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Sample records for 2-methyltetrols c5-alkene triols

  1. Gas/particle partitioning of 2-methyltetrols and levoglucosan at an urban site in Denver.

    PubMed

    Xie, Mingjie; Hannigan, Michael P; Barsanti, Kelley C

    2014-01-01

    In this study, a medium volume sampler incorporating quartz fiber filters (QFFs) and a polyurethane foam (PUF)/XAD/PUF sandwich (PXP) was used to collect 2-methyltetrols (isoprene tracer) and levoglucosan (biomass burning tracer) in gaseous and particle (PM2.5) phases. The measured gas/particle (G/P) partitioning coefficients (Kp,OMm) of 2-methyltetrols and levoglucosan were calculated and compared to their predicted G/P partitioning coefficients (Kp,OMt) based on an absorptive partitioning theory. The breakthrough experiments showed that gas-phase 2-methyltetrols and levoglucosan could be collected using the PXP or PUF adsorbent alone, with low breakthrough; however, the recoveries of levoglucosan in PXP samples were lower than 70% (average of 51.9–63.3%). The concentration ratios of 2-methyltetrols and levoglucosan in the gas phase to those in the particle phase were often close to or higher than unity in summer, indicating that these polar species are semi-volatile and their G/P partitioning should be considered when applying particle-phase data for source apportionment. The Kp,OMm values of 2-methyltetrols had small variability in summer Denver, which was ascribed to large variations in concentrations of particulate organic matter (5.14 ± 3.29 μg m–3) and small changes in ambient temperature (21.8 ± 4.05 °C). The regression between log Kp,OMm and log Kp,OMt suggested that the absorptive G/P partitioning theory could reasonably predict the measured G/P partitioning of levoglucosan in ambient samples.

  2. Primary and secondary organics in tropical Amazonian rainforest aerosols: Chiral analysis of 2-methyltetrols

    SciTech Connect

    Gonzalez, Nelida; Borg-Karlson, Anna-Karin; Artaxo, Paulo; Guenther, Alex B.; Krejci, R.; Noziere, Barbara; Noone, Kevin

    2014-06-01

    This work presents the application of a newly developed method to facilitate the distinction between primary and secondary organic compounds in ambient aerosols based on their chiral analysis. The organic constituents chosen for chiral analysis are the four stereomers of the 2-methyltetrols, (2R,3S)- and (2S,3R)- methylerythritol and (2S,3S)- and (2R,3R)- methylthreitol. Ambient PM10 aerosol samples were collected between June 2008 and June 2009 near Manaus, Brazil, in a remote tropical rainforest environment of central Amazonia. The samples were analyzed for the presence of these four stereomers because qualitatively, in a previous study, they have been demonstrated to have partly primary origins. Thus the origin of these compounds may be primary and secondary from the biosynthesis and oxidation processes of isoprene within plants and also in the atmosphere. Using authentic standards, the quantified concentrations were in average 78.2 and 72.8 ng m-3 for (2R,3S)- and (2S,3R)- methylerythritol and 3.1 and 3.3 ng m-3 for (2S,3S)- and (2R,3R)- methylthreitol during the dry season and 7.1, 6.5, 2.0, and 2.2 ng m-3 during the wet season, respectively. Furthermore, these compounds were found to be outside the confidence interval for racemic mixtures (enantiomeric fraction, Ef = 0.5 -0.01) in nearly all the samples, with deviations of up to 32 % (Ef = 0.61) for (2R,3S)-methylerythritol and 47 % (Ef = 0.65) for (2S,3S)-methylthreitol indicating (99% confidence level) biologically-produced 2-methyltetrols. The minimum primary origin contribution ranged between 0.19 and 29.67 ng m-3 for the 2-methylerythritols and between 0.15 and 1.2 ng m-3 for the 2-methylthreitols. The strong correlation of the diatereomers (racemic 2-methylerythritol and 2-methylthreitol) in the wet season implied a secondary origin. Assuming the maximum secondary contribution in the dry season, the secondary fraction in the wet season was 81-99 % and in the dry season, 10 - 95 %. Nevertheless, from the

  3. Polyurethane networks from fatty-acid-based aromatic triols: synthesis and characterization.

    PubMed

    Lligadas, Gerard; Ronda, Joan C; Galià, Marina; Cadiz, Virginia

    2007-06-01

    Novel biobased aromatic triols (1,3,5-(9-hydroxynonyl)benzene and 1,3,5-(8-hydroxyoctyl)-2,4,6-octylbenzene) were synthesized through the transition-metal-catalyzed cyclotrimerization of two alkyne fatty acid methyl esters (methyl 10-undecynoate and methyl 9-octadecynoate) followed by the reduction of the ester groups to give terminal primary hydroxyl groups. A series of biobased segmented polyurethanes based on these triols, 1,4-butanediol as a chain extender and 4,4'-methylenebis(phenyl isocyanate) as a coupling agent, were synthesized. Samples were prepared with hard-segment contents up to 50%. The morphologies and thermal properties of these polyurethanes were studied by Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis. Partial crystallinity and phase separation were detected in samples with hard-segment content of 50%.

  4. Concentration, distribution and variation of polar organic aerosol tracers in Ya'an, a middle-sized city in western China

    NASA Astrophysics Data System (ADS)

    Li, Li; Dai, Dongjue; Deng, Shihuai; Feng, Jialiang; Zhao, Min; Wu, Jun; Liu, Lu; Yang, Xiaohui; Wu, Sishi; Qi, Hui; Yang, Gang; Zhang, Xiaohong; Wang, Yingjun; Zhang, Yanzong

    2013-02-01

    PM2.5 (particulate matter with an aerodynamic diameter < 2.5 μm) and TSP (total suspended particulates) aerosol samples were collected in Ya'an, a middle-sized city with extensive wood resources in Southwestern China, to characterize the contribution of secondary organic aerosols (SOA) to the regional troposphere, the composition of the organic tracers as well as factors affecting their concentrations. A total of 34 samples were gathered on the Campus of Sichuan Agricultural University (SAU, urban site, in the city zone of Ya'an), while 49 samples were collected at Baima Spring Scenic Area (BSSA, forest site, situated about 30 km to the northeast of SAU) during June to July, 2010. Using GC/MS analysis with prior trimethylsilylation, organic tracers including isoprene oxidation products (2-methyltetrols, C5-alkene triols and 2-methylglyceric acid), α-/β-pinene oxidation products (norpinic acid, 3-hydroxyglutaric acid, 3-hydroxy-4,4-dimethylglutaric acid, and 3-methyl-1,2,3- butanetricarboxylic acid), a sesquiterpene oxidation product (β-caryophyllinic acid), sugars (glucose and fructose), sugar alcohols (arabitol, mannitol, erythritol, sorbitol and xylitol), anhydrosugars (levoglucosan, mannosan and galactosan) and malic acid were determined. The factors that could potentially affect the SOA tracer concentrations, i.e. trace gases (SO2, NOx, O3, NH3), aerosol acidity and meteorological parameters, were monitored. The results showed that the concentrations of total isoprene oxidation products were 72 and 82 ng/m3 at the two sampling locations, with 29 ± 18, 37 ± 9, 6 ± 2 ng/m3 at SAU and 57 ± 34, 33 ± 33, 4 ± 2 ng/m3 at BSSA for 2-methyltetrols, C5-alkene triols and 2-methylglyceric acid respectively. Compared with the concentrations of isoprene oxidation products, those of α-/β-pinene oxidation products and β-caryophyllinic acid were much lower, being 6 ± 33 and 0.5 ± 1.9 ng/m3 at SAU, and 9 ± 14 and 1.0 ± 1.2 ng/m3 at BSSA, respectively. The unique

  5. Determination of isoprene and alpha-/beta-pinene oxidation products in boreal forest aerosols from Hyytiälä, Finland: diel variations and possible link with particle formation events.

    PubMed

    Kourtchev, I; Ruuskanen, T M; Keronen, P; Sogacheva, L; Dal Maso, M; Reissell, A; Chi, X; Vermeylen, R; Kulmala, M; Maenhaut, W; Claeys, M

    2008-01-01

    Biogenic volatile organic compounds (VOCs), such as isoprene and alpha-/beta-pinene, are photo-oxidized in the atmosphere to non-volatile species resulting in secondary organic aerosol (SOA). The goal of this study was to examine time trends and diel variations of oxidation products of isoprene and alpha-/beta-pinene in order to investigate whether they are linked with meteorological parameters or trace gases. Separate day-night aerosol samples (PM(1)) were collected in a Scots pine dominated forest in southern Finland during 28 July-11 August 2005 and analyzed with gas chromatography/mass spectrometry (GC/MS). In addition, inorganic trace gases (SO(2), CO, NO(x), and O(3)), meteorological parameters, and the particle number concentration were monitored. The median total concentration of terpenoic acids (i.e., pinic acid, norpinic acid, and two novel compounds, 3-hydroxyglutaric acid and 2-hydroxy-4-isopropyladipic acid) was 65 ng m(-3), while that of isoprene oxidation products (i.e., 2-methyltetrols and C(5) alkene triols) was 17.2 ng m(-3). The 2-methyltetrols exhibited day/night variations with maxima during day-time, while alpha-/beta-pinene oxidation products did not show any diel variation. The sampling period was marked by a relatively high condensation sink, caused by pre-existing aerosol particles, and no nucleation events. In general, the concentration trends of the SOA compounds reflected those of the inorganic trace gases, meteorological parameters, and condensation sink. Both the isoprene and alpha-/beta-pinene SOA products were strongly influenced by SO(2), which is consistent with earlier reports that acidity plays a role in SOA formation. The results support previous proposals that oxygenated VOCs contribute to particle growth processes above boreal forest.

  6. (Citric acid-co-polycaprolactone triol) polyester: a biodegradable elastomer for soft tissue engineering.

    PubMed

    Thomas, Lynda V; Nair, Prabha D

    2011-01-01

    Tissue engineering holds enormous challenges for materials science, wherein the ideal scaffold to be used is expected to be biocompatible, biodegradable and possess mechanical and physical properties that are suitable for target application. In this context, we have prepared degradable polyesters in different ratios by a simple polycondensation technique with citric acid and polycaprolactone triol. Differential scanning calorimetry indicated that the materials were amorphous based the absence of a crystalline melting peak and the presence of a glass transition temperature below 37°C. These polyesters were found to be hydrophilic and could be tailor-made into tubes and films. Porosity could also be introduced by addition of porogens. All the materials were non-cytotoxic in an in vitro cytotoxicity assay and may degrade via hydrolysis to non-toxic degradation products. These polyesters have potential implications in the field of soft tissue engineering on account of their similarity of properties.

  7. The 1H NMR method for the determination of the absolute configuration of 1,2,3-prim,sec,sec-triols.

    PubMed

    Lallana, Enrique; Freire, Félix; Seco, José Manuel; Quiñoa, Emilio; Riguera, Ricardo

    2006-09-28

    The absolute configuration of 1,2,3-prim,sec,sec-triols can be assigned by comparison of the 1H NMR spectra of the tris-(R)- and the tris-(S)-MPA ester derivatives. An experimental demonstration of this correlation with 24 triols of known absolute configuration and a protocol using two parameters-Deltadelta(RS)(H3) and the difference between Deltadelta RS (H2) and Deltadelta RS (H3) = absolute value (Delta(Deltadelta RS))-for its application to the determination of the absolute configuration of other triols are presented.

