142 members of the governing board, senior administrators, and faculty leaders indicate that competent, patient leaders who are constantly attentive to relationships and meaning are the most highly valued. (SLD)

  7. Earth GRAM-99 and Trace Constituents

    NASA Technical Reports Server (NTRS)

    Justus, C. G.; Duvall, Aleta; Keller, Vernon W.

    2004-01-01

    Global Reference Atmospheric Model (GRAM-99) is an engineering-level model of Earth's atmosphere. It provides both mean values and perturbations for density, temperature, pressure, and winds, as well as monthly- and geographically-varying trace constituent concentrations. From 0-27 km, GRAM thermodynamics and winds are based on National Oceanic and Atmospheric Administration Global Upper Air Climatic Atlas (GUACA) climatology. Above 120 km, GRAM is based on the NASA Marshall Engineering Thermosphere (MET) model. In the intervening altitude region, GRAM is based on Middle Atmosphere Program (MAP) climatology that also forms the basis of the 1986 COSPAR International Reference Atmosphere (CIRA). Atmospheric composition is represented in GRAM by concentrations of both major and minor species. Above 120 km, MET provides concentration values for N2, O2, Ar, O, He, and H. Below 120 km, species represented also include H2O, O3, N2O, CO, CH4, and CO2. At COSPAR 2002 a comparison was made between GRAM constituents below 120 km and those provided by Naval Research Laboratory (NRL) climatology. No current need to update GRAM constituent climatology in that height range was identified. This report examines GRAM (MET) constituents between 100 and 1000 km altitudes. Discrepancies are noted between GRAM (MET) constituent number densities and mass density or molecular weight. Near 110 km altitude, there is up to about 25% discrepancy between MET number density and mass density (with mass density being valid and number densities requiring adjustment). Near 700 km altitude there is also up to about 25% discrepancy between MET number density and mean molecular weight (with molecular weight requiring adjustment). In neither case are MET mass density estimates invalidated. These discrepancies have been traced to MET subroutines SLV (which affects 90-170 km height range) and SLVH (which affects helium above 440 km altitude). With these discrepancies corrected, results are presented to

  8. Synthesis, antitumor activity and molecular docking study of some novel 3-benzyl-4(3H)quinazolinone analogues.

    PubMed

    Al-Suwaidan, Ibrahim A; Abdel-Aziz, Alaa A-M; Shawer, Taghreed Z; Ayyad, Rezk R; Alanazi, Amer M; El-Morsy, Ahmad M; Mohamed, Menshawy A; Abdel-Aziz, Naglaa I; El-Sayed, Magda A-A; El-Azab, Adel S

    2016-01-01

    A novel series of 3-benzyl-substituted-4(3H)-quinazolinones were designed, synthesized and evaluated for their in vitro antitumor activity. The results of this study demonstrated that 2-(3-benzyl-6-methyl-4-oxo-3,4-dihydroquinazolin-2-ylthio)-N-(3,4,5-trimethoxyphenyl)acetamide, 2-(3-benzyl-6,7-dimethoxy-4-oxo-3,4-dihydroquinazolin-2-ylthio)-N-(3,4,5-trimethoxyphenyl)acetamide and 3-(3-benzyl-6-methyl-4-oxo-3,4-dihydroquinazolin-2-ylthio)-N-(3,4,5-trimethoxyphenyl)-propanamide have shown amazing broad spectrum antitumor activity with mean GI(50) (10.47, 7.24 and 14.12 µM. respectively), and are nearly 1.5-3.0-fold more potent compared with the positive control 5-FU with mean GI50, 22.60 µM. On the other hand, compounds 6 and 10 yielded selective activities toward CNS, renal and breast cancer cell lines, whereas compound 9 showed selective activities towards leukemia cell lines. Molecular docking methodology was performed for compounds 7 and 8 into ATP binding site of EGFR-TK which showed similar binding mode to erlotinib, while compound 11 into ATP binding site of B-RAF kinase inhibited the growth of melanoma cell lines through inhibition of B-RAF kinase, similar to PLX4032. PMID:25815668

  9. An Oxidation of Benzyl Methyl Ethers with NBS that Selectively Affords Either Aromatic Aldehydes or Aromatic Methyl Esters

    PubMed Central

    Mayhoub, Abdelrahman S.; Talukdar, Arindam; Cushman, Mark

    2010-01-01

    Either mono- or di-bromination of benzyl methyl ethers can be achieved by controlling the amount of NBS and the temperature. Elimination of methyl bromide from the monobrominated intermediates produces aromatic aldehydes, whereas hydrolysis of the dibrominated intermediates affords aromatic methyl esters in good yields. PMID:20373742

  10. 40 CFR 721.10457 - 1,2-Benzenedicarboxylic acid, mixed esters with benzyl alc., cyclohexanol, 2-ethyl-1-hexanol...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... esters with benzyl alc., cyclohexanol, 2-ethyl-1-hexanol, fumaric acid and propylene glycol. 721.10457...-hexanol, fumaric acid and propylene glycol. (a) Chemical substance and significant new uses subject to... alc., cyclohexanol, 2-ethyl-1-hexanol, fumaric acid and propylene glycol (PMN P-03-154; CAS No....

  11. 40 CFR 721.10457 - 1,2-Benzenedicarboxylic acid, mixed esters with benzyl alc., cyclohexanol, 2-ethyl-1-hexanol...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... esters with benzyl alc., cyclohexanol, 2-ethyl-1-hexanol, fumaric acid and propylene glycol. 721.10457...-hexanol, fumaric acid and propylene glycol. (a) Chemical substance and significant new uses subject to... alc., cyclohexanol, 2-ethyl-1-hexanol, fumaric acid and propylene glycol (PMN P-03-154; CAS No....

  12. Polythiophene-block-poly(γ-benzyl L-glutamate): Synthesis and study of a new rod-rod block copolymer

    SciTech Connect

    Wu, Zong-Quan; Ono, Robert J.; Chen, Zheng; Li, Zicheng; Bielawski, Christopher W.

    2011-01-01

    Coupling of ethynyl terminated poly(3-hexylthiophene) with azide terminated poly(γ-benzyl L-glutamate) afforded the respective block copolymer in good yield and high purity; this material was found to self assemble into hierarchal structures in solution and in the solid state.

  13. Decarboxylative Csp(3)-Csp(3) coupling for benzylation of unstable ketone enolates: synthesis of p-(acylethyl)phenols.

    PubMed

    Wang, Sasa; Chen, Xinzheng; Ao, Qiaoqiao; Wang, Huifei; Zhai, Hongbin

    2016-08-01

    A new decarboxylative Csp(3)-Csp(3) coupling approach for the benzylation of ketone enolates has been developed. A variety of raspberry ketone derivatives were conveniently synthesized in good to excellent yields under mild conditions. A crossover reaction shed light on the mechanism of this tandem reaction. PMID:27378390

  14. Nickel-catalyzed synthesis of (E)-olefins from benzylic alcohol derivatives and arylacetonitriles via C-O activation.

    PubMed

    Xiao, Jing; Yang, Jia; Chen, Tieqiao; Han, Li-Biao

    2016-02-01

    An efficient Ni-catalyzed synthesis of (E)-olefins using the readily available benzylic alcohol derivatives and arylacetonitriles is described. This transformation should proceed via a tandem process involving nickel-catalyzed cross coupling via C-O activation and subsequent stereoselective E2 elimination. PMID:26699396

  15. Synthesis Antimicrobial and Anticancer Evaluation of 1-Aryl-5-(o-methoxyphenyl)-2-S-benzyl Isothiobiurets

    PubMed Central

    Ansari, Mohammed M.; Deshmukh, Shirish P.; Khan, Rizwan; Musaddiq, Mohammed

    2014-01-01

    A series of S-benzyl aryl thiourea were condensed with o-Methoxy phenyl isocyanate to yield respective isothiobiuret derivatives. The newly synthesized compounds were characterized by 1H-NMR, IR, and Mass Spectral studies and tested for biological activities. PMID:25505990

  16. Simple palladium(II) precatalyst for Suzuki-Miyaura couplings: efficient reactions of benzylic, aryl, heteroaryl, and vinyl coupling partners.

    PubMed

    Burns, Michael J; Fairlamb, Ian J S; Kapdi, Anant R; Sehnal, Petr; Taylor, Richard J K

    2007-12-20

    trans-PdBr(N-Succ)(PPh3)2 (1) is a universally effective precatalyst for Suzuki-Miyaura cross-couplings of benzylic halides with aryl- or heteroarylboronic acids. Substituted aryl halides and halogenated cyclic enones can be cross-coupled with aryl- or vinylboronic acids in excellent yields. Catalyst recycling is also demonstrated. PMID:18047357

  17. Dietary isothiocyanates, glutathione S-transferase polymorphisms and colorectal cancer risk in the Singapore Chinese Health Study.

    PubMed

    Seow, Adeline; Yuan, Jian-Min; Sun, Can-Lan; Van Den Berg, David; Lee, Hin-Peng; Yu, Mimi C

    2002-12-01

    Dietary intake of cruciferous vegetables (Brassica spp.) has been inversely related to colorectal cancer risk, and this has been attributed to their high content of glucosinolate degradation products such as isothiocyanates (ITCs). These compounds act as anticarcinogens by inducing phase II conjugating enzymes, in particular glutathione S-transferases (GSTs). These enzymes also metabolize ITCs, such that the protective effect of cruciferous vegetables may predicate on GST genotype. The Singapore Chinese Health Study is a prospective investigation among 63 257 middle-aged men and women, who were enrolled between April 1993 and December 1998. In this nested case-control analysis, we compared 213 incident cases of colorectal cancer with 1194 controls. Information on dietary ITC intake from cruciferous vegetables, collected at recruitment via a semi-quantitative food frequency questionnaire, was combined with GSTM1, T1 and P1 genotype from peripheral blood lymphocytes or buccal mucosa. When categorized into high (greater than median) and low (less than/equal to median) intake, dietary ITC was slightly lower in cases than controls but the difference was not significant [odds ratio (OR) 0.81, 95% confidence interval (CI) 0.59-1.12]. There were no overall associations between GSTM1, T1 or P1 genotypes and colorectal cancer risk. However, among individuals with both GSTM1 and T1 null genotypes, we observed a 57% reduction in risk among high versus low consumers of ITC (OR 0.43, 95% CI 0.20-0.96), in particular for colon cancer (OR 0.31, 0.12-0.84). Our results are compatible with the hypothesis that ITCs from cruciferous vegetables modify risk of colorectal cancer in individuals with low GST activity. Further, this gene-diet interaction may be important in studies evaluating the effect of risk-enhancing compounds in the colorectum. PMID:12507929

  18. Comparative systems biology analysis to study the mode of action of the isothiocyanate compound Iberin on Pseudomonas aeruginosa.

    PubMed

    Tan, Sean Yang-Yi; Liu, Yang; Chua, Song Lin; Vejborg, Rebecca Munk; Jakobsen, Tim Holm; Chew, Su Chuen; Li, Yingying; Nielsen, Thomas E; Tolker-Nielsen, Tim; Yang, Liang; Givskov, Michael

    2014-11-01

    Food is now recognized as a natural resource of novel antimicrobial agents, including those that target the virulence mechanisms of bacterial pathogens. Iberin, an isothiocyanate compound from horseradish, was recently identified as a quorum-sensing inhibitor (QSI) of the bacterial pathogen Pseudomonas aeruginosa. In this study, we used a comparative systems biology approach to unravel the molecular mechanisms of the effects of iberin on QS and virulence factor expression of P. aeruginosa. Our study shows that the two systems biology methods used (i.e., RNA sequencing and proteomics) complement each other and provide a thorough overview of the impact of iberin on P. aeruginosa. RNA sequencing-based transcriptomics showed that iberin inhibits the expression of the GacA-dependent small regulatory RNAs RsmY and RsmZ; this was verified by using gfp-based transcriptional reporter fusions with the rsmY or rsmZ promoter regions. Isobaric tags for relative and absolute quantitation (iTRAQ) proteomics showed that iberin reduces the abundance of the LadS protein, an activator of GacS. Taken together, the findings suggest that the mode of QS inhibition in iberin is through downregulation of the Gac/Rsm QS network, which in turn leads to the repression of QS-regulated virulence factors, such as pyoverdine, chitinase, and protease IV. Lastly, as expected from the observed repression of small regulatory RNA synthesis, we also show that iberin effectively reduces biofilm formation. This suggests that small regulatory RNAs might serve as potential targets in the future development of therapies against pathogens that use QS for controlling virulence factor expression and assume the biofilm mode of growth in the process of causing disease. PMID:25155599

  19. Protection of humans by plant glucosinolates: efficiency of conversion of glucosinolates to isothiocyanates by the gastrointestinal microflora.

    PubMed

    Fahey, Jed W; Wehage, Scott L; Holtzclaw, W David; Kensler, Thomas W; Egner, Patricia A; Shapiro, Theresa A; Talalay, Paul

    2012-04-01

    Plant-based diets rich in crucifers are effective in preventing cancer and other chronic diseases. Crucifers contain very high concentrations of glucosinolates (GS; β-thioglucoside-N-hydroxysulfates). Although not themselves protective, GS are converted by coexisting myrosinases to bitter isothiocyanates (ITC) which defend plants against predators. Coincidentally, ITC also induce mammalian genes that regulate defenses against oxidative stress, inflammation, and DNA-damaging electrophiles. Consequently, the efficiency of conversion of GS to ITC may be critical in controlling the health-promoting benefits of crucifers. If myrosinase is heat-inactivated by cooking, the gastrointestinal microflora converts GS to ITC, a process abolished by enteric antibiotics and bowel cleansing. When single oral doses of GS were administered as broccoli sprout extracts (BSE) to two dissimilar populations (rural Han Chinese and racially mixed Baltimoreans) patterns of excretions of urinary dithiocarbamates (DTC) were very similar. Individual conversions in both populations varied enormously, from about 1% to more than 40% of dose. In contrast, administration of ITC (largely sulforaphane)-containing BSE resulted in uniformly high (70%-90%) conversions to urinary DTC. Despite the remarkably large range of conversion efficiencies between individuals, repeated determinations within individuals were much more consistent. The rates of urinary excretion (slow or fast) were unrelated to the ultimate magnitudes (low or high) of these conversions. Although no demographic factors affecting conversion efficiency have been identified, there are clearly diurnal variations: conversion of GS to DTC was greater during the day, but conversion of ITC to DTC was more efficient at night. PMID:22318753

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

    PubMed

    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. PMID:27052706

  1. The MAPK Pathway Signals Telomerase Modulation in Response to Isothiocyanate-Induced DNA Damage of Human Liver Cancer Cells

    PubMed Central

    Lamy, Evelyn; Herz, Corinna; Lutz-Bonengel, Sabine; Hertrampf, Anke; Márton, Melinda-Rita; Mersch-Sundermann, Volker

    2013-01-01

    4-methylthiobutyl isothiocyanate (MTBITC), an aliphatic, sulphuric compound from Brassica vegetables, possesses in vitro and in vivo antitumor activity. Recently we demonstrated the potent growth inhibitory potential of the DNA damaging agent MTBITC in human liver cancer cells. Here we now show that MTBITC down regulates telomerase which sensitizes cells to apoptosis induction. This is mediated by MAPK activation but independent from production of reactive oxygen species (ROS). Within one hour, MTBITC induced DNA damage in cancer cells correlating to a transient increase in hTERT mRNA expression which then turned into telomerase suppression, evident at mRNA as well as enzyme activity level. To clarify the role of MAPK for telomerase regulation, liver cancer cells were pre-treated with MAPK-specific inhibitors prior to MTBITC exposure. This clearly showed that transient elevation of hTERT mRNA expression was predominantly mediated by the MAPK family member JNK. In contrast, activated ERK1/2 and P38, but not JNK, signalled to telomerase abrogation and consequent apoptosis induction. DNA damage by MTBITC was also strongly abolished by MAPK inhibition. Oxidative stress, as analysed by DCF fluorescence assay, electron spin resonance spectroscopy and formation of 4-hydroxynonenal was found as not relevant for this process. Furthermore, N-acetylcysteine pre-treatment did not impact MTBITC-induced telomerase suppression or depolarization of the mitochondrial membrane potential as marker for apoptosis. Our data therefore imply that upon DNA damage by MTBITC, MAPK are essential for telomerase regulation and consequent growth impairment in liver tumor cells and this detail probably plays an important role in understanding the potential chemotherapeutic efficacy of ITC. PMID:23382840

  2. Prevention of cigarette smoke–induced lung tumors in mice by budesonide, phenethyl isothiocyanate, and N-acetylcysteine

    PubMed Central

    Balansky, Roumen; Ganchev, Gancho; Iltcheva, Marietta; Steele, Vernon E.; De Flora, Silvio

    2009-01-01

    Lung cancer is the most important cause of death among neoplastic diseases worldwide, and cigarette smoke (CS) is the major risk factor for cancer. Complementarily to avoidance of exposure to CS, chemoprevention will lower the risk of cancer in passive smokers, ex-smokers, and addicted current smokers who fail to quit smoking. Unfortunately, chemoprevention clinical trials have produced disappointing results to date and, until recently, a suitable animal model evaluating CS carcinogenicity was not available. We previously demonstrated that mainstream CS induces a potent carcinogenic response when exposure of mice starts at birth. In the present study, neonatal mice (strain H) were exposed to CS for 120 consecutive days, starting at birth. The chemopreventive agents budesonide (2.4 mg/kg diet), phenethyl isothiocyanate (PEITC, 1,000 mg/kg diet), and N-acetyl-l-cysteine (NAC, 1,000 mg/kg body weight) were administered orally according to various protocols. The experiment was stopped after 210 days. Exposure to CS resulted in a high incidence and multiplicity of benign lung tumors and in significant increases of malignant lung tumors and other histopathological alterations. All three chemopreventive agents, administered to current smokers after weanling, were quite effective in protecting both male and female mice from CS pulmonary carcinogenicity. When given to ex-smokers after withdrawal of exposure to CS, the protective capacity of budesonide was unchanged, while PEITC lost part of its cancer chemopreventive activity. In conclusion, the proposed experimental model provides convincing evidence that it is possible to prevent CS-induced lung cancer by means of dietary and pharmacological agents. PMID:19816928

  3. Efficacy of postmilking disinfection with benzyl alcohol versus lodophor in the prevention of new intramammary infections in lactating cows.