  8. Cell Transfection with a β-Cyclodextrin-PEI-Propane-1,2,3-Triol Nanopolymer

    PubMed Central

    Lai, Wing-Fu; Jung, Han-Sung

    2014-01-01

    Successful gene therapy necessitates safe and efficient gene transfer. This article describes the use of a cationic polymer, which was synthesized by cross-linking low molecular weight branched poly(ethylenimine) (PEI) with both β-cyclodextrin and propane-1,2,3-triol, for efficient and safe non-viral gene delivery. Experimentation demonstrated that the polymer had a pH buffering capacity and DNA condensing ability comparable to those of PEI 25 kDa. In B16-F0 cells, the polymer increased the transfection efficiency of naked DNA by 700-fold and yielded better transfection efficiencies than Fugene HD (threefold higher) and PEI 25 kDa (fivefold higher). The high transfection efficiency of the polymer was not affected by the presence of serum during transfection. In addition to B16-F0 cells, the polymer enabled efficient transfection of HepG2 and U87 cells with low cytotoxicity. Our results indicated that our polymer is a safe and efficient transfection reagent that warrants further development for in vitro, in vivo and clinical applications. PMID:24956480

  9. Unprecedented χ isomers of single-side triol-functionalized Anderson polyoxometalates and their proton-controlled isomer transformation.

    PubMed

    Zhang, Jiangwei; Liu, Zhenhua; Huang, Yichao; zhang, Jin; Hao, Jian; Wei, Yongge

    2015-06-04

    The μ2-O atom in Anderson polyoxometalates was regioselectively activated by the introduction of protons, which, upon functionalization with triol ligands, could afford a series of unique χ isomers of the organically-derived Anderson cluster {[RCC(CH2O)3]MMo6O18(OH)3}(3-). Herein proton-controlled isomer transformation between the δ and χ isomer was observed by using the fingerprint region in the IR spectra and (13)C NMR spectra.

  10. Neuroprotectant androst-3β, 5α, 6β-triol suppresses TNF-α-induced endothelial adhesion molecules expression and neutrophil adhesion to endothelial cells by attenuation of CYLD-NF-κB pathway.

    PubMed

    Yan, Min; Leng, Tiandong; Tang, Lipeng; Zheng, Xiaoke; Lu, Bingzheng; Li, Yuan; Sheng, Longxiang; Lin, Suizhen; Shi, Haitao; Yan, Guangmei; Yin, Wei

    2017-02-05

    Neuroinflammation is one of key pathologic element in neurological diseases including stroke, traumatic brain injury, Alzheimer' s Disease, Parkinson's Disease, and multiple sclerosis as well. Up-regulation of endothelial adhesion molecules, which facilitate leukocyte adhesion to the endothelium, is the vital process of endothelial cells mediated neuroinflammation. Androst-3β, 5α, 6β-triol (Triol) is a synthetic steroid which has been reported to have neuroprotective effects in hypoxia/re-oxygenation-induced neuronal injury model. In the present study, we firstly investigated whether Triol inhibited the TNF-α-induced inflammatory response in rat brain microvascular endothelial cells (RBMECs). Our data showed that Triol decreased TNF-α-induced expression of vascular cell adhesion molecule-1 (VCAM-1) and intercellular adhesion molecule-1 (ICAM-1) and the adhesion of neutrophil to RBMECs. We also found that Triol inhibited TNF-α-induced degradation of IκBα and phosphorylation of NF-κBp65 that are required for NF-κB activation. Furthermore, Triol significantly reversed TNF-α-induced down-expression of CYLD, which is a deubiquitinase that negatively regulates activation of NF-κB. These results suggest that Triol displays an anti-inflammatory effect on TNF-α-induced RBMECs via downregulating of CYLD-NF-κB signaling pathways and might have a potential benefit in therapeutic neuroinflammation related diseases.

  11. Preparation and characterization of the deepoxy trichothecenes: deepoxy HT-2, deepoxy T-2 triol, deepoxy T-2 tetraol, deepoxy 15-monoacetoxyscirpenol, and deepoxy scirpentriol.

    PubMed Central

    Swanson, S P; Rood, H D; Behrens, J C; Sanders, P E

    1987-01-01

    The production of deepoxy metabolites of the trichothecene mycotoxins T-2 toxin and diacetoxyscirpenol, including deepoxy HT-2 (DE HT-2), deepoxy T-2 triol, deepoxy T-2 tetraol, deepoxy 15-monoacetoxyscirpenol, and deepoxy scirpentriol is described. The metabolites were prepared by in vitro fermentation with bovine rumen microorganisms under anaerobic conditions and purified by normal and reverse-phase high-pressure liquid chromatography. Capillary gas chromatographic retention times and mass spectra of the derivatized metabolites were obtained. The deepoxy metabolites were significantly less toxic to brine shrimp than were the corresponding epoxy analogs. Polyclonal and monoclonal T-2 antibodies were examined for cross-reactivity to several T-2 metabolites. Both HT-2 and DE HT-2 cross-reacted with mouse immunoglobulin monoclonal antibody 15H6 to a greater extent than did T-2 toxin. Rabbit polyclonal T-2 antibodies displayed greater specificity to T-2 toxin compared with the monoclonal antibody, with relative cross-reactivities of only 17.4, 14.6, and 9.2% for HT-2, DE HT-2, and deepoxy T-2 triol, respectively. Cross-reactivity of both antibodies was weak for T-2 triol, T-2 tetraol, 3'OH T-2, and 3'OH HT-2. PMID:3435145

  12. Molecular Targets for 17α-Ethynyl-5-Androstene-3β,7β,17β-Triol, an Anti-Inflammatory Agent Derived from the Human Metabolome

    PubMed Central

    Reading, Christopher L.; Frincke, James M.; White, Steven K.

    2012-01-01

    HE3286, 17α-ethynyl-5-androstene-3β, 7β, 17β-triol, is a novel synthetic compound related to the endogenous sterol 5-androstene-3β, 7β, 17β-triol (β-AET), a metabolite of the abundant adrenal steroid dehydroepiandrosterone (DHEA). HE3286 has shown efficacy in clinical studies in impaired glucose tolerance and type 2 diabetes, and in vivo models of types 1 and 2 diabetes, autoimmunity, and inflammation. Proteomic analysis of solid-phase HE3286-bound bead affinity experiments, using extracts from RAW 264.7 mouse macrophage cells, identified 26 binding partners. Network analysis revealed associations of these HE3286 target proteins with nodes in the Kyoto Encyclopedia of Genes and Genomes (KEGG) pathways for type 2 diabetes, insulin, adipokine, and adipocyte signaling. Binding partners included low density lipoprotein receptor-related protein (Lrp1), an endocytic receptor; mitogen activated protein kinases 1 and 3 (Mapk1, Mapk3), protein kinases involved in inflammation signaling pathways; ribosomal protein S6 kinase alpha-3 (Rsp6ka3), an intracellular regulatory protein; sirtuin-2 (Sirt2); and 17β-hydroxysteroid dehydrogenase 1 (Hsd17β4), a sterol metabolizing enzyme. PMID:22384159

  13. Polar organic marker compounds in atmospheric aerosols during the LBA-SMOCC 2002 biomass burning experiment in Rondônia, Brazil: sources and source processes, time series, diel variations and size distributions

    NASA Astrophysics Data System (ADS)

    Claeys, M.; Kourtchev, I.; Pashynska, V.; Vas, G.; Vermeylen, R.; Wang, W.; Cafmeyer, J.; Chi, X.; Artaxo, P.; Andreae, M. O.; Maenhaut, W.

    2010-04-01

    Measurements of polar organic marker compounds were performed on aerosols that were collected at a pasture site in the Amazon basin (Rondônia, Brazil) using a High-Volume dichotomous sampler (HVDS) and a Micro-Orifice Uniform Deposit Impactor (MOUDI). The samplings were conducted within the framework of the LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazônia - Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate) campaign, which took place from 9 September till 14 November 2002, spanning the late dry season (biomass burning), the transition period, and the onset of the wet season (clean conditions). In the present study a more detailed discussion is presented compared to previous reports on the behavior of selected polar marker compounds, including: (a) levoglucosan, a tracer for biomass burning, (b) malic acid, a tracer for the oxidation of semivolatile carboxylic acids, (c) tracers for secondary organic aerosol (SOA) from isoprene, i.e., the 2-methyltetrols (2-methylthreitol and 2-methylerythritol) and the C5-alkene triols [2-methyl-1,3,4-trihydroxy-1-butene (cis and trans) and 3-methyl-2,3,4-trihydroxy-1-butene], and (d) sugar alcohols (arabitol, mannitol, and erythritol), tracers for fungal spores. The results obtained for levoglucosan are covered first with the aim to address its contrasting behavior with that of malic acid, the isoprene SOA tracers, and the fungal spore tracers. The tracer data are discussed taking into account new insights that recently became available into their stability and/or aerosol formation processes. During all three periods, levoglucosan was the most dominant identified organic species in the PM2.5 size fraction of the HVDS samples. In the dry period levoglucosan reached concentrations of up to 7.5 μg m-3 and exhibited diel variations with a nighttime prevalence. It was closely associated with the PM mass in the size-segregated samples and was mainly

  14. Cholestane-3β,5α,6β-triol: high levels in Niemann-Pick type C, cerebrotendinous xanthomatosis, and lysosomal acid lipase deficiency.

    PubMed

    Pajares, Sonia; Arias, Angela; García-Villoria, Judit; Macías-Vidal, Judit; Ros, Emilio; de las Heras, Javier; Girós, Marisa; Coll, Maria J; Ribes, Antonia

    2015-10-01

    Niemann-Pick type C (NPC) is a progressive neurodegenerative disease characterized by lysosomal/endosomal accumulation of unesterified cholesterol and glycolipids. Recent studies have shown that plasma cholestane-3β,5α,6β-triol (CT) and 7-ketocholesterol (7-KC) could be potential biomarkers for the diagnosis of NPC patients. We aimed to know the sensitivity and specificity of these biomarkers for the diagnosis of NPC compared with other diseases that can potentially lead to oxysterol alterations. We studied 107 controls and 122 patients including 16 with NPC, 3 with lysosomal acid lipase (LAL) deficiency, 8 with other lysosomal diseases, 5 with galactosemia, 11 with cerebrotendinous xanthomatosis (CTX), 3 with Smith-Lemli-Opitz, 14 with peroxisomal biogenesis disorders, 19 with unspecific hepatic diseases, 13 with familial hypercholesterolemia, and 30 with neurological involvement and no evidence of an inherited metabolic disease. CT and 7-KC were analyzed by HPLC-ESI-MS/MS as mono-dimethylglycine derivatives. Levels of 7-KC were high in most of the studied diseases, whereas those of CT were only high in NPC, LAL, and CTX patients. Consequently, although CT is a sensitive biomarker of NPC disease, including those cases with doubtful filipin staining, it is not specific. 7-KC is a very unspecific biomarker.

  15. Synthesis of Poly(4-((phenylimino)methyl)benzene-1,2,3-triol) and Its Application for Improving the Heterostructure Device Characteristics

    NASA Astrophysics Data System (ADS)

    Demir, Haci Okkes; Ozkaya, Suat

    2017-01-01

    A trihydroxy substituted poly(4-((phenylimino)methyl)benzene-1,2,3-triol) abbreviated as poly(2,3,4-PIMB), poly(phenoxy-imine)-type polymer, has been successfully synthesized by oxidative coupling polymerization in an aqueous alkaline medium using sodium hypochlorite. Detailed structural characterization of the phenoxy-imine type monomer and its polymer were investigated by Fourier transform infrared (FT-IR), proton nuclear magnetic resonance (1H-NMR), ultraviolet-visible (UV-Vis), and gel permeation chromatography spectroscopy techniques. According to these analyses, the synthesized polymer has its backbone made of oxyphenylene linkages only. The solubility, thermal stability, electrochemical, and optic features of the polymer and its monomer were also evaluated. Furthermore, seven Ni/poly(2,3,4-PIMB)/ p-Si/Al heterostructure devices were fabricated, and they showed good rectifying behavior such that the ideality factor and the barrier height values ranged from 1.54 eV to 1.78 eV and from 0.62 eV to 0.67 eV, respectively. The capacitance-voltage measurements of one Ni/poly(2,3,4-PIMB)/ p-Si/Al heterostructure device were also analyzed.

  16. Cholestane-3β,5α,6β-triol: high levels in Niemann-Pick type C, cerebrotendinous xanthomatosis, and lysosomal acid lipase deficiency[S

    PubMed Central

    Pajares, Sonia; Arias, Angela; García-Villoria, Judit; Macías-Vidal, Judit; Ros, Emilio; de las Heras, Javier; Girós, Marisa; Coll, Maria J.; Ribes, Antonia

    2015-01-01

    Niemann-Pick type C (NPC) is a progressive neurodegenerative disease characterized by lysosomal/endosomal accumulation of unesterified cholesterol and glycolipids. Recent studies have shown that plasma cholestane-3β,5α,6β-triol (CT) and 7-ketocholesterol (7-KC) could be potential biomarkers for the diagnosis of NPC patients. We aimed to know the sensitivity and specificity of these biomarkers for the diagnosis of NPC compared with other diseases that can potentially lead to oxysterol alterations. We studied 107 controls and 122 patients including 16 with NPC, 3 with lysosomal acid lipase (LAL) deficiency, 8 with other lysosomal diseases, 5 with galactosemia, 11 with cerebrotendinous xanthomatosis (CTX), 3 with Smith-Lemli-Opitz, 14 with peroxisomal biogenesis disorders, 19 with unspecific hepatic diseases, 13 with familial hypercholesterolemia, and 30 with neurological involvement and no evidence of an inherited metabolic disease. CT and 7-KC were analyzed by HPLC-ESI-MS/MS as mono-dimethylglycine derivatives. Levels of 7-KC were high in most of the studied diseases, whereas those of CT were only high in NPC, LAL, and CTX patients. Consequently, although CT is a sensitive biomarker of NPC disease, including those cases with doubtful filipin staining, it is not specific. 7-KC is a very unspecific biomarker. PMID:26239048

  17. In vitro and in vivo antiherpetic effects of (1R,2R)-1-(5'-methylful-3'-yl)propane-1,2,3-triol.

    PubMed

    Sasaki, Kohei; Hayashi, Kyoko; Matsuya, Yuji; Sugimoto, Kenji; Lee, Jung-Bum; Kurosaki, Fumiya; Hayashi, Toshimitsu

    2016-04-01

    In this study, we demonstrated the in vitro and in vivo antiherpetic activities of a stable furan derivative, (1R,2R)-1-(5'-methylful-3'-yl)propane-1,2,3-triol (MFPT), which had originally been isolated from Streptomyces sp. strain FV60. In the present study, we synthesized MFPT from (5-methylfuran-3-yl)methanol in 6 steps for use in the experiments. MFPT showed potent in vitro antiviral activities against two acyclovir (ACV)-sensitive (KOS and HF) strains and an ACV-resistant (A4-3) strain of herpes simplex virus type 1 (HSV-1) and an ACV-sensitive HSV type 2 (HSV-2) UW 268 strain, their selectivity indices ranging from 310 to 530. By intravaginal application of MFPT to mice, the virus yields decreased dose-dependently against the three strains of HSV-1 and HSV-2. When MFPT was applied at a dose of 1.0 mg/day, the lesion scores, as clinical signs manifested by viral infection, were extensively suppressed in HSV-1-infected mice, whereas the lesion scores in HSV-2-infected mice were not markedly decreased. Interestingly, MFPT exerted an inhibitory effect against ACV-resistant HSV-1 in mice to a similar degree as in ACV-sensitive HSV-1-infected mice. Therefore, the compound might have potential for developing a topical antiviral agent that could be also applied to the infections caused by ACV-resistant viruses.

  18. Stereoselective synthesis of cis-p-menth-8-ene-1,7-diol, cis-p-menthane-1,7-diol, and cis-p-menthane-1,7,8-triol.

    PubMed

    Kobler, Christoph; Effenberger, Franz

    2005-04-22

    The natural products cis-p-menthane-1,7-diol (cis-IV), cis-p-menth-8-ene-1,7-diol (cis-I) and cis-p-menthane-1,7,8-triol (cis-II) are obtained starting from the corresponding cis-cyanohydrins, cis-2 and cis-7, respectively, by chemical transformation of the cyano into the hydroxymethyl group. The key step of the synthesis is the very high cis-selectivity (> or = 96 %) of the MeHNL-catalyzed HCN addition to 4-alkylcyclohexanones. From 4-isopropylcyclohexanone (1) the cyanohydrin cis-2 and from 4-(1-methylvinyl)cyclohexanone (6) the cyanohydrin cis-7 result almost quantitatively. Regioselective hydroxylation of cis-I affords the triol cis-II. X-ray crystal structure determinations of the final products confirm their cis-configuration.

  19. Influence of urban pollution on the production of organic particulate matter from isoprene epoxydiols in central Amazonia

    DOE PAGES

    de Sa, Suzane S.; Palm, Brett B.; Campuzano-Jost, Pedro; ...

    2016-12-13

    The atmospheric chemistry of isoprene contributes to the production of a substantial mass fraction of the particulate matter (PM) over tropical forests. Isoprene epoxydiols (IEPOX) produced in the gas phase by the oxidation of isoprene under HO2-dominant conditions are subsequently taken up by particles, thereby leading to production of secondary organic PM. The present study investigates possible perturbations to this pathway by urban pollution. The measurement site in central Amazonia was located 4 to 6 hours downwind of Manaus, Brazil. Measurements took place from February through March 2014 of the wet season, as part of the GoAmazon2014/5 experiment. Mass spectramore » of organic PM collected with an Aerodyne Aerosol Mass Spectrometer were analyzed by positive-matrix factorization. One resolved statistical factor (“IEPOX-SOA factor”) was associated with PM production by the IEPOX pathway. Loadings of this factor correlated with independently measured mass concentrations of tracers of IEPOX-derived PM, namely C5-alkene triols and 2-methyltetrols (R = 0.96 and 0.78, respectively). Factor loading, as well as the ratio of the factor loading to organic PM mass concentration, decreased under polluted compared to background conditions. For the study period, sulfate concentration explained 37 % of the variability in the factor loading. After segregation of the data set by NOy concentration, the sulfate concentration explained up to 75 % of the variability in factor loading within the NOy subsets. The sulfate-detrended IEPOX-SOA factor loading decreased by two- to three-fold for an increase in NOy concentration from 0.5 to 2 ppb. Here, the suppressing effects of elevated NO dominated over the enhancing effects of higher sulfate with respect to the production of IEPOX-derived PM. Relative to background conditions, the Manaus pollution contributed more significantly to NOy than to sulfate. In this light, increased emissions of nitrogen oxides, as anticipated for

  20. Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site

    NASA Astrophysics Data System (ADS)

    Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

    2015-08-01

    A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 > 0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black

  1. Two natural products, trans-phytol and (22E)-ergosta-6,9,22-triene-3β,5α,8α-triol, inhibit the biosynthesis of estrogen in human ovarian granulosa cells by aromatase (CYP19).

    PubMed

    Guo, Jiajia; Yuan, Yun; Lu, Danfeng; Du, Baowen; Xiong, Liang; Shi, Jiangong; Yang, Lijuan; Liu, Wanli; Yuan, Xiaohong; Zhang, Guolin; Wang, Fei

    2014-08-15

    Aromatase is the only enzyme in vertebrates to catalyze the biosynthesis of estrogens. Although inhibitors of aromatase have been developed for the treatment of estrogen-dependent breast cancer, the whole-body inhibition of aromatase causes severe adverse effects. Thus, tissue-selective aromatase inhibitors are important for the treatment of estrogen-dependent cancers. In this study, 63 natural products with diverse structures were examined for their effects on estrogen biosynthesis in human ovarian granulosa-like KGN cells. Two compounds-trans-phytol (SA-20) and (22E)-ergosta-6,9,22-triene-3β,5α,8α-triol (SA-48)-were found to potently inhibit estrogen biosynthesis (IC50: 1μM and 0.5μM, respectively). Both compounds decreased aromatase mRNA and protein expression levels in KGN cells, but had no effect on the aromatase catalytic activity in aromatase-overexpressing HEK293A cells and recombinant expressed aromatase. The two compounds decreased the expression of aromatase promoter I.3/II. Neither compound affected intracellular cyclic AMP (cAMP) levels, but they inhibited the phosphorylation or protein expression of cAMP response element-binding protein (CREB). The effects of these two compounds on extracellular regulated kinase (ERK), c-Jun N-terminal kinase (JNK), p38 mitogen-activated protein kinases (MAPKs), and AKT/phosphoinositide 3-kinase (PI3K) pathway were examined. Inhibition of p38 MAPK could be the mechanism underpinning the actions of these compounds. Our results suggests that natural products structurally similar to SA-20 and SA-48 may be a new source of tissue-selective aromatase modulators, and that p38 MAPK is important in the basal control of aromatase in ovarian granulosa cells. SA-20 and SA-48 warrant further investigation as new pharmaceutical tools for the prevention and treatment of estrogen-dependent cancers.

  2. Two natural products, trans-phytol and (22E)-ergosta-6,9,22-triene-3β,5α,8α-triol, inhibit the biosynthesis of estrogen in human ovarian granulosa cells by aromatase (CYP19)

    SciTech Connect

    Guo, Jiajia; Yuan, Yun; Lu, Danfeng; Du, Baowen; Xiong, Liang; Shi, Jiangong; Yang, Lijuan; Liu, Wanli; Yuan, Xiaohong; Zhang, Guolin; Wang, Fei

    2014-08-15

    Aromatase is the only enzyme in vertebrates to catalyze the biosynthesis of estrogens. Although inhibitors of aromatase have been developed for the treatment of estrogen-dependent breast cancer, the whole-body inhibition of aromatase causes severe adverse effects. Thus, tissue-selective aromatase inhibitors are important for the treatment of estrogen-dependent cancers. In this study, 63 natural products with diverse structures were examined for their effects on estrogen biosynthesis in human ovarian granulosa-like KGN cells. Two compounds—trans-phytol (SA-20) and (22E)-ergosta-6,9,22-triene-3β,5α,8α-triol (SA-48)—were found to potently inhibit estrogen biosynthesis (IC{sub 50}: 1 μM and 0.5 μM, respectively). Both compounds decreased aromatase mRNA and protein expression levels in KGN cells, but had no effect on the aromatase catalytic activity in aromatase-overexpressing HEK293A cells and recombinant expressed aromatase. The two compounds decreased the expression of aromatase promoter I.3/II. Neither compound affected intracellular cyclic AMP (cAMP) levels, but they inhibited the phosphorylation or protein expression of cAMP response element-binding protein (CREB). The effects of these two compounds on extracellular regulated kinase (ERK), c-Jun N-terminal kinase (JNK), p38 mitogen-activated protein kinases (MAPKs), and AKT/phosphoinositide 3-kinase (PI3K) pathway were examined. Inhibition of p38 MAPK could be the mechanism underpinning the actions of these compounds. Our results suggests that natural products structurally similar to SA-20 and SA-48 may be a new source of tissue-selective aromatase modulators, and that p38 MAPK is important in the basal control of aromatase in ovarian granulosa cells. SA-20 and SA-48 warrant further investigation as new pharmaceutical tools for the prevention and treatment of estrogen-dependent cancers. - Highlights: • Two natural products inhibited estrogen biosynthesis in human ovarian granulosa cells. • They

  3. Source apportionment of submicron organic aerosol at an urban background and a road site in Barcelona (Spain) during SAPUSS

    NASA Astrophysics Data System (ADS)

    Alier, M.; van Drooge, B. L.; Dall'Osto, M.; Querol, X.; Grimalt, J. O.; Tauler, R.