    PubMed

    Erskine, R J; Sears, P M; Bartlett, P C; Gage, C R

    1998-01-01

    Five Michigan dairy herds participated in a split-herd study to compare the efficacy of two postmilking teat dips in the prevention of new intramammary infections (IMI) in lactating cows. Three hundred seventy cows were assigned to 4% benzyl alcohol, and 387 cows were assigned to 1% iodophor germicidal teat dip. The teat dips were applied by directly immersing the teats immediately after milking. Once a group was assigned to a teat dip, cows in that group maintained on that same teat dip throughout the trial. Total new IMI numbered 254 and 201 for cows treated with benzyl alcohol and iodophor germicidal teat dip, respectively. Staphylococcus spp. (52.0%), Staphylococcus aureus (20.1%), and Corynebacterium bovis (12.2%) were the predominant pathogens that caused new IMI in cows treated with benzyl alcohol. Staphylococcus spp., Staph. aureus, and C. bovis, respectively, were the pathogens responsible for 69.7, 12.4, and 4.5% of the new IMI in cows treated with iodophor. The incidences of new IMI caused by Staph. aureus (0.66 new IMI/100 milking quarters per mo), C. bovis (0.38 new IMI/100 milking quarters per mo), and all pathogens (3.15 new IMI/100 milking quarters per mo) were higher in cows treated with benzyl alcohol than in cows treated with iodophor (0.29, 0.11, and 2.35 new IMI/100 milking quarters per mo, respectively). Incidence of new IMI did not differ between groups for other pathogens. One percent iodophor prevented new IMI caused by contagious pathogens more effectively than did benzyl alcohol. PMID:9493086

  4. Lack of [3H]quinuclidinyl benzylate binding to biologically relevant binding sites on mononuclear cells.

    PubMed

    Adams, E M; Lubrano, T M; Gordon, J; Fields, J Z

    1992-09-01

    We analyzed the binding characteristics of [3H]quinuclidinyl benzylate ([3H]QNB), a muscarinic cholinergic ligand, to rat and human mononuclear cells (MNC). Under various assay conditions, atropine-sensitive, saturable binding occurred with an apparent Kd of 10 nM. Conditions which disrupted the MNC membrane reduced total binding and eliminated specific binding. Muscarinic agonists were unable to inhibit [3H]QNB binding to MNC at concentrations up to 10(-2) M. Stereoisomers dexetimide and levetimide were equipotent inhibitors of binding (IC50 2 x 10(-5) M). We conclude that, although atropine-sensitive binding of [3H]QNB to MNC occurs, the binding is not consistent with the presence of a biologically relevant muscarinic cholinergic receptor. PMID:1392105

  5. (E)-N'-(2-Benzyl-oxybenzyl-idene)isonicotinohydrazide methanol solvate monohydrate.

    PubMed

    Naveenkumar, H S; Sadikun, Amirin; Ibrahim, Pazilah; Hemamalini, Madhukar; Fun, Hoong-Kun

    2010-01-01

    The title compound, C(20)H(17)N(3)O(2)·CH(4)O·H(2)O, was synthesized by the condensation reaction of 2-benzyl-oxybenzaldehyde with isoniazid (isonicotinic acid hydrazide). The tricyclic compound displays a trans configuration with respect to the C=N double bond. The central benzene ring makes dihedral angles of 8.83 (7) and 70.39 (8)° with the pyridine ring and the terminal benzene ring, respectively. The dihedral angle between the pyridine ring and the terminal benzene ring is 73.11 (8)°. In the crystal structure, mol-ecules are connected by inter-molecular N-H⋯O, O-H⋯O, O-H⋯(N,N) and C-H⋯O hydrogen bonds, forming a two-dimensional network perpendicular to the a axis. PMID:21579427

  6. Removal of the endocrine disrupter butyl benzyl phthalate from the environment

    PubMed Central

    Karlovsky, Petr

    2010-01-01

    Butyl benzyl phthalate (BBP), an aryl alkyl ester of 1,2-benzene dicarboxylic acid, is extensively used in vinyl tiles and as a plasticizer in PVC in many commonly used products. BBP, which readily leaches from these products, is one of the most important environmental contaminants, and the increased awareness of its adverse effects on human health has led to a dramatic increase in research aimed at removing BBP from the environment via bioremediation. This review highlights recent progress in the degradation of BBP by pure and mixed bacterial cultures, fungi, and in sludge, sediment, and wastewater. Sonochemical degradation, a unique abiotic remediation technique, and photocatalytic degradation are also discussed. The degradation pathways for BBP are described, and future research directions are considered. PMID:20396882

  7. Crystal structure of 1-benzyl-4-formyl-1H-pyrrole-3-carb-oxamide.

    PubMed

    Zhong, Qi-Di; Hu, Sheng-Quan; Yan, Hong

    2016-02-01

    In the title compound, C13H12N2O2 (I), the mean planes of the pyrrole and benzyl rings are approximately perpendicular, forming a dihedral angle of 87.07 (4) °. There is an intra-molecular N-H⋯O hydrogen bond forming an S(7) ring motif. In the crystal, mol-ecules are linked via a pair of N-H⋯O hydrogen bonds forming inversion dimers. C-H⋯O hydrogen bonds link the dimers into chains along direction [10-1]. The chains are further linked by weak C-H⋯π inter-actions forming layers parallel to the ac plane. PMID:26958371

  8. Crystal structure of di­benzyl­dimethyl­silane

    PubMed Central

    Knauer, Lena; Golz, Christopher; Kroesen, Ulrike; Koller, Stephan G.; Strohmann, Carsten

    2015-01-01

    In the title compound, C16H20Si, a geometry different from an ideal tetra­hedron can be observed at the Si atom. The bonds from Si to the benzylic C atoms [Si—C = 1.884 (1) and 1.883 (1) Å] are slightly elongated compared to the Si—Cmeth­yl bonds [Si—C = 1.856 (1) and 1.853 (1) Å]. The Cbenz­yl—Si—Cbenz­yl bond angle [C—Si—C = 107.60 (6)°] is decreased from the ideal tetra­hedral angle by 1.9°. These distortions can be explained easily by Bent’s rule. In the crystal, mol­ecules inter­act only by van der Waals forces. PMID:26090183

  9. Crystal structure of benzyl­tri­phenyl­phospho­nium chloride monohydrate

    PubMed Central

    Ahmad, Jimmy; Abdul Halim, Siti Nadiah; How, Fiona N.-F.

    2015-01-01

    The title compound, Ph3(PhCH2)P+·Cl−·H2O, was obtained unintentionally as the product of an attempted synthesis of a silver di­thio­carbamate complex using benzyl­tri­phenyl­phospho­nium as the counter-ion. The asymmetric unit consists of a phospho­nium cation and a chloride anion, and a water mol­ecule of crystallization. In the crystal, the chloride ion is linked to the water mol­ecule by an O—H⋯Cl hydrogen bond. The three units are further linked via C—H⋯Cl and C—H⋯O hydrogen bonds and C—H⋯ π inter­actions, forming a three-dimensional structure. PMID:26090195

  10. Role of tetraalkyl(benzyl)ammonium alkoxides in the catalysis of the alkaline dehydrochlorination reaction

    SciTech Connect

    Shavanov, S.S.; Tolstikov, G.A.; Shutenkova, T.V.; Viktorov, G.A.

    1988-01-10

    The reaction was conducted by the action of aqueous NaOH taken as a 50% solution at a molar ratio to dichloroethane of 2:1 at 50-55 C in the 1% of catalyst on the dichloroethane. The results of the experiments indicated the rising activity of the tetra-alkyl(benzyl) ammonium alkoxides as the lipophilicity of the anion increased, which proceeds in the organic phase. Reaction was effected through a complex formed by the association of quaternary ammonium salts with a hydroxyl-containing compound, the solvation of the associated species with the organochlorine substrate, and coordination with NaOH. The reaction goes in the organic phase and on the interphase surface.

  11. Planar microphone based on piezoelectric electrospun poly(γ-benzyl-α,L-glutamate) nanofibers.

    PubMed

    Ren, Kailiang; West, James E; Yu, S Michael

    2014-06-01

    Velocity and pressure microphones composed of piezoelectric poly(γ-benzyl-α,L-glutamate) (PBLG) nanofibers were produced by adhering a single layer of PBLG film to a Mylar diaphragm. The device exhibited a sensitivity of -60 dBV/Pa in air, and both pressure and velocity response showed a broad frequency response that was primarily controlled by the stiffness of the supporting diaphragm. The pressure microphone response was ±3 dB between 200 Hz and 4 kHz when measured in a semi-anechoic chamber. Thermal stability, easy fabrication, and simple design make this single element transducer ideal for various applications including those for underwater and high temperature use. PMID:24907836

  12. (4-Benzyl-2-oxo-1,3-oxazolidin-5-yl)methyl methane­sulfonate

    PubMed Central

    Cunico, Wilson; Gomes, Claudia R. B.; Tiekink, Edward R. T.; Vellasco Junior, Walcimar T.; Wardell, James L.; Wardell, Solange M. S. V.

    2010-01-01

    The title compound, C12H15NO5S, features an approximately planar five-membered oxazolidin ring (r.m.s. deviation = 0.045 Å) with the peripheral benzyl and methyl methane­sulfonate residues lying to either side of the plane. In the crystal, N—H⋯O hydrogen bonds, involving one of the sulfur-bound oxo groups as acceptor, lead to the formation of supra­molecular chains along the b axis. These chains are reinforced by C—H⋯O contacts with the carbonyl O atom accepting three such inter­actions. The structure was refined as a racemic twin, with the major component being present 89% of the time. PMID:21579707

  13. Synthesis, antioxidant, enzyme inhibition and DNA binding studies of novel N-benzylated derivatives of sulfonamide

    NASA Astrophysics Data System (ADS)

    Abbas, Aadil; Murtaza, Shahzad; Tahir, Muhammad Nawaz; Shamim, Saima; Sirajuddin, Muhammad; Rana, Usman Ali; Naseem, Khadija; Rafique, Hummera

    2016-08-01

    A series of novel N-benzylated derivatives of sulfonamide were synthesized and characterized by FT-IR, NMR and XRD analysis. The synthesized compounds were assayed for their biological potential. The biological studies involved antioxidant, enzyme inhibition, and DNA interaction studies. Antioxidant potential was investigated by Ferric Reducing Antioxidant Power assay (FRAP) and DPPH free radical scavenging method, the capacity of synthesized compounds to inhibit the enzyme's activity was assayed by using the well-known Elman method whereas DNA interaction studies were carried out with the help UV-Vis absorption titration method. Moreover, a direct correlation between enzyme inhibition activity and concentration of the compounds was observed both in experimental and molecular docking studies. DNA interaction studies of the synthesized compounds showed weak interaction.

  14. Benzyl alcohol oxidation in supercritical carbon dioxide: spectroscopic insight into phase behaviour and reaction mechanism.

    PubMed

    Caravati, Matteo; Grunwaldt, Jan-Dierk; Baiker, Alfons

    2005-01-21

    Selective oxidation of benzyl alcohol to benzaldehyde with molecular oxygen over an alumina-supported palladium catalyst was performed with high rate at about 95% selectivity in supercritical carbon dioxide. The experiments in a continuous flow fixed-bed reactor showed that the pressure has a strong influence on the reaction rate. A marked increase of the rate (turnover frequency) from 900 h(-1) to 1800 h(-1) was observed when increasing the pressure from 140 to 150 bar. Video monitoring of the bulk fluid phase behavior and the simultaneous investigation by transmission and attenuated total reflection (ATR) infrared spectroscopy at two positions of the view cell showed that the sharp increase in activity is correlated to a transition from a biphasic to a monophasic reaction mixture. In the single phase region, both oxygen and benzyl alcohol are dissolved in the supercritical CO2 phase, which leads to a reduction of the mass transport resistances (both in the external fluid film and in the catalyst pores) and thus to the high reaction rate measured in the catalytic experiments. The phase transition could be effectively and easily monitored by transmission and ATR-IR spectroscopy despite the small concentration of the dense liquid like phase. Deposition of the Pd/Al2O3 catalyst on the ATR-crystal at the bottom of the view cell allowed to gain insight into the chemical changes and mass transfer processes occurring in the solid/liquid interface region during reaction. Analyzing the shift of the upsilon2 bending mode of CO2 gave information on the fluid composition in and outside the catalyst pores. Moreover, the catalytic reaction could be investigated in situ in this spectroscopic batch reactor cell by monitoring simultaneously the reaction progress, the phase behaviour and the catalytic interface. PMID:19785149

  15. Spectroscopy of Benzyl-Type Radicals Generated by Electric Discharge : Jet-Cooled Dichlorobenzyl Radicals

    NASA Astrophysics Data System (ADS)

    Yoon, Young Wook; Lee, Sang Kuk

    2013-06-01

    The technique of corona excited supersonic expansion coupled with a pinhole-type glass nozzle has been proved a useful laser-free spectroscopic tool for observation of vibronic emission spectra of large aromatic molecules, especially for molecular radicals which are long believed to play an important role as a reaction intermediate in aromatic chemical reactions. The vibronic emission spectra recorded with a long-path monochromator exhibit the electronic transition energy in the D_1 → D_0 transition and vibrational mode frequencies at the D_0 state. In this laboratory, all six isomeric dichlorobenzyl radicals have been produced from the corona discharge of corresponding dichlorotoluenes seeded in a large amount of inert carrier gas He. The vibronic emission spectra show very weak intensity due to the existence of Cl atoms in the precursor molecules and possible breakdown of benzene ring by free Cl atoms. Nevertheless, we clearly identified the origin band and a few well-known vibrational modes for each isomer. From an analysis of the spectra observed, we determined the energy of electronic transition and several vibrational modes in the ground electronic state. Also, the red-shift of the origin band from the parental benzyl radical clearly shows the substituent effect of Cl atoms on electronic energy, for which we satisfactorily explain in terms of the shape of the molecular planes and position of the nodal points at a given electronic state, recently developed in this laboratory for identification of isomeric multi-substituted benzyl-type radicals. Y. W. Yoon, C. S. Huh, and S. K. Lee, Chem. Phys. Lett. {550}, 58 (2012). S. K. Lee and S. J. Kim, Chem. Phys. Lett. {412}, 88 (2005).

  16. Finite-difference modelling of wavefield constituents

    NASA Astrophysics Data System (ADS)

    Robertsson, Johan O. A.; van Manen, Dirk-Jan; Schmelzbach, Cedric; Van Renterghem, Cederic; Amundsen, Lasse

    2015-11-01

    The finite-difference method is among the most popular methods for modelling seismic wave propagation. Although the method has enjoyed huge success for its ability to produce full wavefield seismograms in complex models, it has one major limitation which is of critical importance for many modelling applications; to naturally output up- and downgoing and P- and S-wave constituents of synthesized seismograms. In this paper, we show how such wavefield constituents can be isolated in finite-difference-computed synthetics in complex models with high numerical precision by means of a simple algorithm. The description focuses on up- and downgoing and P- and S-wave separation of data generated using an isotropic elastic finite-difference modelling method. However, the same principles can also be applied to acoustic, electromagnetic and other wave equations.

  17. [Study on chemical constituents of Picrasma quassioides].

    PubMed

    Zhu, Chenchen; Deng, Guihua; Lin, Chaozhan

    2011-04-01

    To study the chemical constituents of Picrasma quassioides. The chemical constituents were isolated and purified by chromatographic methods over Sephadex LH-20 and silica gel column, and structurally elucidated by spectral analysis, including UV, IR, MS, 1H-NMR, 13C-NMR. Fourteen compounds were obtained and identified as trifolirhizin(1), maackiain(2), 3', 7-dihydroxy-4'-methoxylisoflavone(3), umbelliferone(4), emodin(5), nigakilactone F(6), picrasin B(7),picraqualide B (8),4-methoxy-5-hydroxycanthin-6-one(9), 4,5-dimethoxycanthin-6-one (10),5-methoxycanthin-6-one(11), 11-hydroxycanthin-6-one(12) , 1-methoxycarbonyl-beta-carboline(13), 1-hydroxymethyl-beta-carboline(14). Compounds 1-5 are reported from the first time for the genus Pricrasma. PMID:21761728

  18. Beer constituents as potential cancer chemopreventive agents.

    PubMed

    Gerhäuser, Clarissa

    2005-09-01

    Beer is a complex alcoholic beverage made from barley (malt), hop, water and yeast. Phenolic constituents of beer are derived from malt (70-80%) and hop (20-30%). Structural classes include simple phenols, benzoic- and cinnamic acid derivatives, coumarins, catechins, di-, tri- and oligomeric proanthocyanidins, (prenylated) chalcones and flavonoids as well as alpha- and iso-alpha-acids derived from hop. Compounds belonging to different structural classes have distinct profiles of biological activity in in vitro test systems, and in combination might lead to enhanced effects. Scientific evidence has accumulated over the past 10 years pointing to the cancer preventive potential of selected hop-derived beer constituents, i.e., prenylflavonoids including xanthohumol and isoxanthohumol, and hop bitter acids. Chemopreventive activities observed with these compounds relevant to inhibition of carcinogenesis at the initiation, promotion and progression phases, as well as results from in vivo studies on metabolism, bioavailability and efficacy are summarised in this review. PMID:15953717

  19. Volatile Constituents of Artemisia vestita Oil1.

    PubMed

    Weyerstahl, P; Kaul, V K; Weirauch, M; Marschall-Weyerstahl, H

    1987-02-01

    The essential oil of ARTEMISIA VESTITA (Compositae) was investigated by GLC, NMR, and mass spectrometry. Main constituents are alpha-, beta-, gamma-himachalene, caryophyllene, germacrene D, himachalol, allohimachalol, alpha-, gamma-atlantone, 1,8-cineole, yomogi alcohol, artemisia, and santolina alcohol and their acetates, and the thujones and thujanols. The characteristic oder of the oil is determined by the freshly smelling, 1, 8-cineole and thujone, and by the woody and sweet note of himachalol and atlantone. PMID:17268966

  20. Headspace constituents of Parkia speciosa seeds.

    PubMed

    Miyazawa, M; Osman, F

    2001-01-01

    The headspace of Parkia speciosa seeds was analysed by means of GC and GC-MS and found to contain 21 volatile components. The main constituents were hydrogen sulphide (41.30%), ethanol (39.15%), 1,2,4-trithiolane (4.75%) and acetaldehyde (3.59%), of which 1,2,4-trithiolane was found as one of the main component for the characteristic odour. PMID:11858549

  1. Phytochemical constituents of some Indian medicinal plants.

    PubMed

    Dhandapani, R; Sabna, B

    2008-04-01

    Alkaloids, tannins, saponins, steroid, terpenoid, flavonoids, phlobatannin and cardie glycoside distribution in seven medicinal plants belonging to different families were assessed and compared. The medicinal plants investigated were Aegle marmelos, Cynodon dactylon, Eclipta prostrata, Moringa pterygosperma, Pongamia pinnata, Sida acuta and Tridax procumbens. The significance of the plants in traditional medicine and the importance of the distribution of these chemical constituents were discussed with respect to the role of these plants in ethnomedicine in India. PMID:22557280

  2. Model for quark and lepton constituents

    NASA Astrophysics Data System (ADS)

    Fairlie, D.; Nuyts, J.; Taormina, A.

    1983-01-01

    A model of subconstituents for quarks and leptons is presented in which each of three different types transforms under a different group which is gauged. The binding is taken as magnetic, the dual of the usual electric charge, and hence very strong. The spin of the constituents is zero. The spin of the bound states arises dynamically. Weak interactions violate parity maximally and the Weinberg angle, related to the generation problem, comes out well numerically. Two exotic states are predicted.

  3. Potential Antidepressant Constituents of Nigella sativa Seeds

    PubMed Central

    Elkhayat, Ehab S.; Alorainy, Mohammad S.; El-Ashmawy, Ibrahim M.; Fat’hi, Shawkat

    2016-01-01

    Background: Nigella sativa Linn. is well known seed in the Middle East, Asia, and the Far East as a natural remedy for many ailments and as a flavoring agent proclaimed medicinal usage dating back to the ancient Egyptians, Greeks, and Romans. An authentic saying of the Prophet Muhammad (Peace Be Upon Him) about black seed is also quoted in Al-Bukhari. Objective: This study was carried out to evaluate the antidepressant effect and isolate the potential antidepressant constituents of the polar extract of N. sativa seeds. Materials and Methods: The antidepressant effect was evaluated through the immobility duration in tail suspension and forced swim tests (FSTs). Albino mice were orally treated with N. sativa polar extract and its RP-18 column chromatography fractions (50 and 100 mg/kg,). Results: The polar extract and two of its sub-fractions were significantly able to decrease the immobility time of mice when subjected to both tail suspension and FSTs, the effects are comparable to standard drug (Sertraline, 5 mg/kg). However, these treatments did not affect the number of crossings and rearing in the open field test. Phytochemical investigation of the two active fractions led to the isolation of quercetin-3-O-α-L-rhamnopyranoside 1, quercetin-7-O-β-D-gluco- pyranoside 2, tauroside E 3, and sapindoside B as the potential antidepressant constituents. SUMMARY Phytochemical and biological evaluation the antidepressant constituents in Nigella sativa using the tail suspension and forced swim methods afforded the isolation and identification of quercetin-3-O-α-L rhamnopyranoside, quercetin-7-O-β-D gluco pyranoside, tauroside E, and sapindoside B as the potential antidepressant constituents in the polar extract of N. sativa. The isolated compounds were identified through extensive NMR analysis (1D, 2D, ESI MS). Abbreviations used: TST: Tail suspension test, FST: Forced swim test, OFT: An Open field test PMID:27041854

  4. Constituent Particle Clustering and Pitting Corrosion

    NASA Astrophysics Data System (ADS)

    Harlow, D. Gary

    2012-08-01

    Corrosion is a primary degradation mechanism that affects the durability and integrity of structures made of aluminum alloys, and it is a concern for commercial transport and military aircraft. In aluminum alloys, corrosion results from local galvanic coupling between constituent particles and the metal matrix. Due to variability in particle sizes, spatial location, and chemical composition, to name a few critical variables, corrosion is a complex stochastic process. Severe pitting is caused by particle clusters that are located near the material surface, which, in turn, serve as nucleation sites for subsequent corrosion fatigue crack growth. These evolution processes are highly dependent on the spatial statistics of particles. The localized corrosion growth rate is primarily dependent on the galvanic process perpetuated by particle-to-particle interactions and electrochemical potentials. Frequently, severe pits are millimeters in length, and these pits have a dominant impact on the structural prognosis. To accommodate large sizes, a model for three-dimensional (3-D) constituent particle microstructure is proposed. To describe the constituent particle microstructure in three dimensions, the model employs a fusion of classic stereological techniques, spatial point pattern analyses, and qualitative observations. The methodology can be carried out using standard optical microscopy and image analysis techniques.

  5. CHEMICAL SPECIATION OF FLUE GAS DESULFURIZATION SLUDGE CONSTITUENTS

    EPA Science Inventory

    This project addresses the problem of flue gas desulfurization (FGD) sludge disposal to land. Specifically, the chemical species of FGD sludge constituents are thermodynamically modeled using the equilibrium constant approach, in an attempt to predict the constituent concentratio...

  6. The influence of the aromatic aglycon of galactoclusters on the binding of LecA: a case study with O-phenyl, S-phenyl, O-benzyl, S-benzyl, O-biphenyl and O-naphthyl aglycons.

    PubMed

    Casoni, Francesca; Dupin, Lucie; Vergoten, Gérard; Meyer, Albert; Ligeour, Caroline; Géhin, Thomas; Vidal, Olivier; Souteyrand, Eliane; Vasseur, Jean-Jacques; Chevolot, Yann; Morvan, François

    2014-12-01

    A library of 24 new mannose-centered tetragalactoclusters with four different linkers (di- and triethyleneglycol with phosphodiester or phosphorothioate linkages) and six different aromatic aglycons (O-phenyl, S-phenyl, O-benzyl, S-benzyl, O-biphenyl and O-naphthyl) was synthesized. Their interactions with LecA were evaluated on a DNA Directed Immobilization (DDI) based glycocluster array allowing the determination of their IC50 against lactose and the evaluation of their dissociation constant (Kd). Finally, the docking simulations confirm the experimental results and demonstrated that the better affinity of O-biphenyl- and O-naphthyl-galactoside is due to a double interaction between the aromatic ring and the histidine 50 and proline 51 of LecA. PMID:25295668

  7. FeCl3-Mediated Radical Tandem Reactions of 3-Benzyl-2-oxindoles with Styrene Derivatives for the Stereoselective Synthesis of Spirocyclohexene Oxindoles.

    PubMed

    Wu, Hong-Ru; Cheng, Liang; Kong, De-Long; Huang, Hong-Yan; Gu, Chun-Ling; Liu, Li; Wang, Dong; Li, Chao-Jun

    2016-03-18

    A novel FeCl3-mediated reaction of 3-benzyl-2-oxindoles with styrene derivatives was developed. The reaction provided spirocyclohexene oxindoles in good yields and excellent diastereoselectivities via a tandem radical addition/cyclization process. PMID:26950164

  8. Ambient methods and apparatus for rapid laser trace constituent analysis

    DOEpatents

    Snyder, Stuart C.; Partin, Judy K.; Grandy, Jon D.; Jeffery, Charles L.

    2002-01-01

    A method and apparatus are disclosed for measuring trace amounts of constituents in samples by using laser induced breakdown spectroscopy and laser induced fluorescence under ambient conditions. The laser induced fluorescence is performed at a selected wavelength corresponding to an absorption state of a selected trace constituent. The intensity value of the emission decay signal which is generated by the trace constituent is compared to calibrated emission intensity decay values to determine the amount of trace constituent present.

  9. The Stabilized Cation Pool Method: Metal- and Oxidant-Free Benzylic C-H/Aromatic C-H Cross-Coupling.

    PubMed

    Hayashi, Ryutaro; Shimizu, Akihiro; Yoshida, Jun-Ichi

    2016-07-13

    Electrochemical oxidation of toluene derivatives in the presence of a sulfilimine gave benzylaminosulfonium ions as stabilized benzyl cation pools, which reacted with subsequently added aromatic nucleophiles to give the corresponding cross-coupling products. The transformation serves as a powerful metal- and chemical-oxidant-free method for benzylic C-H/aromatic C-H cross-coupling. The method has been successfully applied to synthesis of TP27, an inhibitor of PTPase. PMID:27341676

  10. Fluorescence from Samarium(II) iodide and its electron transfer quenching: Dynamics of the reaction of benzyl radicals with Sm(II)

    SciTech Connect

    Skene, W.G.; Scaiano, J.C.; Cozens, F.L.

    1996-11-01

    Electron acceptors quench the fluorescence of SmI{sub 2} in THF. As an example, the quenching rate constant for dichloromethane is 2.7 x 10{sup 8} M{sup {minus}1}S{sup {minus}1}. For benzyl chloride, electron transfer produces benzyl radicals that react with SmI{sub 2} with a rate constant of (5.3{+-}1.4) x 10{sup 7} M{sup {minus}1}S{sup {minus}1}.

  11. Global Reference Atmospheric Model and Trace Constituents

    NASA Technical Reports Server (NTRS)

    Justus, C.; Johnson, D.; Parker, Nelson C. (Technical Monitor)

    2002-01-01

    Global Reference Atmospheric Model (GRAM-99) is an engineering-level model of the Earth's atmosphere. It provides both mean values and perturbations for density, temperature, pressure, and winds, as well as monthly- and geographically-varying trace constituent concentrations. From 0-27 km, thermodynamics and winds are based on National Oceanic and Atmospheric Administration Global Upper Air Climatic Atlas (GUACA) climatology. Above 120 km, GRAM is based on the NASA Marshall Engineering Thermosphere (MET) model. In the intervening altitude region, GRAM is based on Middle Atmosphere Program (MAP) climatology that also forms the basis of the 1986 COSPAR Intemationa1 Reference Atmosphere (CIRA). MAP data in GRAM are augmented by a specially-derived longitude variation climatology. Atmospheric composition is represented in GRAM by concentrations of both major and minor species. Above 120 km, MET provides concentration values for N2, O2, Ar, O, He, and H. Below 120 km, species represented also include H2O, O3, N2O, CO, CH, and CO2. Water vapor in GRAM is based on a combination of GUACA, Air Force Geophysics Laboratory (AFGL), and NASA Langley Research Center climatologies. Other constituents below 120 km are based on a combination of AFGL and h4AP/CIRA climatologies. This report presents results of comparisons between GRAM Constituent concentrations and those provided by the Naval Research Laboratory (NRL) climatology of Summers (NRL,/MR/7641-93-7416, 1993). GRAM and NRL concentrations were compared for seven species (CH4, CO, CO2, H2O, N2O, O2, and O3) for months January, April, July, and October, over height range 0-115 km, and latitudes -90deg to + 90deg at 10deg increments. Average GRAM-NRL correlations range from 0.878 (for CO) to 0.975 (for O3), with an average over all seven species of 0.936 (standard deviation 0.049).

  12. Nucleon structure functions from constituent quark

    NASA Astrophysics Data System (ADS)

    Khorramian, Ali N.; Arash, Firooz

    1999-10-01

    We have used a constituent quarks model to describe the nucleon structure function, F2( χ, Q2), for a wide range of χ=[10 -6,1] and Q2 = [0.5, 5000] GeV2. We have found that although F2 rises as χ decreases, but there exists some χ0 ≤ 10 -4 - 10 -5, below which the rise of F2 subsides drastically and hence, exhibits an almost flat behavior, compatible with the latest results from HERA, at least for low Q2.

  13. Atmospheric constituent measurements using commercial 747 airliners

    NASA Technical Reports Server (NTRS)

    Perkins, P. J.; Reck, G. M.

    1973-01-01

    NASA is implementing a Global Atmospheric Monitoring Program to measure the temporal and spatial distribution of particulate and gaseous constituents related to aircraft engine emissions in the upper troposphere and lower stratosphere (6 to 12 Km). Several 747 aircraft operated by different airlines flying routes selected for maximum world coverage will be instrumented. An instrumentation system is being assembled and tested and is scheduled for operation in airline service in late 1974. Specialized instrumentation and an electronic control unit are required for automatic unattended operation on commercial airliners. An ambient air sampling system was developed to provide undisturbed outside air to the instruments in the pressurized aircraft cabin.

  14. Lunar soil: Size distribution and mineralogical constituents

    USGS Publications Warehouse

    Duke, M.B.; Woo, C.C.; Bird, M.L.; Sellers, G.A.; Finkelman, R.B.

    1970-01-01

    The lunar soil collected by Apollo 11 consists primarily of submillimeter material and is finer in grain size than soil previously recorded photographically by Surveyor experiments. The main constituents are fine-grained to glassy rocks of basaltic affinity and coherent breccia of undetermined origin. Dark glass, containing abundant nickel-iron spheres, coats many rocks, mineral, and breccia fragments. Several types of homogeneous glass occur as fragments and spheres. Colorless spheres, probably an exotic component, are abundant in the fraction finer than 20 microns.

  15. Polydopamine-Coated TiO2 Nanotubes for Selective Photocatalytic Oxidation of Benzyl Alcohol to Benzaldehyde Under Visible Light.

    PubMed

    Tripathy, Jyotsna; Loget, Gabriel; Altomare, Marco; Schmuki, Patrik

    2016-05-01

    TiO2 nanotube arrays grown by anodization were coated with thin layers of polydopamine as visible light sensitizer. The PDA-coated TiO2 scaffolds were used as photocatalyst for selective oxidation of benzyl alcohol under monochromatic irradiation at 473 nm. Benzaldehyde was selectively formed and no by-products could be detected. A maximized reaction yield was obtained in O2-saturated acetonitrile. A mechanism is proposed that implies firstly the charge carrier generation in polydopamine as a consequence of visible light absorption. Secondly, photo-promoted electrons are injected in TiO2 conduction band, and subsequently transferred to dissolved O2 to form O*2- radicals. These radicals react with benzyl alcohol and lead to its selective dehydrogenation oxidation towards benzaldehyde. PMID:27483930

  16. Pd@Cu(II)-MOF-Catalyzed Aerobic Oxidation of Benzylic Alcohols in Air with High Conversion and Selectivity.

    PubMed

    Chen, Gong-Jun; Wang, Jing-Si; Jin, Fa-Zheng; Liu, Ming-Yang; Zhao, Chao-Wei; Li, Yan-An; Dong, Yu-Bin

    2016-03-21

    A new 3D porous Cu(II)-MOF (1) was synthesized based on a ditopic pyridyl substituted diketonate ligand and Cu(OAc)2 in solution, and it features a 3D NbO motif which is determined by the X-ray crystallography. Furthermore, the Pd NPs-loaded hybrid material Pd@Cu(II)-MOF (2) was prepared based on 1 via solution impregnation, and its structure was confirmed by HRTEM, SEM, XRPD, gas adsorption-desorption, and ICP measurement. 2 exhibits excellent catalytic activity (conversion, 93% to >99%) and selectivity (>99% to benzaldehydes) for various benzyl alcohol substrates (benzyl alcohol and its derivatives with electron-withdrawing and electron-donating groups) oxidation reactions in air. In addition, 2 is a typical heterogeneous catalyst, which was confirmed by hot solution leaching experiment, and it can be recycled at least six times without significant loss of its catalytic activity and selectivity. PMID:26959340

  17. Synthesis and Anticonvulsant Activities of (R)-N-(4′-Substituted) benzyl 2-Acetamido-3-methoxypropionamides

    PubMed Central

    Salomé, Christophe; Salomé-Grosjean, Elise; Park, Ki Duk; Morieux, Pierre; Swendiman, Robert; DeMarco, Erica; Stables, James P.; Kohn, Harold

    2010-01-01

    The structure-activity relationship (SAR) for the N-benzyl group in the clinical antiepileptic agent (R)-lacosamide ((R)-N-benzyl 2-acetamido-3-methoxypropionamide, (R)-3) has been explored. Forty-three compounds were prepared and then evaluated at the National Institute of Neurological Disorders and Stroke Anticonvulsant Screening Program for seizure protection in the maximal electroshock (MES) and subcutaneous Metrazol models. Comparing activities for two series of substituted aryl regioisomers (2′, 3′, 4′) showed that 4′-modified derivatives had the highest activity. Significantly, structural latitude existed at the 4′-site. The SAR indicated that non-bulky 4′-substituted (R)-3 derivatives exhibited superb activity, independent of their electronic properties. Activities in the MES test of several compounds were either comparable with or exceeded that of (R)-3, and surpassed the activities observed for the traditional antiepileptic agents phenytoin, phenobarbital, and valproate. PMID:20041718

  18. Transformation of masked benzyl alcohols to o-aminobenzaldehydes through C-H activation: a facile approach to quinazolines.

    PubMed

    Chen, Xiaolan; Han, Jian; Zhu, Yan; Yuan, Chunchen; Zhang, Jingyu; Zhao, Yingsheng

    2016-08-11

    Direct transformation of a directing group to important synthetic units would provide a high atom efficiency synthetic approach in synthetic chemistry. Herein, a convenient protocol for the synthesis of o-aminobenzaldehyde and benzoxazole derivatives from benzyl alcohols has been developed by employing (N,N-dimethyl)oxamoyl amide as a directing group in a palladium-catalyzed intramolecular amination. Furthermore, the attached directing center may not only be transformed into the product, but may also be further applied to generate synthetically important quinazoline and quinoline units. Finally, a high atom efficiency one-pot, two-step approach to form quinazolines from benzyl alcohol derivatives has been achieved in good yields, thus demonstrating its high utility. PMID:27470264

  19. Photochemical transformations. 30. Photosolvolysis of benzyl chlorides in tert-butyl alcohol. 2. Nature of excited states

    SciTech Connect

    Cristol, S.J.; Bindel, T.H.

    1981-12-02

    The photosolvolysis of a number of benzyl chlorides in tert-butyl alcohol, both as a result of direct irradiation and ketone triplet sensitization, has been studied. A variety of sensitization and quenching techniques have been used. The results obtained are rationalized by the assumption that there are two triplet states of the benzyl chlorides accessible in these experiments-one a short-lived upper state, which leads to solvolysis product, and another a long-lived (lower energy) state, which reverts to ground-state reactant. Consistent with this idea, m-methoxybenzyl chloride is shown to quench the photoreactions of benzophenone with benzhydrol without the formation of a significant amount of reactive species. The effects of wavelength on the reactions of p-acetobenzyl chloride are measured and discussed in terms of the two-triplet concept.

  20. A green four-component synthesis of zwitterionic alkyl/benzyl pyrazolyl barbiturates and their photophysical studies.

    PubMed

    Bihani, Manisha; Bora, Pranjal P; Bez, Ghanashyam; Askari, Hassan

    2014-11-01

    A novel series of unsymmetrically substituted alkyl/benzyl pyrazolyl barbiturates incorporating highly biologically active pyrazolone and barbiturate moieties was synthesized by four-component reactions of a mixture of ethyl acetoacetate, hydrazine hydrate, aldehydes and barbituric acid/thiobarbituric acid in ethanol without using a catalyst. The photophysical properties of the newly designed alkyl/benzyl pyrazolyl barbiturates were studied, and good quantum yield of some products indicated a definitive scope in the field of biochemical applications. Single-crystal X-ray crystallographic studies revealed that the newly synthesized compounds exist in zwitterionic form. The zwitterionic nature of the new chimera makes them interesting candidates for drug delivery as zwitterionic drugs are known to have highly water soluble properties, specific protein absorption, slow recognition by immune system, slow blood clearance from body and can constantly diffuse and deposit throughout the physiological pH. PMID:25005075

  1. Laser-induced fluorescence, dispersed fluorescence and lifetime measurements of jet-cooled chloro-substituted benzyl radicals

    NASA Astrophysics Data System (ADS)

    Hamatani, Satoshi; Tsuji, Kazuhide; Kawai, Akio; Shibuya, Kazuhiko

    2002-07-01

    We measured the laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of jet-cooled α-, o- and m-chlorobenzyl radicals after they were generated by the 193 nm photolysis of the corresponding parent molecules. The vibronically resolved spectra were obtained to analyze their D1-D0 transitions. The fluorescence lifetimes of α-, o-, m- and p-chlorobenzyls in the zeroth vibrational levels of the D1 states were measured to estimate the oscillator strengths of a series of benzyl derivatives. It was found that the α-substitution is inefficient to break the `accidental forbiddenness' of the D1-D0 transition of benzyl, while the ring-substitution enhances the oscillator strength by 50%.

  2. Effects of pressure and potassium chloride on the aggregation of poly(gamma-benzyl-L-glutamate) in liposomal bilayers.

    PubMed

    Tamura, K; Nii, N; Suzuki, A

    1986-12-15

    Fluorescence depolarization studies were made on dimyristoylphosphatidylcholine liposomes containing four kinds of dansylated poly(gamma-benzyl-L-glutamate) with different degrees of polymerization or hydrocarbon chain lengths under high pressure at up to 981 bar (1 bar = 10 MPa). Potassium chloride promoted the aggregation of the synthetic peptides in liposomal bilayers at both atmospheric and high pressure. The chain lengths of the hydrocarbons of the peptides had more influence than their degrees of polymerization on aggregation. PMID:2434153

  3. Reaction of 1-chloro-1-methylcyclohexane with phenyl- and benzyl-trimethylsilanes in the presence of aluminum chloride

    SciTech Connect

    Bolestova, G.I.; Parnes, Z.N.; Vol'pin, M.E.

    1988-10-20

    In the reaction of 1-chloro-1-methylcyclohexane with phenyltrimethylsilane and benzyltrimethylsilane in the presence of aluminum chloride the chlorine atom is substituted by a phenyl or benzyl group with the formation of 1-methyl-1-phenyl- and 1-methyl-1-benzylcyclohexane, respectively. In the case of benzyltrimethylsilane the products from alkylation of the benzene ring of the benzyltrimethylsilane by the 1-methylcyclohexyl carbocation in the Friedel-Crafts reaction are formed in addition to 1-methyl-1-benzylcyclohexane.