    2013-10-01

    This study investigates the contribution of potential sources to the submicron (PM1) organic aerosol (OA) simultaneously detected at an urban background (UB) and a road site (RS) in Barcelona during the 30 days of the intensive field campaign of SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies, September-October 2010). A total of 103 filters at 12 h sampling time resolution were collected at both sites. Thirty-six neutral and polar organic compounds of known emission sources and photo-chemical transformation processes were analyzed by gas chromatography-mass spectrometry (GC-MS). The concentrations of the trace chemical compounds analyzed are herein presented and discussed. Additionally, OA source apportionment was performed by multivariate curve resolution-alternating least squares (MCR-ALS) and six OA components were identified at both sites: two were of primary anthropogenic OA origin and three of secondary OA origin, while a sixth one was not clearly defined. Primary organics from emissions of local anthropogenic activities (urban primary organic aerosol, or POA Urban), mainly traffic emissions but also cigarette smoke, contributed 43% (1.5 μg OC m-3) and 18% (0.4 μg OC m-3) to OA at RS and UB, respectively. A secondary primary source - biomass burning (BBOA) - was found in all the samples (average values 7% RS; 12% UB; 0.3 μg OC m-3), but this component was substantially contributing to OA only when the sampling sites were under influence of regional air mass circulation (REG.). Three secondary organic aerosol (SOA) components (describing overall 60% of the variance) were observed in the urban ambient PM1. Products of isoprene oxidation (SOA ISO) - i.e. 2-methylglyceric acid, C5 alkene triols and 2-methyltetrols - showed the highest abundance at both sites when the city was under influence of inland air masses. The overall concentrations of SOA ISO were similar at both sites (0.4 and 0.3 μg m-3, or 16% and 7%, at UB and RS, respectively

  4. Source apportionment of submicron organic aerosol at an urban background and a road site in Barcelona, Spain

    NASA Astrophysics Data System (ADS)

    Alier, M.; van Drooge, B. L.; Dall'Osto, M.; Querol, X.; Grimalt, J. O.; Tauler, R.

    2013-04-01

    This study investigates the contribution of potential sources to the sub-micron (PM1) organic aerosol (OA) simultaneously detected at an urban background (UB) and a road site (RS) in Barcelona during the 30 days of the intensive field campaign of SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies, September-October 2010). 103 filters at 12 h sampling time resolution were collected at both sites. Thirty-six neutral and polar organic compounds of known emission sources and photo-chemical transformation processes were analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). The concentrations of the trace chemical compounds analyzed are herein presented and discussed. Additionally, OA source apportionment was performed by Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) and six OA components were identified at both sites: two were of primary anthropogenic OA origin, three of secondary OA origin while a sixth one was not clearly defined. Primary organics from emissions of local anthropogenic activities (Urban primary organic aerosol, Urban POA) contributed for 43% (1.5 μg OC m-3) and 18% (0.4 μg OC m-3) to OA in RS and UB, respectively. A secondary primary source - biomass burning (BBOA) - was found in all the samples (average values 7% RS; 12% UB; 0.3 μg OC m-3), but this component was substantially contributing to OA only when the sampling sites were under influence of regional air mass circulation. Three Secondary Organic Aerosol (SOA) components (describing overall 60% of the variance) were observed in the urban ambient PM1. Products of isoprene oxidation (SOA ISO), i.e. 2-methylglyceric acid, C5 alkene triols and 2-methyltetrols, showed the highest abundance at both sites when the city was under influence of inland air masses. The overall concentrations of SOA ISO were similar at both sites (0.4 and 0.3 μg m-3, 16% and 7%, at UB and RS, respectively). By contrast, a SOA biogenic component attributed to α-pinene oxidation (SOA

  5. Spectroscopic studies (FTIR, FT-Raman and UV), potential energy surface scan, normal coordinate analysis and NBO analysis of (2R,3R,4R,5S)-1-(2-hydroxyethyl)-2-(hydroxymethyl) piperidine-3,4,5-triol by DFT methods.

    PubMed

    Isac Paulraj, E; Muthu, S

    2013-05-01

    This work presents the characterization of (2R,3R,4R,5S)-1-(2-hydroxyethyl)-2-(hydroxymethyl)piperidine-3,4,5-triol (abbreviated as HEHMPT) by quantum chemical calculations and spectral techniques. The spectroscopic properties were investigated by FT-IR, FT-Raman and UV-Vis techniques. The FT-IR spectrum (4000-400 cm(-1)) and FT-Raman spectrum (4000-100 cm(-1)) in solid phase was recorded for HEHMPT. The UV-Vis absorption spectrum of the HEHMPT that dissolved in water was recorded in the range of 100-400 nm. The structural and spectroscopic data of the molecule were obtained from B3LYP and M06-2X with 6-31G(d,p) basis set calculations. The theoretical wavenumbers were scaled and compared with experimental FT-IR and FT-Raman spectra. The complete assignments were performed on the basis of the normal co-ordinate analysis (NCA), experimental results and potential energy distribution (PED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method, interpreted in terms of fundamental modes. The stable geometry of the compound has been determined from the potential energy surface scan. The stability of molecule has been analyzed by NBO analysis. The molecule orbital contributions were studied by using the total (TDOS), partial (PDOS), and overlap population (OPDOS) density of states. The electronic properties like UV spectral analysis and HOMO-LUMO energies were reported. The calculated HOMO and LUMO energies shows that charge transfer interactions taking place within the molecule. Mulliken population analysis on atomic charges is also calculated.

  6. Diastereocontrolled construction of pactamycin's complex ureido triol functional array.

    PubMed

    Malinowski, Justin T; McCarver, Stefan J; Johnson, Jeffrey S

    2012-06-01

    An advanced intermediate in a projected synthesis of pactamycin has been prepared. Early installation of the C1-dimethylurea functionality allows for its participation in a diastereoselective, chelation-controlled addition of organometal nucleophiles to the C5 prochiral ketone. Four of the molecule's six stereocenters are set with a ketone functional handle provided for subsequent manipulation.

  7. Enabling the identification, quantification, and characterization of organics in complex mixtures to understand atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Isaacman, Gabriel Avram

    -phase organic compounds in the atmosphere. High time resolution measurement of oxygenated compounds is achieved through a reproducible and quantitative methodology for in situ "derivatization" -- replacing highly polar functional groups that cannot be analyzed by traditional gas chromatography with less polar groups. Implementation of a two-channel sampling system for the simultaneous collection of particle-phase and total gas-plus-particle phase samples allows for the first direct measurements of gas/particle partitioning in the atmosphere, significantly advancing the study of atmospheric composition and variability, as well as the processes governing condensation and re-volatilization. This work presents the first in situ measurements of a large suite of highly oxygenated biogenic oxidation products in both the gas- and particle-phase. Isoprene, the most ubiquitous biogenic emission, oxidizes to form 2-methyltetrols and C5 alkene triols, while α-pinene, the most common monoterpene, forms pinic, pinonic, hydroxyglutaric, and other acids. These compounds are reported in Chapter 7 with unprecedented time resolution and are shown for the first time to have a large gas-phase component, contrary to typical assumptions. Hourly comparisons of these products with anthropogenic aerosol components elucidate the interaction of human and natural emissions at two rural sites: the southeastern, U.S. and Amazonia, Brazil. Anthropogenic influence on SOA formation is proposed to occur through the increase in liquid water caused by anthropogenic sulfate. Furthermore, these unparalleled observations of gas/particle partitioning of biogenic oxidation products demonstrate that partitioning of oxygenates is unexpectedly independent of volatility: many volatile, highly oxygenated compounds have a large particle-phase component that is poorly described by traditional models. These novel conclusions are reached in part by applying the new frameworks developed in previous chapters to understand the

  8. Ice core records of monoterpene- and isoprene-SOA tracers from Aurora Peak in Alaska since 1660s: Implication for climate change variability in the North Pacific Rim

    NASA Astrophysics Data System (ADS)

    Pokhrel, Ambarish; Kawamura, Kimitaka; Ono, Kaori; Seki, Osamu; Fu, Pingqing; Matoba, Sumio; Shiraiwa, Takayuki

    2016-04-01

    Monoterpene and isoprene secondary organic aerosol (SOA) tracers are reported for the first time in an Alaskan ice core to better understand the biological source strength before and after the industrial revolution in the Northern Hemisphere. We found significantly high concentrations of monoterpene- and isoprene-SOA tracers (e.g., pinic, pinonic, and 2-methylglyceric acids, 2-methylthreitol and 2-methylerythritol) in the ice core, which show historical trends with good correlation to each other since 1660s. They show positive correlations with sugar compounds (e.g., mannitol, fructose, glucose, inositol and sucrose), and anti-correlations with α-dicarbonyls (glyoxal and methylglyoxal) and fatty acids (e.g., C18:1) in the same ice core. These results suggest similar sources and transport pathways for monoterpene- and isoprene-SOA tracers. In addition, we found that concentrations of C5-alkene triols (e.g., 3-methyl-2,3,4-trihydroxy-1-butene, cis-2-methyl 1,3,4-trihydroxy-1-butene and trans-2-methyl-1,3,4-trihydroxy-1-butene) in the ice core have increased after the Great Pacific Climate Shift (late 1970s). They show positive correlations with α-dicarbonyls and fatty acids (e.g., C18:1) in the ice core, suggesting that enhanced oceanic emissions of biogenic organic compounds through the marine boundary layer are recorded in the ice core from Alaska. Photochemical oxidation process for these monoterpene- and isoprene-/sesquiterpene-SOA tracers are suggested to be linked with the periodicity of multi-decadal climate oscillations and retreat of sea ice in the Northern Hemisphere.

  9. Polar organic marker compounds in atmospheric aerosols: Determination, time series, size distributions and sources

    NASA Astrophysics Data System (ADS)

    Kourtchev, Ivan

    Terrestrial vegetation releases substantial amounts of reactive volatile organic compounds (VOCs; e.g., isoprene, monoterpenes) into the atmosphere. The VOCs can be rapidly photooxidized under conditions of high solar radiation, yielding products that can participate in new particle formation and growth processes above forests. This thesis focuses on the characterization, identification and quantification of oxidation products of biogenic VOC (BVOCs) as well as other species (tracer compounds) that provide information on aerosol sources and source processes. Atmospheric aerosols from various forested sites (i.e., Hyytiala, southern Finland; Rondonia, Brazil; K-Puszta, Hungary and Julich, Germany) were analyzed with Gas Chromotography/Mass Spectrometry (GC/MS) using analytical procedure that targets polar organic compounds. The study demonstrated that isoprene (i.e., 2-methyerythritol, 2-methylthreitol, 2-methylglyceric acid and C5-alkene triols (2-methyl-1,3,4-trihydroxy-l-butene (cis and trans) and 3 methyl-2,3,4-trihydroxy-1-butene)) and monoterpene (pinic acid, norpinic acid, 3-hydroxyglutaric acid and 3-methyl-1,2,3-butanetricarboxylic acid) oxidation products were present in substantial concentrations in atmospheric aerosols suggesting that oxidation of BVOC from the vegetation is an important process in all studied sites. On the other hand, presence of levoglucosan, biomass burning marker, especially in Amazonian rain forest site at Rondonia, Brazil, pointed that all sites were affected by anthropogenic activities, namely biomass burning. Other identified compounds included plyols, arabitol, mannitol and erythritol, which are marker compounds for fungal spores and monosacharides, glucose and fructose, markers for plant polens. Temporal variations as well as mass size distributions of the detected species confirmed the possible formation mechanisms of marker compounds.