  4. Mild and Copper-Free Stereoselective Cyanation of gem-Difluoroalkenes by Using Benzyl Nitrile as a Cyanating Reagent.

    PubMed

    Zhang, Juan; Xu, Chengyuan; Wu, Wei; Cao, Song

    2016-07-11

    A novel copper-free highly stereoselective cyanation of gem-difluoroalkenes by using benzyl nitrile as a cyanating reagent with the assistance of tBuOLi under air atmosphere at room temperature was developed. A variety of versatile fluorinated alkenyl nitriles were obtained. The proposed mechanism involved the C-H bond oxidation, C-CN bond cleavage, and then nucleophilic vinylic substitution (SN V). PMID:27127940

  5. Crystal structure and photochromism of 1-phenyl-3-methyl-4-benzyl-5-one-pyrazole S-methyl thiosemicarbazone

    NASA Astrophysics Data System (ADS)

    Liu, Lang; Jia, Dian-zeng; Ji, Ya-li; Yu, Kai-bei

    2003-07-01

    A new organic photochromic compound containing pyrazolone-ring photochromic functional unit: 1-phenyl-3-methyl-4-benzyl-5-one pyrazole S-methyl thiosemicarbazone (PMBP-smtsc) was synthesized. The photochromic properties and photochemical kinetics of PMBP-smtsc have been studied by UV reflectance spectra under irradiation of 365 nm light. The crystal structure analyses of photocolored product show the photochromism is due to the photoisomerization from enol form to keto form through an intermolecular proton transfer.

  6. The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical.

    PubMed

    Buckingham, Grant T; Porterfield, Jessica P; Kostko, Oleg; Troy, Tyler P; Ahmed, Musahid; Robichaud, David J; Nimlos, Mark R; Daily, John W; Ellison, G Barney

    2016-07-01

    Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H5 (13)CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H5 (13)CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K). PMID:27394106

  7. Synthesis of Biaryl Ethers by the Copper-Catalyzed Chan-Evans-Lam Etherification from Benzylic Amine Boronate Esters.

    PubMed

    Marcum, Justin S; McGarry, Kathryn A; Ferber, Carl J; Clark, Timothy B

    2016-09-01

    The copper-catalyzed etherification of ortho-borylated benzylic amines with phenols has been achieved to provide biaryl ethers that are prevalent in biologically active compounds. A variety of substitution patterns on the aryl boronate ester and the phenol are tolerated under the reaction conditions, providing moderate to high yields. A competition reaction between phenol and aniline revealed condition-dependent selectivity in which the phenol could be highly favored over the aniline. PMID:27490146

  8. Synthesis and Structure-Activity Studies of Benzyl Ester Meperidine and Normeperidine Derivatives as Selective Serotonin Transporter Ligands

    PubMed Central

    Gu, Xiaobo; Izenwasser, Sari; Wade, Dean; Housman, Amy; Gulasey, Gerard; Rhoden, Jill B.; Savoie, Christopher D.; Mobley, David L.; Lomenzo, Stacey A.; Trudell, Mark L.

    2013-01-01

    A series of benzyl esters of meperidine and normeperidine were synthesized and evaluated for binding affinity at serotonin, dopamine and norepinephrine transporters. The 4-methoxybenzyl ester 8b and 4-nitrobenzyl ester 8c in the meperidine series and 4-methoxybenzyl ester 14a in the normeperidine series exhibited low nanomolar binding affinities at the SERT (Ki values < 2 nM) and high SERT selectivity (DAT/SERT >1500 and NET/SERT > 1500). PMID:20980153

  9. The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical

    NASA Astrophysics Data System (ADS)

    Buckingham, Grant T.; Porterfield, Jessica P.; Kostko, Oleg; Troy, Tyler P.; Ahmed, Musahid; Robichaud, David J.; Nimlos, Mark R.; Daily, John W.; Ellison, G. Barney

    2016-07-01

    Cycloheptatrienyl (tropyl) radical, C7H7, was cleanly produced in the gas-phase, entrained in He or Ne carrier gas, and subjected to a set of flash-pyrolysis micro-reactors. The pyrolysis products resulting from C7H7 were detected and identified by vacuum ultraviolet photoionization mass spectrometry. Complementary product identification was provided by infrared absorption spectroscopy. Pyrolysis pressures in the micro-reactor were roughly 200 Torr and residence times were approximately 100 μs. Thermal cracking of tropyl radical begins at 1100 K and the products from pyrolysis of C7H7 are only acetylene and cyclopentadienyl radicals. Tropyl radicals do not isomerize to benzyl radicals at reactor temperatures up to 1600 K. Heating samples of either cycloheptatriene or norbornadiene never produced tropyl (C7H7) radicals but rather only benzyl (C6H5CH2). The thermal decomposition of benzyl radicals has been reconsidered without participation of tropyl radicals. There are at least three distinct pathways for pyrolysis of benzyl radical: the Benson fragmentation, the methyl-phenyl radical, and the bridgehead norbornadienyl radical. These three pathways account for the majority of the products detected following pyrolysis of all of the isotopomers: C6H5CH2, C6H5CD2, C6D5CH2, and C6H513CH2. Analysis of the temperature dependence for the pyrolysis of the isotopic species (C6H5CD2, C6D5CH2, and C6H513CH2) suggests the Benson fragmentation and the norbornadienyl pathways open at reactor temperatures of 1300 K while the methyl-phenyl radical channel becomes active at slightly higher temperatures (1500 K).

  10. The respiratory molybdo-selenoprotein formate dehydrogenases of Escherichia coli have hydrogen: benzyl viologen oxidoreductase activity

    PubMed Central

    2011-01-01

    Background Escherichia coli synthesizes three membrane-bound molybdenum- and selenocysteine-containing formate dehydrogenases, as well as up to four membrane-bound [NiFe]-hydrogenases. Two of the formate dehydrogenases (Fdh-N and Fdh-O) and two of the hydrogenases (Hyd-1 and Hyd-2) have their respective catalytic subunits located in the periplasm and these enzymes have been shown previously to oxidize formate and hydrogen, respectively, and thus function in energy metabolism. Mutants unable to synthesize the [NiFe]-hydrogenases retain a H2: benzyl viologen oxidoreductase activity. The aim of this study was to identify the enzyme or enzymes responsible for this activity. Results Here we report the identification of a new H2: benzyl viologen oxidoreductase enzyme activity in E. coli that is independent of the [NiFe]-hydrogenases. This enzyme activity was originally identified after non-denaturing polyacrylamide gel electrophoresis and visualization of hydrogen-oxidizing activity by specific staining. Analysis of a crude extract derived from a variety of E. coli mutants unable to synthesize any [NiFe]-hydrogenase-associated enzyme activity revealed that the mutants retained this specific hydrogen-oxidizing activity. Enrichment of this enzyme activity from solubilised membrane fractions of the hydrogenase-negative mutant FTD147 by ion-exchange, hydrophobic interaction and size-exclusion chromatographies followed by mass spectrometric analysis identified the enzymes Fdh-N and Fdh-O. Analysis of defined mutants devoid of selenocysteine biosynthetic capacity or carrying deletions in the genes encoding the catalytic subunits of Fdh-N and Fdh-O demonstrated that both enzymes catalyze hydrogen activation. Fdh-N and Fdh-O can also transfer the electrons derived from oxidation of hydrogen to other redox dyes. Conclusions The related respiratory molybdo-selenoproteins Fdh-N and Fdh-O of Escherichia coli have hydrogen-oxidizing activity. These findings demonstrate that the

  11. The benzyl ligand in materials chemistry: Synthetic, structural, and chemical vapor deposition (CVD) investigations

    NASA Astrophysics Data System (ADS)

    Remington, Michael Perry, Jr.

    A series of new organometallic precursors and/or reactions have been investigated for the facile production of main group compound semiconductors at relatively low temperature. The common feature among the organometallic compounds used in this study is that they all contain the benzyl ligand, Bn = CH2C6H5. Novel dual source reactions between benzylated organometallic compounds, and elemental sulfur or selenium produce the underrepresented Group 14/16 and Group 15/16 solid-state binary semiconductors as well as the corresponding Sn(SxSe1-x) and (Bi xSb1-x)2S3 solid solutions. In addition, new single-source precursors that produce germanium sulfide, selenide, tin telluride, and bismuth sulfide under mild conditions have been synthesized. By judicious choice of the precursor and the reaction conditions, synthetic control over the size and microstructure of Bi2S3 particles is achieved. Decomposition of (BnS)3Bi at mild temperatures forms small (˜1 mum) aggregates of nearly spherical botryoidal particles or 6 mum diameter spherical particles composed of radiating acicular crystallites. The reaction of Bn3Bi with sulfur produces small spherical crystallites 200--300 nm in size; rod-like crystallites 500--700 nm in width and 4--5 mum in length; or dense, prismatic rods ˜1 mum in length and 500 nm wide. Two new chemical vapor deposition (CVD) sources of the technologically important elements antimony and bismuth have been identified. Bn3Sb and Bn3Bi were shown to grow films of these elements under low-pressure conditions (LPCVD). Depositions on glass and Si(100) substrates were performed. Resulting films are of high purity, good adherence, and highly crystalline as determined by X-ray powder diffraction (XRPD). The films also exhibit a high degree of texture. The texture of Sb films could be controlled by varying the distance of the deposition substrate to that of the precursor. Bi films were highly oriented in the (012) crystallographic direction, where most deposition

  12. A framework for building effective public health constituencies.

    PubMed

    Nicola, R M; Hatcher, M T

    2000-03-01

    Population-based health improvements that require behavioral and social change at the community level are dependent on effective constituency participation. To achieve needed constituency involvement, a public health leader must understand what motivates and moves constituents to action on public health issues. This article provides a framework and guidance on building effective constituent involvement to achieve community health improvement. Within this framework, aspects of managing the organizational practice of constituency building and community engagement are discussed and linked with current public health planning and mobilization models that support community-based health interventions. PMID:10787773

  13. Radiation cross-linking of ethylene vinyl alcohol copolymer functionalized with m-isopropenyl-[alpha],[alpha]-dimethyl benzyl isocyanate

    SciTech Connect

    Ekman, K.B.; Naesman, J.H. . Lab. of Polymer Technology)

    1993-10-10

    An ethylene vinyl alcohol copolymer was functionalized with m-isopropenyl-[alpha],[alpha]-dimethyl benzyl isocyanate using reactive processing in a mixer. The functionalization introduces pendant unsaturation to the polymer, which allows radiation cross-linked to gel contents >70% at radiation doses below 100 kGy. Unfunctionalized ethylene vinyl alcohol copolymer, on the other hand, forms no gel upon irradiation. The functionalization was completed within a few minutes of reactive mixing, which was confirmed with both FTIR and [sup 13]C-NMR measurements. The oxygen permeability of ethylene vinyl alcohol copolymer increased with increasing degree of functionalization, and irradiation of the samples formed trapped radicals, which act as oxygen scavengers. Consequently no oxygen permeability was detected. However, radical activity was inhibited by annealing the samples at 110 C resulting in a 24% higher oxygen permeability value for the irradiated unfunctionalized copolymer. The oxygen permeability values of the irradiated functionalized samples were approximately 13% lower. Laminates of m-isopropenyl-[alpha],[alpha]-dimethyl benzyl isocyanate functionalized ethylene vinyl alcohol copolymer and m-isopropenyl-[alpha],[alpha]-dimethyl benzyl isocyanate functionalized ethylene hydroxyethyl methacrylate copolymer acquired improved adhesive strength both at dry and wet conditions as well as at elevated temperature upon exposure to radiation.

  14. Constituent gluons and the static quark potential

    NASA Astrophysics Data System (ADS)

    Greensite, Jeff; Szczepaniak, Adam P.

    2016-04-01

    We suggest that Hamiltonian matrix elements between physical states in QCD might be approximated, in Coulomb gauge, by "lattice-improved" tree diagrams; i.e. tree diagram contributions with dressed ghost, transverse gluon, and Coulomb propagators obtained from lattice simulations. Such matrix elements can be applied to a truncated-basis treatment of hadronic states which include constituent gluons. As an illustration, we apply this hybrid approach to the heavy quark potential, for quark-antiquark separations up to 2.4 fm. The Coulomb string tension in SU(3) gauge theory is about a factor of 4 times greater than the asymptotic string tension. In our approach we show that a single constituent gluon is in principle sufficient, up to 2.4 fm, to reduce this overshoot by the factor required. The static potential remains linear, although the precise value of the string tension depends on details of the Couloumb gauge ghost and gluon propagators in the infrared regime. In this connection we present new lattice results for the transverse gluon propagator in position space.

  15. Successes and failures of the constituent quark model

    SciTech Connect

    Lipkin, H.J.

    1982-01-01

    Our approach considers the model as a possible bridge between QCD and the experimental data and examines its predictions to see where these succeed and where they fail. We also attempt to improve the model by looking for additional simple assumptions which give better fits to the experimental data. But we avoid complicated models with too many ad hoc assumptions and too many free parameters; these can fit everything but teach us nothing. We define our constituent quark model by analogy with the constituent electron model of the atom and the constituent nucleon model of the nucleus. In the same way that an atom is assumed to consist only of constituent electrons and a central Coulomb field and a nucleus is assumed to consist only of constituent nucleons hadrons are assumed to consist only of their constituent valence quarks with no bag, no glue, no ocean, nor other constituents. Although these constituent models are oversimplified and neglect other constituents we push them as far as we can. Atomic physics has photons and vacuum polarization as well as constituent electrons, but the constituent model is adequate for calculating most features of the spectrum when finer details like the Lamb shift are neglected. 54 references.

  16. Access to Secondary School Education through the Constituency Bursary Fund in Kanduyi Constituency, Kenya

    ERIC Educational Resources Information Center

    Wachiye, J. Herman; Nasongo, W. Joseph

    2010-01-01

    Secondary school education is very critical in any education system because of the crucial role, it plays in catalyzing national development. Consequently, maintaining a high student enrolment at this level should be a priority for all countries. The Constituency Bursary Fund (CBF) was established by the government of Kenya through an act of…

  17. N-type doping of black phosphorus by using benzyl viologen

    NASA Astrophysics Data System (ADS)

    Yue, Dewu; Lee, Daeyeong; Ryu, Jungjin; Choi, Min Sup; Nam, Hye Jin; Jung, Duk-Young; Yoo, Won Jong; NDPL Collaboration

    Black phosphorus (BP) meets several critical material requirements for the development of future nanoelectronic applications, but the realization of n-type semiconductor behavior form it has remained elusive. Here, we report the ambipolar characteristics of few-layer BP, induced using an novel technique: chemical doping with benzyl viologen (BV), which serves as a surface charge transfer donor for BP flakes. The n-doped BP devices exhibit excellent electron mobility up to ~83 cm2V-1s-1 from 2-terminal measurement at 300K, thereby demonstrating n-type behavior. On the basis of ambipolar BP devices, we also comprehensively analyzes temperature and BP thickness dependence of ambipolar devices, in which we found the degenerate doping limit below around 150K and highest electron transport performance in ~10 nm BP flakes at 300K. As a proof of concept, ultrafast BP photodetectors were fabricated with a very high photoresponsivity of ~104 mA/W over the UV, visible, and IR spectral ranges. Furthermore, we fabricated a homogeneous BP based inverter through BV doping and h-BN capping that offers a feasible approach to fabricating a key building block of future 2D logic semiconductors.

  18. ROLE OF BENZYL ALCOHOL IN THE UNFOLDING AND AGGREGATION OF INTERFERON α-2A†

    PubMed Central

    Bis, Regina L.; Singh, Surinder M.; Cabello-Villegas, Javier; Mallela, Krishna M.G.

    2014-01-01

    Benzyl alcohol (BA) is the most widely used antimicrobial preservative in multi-dose protein formulations, and has been shown to cause protein aggregation. Our previous work on a model protein cytochrome c demonstrated that this phenomenon occurs via partial unfolding. Here, we examine the validity of these results by investigating the effect of BA on a pharmaceutically relevant protein, interferon α-2a (IFNA2). IFNA2 therapeutic formulations available on the pharmaceutical market contain BA as a preservative. Isothermal aggregation kinetics and temperature scanning demonstrated that BA induced IFNA2 aggregation in a concentration dependent manner. With increasing concentration of BA, the apparent aggregation temperature of IFNA2 linearly decreased. Denaturant melts measured using intrinsic protein fluorescence and that of the ANS dye indicated that IFNA2 stability decreased with increasing BA concentration populating a partially unfolded intermediate. Changes in NMR chemical shifts and hydrogen exchange rates identified the structural nature of this intermediate, which correlated with an aggregation “hot-spot” predicted by computational methods. These results indicate that BA induces IFNA2 aggregation by partial unfolding rather than global unfolding of the entire protein, and is consistent with our earlier conclusions from model protein studies. PMID:25100180

  19. Conformational analysis, tautomerization, IR, Raman, and NMR studies of benzyl acetoacetate

    NASA Astrophysics Data System (ADS)

    Tayyari, Sayyed Faramarz; Naghavi, Farnaz; Pojhan, Sahar; McClurg, Ryan W.; Sammelson, Robert E.

    2011-02-01

    A complete conformational analysis of the keto and enol forms of benzyl acetoacetate (BAA), a β-dicarbonyl compound, was carried out by ab initio calculations, at the density functional theory (DFT) level. By inspection of all possible conformers and tautomers, 22 stable cis-enol, 28 stable trans-enol, and five keto conformers were obtained. Among all stable cis-enol forms only six of them are engaged in intramolecular hydrogen bond. The hydrogen bond strength of the most stable conformer of BAA is compared with that of acetylacetone (AA) and dimethyl oxaloacetate (DMOA). Harmonic vibrational frequencies of the most stable enol and keto forms and their deuterated analogues were also calculated and compared with the experimental data. According to the theoretical calculations, the hydrogen bond strength of the most stable enol conformer of BAA is 56.7 kJ/mol (calculated at the B3LYP/6-311++G ∗∗ level), about 10 kJ/mol less than that of AA. This weakening of hydrogen bond is consistent with the spectroscopic results. NMR studies indicate that BAA exists mainly as a keto tautomer in all considered solutions. The Gibbs energies for keto/enol tautomerization were calculated at the B3LYP level, with several basis sets, in both gas phase and CH 3CN solution (using PCM model), for the most stable enol and keto conformers.

  20. Effect of benzyl butyl phthalate on physiology and proteome characterization of water celery (Ipomoea aquatica Forsk.).