  10. Influence of urban pollution on the production of organic particulate matter from isoprene epoxydiols in central Amazonia

    SciTech Connect

    de Sa, Suzane S.; Palm, Brett B.; Campuzano-Jost, Pedro; Day, Douglas A.; Newburn, Matthew K.; Hu, Weiwei; Isaacman-VanWertz, Gabriel; Yee, Lindsay D.; Thalman, Ryan; Brito, Joel; Carbone, Samara; Artaxo, Paulo; Goldstein, Allen H.; Manzi, Antonio O.; Souza, Rodrigo A. F.; Mei, Fan; Shilling, John E.; Springston, Stephen R.; Wang, Jian; Surratt, Jason D.; Alexander, M. Lizabeth; Jimenez, Jose L.; Martin, Scot T.

    2016-12-13

    The atmospheric chemistry of isoprene contributes to the production of a substantial mass fraction of the particulate matter (PM) over tropical forests. Isoprene epoxydiols (IEPOX) produced in the gas phase by the oxidation of isoprene under HO2-dominant conditions are subsequently taken up by particles, thereby leading to production of secondary organic PM. The present study investigates possible perturbations to this pathway by urban pollution. The measurement site in central Amazonia was located 4 to 6 hours downwind of Manaus, Brazil. Measurements took place from February through March 2014 of the wet season, as part of the GoAmazon2014/5 experiment. Mass spectra of organic PM collected with an Aerodyne Aerosol Mass Spectrometer were analyzed by positive-matrix factorization. One resolved statistical factor (“IEPOX-SOA factor”) was associated with PM production by the IEPOX pathway. Loadings of this factor correlated with independently measured mass concentrations of tracers of IEPOX-derived PM, namely C5-alkene triols and 2-methyltetrols (R = 0.96 and 0.78, respectively). Factor loading, as well as the ratio of the factor loading to organic PM mass concentration, decreased under polluted compared to background conditions. For the study period, sulfate concentration explained 37 % of the variability in the factor loading. After segregation of the data set by NOy concentration, the sulfate concentration explained up to 75 % of the variability in factor loading within the NOy subsets. The sulfate-detrended IEPOX-SOA factor loading decreased by two- to three-fold for an increase in NOy concentration from 0.5 to 2 ppb. Here, the suppressing effects of elevated NO dominated over the enhancing effects of higher sulfate with respect to the production of IEPOX-derived PM. Relative to background conditions, the Manaus pollution contributed more significantly to NOy than to sulfate. In this light

  11. Ice core records of monoterpene- and isoprene-SOA tracers from Aurora Peak in Alaska since 1660s: Implication for climate variability in the North Pacific Rim

    NASA Astrophysics Data System (ADS)

    Pokhrel, A.; Kawamura, K.; Seki, O.; Ono, K.; Matoba, S.; Shiraiwa, T.

    2015-12-01

    180 m long ice core (ca. 343 years old) was drilled in the saddle of the Aurora Peak of Alaska, which is located southeast of Fairbanks (63.52°N; 146.54°W, elevation: 2,825 m). Samples were directly transported to the Institute of Low Temperature Science, Hokkaido University and have been analyzed for monoterpene- and isoprene-SOA tracers using gas chromatograph (GC; HP 6890) and mass spectrometry system (GC/MS; Agilent). Ice core collected from mountain glacier has not been explored for SOA yet. We found significantly high concentrations of these tracers (e.g., pinic, pinonic, and 2-methylglyceric acids, 2-methylthreitol and 2-methylrythritol), which show historical trends with good correlation with each other since 1665-2008. They show positive correlations with sugar compounds (e.g., mannitol, glucose, fructose, inositol, and sucrose), and anti-correlations with diacids (e.g., C9), w-oxocarboxylic (wC4-wC9), a-dicarbonyls and low molecular weight fatty acids (LFAs) (e.g., C18:1). LFAs show strong correlations with MSA- and nss-SO42- in the same ice core. These results suggest source regions of SOA tracers and ice core chemistry of Alaska. Concentrations of C5-alkene triols (e.g., 3-methyl-2,3,4-trihydroxy-1-butene, cis-2-methyl 1,3,4-trihydroxy-1-butene and trans-2-methyl-1,3,4-trihydroxy-1-butene) have increased in the ice core after the Great Pacific Climate Shift (late 1970's). They show positive correlations with a-dicarbonyls and LFAs (e.g., C18:1) in the ice core, suggesting that enhanced oceanic emissions of biogenic organic compounds through the surface microlayer are recorded in the ice core. Photochemical oxidation processes for these monoterpene- and isoprene-/sesquiterpene-SOA tracers are suggested to be linked with the periodicity of multi-decadal climate oscillations (e.g., North Pacific Index) and we can look at a whole range of environmental parameters in parallel with the robust reconstructed temperature changes in the Northern Hemisphere.

  12. Improved oral bioavailability of 20(R)-25-methoxyl-dammarane-3β, 12β, 20-triol using nanoemulsion based on phospholipid complex: design, characterization, and in vivo pharmacokinetics in rats

    PubMed Central

    Zhang, Xiangrong; Zhang, Yi; Guo, Shuang; Bai, Feifei; Wu, Tong; Zhao, Yuqing

    2016-01-01

    The aim of the study was to improve the oral absorption of the compound 25-OCH3-PPD with poor hydrophilicity and lipophilicity. 25-OCH3-PPD-phospholipid complex was prepared by solvent evaporation, then characterized by differential scanning calorimetry, scanning electron microscopy, and infrared absorption spectroscopy. The aqueous solubility and oil–water partition coefficient were compared with the free compound. A nanoemulsion loaded with 25-OCH3-PPD-phospholipid complex was developed by dissolving the complex in water in the presence of hydrophilic surfactant under sonication. After oral administration of the nanoemulsion and the suspension of 25-OCH3-PPD in rats, the concentrations of 25-OCH3-PPD in plasma were determined by high-performance liquid chromatography–tandem mass spectrometry method. The results showed that the solubility of the complex in water and n-octanol was enhanced. The oil–water partition coefficient improved 1.7 times. Peak plasma concentration and area under the curve(0–24 h) of the nanoemulsion of 25-OCH3-PPD-phospholipid complex were higher than that of free compound by 3.9- and 3.5-folds. PMID:27877020

  13. Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    NASA Astrophysics Data System (ADS)

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; Day, D. A.; Ortega, A. M.; Hayes, P. L.; Krechmer, J. E.; Chen, Q.; Kuwata, M.; Liu, Y. J.; de Sá, S. S.; McKinney, K.; Martin, S. T.; Hu, M.; Budisulistiorini, S. H.; Riva, M.; Surratt, J. D.; St. Clair, J. M.; Isaacman-Van Wertz, G.; Yee, L. D.; Goldstein, A. H.; Carbone, S.; Brito, J.; Artaxo, P.; de Gouw, J. A.; Koss, A.; Wisthaler, A.; Mikoviny, T.; Karl, T.; Kaser, L.; Jud, W.; Hansel, A.; Docherty, K. S.; Alexander, M. L.; Robinson, N. H.; Coe, H.; Allan, J. D.; Canagaratna, M. R.; Paulot, F.; Jimenez, J. L.

    2015-10-01

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accounted by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12-40 ‰) but varies substantially between locations, which is shown to reflect

  14. Characterization of a real-time tracer for isoprene epoxydiols-derived secondary organic aerosol (IEPOX-SOA) from aerosol mass spectrometer measurements

    DOE PAGES

    Hu, W. W.; Campuzano-Jost, P.; Palm, B. B.; ...

    2015-10-23

    Substantial amounts of secondary organic aerosol (SOA) can be formed from isoprene epoxydiols (IEPOX), which are oxidation products of isoprene mainly under low-NO conditions. Total IEPOX-SOA, which may include SOA formed from other parallel isoprene oxidation pathways, was quantified by applying positive matrix factorization (PMF) to aerosol mass spectrometer (AMS) measurements. The IEPOX-SOA fractions of organic aerosol (OA) in multiple field studies across several continents are summarized here and show consistent patterns with the concentration of gas-phase IEPOX simulated by the GEOS-Chem chemical transport model. During the Southern Oxidant and Aerosol Study (SOAS), 78 % of PMF-resolved IEPOX-SOA is accountedmore » by the measured IEPOX-SOA molecular tracers (2-methyltetrols, C5-Triols, and IEPOX-derived organosulfate and its dimers), making it the highest level of molecular identification of an ambient SOA component to our knowledge. An enhanced signal at C5H6O+ (m/z 82) is found in PMF-resolved IEPOX-SOA spectra. To investigate the suitability of this ion as a tracer for IEPOX-SOA, we examine fC5H6O (fC5H6O= C5H6O+/OA) across multiple field, chamber, and source data sets. A background of ~ 1.7 ± 0.1 ‰ (‰ = parts per thousand) is observed in studies strongly influenced by urban, biomass-burning, and other anthropogenic primary organic aerosol (POA). Higher background values of 3.1 ± 0.6 ‰ are found in studies strongly influenced by monoterpene emissions. The average laboratory monoterpene SOA value (5.5 ± 2.0 ‰) is 4 times lower than the average for IEPOX-SOA (22 ± 7 ‰), which leaves some room to separate both contributions to OA. Locations strongly influenced by isoprene emissions under low-NO levels had higher fC5H6O (~ 6.5 ± 2.2 ‰ on average) than other sites, consistent with the expected IEPOX-SOA formation in those studies. fC5H6O in IEPOX-SOA is always elevated (12–40 ‰) but varies substantially between locations, which is shown

  15. Cellulose acetate butyrate/poly(caprolactonetriol) blends: Miscibility, mechanical properties, and in vivo inflammatory response.

    PubMed

    Kanis, Luiz A; Marques, Ellen L; Zepon, Karine M; Pereira, Jefferson R; Pamato, Saulo; de Oliveira, Marcelo T; Danielski, Lucinéia G; Petronilho, Fabricia C

    2014-11-01

    This study reports the results of the characterization of cellulose acetate butyrate and polycaprolactone-triol blends in terms of miscibility, swelling capacity, mechanical properties, and inflammatory response in vivo. The cellulose acetate butyrate film was opaque and rigid, with glass transition (T g ) at 134℃ and melting temperature of 156℃. The cellulose acetate butyrate/polycaprolactone-triol films were transparent up to a polycaprolactone-triol content of 60%. T g of the cellulose acetate butyrate films decreased monotonically as polycaprolactone-triol was added to the blend, thus indicating miscibility. FTIR spectroscopy revealed a decrease in intramolecular hydrogen bonding in polycaprolactone-triol, whereas no hydrogen bonding was observed between cellulose acetate butyrate and -OH from polycaprolactone-triol. The increase in polycaprolactone-triol content in the blend decreased the water uptake. An increase in polycaprolactone-triol content decreased the modulus of elasticity and increased the elongation at break. A cellulose acetate butyrate/polycaprolactone-triol 70/30 blend implanted in rats showed only an acute inflammatory response 7 days after surgery. No change in inflammation mediators was observed.

  16. Highly Tunable Selectivity for Syngas-Derived Alkenes over Zinc and Sodium-Modulated Fe5 C2 Catalyst.

    PubMed

    Zhai, Peng; Xu, Cong; Gao, Rui; Liu, Xi; Li, Mengzhu; Li, Weizhen; Fu, Xinpu; Jia, Chunjiang; Xie, Jinglin; Zhao, Ming; Wang, Xiaoping; Li, Yong-Wang; Zhang, Qianwen; Wen, Xiao-Dong; Ma, Ding

    2016-08-16

    Zn- and Na-modulated Fe catalysts were fabricated by a simple coprecipitation/washing method. Zn greatly changed the size of iron species, serving as the structural promoter, while the existence of Na on the surface of the Fe catalyst alters the electronic structure, making the catalyst very active for CO activation. Most importantly, the electronic structure of the catalyst surface suppresses the hydrogenation of double bonds and promotes desorption of products, which renders the catalyst unexpectedly reactive toward alkenes-especially C5+ alkenes (with more than 50% selectivity in hydrocarbons)-while lowering the selectivity for undesired products. This study enriches C1 chemistry and the design of highly selective new catalysts for high-value chemicals.