    PubMed

    Chen, Wen-Ching; Huang, Han-Ching; Wang, Yei-Shung; Yen, Jui-Hung

    2011-07-01

    This study examined the effect of benzyl butyl phthalate (BBP), a phthalate ester (PAE) and an endocrine disruptor, on water celery, Ipomoea aquatica Forsk., one of the most popular leaf vegetables in Taiwan. After 28 days of cultivation, treatment with 100 mgL⁻¹ BBP retarded plant growth and decreased biomass and number of mature leaves and caused the accumulation of proline in leaves of water celery, but the concentrations of chlorophyll a and b in the leaves remained constant. 2-D gel electrophoresis and matrix-assisted laser desorption ionization time-of-flight mass spectrometry analysis of the proteome of leaf tissue revealed five protein spots with up- and down-regulated expression. The predicted protein XP_001417439 was down-regulated, which explained inhibition of plant growth, and the proteina XP_001417040, calreticulin, GAI-like protein 1, and (-)-linalool synthase were up-regulated, which indicates interference with the cell cycle and protein synthesis, as well as dwarfism of water celery. BBP is a stressor on the growth of water celery, and proteome analysis revealed the up- and down-regulation of genes involved in plant growth with BBP treatment. PMID:21496923

  1. A new multifunctional, shine-enhancing emollient: PPG-3 benzyl ether myristate.

    PubMed

    Gao, Timothy; Pereira, Abel; Obukowho, Patrick

    2004-01-01

    A new emollient ester--Crodamol STS (INCI name: PPG-3 Benzyl Ether Myristate) has been developed and characterized. This special non-volatile emollient is safe to use and provides silicone-like feel and multiple cosmetic functionality. It is a liquid with a viscosity about 100 cps at room temperature. It has a high refractive index--1.4696, which enhances hair shine, contributes to high gloss in lip products, and reduces whitening effect of fatty alcohols and silica in anti-perspirants/deodorants applications. This emollient has high solubility of UV filters, low skin-spreading factor, and good pigment wetting behavior, which are preferable in sunscreen and make-up formulas to enhance the pigment localization and improve SPF value. In this paper, the chemical structure, physical properties, and various cosmetic applications of the emollient will be discussed. Especially, an objective hair shine (luster) test method (color image analysis) has been established and applied to study the enhancement in hair shine by Crodamol STS in hair spray and hair gel formulations. The objective measurements in hair shine showed good agreement with the results obtained from subjective evaluations. The substantivity of Crodamol STS on hair surface, which was delivered from a rinse-off cream, was also determined by a solvent extraction method. PMID:15645090

  2. Correlation between the structure of benzyl aryl ethers and their thermolysis kinetics

    SciTech Connect

    Korobkov, V.Yu.; Bykov, V.I.; Grigor'eva, E.N.; Kalechits, I.V.

    1988-02-01

    One of the areas which has been widely studied recently, pursuant to the goal of optimizing processes for the preparation of synthetic liquid fuels from petroleum, is the kinetics of thermolysis of simple ethers, which can serve as model compounds of the oxygen-methylene bridged linking aromatic clusters within the organic mass of petroleum. We have found that the observed rate constants for the thermolysis of para- and meta-substituted benzyl aryl ethers in excess tetralin (weight ratio of solvent: substrate equal to 10:1) in a hydrogen medium at 325/sup 0/C and 8.5 MPa correlate well with Hammett sigma-constants, giving a value of the reaction constant rho = -2.75. Toluene and the corresponding phenols and benzylphenols are formed as the ether thermolysis products, while naphthalene and bi-tetralyl are formed as the conversion products of tetralin, which is used as the solvent, in the presence of hydrogen donor. The concentrations of components in the reaction mixture were determined by GLC, while the reaction products were identified by chromato-mass spectrometry and PMR spectroscopy.

  3. Composite film formation on iron in sulfuric acid by bismuth(III) chloride and benzyl thiocyanate

    SciTech Connect

    Ohi, M.; Nishihara, H.; Aramaki, K. . Dept. of Chemistry)

    1994-03-01

    A synergistic inhibitory effect of bismuth(3) chloride and benzyl thiocyanate (C[sub 6]H[sub 5]CH[sub 2]SCN) on corrosion of iron (Fe) in 1 N sulfuric acid was investigated using polarization and impedance measurements. A composite protective film formed on the Fe surface by a combination of both compounds. The film was analyzed by x-ray photo-electron spectroscopy and electron probe microanalysis. Inhibition efficiency of > 99% was obtained by the formation of the protective film. The film comprised an inner layer of metallic bismuth (Bi) and an outer layer of metallic oxide containing a deposited oxidative-addition product of C[sub 6]h[sub 5]CH[sub 2]SCN. A small spot uncoated with the Bi layer was covered mostly with the product layer, suppressing the anodic process of Fe corrosion. The cathodic process was inhibited by the high hydrogen (H) overpotential of the metallic Bi deposited on most of the substrate surface.

  4. (2R,3R)-3-O-Benzoyl-N-benzyl­tartramide1

    PubMed Central

    Madura, Izabela D.; Zachara, Janusz; Bernaś, Urszula; Hajmowicz, Halina; Synoradzki, Ludwik

    2012-01-01

    The title compound, C18H17NO6 [systematic name: (2R,3R)-4-benzyl­amino-2-benzo­yloxy-3-hy­droxy-4-oxobutanoic acid], is the first structurally characterized unsymmetrical monoamide–monoacyl tartaric acid derivative. The mol­ecule shows a staggered conformation around the tartramide Csp3—Csp3 bond with trans-oriented carboxyl and amide groups. The mol­ecular conformation is stabilized by an intra­molecular N—H⋯O hydrogen bond. In the crystal, mol­ecules are linked by O—H⋯O hydrogen bonds between the carboxyl and amide carbonyl groups, forming translational chains along [001]. Further O—H⋯O and N—H⋯O hydrogen bonds as well as weaker C—H⋯O and C—H⋯π inter­molecular inter­actions extend the supra­molecular assembly into a double-layer structure parallel to (100). There are no directional inter­actions between the double layers. PMID:22719648

  5. Chemoselective Oxidation of Benzyl, Amino, and Propargyl Alcohols to Aldehydes and Ketones under Mild Reaction Conditions

    PubMed Central

    Reddy, C B Rajashekar; Reddy, Sabbasani Rajasekhara; Naidu, Shivaji

    2015-01-01

    Catalytic oxidation reactions often suffer from drawbacks such as low yields and poor selectivity. Particularly, selective oxidation of alcohols becomes more difficult when a compound contains more than one oxidizable functional group. In order to deliver a methodology that addresses these issues, herein we report an efficient, aerobic, chemoselective and simplified approach to oxidize a broad range of benzyl and propargyl alcohols containing diverse functional groups to their corresponding aldehydes and ketones in excellent yields under mild reaction conditions. Optimal yields were obtained at room temperature using 1 mmol substrate, 10 mol % copper(I) iodide, 10 mol % 4-dimethylaminopyridine (DMAP), and 1 mol % 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) in acetonitrile, under an oxygen balloon. The catalytic system can be applied even when sensitive and oxidizable groups such as alkynes, amines, and phenols are present; starting materials and products containing such groups were found to be stable under the developed conditions. PMID:25969806

  6. Chemoselective Oxidation of Benzyl, Amino, and Propargyl Alcohols to Aldehydes and Ketones under Mild Reaction Conditions.

    PubMed

    Reddy, C B Rajashekar; Reddy, Sabbasani Rajasekhara; Naidu, Shivaji

    2015-04-01

    Catalytic oxidation reactions often suffer from drawbacks such as low yields and poor selectivity. Particularly, selective oxidation of alcohols becomes more difficult when a compound contains more than one oxidizable functional group. In order to deliver a methodology that addresses these issues, herein we report an efficient, aerobic, chemoselective and simplified approach to oxidize a broad range of benzyl and propargyl alcohols containing diverse functional groups to their corresponding aldehydes and ketones in excellent yields under mild reaction conditions. Optimal yields were obtained at room temperature using 1 mmol substrate, 10 mol % copper(I) iodide, 10 mol % 4-dimethylaminopyridine (DMAP), and 1 mol % 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) in acetonitrile, under an oxygen balloon. The catalytic system can be applied even when sensitive and oxidizable groups such as alkynes, amines, and phenols are present; starting materials and products containing such groups were found to be stable under the developed conditions. PMID:25969806

  7. Selective inhibition of monoamine oxidase B by aminoethyl substituted benzyl ethers.

    PubMed

    Woodroofe, C C; Mostashari, R; Lu, X; Ramsay, R R; Silverman, R B

    2000-01-01

    Aminoethyl 3-chlorobenzyl ether was shown previously (Ding, C.Z. and Silverman, R.B. (1993). Bioorg. Med. Chem. Lett., 3, 2077-2078) to be a potent and selective time-dependent, but reversible inhibitor of monoamine oxidase B (MAO B). Based on this result, a series of novel aminoethyl substituted benzyl ethers was synthesized and the compounds were examined as potential inhibitors of both isozymic forms of MAO. Each compound in the series inhibits both MAO A and MAO B competitively, and IC50 values for each compound were determined. In general, the B isozyme is much more sensitive to these inhibitors than the A isozyme (except for the o- and p-substituted nitro analogues), in some cases by more than two orders of magnitude. The selectivity in favor of MAO B inhibition is relatively high for all of the meta-substituted analogues and quite low for all of the ortho-substituted analogues. Having the substituent at the ortho-position is most favorable for MAO A inhibition. With MAO B the meta-analogues were, in general, more potent than the corresponding ortho- and para-analogues with respect to their reversible binding constants. The meta-iodo analogue is the most potent analogue. PMID:10850952

  8. Selective Inhibition of Monoamine Oxidase B by Aminoethyl Substituted Benzyl Ethers.

    PubMed

    Woodroofe; Mostashari; Lu; Ramsay; Silverman

    1999-11-01

    Aminoethyl 3-chlorobenzyl ether was shown previously (Ding, C.Z. and Silverman, R.B. (1993). Bioorg. Med. Chem. Lett., 3, 2077-2078) to be a potent and selective time-dependent, but reversible inhibitor of monoamine oxidase B (MAO B). Based on this result, a series of novel aminoethyl substituted benzyl ethers was synthesized and the compounds were examined as potential inhibitors of both isozymic forms of MAO. Each compound in the series inhibits both MAO A and MAO B competitively, and IC(50) values for each compound were determined. In general, the B isozyme is much more sensitive to these inhibitors than the A isozyme (except for the o- and p-substituted nitro analogues), in some cases by more than two orders of magnitude. The selectivity in favor of MAO B inhibition is relatively high for all of the meta-substituted analogues and quite low for all of the ortho-substituted analogues. Having the substituent at the ortho-position is most favorable for MAO A inhibition. With MAO B the meta-analogues were, in general, more potent than the corresponding ortho- and para-analogues with respect to their reversible binding constants. The meta-iodo analogue is the most potent analogue. PMID:10938531

  9. Determination of blood flow to study the penetration of benzyl nicotinate topically applied in different vehicles

    NASA Astrophysics Data System (ADS)

    Jacobi, U.; Erdmenger, U.; Darvin, M.; Sterry, W.; Lademann, J.

    2006-05-01

    The penetration kinetics of topically applied drugs affecting the cutaneous blood flow can be studied by measuring the biological response to the drug using laser Doppler flowmetry noninvasively. In the present study, the kinetics of vasodilation caused by benzyl nicotinate topically applied in two different vehicles was studied by measuring the blood flows of the superficial dermal plexus and the larger deeper capillaries. The drug was topically applied in a balsam and a gel, respectively, on the flexor forearm of 6 male volunteers. Both blood flows measured were correlated with the time. The maximal value ( y max), the time to reach half of this value ( t rise), and the corresponding period Δ t were determined. Significantly increased blood flows were measured in the application areas after treatment with both emulsions. No significant differences were observed for any of the parameters comparing the blood flow after application of the gel with that of the treatment using the balsam. These results indicate similar penetration kinetics and pathways of the drug into the skin independent of the vehicle.

  10. Benzyl butyl phthalate induces epigenetic stress to enhance adipogenesis in mesenchymal stem cells.

    PubMed

    Sonkar, Ravi; Powell, Catherine A; Choudhury, Mahua

    2016-08-15

    Endocrine disruptors, phthalates, may have contributed to recent global obesity health crisis. Our study investigated the potential of benzyl butyl phthalate (BBP) to regulate the mesenchymal stem cell epigenome to drive adipogenesis. BBP exposure enhanced lipid accumulation and adipogenesis in a dose-dependent manner compared to control (P < 0.001). Adipogenesis markers, PPARγ (P < 0.001), C/EBPα (P < 0.01), and aP2 (P < 0.001) were significantly upregulated by increasing concentrations of BBP when compared to DMSO. BBP enhanced H3K9 acetylation while decreasing H3K9 dimethylation. Fifty μM BBP increased histone acetyltransferases, p300 (P < 0.05) and GCN5 (P < 0.01) gene expression. Furthermore, histone deacetylases (HDACs), HDAC3 (P < 0.01) and HDAC10 (P < 0.01, 10 μM BBP; P < 0.001, 50 μM BBP) and histone methyltransferases, SETDB1 (P < 0.01) and G9a (P < 0.01), were significantly downregulated by BBP exposure. BBP acts, in part, through PPARγ, as PPARγ knockdown led to decreased H3K9ac and rescued H3K9me2 during BBP exposure. In conclusion, BBP regulated MSCs towards adipogenesis by tipping the epigenomic balance. PMID:27164441

  11. Facile solvothermal synthesis of NIR absorbing CsxWO3 nanorods by benzyl alcohol route

    NASA Astrophysics Data System (ADS)

    Eyassu, Tsehaye; Hsaio, Tun-Jen; Lin, Chhiu-Tsu

    2015-01-01

    Near infrared absorbing CsxWO3 nanoparticles with uniform particle size distribution were synthesized in two hours by solvothermal method. Benzyl alcohol was used as a main solvent and a reactant to facilitate a controlled reaction and stabilization in the presence of oleic acid as a capping agent. Different reaction conditions such as reaction time, reaction temperature, and oleic acid amount were studied and reported. Hexagonal CsxWO3 nanorods with average size of 80 nm were obtained in 2 h reaction time, at 240 °C reaction temperature, and 10% vol. oleic acid. Aqueous dispersion of the nanorods showed high transparency (about 80-90%) in visible light with strong near infrared (NIR) light shielding (80-90%). This indicates that CsxWO3 is an attractive material to employ in heat-shielding transparent coatings for windows of buildings and automobiles. Using this simple process, it is possible to synthesize homogenous CsxWO3 nanorods with low temperature and short reaction time. Moreover, the process offers an opportunity for large-scale synthesis of NIR absorbing nanorods.

  12. Relativistic constituent quark model with infrared confinement

    SciTech Connect

    Branz, Tanja; Faessler, Amand; Gutsche, Thomas; Lyubovitskij, Valery E.; Ivanov, Mikhail A.; Koerner, Juergen G.

    2010-02-01

    We refine the relativistic constituent quark model developed in our previous papers to include the confinement of quarks. It is done, first, by introducing the scale integration in the space of {alpha} parameters, and, second, by cutting this scale integration on the upper limit which corresponds to an infrared cutoff. In this manner one removes all possible thresholds present in the initial quark diagram. The cutoff parameter is taken to be the same for all physical processes. We adjust other model parameters by fitting the calculated quantities of the basic physical processes to available experimental data. As an application, we calculate the electromagnetic form factors of the pion and the transition form factors of the {omega} and {eta} Dalitz decays.

  13. Interrelation of exhaust-gas constituents

    NASA Technical Reports Server (NTRS)

    Gerrish, Harold C; Voss, Fred

    1938-01-01

    This report presents the results of an investigation conducted to determine the interrelation of the constituents of the exhaust gases of internal-combustion engines and the effect of engine performance on these relations. Six single-cylinder, liquid-cooled tests engines and one 9-cylinder radial air-cooled engine were tested. Various types of combustion chambers were used and the engines were operated at compression ratios from 5.1 to 7.0 using spark ignition and from 13.5 to 15.6 using compression ignition. The investigation covered a range of engine speeds from 1,500 to 2,100 r.p.m. The fuels used were two grades of aviation gasoline, auto diesel fuel, and laboratory diesel fuel. Power, friction, and fuel-consumption data were obtained from the single-cylinder engines at the same time that the exhaust-gas samples were collected.

  14. Antimelanoma and Antityrosinase from Alpinia galangal Constituents

    PubMed Central

    Liu, Po-Len; Lin, Li-Ching; Chen, Yen-Ting; Hseu, You-Cheng; Wen, Zhi-Hong

    2013-01-01

    Two compounds, 1,7-bis(4-hydroxyphenyl)-1,4,6-heptatrien-3-one (BHPHTO) and bisdemethoxycurcumin (BDMC) they have been isolated from the rhizomes of Alpinia galangal, and the structures of both pure constituents were determined using spectroscopic analyses. The study examined the bioeffectivenesses of the two compounds on the human melanoma A2058 and showed that significantly inhibited the proliferation of melanoma cells in the cell viability assay. This research was also taken on the tests to B16-F10 cell line and showed minor inhibitory consequences of cellular tyrosinase activities and melanin contents. Our results revealed the anticancer effects of A. galangal compounds, and therefore, the target compounds could be potentially applied in the therapeutic application and the food industry. PMID:24027439

  15. Deicing chemicals as source of constituents of highway runoff

    USGS Publications Warehouse

    Granato, G.E.

    1996-01-01

    The dissolved major and trace constituents of deicing chemicals as a source of constituents in highway runoff must be quantified for interpretive studies of highway runoff and its effects on surface water and groundwater. Dissolved constituents of the deicing chemicals-sodium chloride, calcium chloride, and premix (a mixture of sodium and calcium chloride)-were determined by analysis of salt solutions created in the laboratory and are presented as mass ratios to chloride. Deicing chemical samples studied are about 98 and 97 percent pure sodium chloride and calcium chloride, respectively: however, each has a distinct major and trace ion constituent signature. The greatest impurity in sodium chloride road sail samples was sulfate, followed by calcium, potassium, bromide, vanadium, magnesium, fluoride, and other constituents with a ratio to chloride of less than 0.0001 by mass. The greatest impurity in the calcium chloride road salt samples was sodium, followed by potassium, sulfate, bromide, silica, fluoride. strontium, magnesium, and other constituents with a ratio to chloride of less than 0.0001 by mass. Major constituents of deicing chemicals in highway runoff may account for a substantial source of annual chemical loads. Comparison of estimated annual loads and first flush concentrations of deicing chemical constituents in highway runoff with those reported in the literature indicate that although deicing chemicals are not a primary source of trace constituents, they are not a trivial source, either. Therefore, deicing chemicals should be considered as a source of many major and trace constituents in highway and urban runoff.

  16. Transport of Manure Constituents in Runoff

    NASA Astrophysics Data System (ADS)

    Shelton, D.; Guber, A.; Sadeghi, A. M.; Sikora, L. M.; Nemes, A.; Pachepsky, Y. A.

    2005-12-01

    Fecal coliforms (FC) are often used as indicators of pathogenic bacteria contamination of surface water from surface-applied manure. Manure constituents other than FC may serve as natural tracers of bacterial contamination provided the rates of release from manure and surface transport mechanisms are similar. The objective of this work was to compare fecal coliforms (FC), organic carbon (OC), and water-soluble phosphorus (P) transport from dissolving manure applied on hillslopes with different soil texture and surface cover conditions under simulated rainfall. Two-by-six meters runoff plots were set in triplicate on vegetated and bare 20% slopes with sandy loam and clay loam soils at the ARS Beltsville Agricultural Research Center. Fresh bovine manure was applied at the top 30-cm wide strip, and at 50 cm x 30 cm miniplots in the immediate vicinity of runoff plots. Rainfall (ca. 6 cm per hour) was simulated for 1 hour on bare plots and for 1.5 hours on vegetated plots. Runoff was collected from gutters at the edge of runoff plots and miniplots at five-min intervals. In general, the volume of runoff was less from vegetated plots than from bare plots, and was less from sandy loam plots than from clay loam plots. Partitioning of fecal coliforms between runoff and suspended sediment was quantified using the partitioning coefficient Kd. The Kd values were greater for the sandy loam plot than the clay loam soil. The value of the partitioning coefficient increased from spring to fall at all plots. Release kinetics of FC and soluble P were similar. The fast release stage of about 20 minutes was followed by aa relatively slow release stage. Both soil texture and vegetation significantly affected transport of the manure constituents. More than 70% of manure FC and OC were transported with runoff over bare plots, and less than 15% over vegetation plots. Overall, manure-borne P appears to be a promising potential tracer for assessing of manure-borne bacteria transport.

  17. Use of 4-sulfophenyl isothiocyanate labeling and mass spectrometry to determine the site of action of the streptococcolytic peptidoglycan hydrolase zoocin A.

    PubMed

    Gargis, Shaw R; Heath, Harry E; Heath, Lucie S; Leblanc, Paul A; Simmonds, Robin S; Abbott, Brian D; Timkovich, Russell; Sloan, Gary L

    2009-01-01

    Zoocin A is a streptococcolytic peptidoglycan hydrolase with an unknown site of action that is produced by Streptococcus equi subsp. zooepidemicus 4881. Zoocin A has now been determined to be a d-alanyl-l-alanine endopeptidase by digesting susceptible peptidoglycan with a combination of mutanolysin and zoocin A, separating the resulting muropeptides by reverse-phase high-pressure liquid chromatography, and analyzing them by mass spectrometry (MS) in both the positive- and negative-ion modes to determine their compositions. In order to distinguish among possible structures for these muropeptides, they were N-terminally labeled with 4-sulfophenyl isothiocyanate (SPITC) and analyzed by tandem MS in the negative-ion mode. This novel application of SPITC labeling and MS/MS analysis can be used to analyze the structure of peptidoglycans and to determine the sites of action of other peptidoglycan hydrolases. PMID:18978086

  18. Recovery of alkali metal constituents from catalytic coal conversion residues

    DOEpatents

    Soung, W.Y.

    In a coal gasification operation (32) or similar conversion process carried out in the presence of an alkali metal-containing catalyst wherein particles containing alkali metal residues are produced, alkali metal constituents are recovered from the particles by contacting them with water or an aqueous solution to remove water-soluble alkali metal constituents and produce an aqueous solution enriched in said constituents. The aqueous solution thus produced is then contacted with carbon dioxide to precipitate silicon constituents, the pH of the resultant solution is increased, preferably to a value in the range between about 12.5 and about 15.0, and the solution of increased pH is evaporated to increase the alkali metal concentration. The concentrated aqueous solution is then recycled to the conversion process where the alkali metal constituents serve as at least a portion of the alkali metal constituents which comprise the alkali metal-containing catalyst.

  19. Role of isothiocyanate conjugate of pterostilbene on the inhibition of MCF-7 cell proliferation and tumor growth in Ehrlich ascitic cell induced tumor bearing mice

    SciTech Connect

    Nikhil, Kumar; Sharan, Shruti; Chakraborty, Ajanta; Bodipati, Naganjaneyulu; Krishna Peddinti, Rama; Roy, Partha

    2014-01-15

    Naturally occurring pterostilbene (PTER) and isothiocyanate (ITC) attract great attention due to their wide range of biological properties, including anti-cancer, anti-leukemic, anti-bacterial and anti-inflammatory activities. A novel class of hybrid compound synthesized by introducing an ITC moiety on PTER backbone was evaluated for its anti-cancer efficacy in hormone-dependent breast cancer cell line (MCF-7) in vitro and Ehrlich ascitic tumor bearing mice model in vivo. The novel hybrid molecule showed significant in vitro anti-cancer activity (IC{sub 50}=25±0.38) when compared to reference compound PTER (IC{sub 50}=65±0.42). The conjugate molecule induced both S and G2/M phase cell cycle arrest as indicated by flow cytometry analysis. In addition, the conjugate induced cell death was characterized by changes in cell morphology, DNA fragmentation, activation of caspase-9, release of cytochrome-c into cytosol and increased Bax: Bcl-2 ratio. The conjugate also suppressed the phosphorylation of Akt and ERK. The conjugate induced cell death was significantly increased in presence of A6730 (a potent Akt1/2 kinase inhibitor) and PD98059 (a specific ERK inhibitor). Moreover, the conjugated PTER inhibited tumor growth in Ehrlich ascitic cell induced tumor bearing mice as observed by reduction in tumor volume compared to untreated animals. Collectively, the pro-apoptotic effect of conjugate is mediated through the activation of caspases, and is correlated with the blockade of the Akt and ERK signaling pathways in MCF-7 cells. - Highlights: • Conjugate was prepared by appending isothiocyanate moiety on pterostilbene backbone. • Conjugate showed anticancer effects at comparatively lower dose than pterostilbene. • Conjugate caused blockage of the Akt and ERK signaling pathways in MCF-7 cells. • Conjugate significantly reduced solid tumor volume as compared to pterostilbene.

  20. 2-Phenethyl Isothiocyanate, Glutathione S-transferase M1 and T1 Polymorphisms, and Detoxification of Volatile Organic Carcinogens and Toxicants in Tobacco Smoke.

    PubMed

    Yuan, Jian-Min; Murphy, Sharon E; Stepanov, Irina; Wang, Renwei; Carmella, Steven G; Nelson, Heather H; Hatsukami, Dorothy; Hecht, Stephen S

    2016-07-01

    Cigarette smoke contains relatively large quantities of volatile organic toxicants or carcinogens such as benzene, acrolein, and crotonaldehyde. Among their detoxification products are mercapturic acids formed from glutathione conjugation, catalyzed in part by glutathione S-transferases (GST). A randomized phase II clinical trial with a crossover design was conducted to evaluate the effect of 2-phenethyl isothiocyanate (PEITC), a natural product formed from gluconasturtiin in certain cruciferous vegetables, on the detoxification of benzene, acrolein, and crotonaldehyde in 82 cigarette smokers. Urinary mercapturic acids of benzene, acrolein, and crotonaldehyde at baseline and during treatment were quantified. Overall, oral PEITC supplementation increased the mercapturic acid formed from benzene by 24.6% (P = 0.002) and acrolein by 15.1% (P = 0.005), but had no effect on crotonaldehyde. A remarkably stronger effect was observed among subjects with the null genotype of both GSTM1 and GSTT1: in these individuals, PEITC increased the detoxification metabolite of benzene by 95.4% (P < 0.001), of acrolein by 32.7% (P = 0.034), and of crotonaldehyde by 29.8% (P = 0.006). In contrast, PEITC had no effect on these mercapturic acids in smokers possessing both genes. PEITC had no effect on the urinary oxidative stress biomarker 8-iso-prostaglandin F2α or the inflammation biomarker prostaglandin E2 metabolite. This trial demonstrates an important role of PEITC in detoxification of environmental carcinogens and toxicants which also occur in cigarette smoke. The selective effect of PEITC on detoxification in subjects lacking both GSTM1 and GSTT1 genes supports the epidemiologic findings of stronger protection by dietary isothiocyanates against the development of lung cancer in such individuals. Cancer Prev Res; 9(7); 598-606. ©2016 AACR. PMID:27099270

  1. Conversion to isothiocyanates via dithiocarbamates for the determination of aromatic primary amines by headspace-solid phase microextraction and gas chromatography.

    PubMed

    Jain, Archana; Reddy-Noone, Kishan; Pillai, Aradhana K K V; Verma, Krishna K

    2013-11-01

    A novel and highly selective method has been developed for the determination of aromatic primary amines by their conversion to dithiocarbamates by reaction with carbon disulphide, and then to isothiocyanates, which are volatile, by heating in the presence of a heavy metal ion. Zinc(II) was selected owing to its low toxicity and optimum yield of isothiocyanates. The latter were sampled by headspace-solid phase microextraction (HS-SPME) on divinylbenzene-carboxen-polydimethylsiloxane fibre, 50/30 μm. The HS-SPME procedure was optimized to provide adequate limits of detection in the analysis of aromatic amines in their real samples by gas chromatography with mass spectrometry (GC-MS) or flame ionization detection (GC-FID). The method gave rectilinear calibration graph, correlation coefficient and limit of detection, respectively, over the range 0.08-100 μg L(-1), 0.9950-0.9990 and 25-240 ng L(-1) in gas chromatography-mass spectrometry, and 0.01-10 mg L(-1), 0.9910-0.9991 and 0.8-3.0 μg L(-1) in gas chromatography-flame ionization detection. At two different levels, 10 and 40 μg L(-1), the range of intra-day RSD was 3.7-8.5% (GC-MS) and 3.3-9.2% (GC-FID), respectively. The proposed method is simple and rapid, and has been applied to determine aromatic primary amines in the environmental waters, food samples of ice cream powder and soft drinks concentrate, and food colours. The intra-day RSD in the analysis of real samples by GC-MS was in the range 3.6-6.2%. The food/colour samples were found to contain elevated levels of aniline and 2-toluidine. PMID:24139574

  2. Pharmacodynamics of dietary phytochemical indoles I3C and DIM: Induction of Nrf2-mediated Phase II drug metabolizing and antioxidant genes and synergism with isothiocyanates

    PubMed Central

    Saw, Constance Lay-Lay; Cintron, Melvilí; Wu, Tien-Yuan; Guo, Yue; Huang, Ying; Jeong, Woo-Sik; Kong, Ah-Ng Tony

    2012-01-01

    The antioxidant response element (ARE) is a critical regulatory element for the expression of many phase II drug metabolizing enzymes (DME), phase III transporters, and anti-oxidant enzymes, mediated by the transcription factor Nrf2. The aim of this study was to examine the potential activation and synergism of Nrf2-ARE-mediated transcriptional activity between four common phytochemicals present in cruciferous vegetables, the indoles; indole-3-carbinol (I3C), 3,3’-diindolylmethane (DIM), and the isothiocyanates (ITCs); phenethyl isothiocyanate (PEITC) and sulforaphane (SFN). The cytotoxicity of the compounds was determined in human liver hepatoma cell line (HepG2-C8). The combination index was calculated to assess the synergistic effects on the induction of ARE-mediated gene expressions. qPCR was employed to measure the mRNA expressions of Nrf2 and Nrf2-mediated genes. I3C and DIM showed less cytotoxicity than SFN and PEITC. Compared to I3C, DIM was found to be a stronger inducer of ARE. Synergism was observed after combined treatments of I3C 6.25 µM + SFN 1 µM, I3C 6.25 µM + PEITC 1 µM and DIM 6.25 µM + PEITC 1 µM, while additive effect was observed for DIM 6.25 µM + SFN 1 µM. Induction of endogenous Nrf2, phase II genes (GSTm2, UGT1A1, and NQO1) and antioxidant genes (HO-1 and SOD1) was also observed. In summary, the indole I3C or DIM alone could induce or syngergistically induce in combination with the ITCs SFN or PEITC, Nrf2-ARE-mediated gene expression, which could potentially enhance cancer chemopreventive activity. PMID:21656528

  3. Butyl benzyl phthalate suppresses the ATP-induced cell proliferation in human osteosarcoma HOS cells

    SciTech Connect

    Liu, P.-S.; Chen, C.-Y.

    2010-05-01

    Butyl benzyl phthalate (BBP), an endocrine disruptor present in the environment, exerts its genomic effects via intracellular steroid receptors and elicits non-genomic effects by interfering with membrane ion-channel receptors. We previously found that BBP blocks the calcium signaling coupled with P2X receptors in PC12 cells (Liu and Chen, 2006). Osteoblast P2X receptors were recently reported to play a role in cell proliferation and bone remodeling. In this present study, the effects of BBP on ATP-induced responses were investigated in human osteosarcoma HOS cells. These receptors mRNA had been detected, named P2X4, P2X7, P2Y2, P2Y4, P2Y5, P2Y9, and P2Y11, in human osteosarcoma HOS cells by RT-PCR. The enhancement of cell proliferation and the decrease of cytoviability had both been shown to be coupled to stimulation via different concentrations of ATP. BBP suppressed the ATP-induced calcium influx (mainly coupled with P2X) and cell proliferation but not the ATP-induced intracellular calcium release (mainly coupled with P2Y) and cytotoxicity in human osteosarcoma HOS cells. Suramin, a common P2 receptor's antagonist, blocked the ATP-induced calcium signaling, cell proliferation, and cytotoxicity. We suggest that P2X is mainly responsible for cell proliferation, and P2Y might be partially responsible for the observed cytotoxicity. BBP suppressed the calcium signaling coupled with P2X, suppressing cell proliferation. Since the importance of P2X receptors during bone metastasis has recently become apparent, the possible toxic risk of environmental BBP during bone remodeling is a public problem of concern.

  4. Analysis of residual products in benzyl chloride used for the industrial synthesis of quaternary compounds by liquid chromatography with diode-array detection.

    PubMed

    Prieto-Blanco, M C; López-Mahía, P; Prada-Rodríguez, D

    2009-02-01

    In industrial and pharmaceutical processes, the study of residual products becomes essential to guarantee the quality of compounds and to eliminate or minimize toxic residual products. Knowledge about the origin of impurities (raw materials, processes, the contamination of industrial plants, etc.) is necessary in preventive treatment and in the control of a product's lifecycle. Benzyl chloride is used as raw material to synthesize several quaternary ammonium compounds, such as benzalkonium chloride, which may have pharmaceutical applications. Benzaldehyde, benzyl alcohol, toluene, chloro derivatives of toluene, and dibenzyl ether are compounds that may be found as impurities in technical benzyl chloride. We proposed a high-performance liquid chromatography method for the separation of these compounds, testing two stationary phases with different dimensions and particle sizes, with the application of photodiode array-detection. The linearity for four possible impurities (benzaldehyde, toluene, alpha,alpha-dichlorotoluene, and 2-chlorotoluene) ranged from 0.1 to 10 microg/mL, limits of detection from 11 to 34 ng/mL, and repeatability from 1% to 2.9% for a 0.3-1.2 microg/mL concentration range. The method was applied to samples of technical benzyl chloride, and alpha,alpha-dichlorotoluene and benzaldehyde were identified by spectral analysis and quantitated. The selection of benzyl chloride with lower levels of impurities is important to guarantee the reduction of residual products in further syntheses. PMID:19222920

  5. CeO2-modified Au@SBA-15 nanocatalysts for liquid-phase selective oxidation of benzyl alcohol

    NASA Astrophysics Data System (ADS)

    Wang, Tuo; Yuan, Xiang; Li, Shuirong; Zeng, Liang; Gong, Jinlong

    2015-04-01

    Tuning the interfacial perimeter and structure is crucial to understanding the origin of catalytic performance. This paper describes the design, characterization, and application of CeO2 modified Au@SBA-15 (Au-CeO2@SBA-15) catalysts in selective oxidation of benzyl alcohol. The reaction results showed that Au-CeO2@SBA-15 catalysts exhibited higher catalytic activity compared with Au@SBA-15 and Au/CeO2 catalysts under identical conditions along with the high selectivity towards benzaldehyde (>99%). The turnover frequency of benzyl alcohol over the Au-100CeO2@SBA-15 catalyst is about nine-fold and four-fold higher than those of Au@SBA-15 and Au/CeO2 catalysts, respectively. The supported catalysts were characterized by N2 adsorption-desorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, transmission electron microscopy, high-angle annular dark-field scanning transmission electron microscopy, scanning transmission electron microscopy-energy dispersive spectrometry, and X-ray photoelectron spectroscopy. It was found that the Au and small CeO2 nanoparticles (~5 nm) were homogeneously mixed in the channels of SBA-15, which led to an increase in the interfacial area between Au and CeO2 and consequently a better catalytic performance of Au-CeO2@SBA-15 catalysts for the selective oxidation of benzyl alcohol to benzaldehyde compared with that of Au/CeO2. The prevention of agglomeration and leaching of Au nanoparticles by restricting them inside the mesopores of SBA-15 was conducive to the stable existence of large quantities of Au-CeO2 interface, which leads to high stability of the Au-CeO2@SBA-15 catalyst.Tuning the interfacial perimeter and structure is crucial to understanding the origin of catalytic performance. This paper describes the design, characterization, and application of CeO2 modified Au@SBA-15 (Au-CeO2@SBA-15) catalysts in selective oxidation of benzyl alcohol. The reaction results showed that Au-CeO2@SBA-15 catalysts

  6. [Chemical constituents of Sapium sebiferum leaves].

    PubMed

    Gao, Li; Tian, Hua; Lv, Pei-jun; Wang, Jia-ping; Wang, Yi-fen

    2015-04-01

    Chemical constituents of ethyl acetate extract of Sapium sebiferum leaves were isolated and purified by various chromatographic methods, including column chromatographies over silica gel, macroporous adsorption resin, and Sephadex LH-20, as well as preparative TLC and semi preparative HPLC. As a results, 15 compounds were separated from Sapium sebiferum leaves and their structures were examined by spectral analysis including NMR and MS data and identified as( + )-(7R,7'R,7"S,7'"S,8S,8'S,8"S,8'"S)-4", 4"'-dihydroxy-3,3',3",3',5,5'-hexamethoxy-7,9';7',9-diepoxy-4,8";4',8'"-bisoxy-8,8'-dineo-lignan-7",7"',9",9"'-tetraol(1) ,1-(4'- hydroxy-3'-methoxyphenyl)-2-[4"-(3-hydroxypropyl) -2", 6"-dimethoxyphenoxy] propane-1, 3-diol (2), Thero-2, 3-bis-(4-hydroxy-3- methoxypheyl)-3-methoxy-propanol(3) , threo-5-hydroxy-3,7-dimethoxyphenyl propane-8,9-diol (4), boropinol B (5), threo-8S-7-methoxysyringylglycerol(6), 5-hydroxymethylfurfural(7), 5-( methoxy-methyl)-1H-pyrrole-2-carbaldehyde (8), quercetin (9) , kaempferol (10), ethyl gallate(11), coniferaldehyde(12), vanillin(13), 7-hydroxy-6-methoxy-2H-1-henzopyran-2-one(14),and 1-heptacosanol (15). All compounds except for compounds 9-11,14 were separated from this plant for the first time. PMID:26281591

  7. An itinerant antiferromagnetic metal without magnetic constituents

    SciTech Connect

    Svanidze, E.; Wang, Jiakui K.; Besara, T.; Liu, L.; Huang, Q.; Siegrist, T.; Frandsen, B.; Lynn, J. W.; Nevidomskyy, Andriy H.; Gamża, Monika B.; Aronson, M. C.; Uemura, Y. J.; Morosan, E.

    2015-07-13

    The origin of magnetism in metals has been traditionally discussed in two diametrically opposite limits: itinerant and local moments. Surprisingly, there are very few known examples of materials that are close to the itinerant limit, and their properties are not universally understood. In the case of the two such examples discovered several decades ago, the itinerant ferromagnets ZrZn2 and Sc3In, the understanding of their magnetic ground states draws on the existence of 3d electrons subject to strong spin fluctuations. Similarly, in Cr, an elemental itinerant antiferromagnet with a spin density wave ground state, its 3d electron character has been deemed crucial to it being magnetic. Here, we report evidence for an itinerant antiferromagnetic metal with no magnetic constituents: TiAu. Antiferromagnetic order occurs below a Néel temperature of 36 K, about an order of magnitude smaller than in Cr, rendering the spin fluctuations in TiAu more important at low temperatures. In conclusion, this itinerant antiferromagnet challenges the currently limited understanding of weak itinerant antiferromagnetism, while providing insights into the effects of spin fluctuations in itinerant–electron systems.