  17. Nonmethane hydrocarbon and oxy hydrocarbon measurements during the 2002 New England Air Quality Study

    NASA Astrophysics Data System (ADS)

    Goldan, Paul D.; Kuster, William C.; Williams, Eric; Murphy, Paul C.; Fehsenfeld, Fred C.; Meagher, James

    2004-11-01

    Nonmethane hydrocarbons (NMHCs) and oxy hydrocarbons (oxy HCs) were measured aboard the National Oceanic and Atmospheric Administration research vessel Ronald H. Brown during the New England Air Quality Study from 13 July to 10 August 2002 by an online dual gas chromatographic instrument with two separate analytical columns equipped, respectively, with flame ionization and mass spectrometer detectors. Measurements, taken each half hour, included C2 to C10 alkanes, C2 to C5 alkenes, alcohols and ketones, C6 to C9 aromatics, and biogenic volatile compounds including six monoterpenes, isoprene and its immediate oxidation products methacrolein and methylvinylketone. All compounds have been categorized by their contribution to the OH loss rate calculated for 298K and 1 atm. Large temporal variability was observed for all compounds. Airflow from the Providence, Rhode Island/Boston, Massachusetts, urban corridor northeast to the New Hampshire coast was usually heavily laden with NMHCs and oxy HCs of anthropogenic origin. Comparison of specific compound ratios with automotive tunnel studies suggested that these were predominantly mobile source emissions. When such flow occurred during daylight hours, these urban plumes were accompanied by increases in ozone in the 80 to 120 ppbv range. About equally as often, much less chemically mature NMHC plumes were encountered near the New Hampshire coast. Ozone was titrated out of these latter plumes, and the unusually high mixing ratios of C4 and C5 alkenes suggested that their source was partly gasoline vapor release rather than mobile source emissions. In the New England coastal region explored, in spite of the large anthropogenic NMHC input during periods of offshore flow, OH loss with hydrocarbons was frequently dominated by compounds of biogenic origin. During periods of cleaner marine air inflow the OH loss rate was dominated by reaction with methane and with oxy HCs, predominantly acetone, formaldehyde, and acetaldehyde.

  18. Liver fluke-induced hepatic oxysterols stimulate DNA damage and apoptosis in cultured human cholangiocytes.

    PubMed

    Jusakul, Apinya; Loilome, Watcharin; Namwat, Nisana; Haigh, W Geoffrey; Kuver, Rahul; Dechakhamphu, Somkid; Sukontawarin, Pradit; Pinlaor, Somchai; Lee, Sum P; Yongvanit, Puangrat

    2012-03-01

    Oxysterols are cholesterol oxidation products that are generated by enzymatic reactions through cytochrome P450 family enzymes or by non-enzymatic reactions involving reactive oxygen and nitrogen species. Oxysterols have been identified in bile in the setting of chronic inflammation, suggesting that biliary epithelial cells are chronically exposed to these compounds in certain clinical settings. We hypothesized that biliary oxysterols resulting from liver fluke infection participate in cholangiocarcinogenesis. Using gas chromatography/mass spectrometry, we identified oxysterols in livers from hamsters infected with Opisthorchis viverrini that develop cholangiocarcinoma. Five oxysterols were found: 7-keto-cholesta-3,5-diene (7KD), 3-keto-cholest-4-ene (3K4), 3-keto-cholest-7-ene (3K7), 3-keto-cholesta-4,6-diene (3KD), and cholestan-3β,5α,6β-triol (Triol). Triol and 3K4 were found at significantly higher levels in the livers of hamsters with O. viverrini-induced cholangiocarcinoma. We therefore investigated the effects of Triol and 3K4 on induction of cholangiocarcinogenesis using an in vitro human cholangiocyte culture model. Triol- and 3K4-treated cells underwent apoptosis. Western blot analysis showed significantly increased levels of Bax and decreased levels of Bcl-2 in these cells. Increased cytochrome c release from mitochondria was found following treatment with Triol and 3K4. Triol and 3K4 also induced formation of the DNA adducts 1,N(6)-etheno-2'-deoxyadenosine, 3,N(4)-etheno-2'-deoxycytidine and 8-oxo-7,8-dihydro-2'-deoxyguanosine in cholangiocytes. The data suggest that Triol and 3K4 cause DNA damage via oxidative stress. Chronic liver fluke infection increases production of the oxysterols Triol and 3K4 in the setting of chronic inflammation in the biliary system. These oxysterols induce apoptosis and DNA damage in cholangiocytes. Insufficient and impaired DNA repair of such mutated cells may enhance clonal expansion and further drive the change in

  19. [Chemical constituents from Lyophyllum decastes].

    PubMed

    Zheng, Hong-Liang; Bau, Tolgor; Bao, Hai-Ying; Lian, Jun-Wen

    2013-12-01

    The chemical constituents from the fruiting bodies of Lyophyllum decastes (Fr.) Singer were studied in this paper. Thirteen compounds were isolated and purified by column chromatographies on silica gel and Sephadex LH-20. Their structures were identified by MS and NMR data analysis as adenosine (1), 2R, 3S, 4S, 8E)-2-[(2'R)-2-hydroxyheneicosanoylamino]-8-octadecene-1, 3, 4-triol (2), (2R, 3S, 4S, 8E)-2-[(2'R)-2-hydroxypentacosanoylamino]-8-octadecene-1, 3, 4-triol (3), nicotinic acid (4), (4E, 8E) -2-N-2-hydroxytetracosanoyl-1-O-beta-D-glycopyranosyl-9-methyl-4, 8-sphingadienine (5), D-mannitol (6), ergosteryl-3-O-beta-D-glucopyranoside (7), tuberoside (8), (2R, 3S, 4S, 8E)-2-[(2'R)-2-hydroxybehenoylamino]-8-octadecene-1, 3, 4-triol (9),(2R, 3S, 4S, 8E)-2-[(2'R) -2-hydroxytricosanoylamino] -8-octadecene-1, 3, 4-triol (10), (22E, 24R)-ergosta-7, 22-dien-3beta, 5alpha, 6beta-triol (11), (22E, 24R)-ergosta-5, 7, 22-trien-3beta-ol (12), and 5alpha, 8alpha-epidiory-(22E, 24R)-ergosta-6, 22-dien-3beta-ol (13), respectively. All the above compounds are first obtained from the mushroom and compounds 2-10 are reported to be obtained from the Lyophyllum for the first time.

  20. A sensitive and specific LC-MS/MS method for rapid diagnosis of Niemann-Pick C1 disease from human plasma[S

    PubMed Central

    Jiang, Xuntian; Sidhu, Rohini; Porter, Forbes D.; Yanjanin, Nicole M.; Speak, Anneliese O.; te Vruchte, Danielle Taylor; Platt, Frances M.; Fujiwara, Hideji; Scherrer, David E.; Zhang, Jessie; Dietzen, Dennis J.; Schaffer, Jean E.; Ory, Daniel S.

    2011-01-01

    Niemann-Pick type C1 (NPC1) disease is a rare, progressively fatal neurodegenerative disease for which there are no FDA-approved therapies. A major barrier to developing new therapies for this disorder has been the lack of a sensitive and noninvasive diagnostic test. Recently, we demonstrated that two cholesterol oxidation products, specifically cholestane-3β,5α,6β-triol (3β,5α,6β-triol) and 7-ketocholesterol (7-KC), were markedly increased in the plasma of human NPC1 subjects, suggesting a role for these oxysterols in diagnosis of NPC1 disease and evaluation of therapeutics in clinical trials. In the present study, we describe the development of a sensitive and specific LC-MS/MS method for quantifying 3β,5α,6β-triol and 7-KC human plasma after derivatization with N,N-dimethylglycine. We show that dimethylglycine derivatization successfully enhanced the ionization and fragmentation of 3β,5α,6β-triol and 7-KC for mass spectrometric detection of the oxysterol species in human plasma. The oxysterol dimethylglycinates were resolved with high sensitivity and selectivity, and enabled accurate quantification of 3β,5α,6β-triol and 7-KC concentrations in human plasma. The LC-MS/MS assay was able to discriminate with high sensitivity and specificity between control and NPC1 subjects, and offers for the first time a noninvasive, rapid, and highly sensitive method for diagnosis of NPC1 disease. PMID:21518695

  1. Phenolic compounds from Selaginella moellendorfii.

    PubMed

    Wu, Bin; Wang, Jia

    2011-09-01

    Chemical investigation of the leaves and roots of Selaginella moellendorfii Hieron has resulted in the isolation and characterization of two new flavone glucosides, 7-O-(β-glucopyranosyl(1→2)-[β-glucopyranosyl(1→6)]-β-glucopyranosyl)flavone-3',4',5,7-tetraol (1) and 7-O-(β-glucopyranosyl(1→2)-[β-glucopyranosyl(1→6)]-β-glucopyranosyl)flavone-4',5,7-triol (2), two new biflavonoids, 2,3-dihydroflavone-5,7,4'-triol-(3'→8″)-flavone-5″,6″,7″,4'''-tetraol (3) and 6-methylflavone-5,7,4'-triol-(3'→O→4''')-6″-methylflavone-5″,7″-diol (4), two new lignans, (7'E)-3,5,3',5'-tetramethoxy-8 : 4'-oxyneolign-7'-ene-4,9,9'-triol (5) and 3,3'-dimethoxylign-8'-ene-4,4',9-triol (6), together with two known monolignans, four known lignans, and four known biflavonoids. Their structures were established by spectroscopic means and by comparison with literature values.

  2. Polar organic marker compounds in atmospheric aerosols during the LBA-SMOCC 2002 biomass burning experiment in Rondônia, Brazil: sources and source processes, time series, diel variations and size distributions

    NASA Astrophysics Data System (ADS)

    Claeys, M.; Kourtchev, I.; Pashynska, V.; Vas, G.; Vermeylen, R.; Wang, W.; Cafmeyer, J.; Chi, X.; Artaxo, P.; Andreae, M. O.; Maenhaut, W.

    2010-10-01

    Measurements of polar organic marker compounds were performed on aerosols that were collected at a pasture site in the Amazon basin (Rondônia, Brazil) using a high-volume dichotomous sampler (HVDS) and a Micro-Orifice Uniform Deposit Impactor (MOUDI) within the framework of the 2002 LBA-SMOCC (Large-Scale Biosphere Atmosphere Experiment in Amazônia - Smoke Aerosols, Clouds, Rainfall, and Climate: Aerosols From Biomass Burning Perturb Global and Regional Climate) campaign. The campaign spanned the late dry season (biomass burning), a transition period, and the onset of the wet season (clean conditions). In the present study a more detailed discussion is presented compared to previous reports on the behavior of selected polar marker compounds, including levoglucosan, malic acid, isoprene secondary organic aerosol (SOA) tracers and tracers for fungal spores. The tracer data are discussed taking into account new insights that recently became available into their stability and/or aerosol formation processes. During all three periods, levoglucosan was the most dominant identified organic species in the PM2.5 size fraction of the HVDS samples. In the dry period levoglucosan reached concentrations of up to 7.5 μg m-3 and exhibited diel variations with a nighttime prevalence. It was closely associated with the PM mass in the size-segregated samples and was mainly present in the fine mode, except during the wet period where it peaked in the coarse mode. Isoprene SOA tracers showed an average concentration of 250 ng m-3 during the dry period versus 157 ng m-3 during the transition period and 52 ng m-3 during the wet period. Malic acid and the 2-methyltetrols exhibited a different size distribution pattern, which is consistent with different aerosol formation processes (i.e., gas-to-particle partitioning in the case of malic acid and heterogeneous formation from gas-phase precursors in the case of the 2-methyltetrols). The 2-methyltetrols were mainly associated with the

  3. Synthesis and configuration of the nonadecenetriol isolated from seeds of Persea americana.

    PubMed

    Yan, Xin; Zhang, Shao-Min; Wu, Yikang; Gao, Po

    2011-10-07

    In an effort to establish the relative as well as absolute configuration of the trypanocidally active natural nonadec-6-en-1,2,4-triol isolated from Persea americana, the (2S,4R), (2S,4S), and (2R,4R) isomers were synthesized. The stereogenic centers taken from enantiopure chiral epoxy building blocks derived from inexpensive and readily available D-glucolactone. The (2R,4R) isomer gave (1)H and (13)C NMR as well as specific rotation in excellent consistence with those reported for the natural triol.