  8. An itinerant antiferromagnetic metal without magnetic constituents

    DOE PAGESBeta

    Svanidze, E.; Wang, Jiakui K.; Besara, T.; Liu, L.; Huang, Q.; Siegrist, T.; Frandsen, B.; Lynn, J. W.; Nevidomskyy, Andriy H.; Gamża, Monika B.; et al

    2015-07-13

    The origin of magnetism in metals has been traditionally discussed in two diametrically opposite limits: itinerant and local moments. Surprisingly, there are very few known examples of materials that are close to the itinerant limit, and their properties are not universally understood. In the case of the two such examples discovered several decades ago, the itinerant ferromagnets ZrZn2 and Sc3In, the understanding of their magnetic ground states draws on the existence of 3d electrons subject to strong spin fluctuations. Similarly, in Cr, an elemental itinerant antiferromagnet with a spin density wave ground state, its 3d electron character has been deemedmore » crucial to it being magnetic. Here, we report evidence for an itinerant antiferromagnetic metal with no magnetic constituents: TiAu. Antiferromagnetic order occurs below a Néel temperature of 36 K, about an order of magnitude smaller than in Cr, rendering the spin fluctuations in TiAu more important at low temperatures. In conclusion, this itinerant antiferromagnet challenges the currently limited understanding of weak itinerant antiferromagnetism, while providing insights into the effects of spin fluctuations in itinerant–electron systems.« less

  9. An itinerant antiferromagnetic metal without magnetic constituents

    PubMed Central

    Svanidze, E.; Wang, Jiakui K.; Besara, T.; Liu, L.; Huang, Q.; Siegrist, T.; Frandsen, B.; Lynn, J. W.; Nevidomskyy, Andriy H.; Gamża, Monika B.; Aronson, M. C.; Uemura, Y. J.; Morosan, E.

    2015-01-01

    The origin of magnetism in metals has been traditionally discussed in two diametrically opposite limits: itinerant and local moments. Surprisingly, there are very few known examples of materials that are close to the itinerant limit, and their properties are not universally understood. In the case of the two such examples discovered several decades ago, the itinerant ferromagnets ZrZn2 and Sc3In, the understanding of their magnetic ground states draws on the existence of 3d electrons subject to strong spin fluctuations. Similarly, in Cr, an elemental itinerant antiferromagnet with a spin density wave ground state, its 3d electron character has been deemed crucial to it being magnetic. Here, we report evidence for an itinerant antiferromagnetic metal with no magnetic constituents: TiAu. Antiferromagnetic order occurs below a Néel temperature of 36 K, about an order of magnitude smaller than in Cr, rendering the spin fluctuations in TiAu more important at low temperatures. This itinerant antiferromagnet challenges the currently limited understanding of weak itinerant antiferromagnetism, while providing insights into the effects of spin fluctuations in itinerant–electron systems. PMID:26166042

  10. [Chemical constituents from roots of Andrographis paniculata].

    PubMed

    Xu, Chong; Wang, Zheng-Tao

    2011-03-01

    To investigate the chemical constituents of the roots of Andrographis paniculata, 28 compounds were isolated and identified from the 80% ethanol extract. There are 20 flavonoids: 5, 5'-dihydroxy-7, 8, 2'-trimetroxyflavone (1), 5-hydroxy-7, 8, 2', 6'-tetramethoxyflavone (2), 5, 3'-dihydroxy-7, 8, 4'-trimethoxyflavone (3), 2'-hydroxy-5, 7, 8-trimethoxyflavone (4), 5-hydroxy-7, 8, 2', 3', 4'-pentamethoxyflavone (6), wightin (7), 5, 2', 6'-trihydroxy-7-methoxyflavone 2'-O-beta-D-glucopyranoside (8), 5, 7, 8, 2'-tetramethoxyflavone (10), 5-hydroxy-7, 8-dimethoxyflavanone (11), 5-hydroxy-7, 8-dimethoxyflavone (12), 5, 2'-dihydroxy-7, 8-dimethoxyflavone (13), 5-hydroxy-7, 8, 2', 5'-tetramethoxyflavone (14), 5-hydroxy-7, 8, 2', 3'-tetramethoxyflavone (15), 5-hydroxy-7, 8, 2'-trimethoxyflavone (16), 5, 4'-dihydroxy-7, 8, 2', 3'-tetramethoxyflavone (17), dihydroneobaicalein (18), andrographidine A (19), andrographidine B (20), andrographidine C (21) and 5, 2'-dihydroxy-7, 8-dimethoxyflavone 2'-O-beta-D-glucopyranoside (22); three diterpenoids: andrograpanin (23), neoandrographolide (24) and andrographolide (25); two phenylpropanoids: trans-cinnamic acid (26) and 4-hydroxy-2-methoxycinnamaldehyde (5); and oleanolic acid (9), beta-sitosterol (27) and beta-daucosterol (28). Compound 1 is a new flavone, compound 4 is a new natural product, compounds 2, 3 and 5 were isolated from the Androggraphis genus for the first time and compounds 6-9 were isolated from this plant for the first time. PMID:21626787

  11. Constituents of south Indian vetiver oils.

    PubMed

    Mallavarapu, Gopal Rao; Syamasundar, Kodakandla V; Ramesh, S; Rao, Bhaskaruni R Rajeswara

    2012-02-01

    The essential oils isolated from vetiver [Vetiveria zizanioides (L.) Nash.] roots collected from four locations in south India were analyzed by GC-FID and GC-MS. Eighty constituents, representing 94.5-97.8% of the oils, have been identified. The oils from Bangalore, Hyderabad, Kundapur, and Mettupalayam were rich in sesquiterpenes and oxygenated sesquiterpenes with cedrane, bisabolane, eudesmane, eremophilane, and zizaane skeletons. The main components of the four essential oils were: eudesma-4,6-diene (delta-selinene) + beta-vetispirene (3.9-6.1%), beta-vetivenene (0.9-9.4%), 13-nor-trans-eudesma-4(15),7-dien-11-one + amorph-4-en-10-ol (5.0-6.4%), trans-eudesma-4(15),7-dien-12-ol (vetiselinenol) + (E)-opposita-4(15),7(11)-dien-12-ol (3.7-5.9%), eremophila-1 (10),11-dien-2alpha-ol (nootkatol) + ziza-6(13)-en-12-ol (khusimol) (16.1-19.2%), and eremophila-1(10),7(11)-dien-2alpha-ol (isonootkatol) + (E)-eremophila-1(10),7(11)-12-ol (isovalencenol) (5.6-6.9%). The important compounds that impart the characteristic vetiver odor are: khusimene, delta-selinene, beta-vetivenene, cyclocopacamphan-12-ol (epimers A and B), vetiselinenol, khusimol, isovalencenol, khusimone, alpha-vetivone, and beta-vetivone. The chemical profiles of the oils are comparable to Haitian vetiver oil. PMID:22474964

  12. Antioxidant Constituents of Cotoneaster melanocarpus Lodd.

    PubMed

    Holzer, Veronika M D; Lower-Nedza, Agnieszka D; Nandintsetseg, Myagmar; Batkhuu, Javzan; Brantner, Adelheid H

    2013-01-01

    The aim of this study was the evaluation of the antioxidant capacity of Cotoneaster melanocarpus Lodd. and the identification of antioxidant active constituents of this plant. C. melanocarpus Lodd. is a shrub indigenous to Mongolia and used in Traditional Mongolian Medicine as a styptic. Before extraction, the plant material was separated into three parts: young sterile shoots, older stems and leaves. All these parts were extracted with water, methanol, ethyl acetate, dichloromethane and hexane, successively. The methanolic extract of the sterile shoots showed the highest antioxidant activity in the DPPH (2,2-diphenyl-1-picrylhydrazyl) radical scavenging assay (IC50 30.91 ± 2.97 µg/mL). This active extract was further analyzed with chromatographic methods. TLC fingerprinting and HPLC indicated the presence of the flavonol glycosides quercetin-3-O-rutinoside (rutin), quercetin-3-O-galactoside (hyperoside) and quercetin-3-O-glucoside (isoquercetin), ursolic acid as well as chlorogenic acid, neochlorogenic acid and cryptochlorogenic acid. The findings were substantiated with LC-MS. All identified compounds have antioxidant properties and therefore contribute to the radical scavenging activity of the whole plant. PMID:26784464

  13. Hydrolytic metabolism of phenyl and benzyl salicylates, fragrances and flavoring agents in foods, by microsomes of rat and human tissues.

    PubMed

    Ozaki, Hitomi; Sugihara, Kazumi; Tamura, Yuki; Fujino, Chieri; Watanabe, Yoko; Uramaru, Naoto; Sone, Tomomichi; Ohta, Shigeru; Kitamura, Shigeyuki

    2015-12-01

    Salicylates are used as fragrance and flavor ingredients for foods, as UV absorbers and as medicines. Here, we examined the hydrolytic metabolism of phenyl and benzyl salicylates by various tissue microsomes and plasma of rats, and by human liver and small-intestinal microsomes. Both salicylates were readily hydrolyzed by tissue microsomes, predominantly in small intestine, followed by liver, although phenyl salicylate was much more rapidly hydrolyzed than benzyl salicylate. The liver and small-intestinal microsomal hydrolase activities were completely inhibited by bis(4-nitrophenyl)phosphate, and could be extracted with Triton X-100. Phenyl salicylate-hydrolyzing activity was co-eluted with carboxylesterase activity by anion exchange column chromatography of the Triton X-100 extracts of liver and small-intestinal microsomes. Expression of rat liver and small-intestinal isoforms of carboxylesterase, Ces1e and Ces2c (AB010632), in COS cells resulted in significant phenyl salicylate-hydrolyzing activities with the same specific activities as those of liver and small-intestinal microsomes, respectively. Human small-intestinal microsomes also exhibited higher hydrolyzing activity than liver microsomes towards these salicylates. Human CES1 and CES2 isozymes expressed in COS cells both readily hydrolyzed phenyl salicylate, but the activity of CES2 was higher than that of CES1. These results indicate that significant amounts of salicylic acid might be formed by microsomal hydrolysis of phenyl and benzyl salicylates in vivo. The possible pharmacological and toxicological effects of salicylic acid released from salicylates present in commercial products should be considered. PMID:26321725

  14. Tetranuclear vanadium complex, (VO)(4)(hpic)(4): a recyclable catalyst for oxidation of benzyl alcohols with molecular oxygen.

    PubMed

    Kodama, Shintaro; Ueta, Yukihiro; Yoshida, Jun; Nomoto, Akihiro; Yano, Shigenobu; Ueshima, Michio; Ogawa, Akiya

    2009-11-28

    Vanadium(iv) complexes bearing 3-hydroxypicolinic acid (H(2)hpic) as ligands, VO(Hhpic)(2) (1) and the cyclic tetramer (VO)(4)(hpic)(4) (2), have excellent catalytic ability for the oxidation of a variety of primary and secondary benzyl alcohols with molecular oxygen in acetonitrile or protic solvents such as ethanol and water, affording the corresponding aldehydes and ketones, respectively. Construction of multi-nuclear complexes by the selection of ligands attains higher turnover numbers and recycling of the catalyst. PMID:19885511

  15. Visible-light-driven selective oxidation of benzyl alcohol and thioanisole by molecular ruthenium catalyst modified hematite.

    PubMed

    Bai, Lichen; Li, Fei; Wang, Yong; Li, Hua; Jiang, Xiaojuan; Sun, Licheng

    2016-08-11

    Molecular ruthenium catalysts were found to selectively catalyze the oxidation of thioanisole to sulfoxide with a yield up to 100% in the presence of visible light and sacrificial reagents when they were anchored onto hematite powder. The composite photocatalysts also showed about 5 times higher efficiencies in benzyl alcohol oxidation than the system composed of dispersed molecular catalysts and hematite particles in aqueous solution. A photoelectrochemical cell based on a molecular catalyst modified hematite photoanode was further fabricated, which exhibited high activity towards the oxidation of organic substrates. PMID:27411498

  16. Vibronic Spectroscopy of Hetero Dihalo-Benzyl Radicals Generated by Corona Discharge : Jet-Cooled Chlorofluorobenzyl Radicals

    NASA Astrophysics Data System (ADS)

    Yoon, Young; Lee, Sang

    2015-06-01

    The technique of corona excited supersonic jet expansion coupled with a pinhole-type glass nozzle was applied to vibronic spectroscopy of jet-cooled chlorofluorobenzyl radicals for the vibronic assignments and measurements of electronic energies of the D_1 → D_0 transition. The vibronic emission spectra were recorded with a long-path monochromator in the visible region. The 2,3-, 2,4-, and 2.5-chlorofluorobenzyl radicals were generated by corona discharge of corresponding precursor molecules, chlorofluorotoluenes seeded in a large amount of helium carrier gas. The emission spectra show the vibronic bands originating from two benzyl-type radicals, chlorofluorobenzyl and fluorobenzyl benzyl radicals, in which fluorobenzyl radicals were obtained by displacement of Cl by H atom produced by the dissociation of methyl C-H bond. From an analysis of the spectra observed, we could determine the electronic energies in D_1 → D_0 transition and vibrational mode frequencies at the D_0 state of chlorofluorobenzyl radicals which show the origin band of the electronic transition to be shifted to red region, comparing with the parental benzyl radical. The red-shift is highly sensitive to the number, position, and kind of substituents in chlorofluorobenzyl radicals. From the quantitative analysis of the red-shift, it has been found that the additivity rule, discovered recently by Lee group predicts the observation very well. In addition, the negligible contribution of the substituent at the 4-position, the nodal point of the Hückel's molecular orbital theory, can be well describes by the disconnection of substituent from molecular plane of the benzene ring available for delocalized π electrons. In this presentation, I will discuss the spectroscopic observation of new chlorofluorobenzyl radicals and substituent effect on electronic transition energy which is useful for identification of isomeric substituted benzyl radicals. C.~S.~Huh, Y.~W.~Yoon, and S.~K.~Lee, J. Chem

  17. Benzyl-1,2,4-triazoles as CB1 Cannabinoid Receptor Ligands: Preparation and In Vitro Pharmacological Evaluation

    PubMed Central

    Hernandez-Folgado, Laura; Decara, Juan; Rodríguez de Fonseca, Fernando; Goya, Pilar; Jagerovic, Nadine

    2016-01-01

    In a previous study, we have identified 3-alkyl-1,5-diaryl-1H-1,2,4-triazoles to be a novel class of cannabinoid type 1 receptor (CB1R) antagonists. In order to expand the number of cannabinoid ligands with a central 1,2,4-triazole scaffold, we have synthesized a novel series of 1-benzyl-1H-1,2,4-triazoles, and some of them were evaluated by CB1R radioligand binding assays. Compound 12a showed the most interesting pharmacological properties, possessing a CB1R affinity in the nanomolar range. PMID:27127651

  18. A study of transglucosylation kinetic in an enzymatic synthesis of benzyl alcohol glucoside by α-glucosidase from S. cerevisiae

    NASA Astrophysics Data System (ADS)

    Pavlović, M.; Dimitrijević, A.; Trbojević, J.; Milosavić, N.; Gavrović-Jankulović, M.; Bezbradica, D.; Veličković, D.

    2013-12-01

    α-1,4-Glucosidase from Saccharomyces cerevisiae is an enzyme which is widely used in synthesis of different drugs. Glucosidase inhibitors are studied as potential drugs for prevention of HIV and diabetes. For understanding of these processes it is very important to have insights in the transglucosylation activity of this enzyme. In this paper the kinetics of transglucosylation reaction catalyzed by this enzyme in the synthesis of benzyl alcohol glucoside was studied and all relevant kinetic constants for this system are found. It was shown one additional property of transglycosylation reactions catalyzed by glycosidases—inhibition by both, glucose acceptor and glucose donor, and mechanisms for these inhibitions were proposed.

  19. Access to “Friedel-Crafts-restricted” tert-alkyl aromatics by activation/methylation of tertiary benzylic alcohols

    PubMed Central

    Hartsel, Joshua A.; Craft, Derek T.; Chen, Qiao-Hong; Ma, Ming

    2012-01-01

    Herein we describe a two-step protocol to prepare m-tert-alkylbenzenes. The appropriate 3° benzylic alcohols are activated with SOCl2 or concentrated HCl, and then treated with trimethylaluminum, affording the desired products in 68–97% yields (22 examples). This reaction sequence is successful in the presence of a variety of functional groups, including acid-sensitive and Lewis-basic groups. In addition to t-Bu groups, 1,1-dimethylpropyl and 1-ethyl-1-methylpropyl groups can also be installed using this method. PMID:22394317

  20. 40 CFR 264.342 - Principal organic hazardous constituents (POHCs).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (CONTINUED) SOLID WASTES (CONTINUED) STANDARDS FOR OWNERS AND OPERATORS OF HAZARDOUS WASTE TREATMENT, STORAGE...) Principal Organic Hazardous Constituents (POHCs) in the waste feed must be treated to the extent required by... permit, from among those constituents listed in part 261, appendix VIII of this chapter, for each...

  1. The Acquisition of Major Constituent Order Rules in English.

    ERIC Educational Resources Information Center

    Bookbinder-Brown, Susan J.; Dimmick, Kenneth D.

    Previous studies dealing with the age at which children acquire constituent order preferences have been in conflict. This study was designed to determine if children with normal language development demonstrate constituent order preferences as early as age three and one-half, or a mean age of four years, one month. To test this competency, an…

  2. [Constituents of the leaves of Ligustrum delavayanum Hariot].

    PubMed

    Nagy, M; Baróniková, S; Grancai, D; Mucaji, P

    2001-11-01

    From the chloroform part of Ligustrum delavayanum Hariot, leaves five constituents were isolated: tyrosol, esculetine, kempferol-7-O-rhamnoside, quercetine-3-O-glucoside, and quercetine. Further six constituents (probably malvidine, two secoiridoid glycosides, caffeic acid monosaccharide ester, quercetine monoglycoside (no hyperoside), and quercetine diglycoside (no rutinoside)) were isolated from the methanolic part of above mentioned drug. PMID:11797198

  3. 40 CFR 264.342 - Principal organic hazardous constituents (POHCs).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... (CONTINUED) SOLID WASTES (CONTINUED) STANDARDS FOR OWNERS AND OPERATORS OF HAZARDOUS WASTE TREATMENT, STORAGE...) Principal Organic Hazardous Constituents (POHCs) in the waste feed must be treated to the extent required by... organic constituents in the waste and on their concentration or mass in the waste feed, considering...

  4. Building a Constituency for Children: A Discussion among Child Advocates.

    ERIC Educational Resources Information Center

    National Association of Child Advocates, Washington, DC.

    A day and a half meeting of executive directors and staff of 11 members of the National Association of Child Advocates (NACA) was convened at the request of Kansas Action for Children to inform its efforts to build a constituency for children in Kansas. Child advocates are increasingly recognizing the need to build and mobilize constituencies for…

  5. A Usage-Based Account of Constituency and Reanalysis

    ERIC Educational Resources Information Center

    Beckner, Clay; Bybee, Joan

    2009-01-01

    Constituent structure is considered to be the very foundation of linguistic competence and often considered to be innate, yet we show here that it is derivable from the domain-general processes of chunking and categorization. Using modern and diachronic corpus data, we show that the facts support a view of constituent structure as gradient (as…

  6. Crystal structures of 3,5-bis-[(E)-3-hy-droxy-benzyl-idene]-1-methyl-piperidin-4-one and 3,5-bis-[(E)-2-chloro-benzyl-idene]-1-methyl-piperidin-4-one.