  4. Synthesis, emulsification and self-assembly properties of sugar-containing semifluorinated amphiphiles

    PubMed Central

    Razgulin, Andrew V.; Mecozzi, Sandro

    2015-01-01

    Surfactants with two and three monosaccharide-based heads and a perfluoroalkyl tail have been synthesized. Perfluoroalkyl C3-symmetric triol and C2-symmetric diol were conveniently prepared via Cu-catalyzed azide-alkyne cycloaddition between a fluorous alkyne and tertiary and secondary azides, respectively. Glycosylation of the perfluoroalkyl diol and triol led to orthoester-type structures, which were evaluated for their capacity to stabilize aqueous emulsions of highly fluorinated anesthetics. The self-assembly properties of the tri-sugar amphiphile were examined by transmission electron microscopy. PMID:25658061

  5. Regio-selective Lipase catalyzed Hydrolysis of Oxanorbornane-based Sugar-like Amphiphiles at Air - Water Interface: a Polarized FT-IRRAS Study.

    PubMed

    Sarangi, Nirod Kumar; Ganesan, M; Muraleedharan, K M; Patnaik, Archita

    2017-02-21

    Interfacial hydrolysis of oxanorbornane-based amphiphile (Triol C16) by Candida rugosa lipase was investigated using real-time polarized Fourier transform-infrared reflection absorption spectroscopy (FT-IRRAS). The kinetics of hydrolysis was studied by analyzing the ester carbonyl ν(C=O) stretching vibration band across the two dimensional (2D) array of molecules at the confined interface. In particular, we demonstrate Triol C16 to form Michaelis-Menten type complex, like that of lipid-substrate analogues, where the Triol C16 head group remained accessible to the catalytic triad of the lipase. The enzyme-induced selective cleavage of the ester bond was spectroscopically monitored by the disappearance of the intense ν (C=O) resonance at 1736cm(-1). Consequently, the in-situ spectroscopic measurements evidenced selective ester hydrolysis of Triol C16 yielding Tetrol C(2)OH and Palmitic acid, which remained predominantly in the undissociated form at the interface. The conformation sensitive amide I (majorly ν (C=O)) and the interfacial water reorganization suggested 2D ordering of the enzyme molecules following which interfacial reactions were employed towards probing the enzyme kinetics at the air/water interface. The investigation demonstrated further the potential of IRRAS spectroscopy for real-time monitoring the hydrolytic product formation and selectivity at biomimetic interfaces.

  6. Biomimetic Catalysts for Hydrolysis (AASERT Award).

    DTIC Science & Technology

    1995-12-31

    diamines containing indicators or metal ions (p- nitrophenol , ferrocene, metal-salen complex). Substrates under study include simple diols and triols...disfunctional mechanism to both coordinate and activate a carbonyl or phosphoryl oxygen in a lewis acid sense, as well as binding and activating a water molecule.

  7. Leveraging the micellar effect: gold-catalyzed dehydrative cyclizations in water at room temperature.

    PubMed

    Minkler, Stefan R K; Isley, Nicholas A; Lippincott, Daniel J; Krause, Norbert; Lipshutz, Bruce H

    2014-02-07

    The first examples of gold-catalyzed cyclizations of diols and triols to the corresponding hetero- or spirocycles in an aqueous medium are presented. These reactions take place within nanomicelles, where the hydrophobic effect is operating, thereby driving the dehydrations, notwithstanding the surrounding water. By the addition of simple salts such as sodium chloride, reaction times and catalyst loadings can be significantly decreased.

  8. Formal Alder-ene reaction of a bicyclo[1.1.0]butane in the synthesis of the tricyclic quaternary ammonium core of daphniglaucins

    PubMed Central

    Ueda, Masafumi; Walczak, Maciej A. A.; Wipf, Peter

    2008-01-01

    A tricyclic substructure of the tetracyclic nitrogen core of the daphniglaucins was formed by an oxidative activation of the allyl side chain of a bicyclo[1.1.0]butylmethylamine, a spontaneous intramolecular formal Alder-ene reaction, and a selective cyclization of a triol intermediate. PMID:19129907

  9. Lipoxygenase inhibitory sphingolipids from Launaea nudicaulis.

    PubMed

    Riaz, Naheed; Parveen, Shehla; Saleem, Muhammad; Ali, Muhammad Shaiq; Malik, Abdul; Ashraf, Muhammad; Afzal, Iftikhar; Jabbar, Abdul

    2012-01-01

    Four new sphingolipids: nudicaulin A [(2S,3S,4R,14E)-2-{[octadecanoyl]amino}tetraeicos-14-ene-1,3,4-triol; 1], nudicaulin B [(2S,3S,4R,14E)-2-{[(2R)-2-hydroxyoctadecanoyl]amino}tetraeicos-14-ene-1,3,4-triol; 2], nudicaulin C [(2S,3S,4R,14E)-2-{[(2R)-2-hydroxyoctadecanoyl]amino}tetraeicos-14-ene-1,3,4-triol-1-O-β-D-glucopyranoside; 3], and nudicaulin D [(2S,3S,4R)-2-{[(2R,3S,12E)-2,3-dihydroxyeicos-12-enoyl]amino}octadecane-1,3,4-triol; 4] together with 1-hexatriacontanol, β-sitosterol, octadecyl 4-hydroxycinnamate, elaidic acid, cholesta-5,22-diene-3,7-diol, oleanolic acid, apigenin, and β-sitosterol 3-O-β-D-glucopyranoside were isolated from the methanolic extract of the whole plant of Launaea nudicaulis. Their structures were elucidated using ¹H and ¹³C NMR spectra and 2D NMR analyses (HMQC, HMBC, and COSY) in combination with mass spectrometry (EI-MS, HR-EI-MS, FAB-MS, and HR-FAB-MS) experiments and comparison with literature data of related compounds. Compounds 1-4 displayed moderate inhibitory potential against enzyme lipoxygenase in concentration-dependent manner with IC₅₀ value ranges 103-193 μM.

  10. Nitrogen Containing Organic Compounds and Oligomers in Secondary Organic Aerosol Formed by Photooxidation of Isoprene

    SciTech Connect

    Nguyen, Tran B.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Serguei

    2011-07-06

    Electrospray ionization high-resolution mass spectrometry (ESI HR-MS) was used to probe molecular structures of oligomers in secondary organic aerosol (SOA) generated in laboratory experiments on isoprene photooxidation at low- and high-NOx conditions. Up to 80-90% of the observed products are oligomers and up to 33% are nitrogen-containing organic compounds (NOC). We observe oligomers with up to 8 monomer units in length. Tandem mass spectrometry (MSn) confirms NOC compounds are organic nitrates and elucidates plausible chemical building blocks contributing to oligomer formation. Most organic nitrates are comprised of methylglyceric acid units. Other important multifunctional C2-C5 monomer units are identified including methylglyoxal, hydroxyacetone, hydroxyacetic acid, glycolaldehyde, and 2-methyltetrols. The majority of the NOC oligomers contain only one nitrate moiety resulting in a low average N:C ratio of 0.019. Average O:C ratios of the detected SOA compounds are 0.54 under the low-NOx conditions and 0.83 under the high-NOx conditions. Our results underscore the importance of isoprene photooxidation as a source of NOC in organic particulate matter.

  11. Molecular Composition and Volatility of Organic Aerosol in the Southeastern U.S.: Implications for IEPOX Derived SOA.

    PubMed

    Lopez-Hilfiker, F D; Mohr, C; D'Ambro, E L; Lutz, A; Riedel, T P; Gaston, C J; Iyer, S; Zhang, Z; Gold, A; Surratt, J D; Lee, B H; Kurten, T; Hu, W W; Jimenez, J; Hallquist, M; Thornton, J A

    2016-03-01

    We present measurements as part of the Southern Oxidant and Aerosol Study (SOAS) during which atmospheric aerosol particles were comprehensively characterized. We present results utilizing a Filter Inlet for Gases and AEROsol coupled to a chemical ionization mass spectrometer (CIMS). We focus on the volatility and composition of isoprene derived organic aerosol tracers and of the bulk organic aerosol. By utilizing the online volatility and molecular composition information provided by the FIGAERO-CIMS, we show that the vast majority of commonly reported molecular tracers of isoprene epoxydiol (IEPOX) derived secondary organic aerosol (SOA) is derived from thermal decomposition of accretion products or other low volatility organics having effective saturation vapor concentrations <10(-3) μg m(-3). In addition, while accounting for up to 30% of total submicrometer organic aerosol mass, the IEPOX-derived SOA has a higher volatility than the remaining bulk. That IEPOX-SOA, and more generally bulk organic aerosol in the Southeastern U.S. is comprised of effectively nonvolatile material has important implications for modeling SOA derived from isoprene, and for mechanistic interpretations of molecular tracer measurements. Our results show that partitioning theory performs well for 2-methyltetrols, once accretion product decomposition is taken into account. No significant partitioning delays due to aerosol phase or viscosity are observed, and no partitioning to particle-phase water or other unexplained mechanisms are needed to explain our results.

  12. Linking biogenic hydrocarbons to biogenic aerosol in the Borneo rainforest

    NASA Astrophysics Data System (ADS)

    Hamilton, J. F.; Alfarra, M. R.; Robinson, N.; Ward, M. W.; Lewis, A. C.; McFiggans, G. B.; Coe, H.; Allan, J. D.

    2013-07-01

    Emissions of biogenic volatile organic compounds are though to contribute significantly to secondary organic aerosol formation in the tropics, but understanding the process of these transformations has proved difficult, due to the complexity of the chemistry involved and very low concentrations. Aerosols from above a South East Asian tropical rainforest in Borneo were characterised using liquid chromatography-ion trap mass spectrometry, high resolution aerosol mass spectrometry and fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) techniques. Oxygenated compounds were identified in ambient organic aerosol that could be directly traced back to isoprene, monoterpenes and sesquiterpene emissions, by combining field data on chemical structures with mass spectral data generated from synthetically produced products created in a simulation chamber. Eighteen oxygenated species of biogenic origin were identified in the rainforest aerosol from the precursors isoprene, α-pinene, limonene, α-terpinene and β-caryophyllene. The observations provide the unambiguous field detection of monoterpene and sesquiterpene oxidation products in SOA above a pristine tropical rainforest. The presence of 2-methyltetrol organosulfates and an associated sulfated dimer provides direct evidence that isoprene in the presence of sulfate aerosol can make a contribution to biogenic organic aerosol above tropical forests. High-resolution mass spectrometry indicates that sulfur can also be incorporated into oxidation products arising from monoterpene precursors in tropical aerosol.