    PubMed

    Eryanti, Yum; Zamri, Adel; Herlina, Tati; Supratman, Unang; Rosli, Mohd Mustaqim; Fun, Hoong-Kun

    2015-12-01

    The title compounds, C20H19NO3, (1), and C20H17Cl2NO, (2), are the 3-hy-droxy-benzyl-idene and 2-chloro-benzyl-idene derivatives, respectively, of curcumin [systematic name: (1E,6E)-1,7-bis-(4-hy-droxy-3-meth-oxy-phen-yl)-1,6-hepta-diene-3,5-dione]. The dihedral angles between the benzene rings in each compound are 21.07 (6)° for (1) and 13.4 (3)° for (2). In both compounds, the piperidinone rings adopt a sofa confirmation and the methyl group attached to the N atom is in an equatorial position. In the crystal of (1), two pairs of O-H⋯N and O-H⋯O hydrogen bonds link the mol-ecules, forming chains along [10-1]. The chains are linked via C-H⋯O hydrogen bonds, forming undulating sheets parallel to the ac plane. In the crystal of (2), mol-ecules are linked by weak C-H⋯Cl hydrogen bonds, forming chains along the [204] direction. The chains are linked along the a-axis direction by π-π inter-actions [inter-centroid distance = 3.779 (4) Å]. For compound (2), the crystal studied was a non-merohedral twin with the refined ratio of the twin components being 0.116 (6):0.886 (6). PMID:26870411

  7. Constituent quarks in the Standard Model

    NASA Astrophysics Data System (ADS)

    Sukhoruchkin, Sergey

    2016-02-01

    Tuning effect in particle masses manifests itself in integer relations between masses of leptons, quarks, meson and baryons. It includes also dimensionless relation between such well-known SM-parameters as masses of the muon and Z-boson, mμ/MZ=115.9·10-5 coinciding with the QED radiative correction α/2π=115.9·10-5 considered for the electron mass me by V. Belokurov and D. Shirkov. Integer presentation of particle masses (n=1,13,16,17,18,115) for values mμ, fπ, mπ, ΔMΔ, neutron mass and (n=3x16, n=3x18) for constituent quarks M"q=mp,mω/2=780 MeV and Mq=3ΔMΔ=mΞ/3=441 MeV were found with the period δ=16me. More accurate relations with δ were found from precise ratio mn/me=1838.6836605(11). The shift δmn=161.65(6) keV of neutron mass from 115δ-me accounts integer ratio δmN/δmn=8(1.0001(1)) with nucleon mass splitting. With fundamental boson masses the parameters Mq=3ΔMΔ=mΞ/3=441 MeV and M”q =mρ/2=388.8(2) MeV are in ratios MZ/Mq=LZ=206.8 and MW/M”q =LW=207.3 coinciding with lepton ratio L=mμ/me=13·16-1=207.

  8. Antioxidant constituents of Nymphaea caerulea flowers.

    PubMed

    Agnihotri, Vijai K; Elsohly, Hala N; Khan, Shabana I; Smillie, Troy J; Khan, Ikhlas A; Walker, Larry A

    2008-07-01

    As part of an ongoing search for antioxidants from medicinal plants, 20 constituents were isolated from the Nymphaea caerulea flowers, including two 2S,3S,4S-trihydroxypentanoic acid (1), and myricetin 3-O-(3''-O-acetyl)-alpha-L-rhamnoside (2), along with the known myricetin 3-O-alpha-L-rhamnoside (3), myricetin 3-O-beta-D-glucoside (4), quercetin 3-O-(3''-O-acetyl)-alpha-L-rhamnoside (5), quercetin 3-O-alpha-L-rhamnoside (6), quercetin 3-O-beta-D-glucoside (7), kaempferol 3-O-(3''-O-acetyl)-alpha-L-rhamnoside (8), kaempferol 3-O-beta-D-glucoside (9), naringenin (10), (S)-naringenin 5-O-beta-D-glucoside (11), isosalipurposide (12), beta-sitosterol (13), beta-sitosterol palmitate (14), 24-methylenecholesterol palmitate (15), 4alpha-methyl-5alpha-ergosta-7,24(28)-diene-3beta,4beta-diol (16), ethyl gallate (17), gallic acid (18), p-coumaric acid (19), and 4-methoxybenzoic acid (20). The structures were determined by spectroscopic means. Compounds were tested for antioxidant activity and nine compounds 2-7, 11, 12 and 18 were considered active with IC(50) of 1.16, 4.1, 0.75, 1.7, 1.0, 0.34, 11.0, 1.7 and 0.95 microg/ml, respectively, while 1 was marginally active (IC(50)>31.25 microg/ml). The most promising activity was found in the EtOAc fraction (IC(50) 0.2 microg/ml). This can be attributed to the synergistic effect of the compounds present in it. PMID:18534639

  9. Excision biopsy in a patient with suspected local anaesthetic allergy: use of 0.9% saline with benzyl alcohol as local anaesthesia.

    PubMed

    Jolliffe, V M L; Sinclair, R D

    2012-12-01

    Dermatologists may see patients with actual or suspected local anaesthetic (LA) allergy who require an urgent dermatological procedure to be performed without time for formal allergy testing. We report a case of shave biopsy and subsequent excision biopsy of an atypical naevus performed using tumescent analgesia with 0.9% saline containing benzyl alcohol preservative. The tumescence itself and the benzyl alcohol present in the 0.9% saline solution provided sufficient analgesia for excision. This technique may be an option for managing urgent procedures in patients suspected or known to have allergy to LA. PMID:23171156

  10. Synthesis and Application of Tetrahydro-2H-fluorenes by a Pd(0)-Catalyzed Benzylic C(sp(3) )-H Functionalization.

    PubMed

    Suetsugu, Satoshi; Muto, Nobusuke; Horinouchi, Misa; Tsukano, Chihiro; Takemoto, Yoshiji

    2016-06-01

    A new method has been developed for the synthesis of tetrahydro-2H-fluorenes based on a Pd(0)-catalyzed benzylic C(sp(3) )-H functionalization. Importantly, the success of the cyclization step was dependent on there being substituents at the two positions ortho to the benzylic group to avoid an undesired C(sp(2) )-H functionalization. This method was subsequently used to prepare the right-hand fragment of the hexacyclic triterpenoid benzohopanes, and therefore represents a powerful tool for the construction of the related compounds. PMID:27124498

  11. N-Benzyl-indolo carboxylic acids: Design and synthesis of potent and selective adipocyte fatty-acid binding protein (A-FABP) inhibitors.

    PubMed

    Barf, Tjeerd; Lehmann, Fredrik; Hammer, Kristin; Haile, Saba; Axen, Eva; Medina, Carmen; Uppenberg, Jonas; Svensson, Stefan; Rondahl, Lena; Lundbäck, Thomas

    2009-03-15

    Small molecule inhibitors of adipocyte fatty-acid binding protein (A-FABP) have gained renewed interest following the recent publication of pharmacologically beneficial effects of such inhibitors. Despite the potential utility of selective A-FABP inhibitors within the fields of metabolic disease, inflammation and atherosclerosis, there are few examples of useful A-FABP inhibitors in the public domain. Herein, we describe the optimization of N-benzyl-tetrahydrocarbazole derivatives through the use of co-crystal structure guided medicinal chemistry efforts. This led to the identification of a potent and selective class of A-FABP inhibitors as illustrated by N-benzyl-hexahydrocyclohepta[b]indole 30. PMID:19217286

  12. Fe(III)-photocatalytic partial oxidation of benzyl alcohol to benzaldehyde under UV-solar simulated radiation.

    PubMed

    Spasiano, Danilo; Marotta, Raffaele; Di Somma, Ilaria; Andreozzi, Roberto; Caprio, Vincenzo

    2013-11-01

    A great deal of interest is recorded among researchers in the identification of new catalytic systems that make possible the selective oxidation of organic species in the presence of non-toxic solvents, primarily water, through the use of inexpensive catalysts. The possibility to selectively oxidize benzyl alcohol to benzaldehyde is studied in the present work by using ferric ions as homogeneous catalysts and oxygen as an oxidant under UV-solar simulated radiation. Due to the possibility that Fe(III) aquo-complex photolysis could generate undesired reactive OH radicals with the consequent occurrence of side reactions, most of the runs are carried out at pH = 0.5 at which these events have a reduced incidence. The results indicate that benzyl alcohol can be partially converted into benzaldehyde with yield and selectivity values higher than 40% and 80% respectively for the conditions adopted, with a minor occurrence of benzoic acid formation. Reaction schemes to account for the experimental observations are provided. PMID:24057651

  13. Benzyl p-guanidinothiobenzoate hydrochloride, a new active-site titrant for trypsin and trypsin-like enzymes.

    PubMed Central

    Cook, R R; Powers, J C

    1983-01-01

    Benzyl p-guanidinothiobenzoate hydrochloride was synthesized and demonstrated to be useful for active-site titration of bovine trypsin, bovine thrombin, human lung tryptase, bovine activated protein C, human Factor XIIa fragment and bovine Factor Xa beta. The titration is based on rapid formation of a stable acyl-enzyme with a stoichiometric release of benzyl thiol. Thiol production is measured quantitatively by including 4,4'-dithiodipyridine in the reaction mixture and measuring the increase in absorbance at 324 nm. Ellman's reagent has also been successfully employed, allowing measurement at 410 nm. Unlike p-nitrophenyl p'-guanidinobenzoate, the thioester titrant reacts slowly with chymotrypsin A alpha thus eliminating interference by this enzyme in most titrations. Advantages of this reagent as a titrant include: flexibility in detection of the released thiol, selectivity between trypsin and chymotrypsin-like enzymes, minimal pH-dependence of the epsilon of the absorbing species, relative stability of the reagent under titration conditions, and high epsilon at pH 7.2 with either 4,4'-dithiodipyridine or Ellman's reagent. The reagent should prove useful as an alternative to p-nitrophenyl p'-guanidinobenzoate hydrochloride for the determination of active-site concentrations of the enzymes employed, as well as of other related enzymes. PMID:6360155

  14. Synthesis and Structure–Activity Relationships of N-Benzyl Phenethylamines as 5-HT2A/2C Agonists

    PubMed Central

    2014-01-01

    N-Benzyl substitution of 5-HT2A receptor agonists of the phenethylamine structural class of psychedelics (such as 4-bromo-2,5-dimethoxyphenethylamine, often referred to as 2C-B) confer a significant increase in binding affinity as well as functional activity of the receptor. We have prepared a series of 48 compounds with structural variations in both the phenethylamine and N-benzyl part of the molecule to determine the effects on receptor binding affinity and functional activity at 5-HT2A and 5-HT2C receptors. The compounds generally had high affinity for the 5-HT2A receptor with 8b having the highest affinity at 0.29 nM but with several other compounds also exhibiting subnanomolar binding affinities. The functional activity of the compounds was distributed over a wider range with 1b being the most potent at 0.074 nM. Most of the compounds exhibited low to moderate selectivity (1- to 40-fold) for the 5-HT2A receptor in the binding assays, although one compound 6b showed an impressive 100-fold selectivity for the 5-HT2A receptor. In the functional assay, selectivity was generally higher with 1b being more than 400-fold selective for the 5-HT2A receptor. PMID:24397362

  15. A Pronounced Halogen Effect on the Organogelation Properties of Peripherally Halogen Functionalized Poly(benzyl ether) Dendrons.

    PubMed

    Feng, Yu; Chen, Hui; Liu, Zhi-Xiong; He, Yan-Mei; Fan, Qing-Hua

    2016-03-24

    An interesting halogen-substituent effect on the organogelation properties of poly(benzyl ether) dendrons is reported. A new class of poly(benzyl ether) dendrons with halo substituents decorating their periphery was synthesized and fully characterized. A systematic study on the gelation abilities, thermotropic behaviors, aggregated microstructures, and mechanical properties of self-assembled organogels was performed to elucidate the halogen-substituent effects on their organogelation propensity. It was found that the exact halogen substitutions on the periphery of dendrons exert a profound effect on the organogelation propensity, and dendrons Gn -Cl (n=2, 3) and G2 -I proved to be highly efficient organogelators. The cooperation of multiple π-π, dispersive halogen, CH-π, and weak C-H⋅⋅⋅X hydrogen-bonding interactions were found to be the key contributor to forming the self-assembled gels. Dendritic organogels formed from Gn -Cl (n=2, 3) in 1,2-dichloroethane exhibited thixotropic-responsive properties, and such thixotropic organogels are promising materials for future research and applications. PMID:26916094

  16. Primary and secondary kinetic deuterium isotope effects and transition-state structures for benzylic chlorination and bromination of toluene

    SciTech Connect

    Hanzlik, R.P.; Schaefer, A.R.; Moon, J.B.; Judson, C.M.

    1987-08-05

    As a chemical model for benzylic hydroxylation effects by cytochrome P-450 enzymes, the chlorination of PhCH/sub 3/, PhCH/sub 2/D, PhCHD/sub 2/, and PhCD/sub 3/ in a two-phase system of hypochlorite/CH/sub 2/Cl/sub 2/ with a phase-transfer catalyst has been investigated. On the basis of the deuterium content of the product benzyl chlorides, relative rate constants were deduced for all possible H- and D-abstractions with these substrates. From this the primary (P) and secondary (S) KDIEs were found to be 5.90 +/- 0.41 and 1.03 +/- 0.02, respectively, and the rule of the geometric mean was found to be closely obeyed. For the analogous bromination of toluene by N-bromosuccinimide in CCl/sub 4/, P and S were 6.37 +/- 0.43 and 1.05 +/- 0.01. The transition states of these processes must therefore involve extensive C-H bond breaking but relatively little rehybridization toward planarity at the reacting carbon.

  17. Design, synthesis and biological evaluation of 3'-benzylated analogs of 3'-epi-neoponkoranol as potent α-glucosidase inhibitors.

    PubMed

    Liu, Dan; He, Weigang; Wang, Zihao; Liu, Long; Wang, Chengqian; Zhang, Chenxi; Wang, Chengcheng; Wang, Yuxuan; Tanabe, Genzoh; Muraoka, Osamu; Wu, Xiaoming; Wu, Liang; Xie, Weijia

    2016-03-01

    A group of 3'-epi-neoponkoranol analogs with different hydrophobic substituents attached at 3'-position of side chain moiety were designed and synthesized in order to further improve the inhibitory activities against α-glucosidases. Biological evaluation of these compounds revealed that sulfonium salts attached with ortho-substituted benzyl groups showed best α-glucosidase inhibitory activities. The most potent compound 10i showed greater inhibitory activities than all natural products. Moreover, docking studies on 10i with ntMGAM presented a new binding mode, indicating that amino residue Asp542 should be the key interacting point for strong inhibitory activity of small molecules against α-glucosidase enzymes. The strongest α-glucosidase inhibitory activity of 10i could be rationalized by van der Waals interactions between the 3'-attached substituent and particularly the ortho-substituted trifluoromethyl on benzyl group with the adjacent hydrophobic amino residues. Cytotoxicity evaluation assay demonstrated a high level of safety profile of the synthesized sulfonium salts against normal cell line. The enzyme kinetic studies showed a fully competitive inhibition of these sulfonium salts on each α-glucosidase. PMID:26840363

  18. Phenylcoumaran Benzylic Ether Reductase Prevents Accumulation of Compounds Formed under Oxidative Conditions in Poplar Xylem[W

    PubMed Central

    Niculaes, Claudiu; Morreel, Kris; Kim, Hoon; Lu, Fachuang; McKee, Lauren S.; Ivens, Bart; Haustraete, Jurgen; Vanholme, Bartel; Rycke, Riet De; Hertzberg, Magnus; Fromm, Jorg; Bulone, Vincent; Polle, Andrea; Ralph, John; Boerjan, Wout

    2014-01-01

    Phenylcoumaran benzylic ether reductase (PCBER) is one of the most abundant proteins in poplar (Populus spp) xylem, but its biological role has remained obscure. In this work, metabolite profiling of transgenic poplar trees downregulated in PCBER revealed both the in vivo substrate and product of PCBER. Based on mass spectrometry and NMR data, the substrate was identified as a hexosylated 8–5-coupling product between sinapyl alcohol and guaiacylglycerol, and the product was identified as its benzyl-reduced form. This activity was confirmed in vitro using a purified recombinant PCBER expressed in Escherichia coli. Assays performed on 20 synthetic substrate analogs revealed the enzyme specificity. In addition, the xylem of PCBER-downregulated trees accumulated over 2000-fold higher levels of cysteine adducts of monolignol dimers. These compounds could be generated in vitro by simple oxidative coupling assays involving monolignols and cysteine. Altogether, our data suggest that the function of PCBER is to reduce phenylpropanoid dimers in planta to form antioxidants that protect the plant against oxidative damage. In addition to describing the catalytic activity of one of the most abundant enzymes in wood, we provide experimental evidence for the antioxidant role of a phenylpropanoid coupling product in planta. PMID:25238751

  19. Cortical representation of the constituent structure of sentences

    PubMed Central

    Pallier, Christophe; Devauchelle, Anne-Dominique; Dehaene, Stanislas

    2011-01-01

    Linguistic analyses suggest that sentences are not mere strings of words but possess a hierarchical structure with constituents nested inside each other. We used functional magnetic resonance imaging (fMRI) to search for the cerebral mechanisms of this theoretical construct. We hypothesized that the neural assembly that encodes a constituent grows with its size, which can be approximately indexed by the number of words it encompasses. We therefore searched for brain regions where activation increased parametrically with the size of linguistic constituents, in response to a visual stream always comprising 12 written words or pseudowords. The results isolated a network of left-hemispheric regions that could be dissociated into two major subsets. Inferior frontal and posterior temporal regions showed constituent size effects regardless of whether actual content words were present or were replaced by pseudowords (jabberwocky stimuli). This observation suggests that these areas operate autonomously of other language areas and can extract abstract syntactic frames based on function words and morphological information alone. On the other hand, regions in the temporal pole, anterior superior temporal sulcus and temporo-parietal junction showed constituent size effect only in the presence of lexico-semantic information, suggesting that they may encode semantic constituents. In several inferior frontal and superior temporal regions, activation was delayed in response to the largest constituent structures, suggesting that nested linguistic structures take increasingly longer time to be computed and that these delays can be measured with fMRI. PMID:21224415

  20. Crystal structures of (E)-N′-(2-hy­droxy-5-methyl­benzyl­idene)isonicotinohydrazide and (E)-N′-(5-fluoro-2-hy­droxy­benzyl­idene)isonicotinohydrazide

    PubMed Central

    Chainok, Kittipong; Makmuang, Sureerat; Kielar, Filip

    2016-01-01

    Two derivatives of the well-known iron chelator, (E)-N′-(2-hy­droxy­benzyl­idene)isonicotinohydrazide (SIH), substituted in the 5-position of the 2-hy­droxy­benzene ring by a methyl and a fluorine group viz. (E)-N′-(2-hy­droxy-5-methyl­benzyl­idene)isonicotinohydrazide, C14H13N3O2, (I), and (E)-N′-(5-fluoro-2-hy­droxy­benzyl­idene)isonicotinohydrazide, C13H10FN3O2, (II), have been prepared and characterized by single-crystal X-ray diffraction, 1H NMR and mass spectrometry. The mol­ecules of both compounds deviate slightly from planarity [r.m.s. deviations are 0.145 and 0.110 Å for (I) and (II), respectively] and adopt an E conformation with respect to the double bond of the hydrazone bridge. In each mol­ecule, there is an intra­molecular O—H⋯N hydrogen bond forming an S(6) ring motif. The dihedral angles between the mean planes of the isonicotinoyl ring and the cresol ring in (I) or the fluoro­phenol ring in (II) are 10.49 (6) and 9.43 (6)°, respectively. In the crystals of both compounds, zigzag chains are formed via N—H⋯N hydrogen bonds, in the [10-1] direction for (I) and [010] for (II). In (I), the chains are linked by weak C—H⋯π and π–π stacking inter­actions [centroid-to-centroid distances = 3.6783 (8) Å; inter-planar angle = 10.94 (5)°], leading to the formation of a three-dimensional supra­molecular architecture. In (II), adjacent chains are connected through C—H⋯O hydrogen bonds to form sheets parallel to (100), which enclose R 4 4(30) ring motifs. The sheets are linked by weak C—H⋯π and π–π [centroid-to-centroid distance = 3.7147 (8) Å; inter-planar angle = 10.94 (5)°] inter­actions, forming a three-dimensional supra­molecular architecture. PMID:27555945