  13. Effect of Organic Coatings, Humidity and Aerosol Acidity on Multiphase Chemistry of Isoprene Epoxydiols

    SciTech Connect

    Riva, Matthieu; Bell, David M.; Hansen, Anne-Maria Kaldal; Drozd, Greg T.; Zhang, Zhenfa; Gold, Avram; Imre, Dan; Surratt, Jason D.; Glasius, Marianne; Zelenyuk, Alla

    2016-06-07

    Multiphase chemistry of isomeric isoprene epoxydiols (IEPOX) has been shown to be the dominant source of isoprene-derived secondary organic aerosol (SOA). Recent studies have reported particles composed of ammonium bisulfate (ABS) mixed with model organics exhibit slower rates of IEPOX uptake. In the present study, we investigate the effect of atmospherically-relevant organic coatings of α-pinene (AP) SOA on the reactive uptake of trans-β-IEPOX onto ABS particles under different conditions and coating thicknesses. Single particle mass spectrometry was used to characterize in real-time particle size, shape, density, and quantitative composition before and after reaction with IEPOX. We find that IEPOX uptake by pure sulfate particles is a volume-controlled process, which results in particles with uniform concentration of IEPOX-derived SOA across a wide range of sizes. Aerosol acidity was shown to enhance IEPOX-derived SOA formation, consistent with recent studies. The presence of water has a weaker impact on IEPOX-derived SOA yield, but significantly enhanced formation of 2-methyltetrols, consistent with offline filter analysis. In contrast, IEPOX uptake by ABS particles coated by AP-derived SOA is strongly dependent on particle size and composition. IEPOX uptake occurred only when weight fraction of AP-derived SOA dropped below 50 %, effectively limiting IEPOX uptake to larger particles.

  14. The Precise Structures and Stereochemistry of Trihydroxy-linoleates Esterified in Human and Porcine Epidermis and Their Significance in Skin Barrier Function

    PubMed Central

    Chiba, Takahito; Thomas, Christopher P.; Calcutt, M. Wade; Boeglin, William E.; O'Donnell, Valerie B.; Brash, Alan R.

    2016-01-01

    Creation of an intact skin water barrier, a prerequisite for life on dry land, requires the lipoxygenase-catalyzed oxidation of the essential fatty acid linoleate, which is esterified to the ω-hydroxyl of an epidermis-specific ceramide. Oxidation of the linoleate moiety by lipoxygenases is proposed to facilitate enzymatic cleavage of the ester bond, releasing free ω-hydroxyceramide for covalent binding to protein, thus forming the corneocyte lipid envelope, a key component of the epidermal barrier. Herein, we report the transformations of esterified linoleate proceed beyond the initial steps of oxidation and epoxyalcohol synthesis catalyzed by the consecutive actions of 12R-LOX and epidermal LOX3. The major end product in human and porcine epidermis is a trihydroxy derivative, formed with a specificity that implicates participation of an epoxide hydrolase in converting epoxyalcohol to triol. Of the 16 possible triols arising from hydrolysis of 9,10-epoxy-13-hydroxy-octadecenoates, using LC-MS and chiral analyses, we identify and quantify specifically 9R,10S,13R-trihydroxy-11E-octadecenoate as the single major triol esterified in porcine epidermis and the same isomer with lesser amounts of its 10R diastereomer in human epidermis. The 9R,10S,13R-triol is formed by SN2 hydrolysis of the 9R,10R-epoxy-13R-hydroxy-octadecenoate product of the LOX enzymes, a reaction specificity characteristic of epoxide hydrolase. The high polarity of triol over the primary linoleate products enhances the concept that the oxidations disrupt corneocyte membrane lipids, promoting release of free ω-hydroxyceramide for covalent binding to protein and sealing of the waterproof barrier. PMID:27151221

  15. Durability Characterization of POSS-Based Polyimides and Carbon-Fiber Composites for Air Force-Related Applications

    DTIC Science & Technology

    2007-12-31

    to 200C with a ramp-rate of 5 ’C/min and hold at 2000C for 2 hours, heated to 240C with same ramp rate and hold at 240C for I hour. A brown-colored...0.81 % I 5 % PhenN.l Triols 0.37 ,o 0.60( % +15% Ethyl Triols 0.68 % 0.90 % Table 2 . Residual mechanical performance of composites after aged at 550’F...control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 1. REPORT DATE (DD-MM-YYYY) 2 . REPORT TYPE 3. DATES COVERED (From - To) 03-3 1

  16. Studies toward the synthesis of the shark repellent pavoninin-5.

    PubMed

    Williams, John R; Chai, Deping; Gong, Hua; Zhao, Wei; Wright, Dominic

    2002-12-01

    Sharks are the most dangerous predators of people in the sea, resulting in people being mauled and killed each year. A shark repellent could help to diminish this danger. The aglycone of the shark repellent pavoninin-5, (25R)-cholest-5-en-3beta,15alpha,26-triol (5a), was synthesized from diosgenin (9). Removing mercury from the Clemmensen reduction of 9 gave a higher yield of (25R)-cholest-5-en-3beta,16beta,26-triol, 10a, and was also more environmentally friendly. Attempted methods for the transposition of the C-16beta hydroxyl to the 15alpha position are described. A successful method for this transposition via the 15alpha-hydroxy-16-ketone, 8a, using the Barton deoxygenation reaction on the 16-alcohol 14b, is reported.

  17. Triterpenoidal glycosides from Justicia betonica.

    PubMed

    Kanchanapoom, Tripetch; Noiarsa, Pawadee; Ruchirawat, Somsak; Kasai, Ryoji; Otsuka, Hideaki

    2004-09-01

    dFrom the aerial portion of Justicia betonica L., four triterpenoidal glycosides (justiciosides A-D) were isolated. Their structures were established through chemical and NMR spectroscopic analyses as olean-12-ene-1beta,3beta,11alpha,28-tetraol 28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside, olean-12-ene-1beta,3beta,11alpha,28-tetraol 28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside, 11alpha-methoxy-olean-12-ene-1beta,3beta,28-triol 28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside, 11alpha-methoxy-olean-12-ene-1beta,3beta,28-triol 28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside, respectively.

  18. Amorphous phase-segregated copoly(ether)esterurethane thermoset networks with oligo(propylene glycol) and oligo[(rac-lactide)-co-glycolide] segments: synthesis and characterization.

    PubMed

    Zotzmann, Jörg; Alteheld, Armin; Behl, Marc; Lendlein, Andreas

    2009-09-01

    Completely amorphous copoly(ether)ester networks based on oligo(propylene glycol) and oligo[(rac-dilactide)-co-glycolide] segments were synthesized by crosslinking star-shaped hydroxyl-telechelic cooligomers using an aliphatic low-molecular weight diisocyanate. Two different network architectures were applied exhibiting differences in the phase-separation behavior. For networks from oligo(propylene glycol)-block-oligo[(rac-lactide)-co-glycolide] triols (G(3)OPG-bl-OLG) only one glass transition was obtained. However, networks from a mixture of oligo(propylene glycol) triols (G(3)OPG) and oligo[(rac-lactide)-co-glycolide] tetrols (P(4)OLG) with a ratio of components in a certain range show two glass transition temperatures (T (g)) being attributed to two segregated amorphous phases. In this way a wide spectrum of mechanical properties can be realized and adjusted to the requirements of a specific application.

  19. Four New Kaurane Diterpenoids from the Chinese Liverwort Jungermannia comata Nees.

    PubMed

    Li, Rui-Juan; Wang, Song; Li, Gang; Zhou, Jin-Chuan; Zhang, Jiao-Zhen; Zhang, You-Ming; Shi, Guo-Sheng; Lou, Hong-Xiang

    2016-12-01

    In our continuing program to find new bioactive compounds from the Chinese liverworts, four new kaurane-type diterpenoids, (6β)-kaur-16-ene-6,9-diol (1), (6β,12β)-kaur-16-ene-6,9,12-triol (2), (6β)-kaur-16-ene-5,6,9-triol (3), and kaur-16-ene-9,19-diol (4), have been isolated from the Chinese liverwort Jungermannia comata Nees. Five known kaurane-type diterpenoids (5 - 9) and four known trachylobane-type diterpenoids (10 - 13) were also obtained. The structures of the new compounds were established unequivocally on the basis of spectroscopic data. The absolute configuration of compound 1 was established by comparing experimental and calculated electronic circular dichroism spectra.

  20. One step synthesis of 6-oxo-cholestan-3β,5α-diol

    SciTech Connect

    Voisin, Maud; Silvente-Poirot, Sandrine; Poirot, Marc

    2014-04-11

    Highlights: • Cholesterol-5,6-epoxides are metabolized into cholestane-3β,5α,6β-triol (CT) in cancer cells. • 6-Oxo-cholestan-3β,5α-diol (OCDO) is a putative metabolite of CT. • The one step syntheses of CT and OCDO from cholesterol are reported. • The one step syntheses of labelled CT and OCDO are reported. - Abstract: Cholesterol metabolism has been recently linked to cancer, highlighting the importance of the characterization of new metabolic pathways in the sterol series. One of these pathways is centered on cholesterol-5,6-epoxides (5,6-ECs). 5,6-ECs can either generate dendrogenin A, a tumor suppressor present in healthy mammalian tissues, or the carcinogenic cholestane-3β,5α,6β-triol (CT) and its putative metabolite 6-oxo-cholestan-3β,5α-diol (OCDO) in tumor cells. We are currently investigating the identification of the enzyme involved in OCDO biosynthesis, which would be highly facilitated by the use of commercially unavailable [{sup 14}C]-cholestane-3β,5α,6β-triol and [{sup 14}C]-6-oxo-cholestan-3β,5α-diol. In the present study we report the one-step synthesis of [{sup 14}C]-cholestane-3β,5α,6β-triol and [{sup 14}C]-6-oxo-cholestan-3β,5α-diol by oxidation of [{sup 14}C]-cholesterol with iodide metaperiodate (HIO{sub 4})

  1. A new triterpenoid compound from stems and leaves of American ginseng.

    PubMed

    Han, Liu; Li, Zhuo; Zheng, Qian; Liu, Jin-Ping; Li, Ping-Ya

    2016-01-01

    A new dammarane-type triterpenoid compound was isolated from stems and leaves of American ginseng. The structure of the new sapogenin was elucidated by the combined analysis of NMR and HR-ESI-MS as dammar-20S, 25S-epoxy-3β, 12β, 26-triol (1). Compound 1 showed cytotoxic effect on human SM7721 and human Hela cells in vitro.

  2. Stereoselective synthesis of carbocyclic analogues of the nucleoside Q precursor (PreQ0)

    PubMed Central

    2014-01-01

    Summary A convergent and stereoselective synthesis of chiral cyclopentyl- and cyclohexylamine derivatives of nucleoside Q precursor (PreQ0) has been accomplished. This synthetic route allows for an efficient preparation of 4-substituted analogues with interesting three-dimensional character, including chiral cyclopentane-1,2-diol and -1,2,3-triol derivatives. This unusual substitution pattern provides a useful starting point for the discovery of novel bioactive molecules. PMID:24991286

  3. Identification and quantification of metabolites common to 17alpha-methyltestosterone and mestanolone in horse urine.

    PubMed

    Yamada, Masayuki; Aramaki, Sugako; Okayasu, Toshimasa; Hosoe, Tomoo; Kurosawa, Masahiko; Kijima-Suda, Isao; Saito, Koichi; Nakazawa, Hiroyuki

    2007-09-21

    Anabolic steroids with the 17alpha-methyl,17beta-hydroxyl group, which were developed as oral formulations for therapeutic purposes, have been abused in the field of human sports. These anabolic steroids are also used to enhance racing performance in racehorses. In humans, structurally related 17alpha-methyltestosterone (MTS) and mestanolone (MSL), which are anabolic steroids with the 17alpha-methyl,17beta-hydroxyl group, have metabolites in common. The purpose of this study was to determine metabolites common to these two steroids in horses, which may serve as readily available screening targets for the doping test of these steroids in racehorses. Urine sample collected after administering MTS and MSL to horses was treated to obtain unconjugated steroid, glucuronide, and sulfate fractions. The fractions were subjected to gas chromatography/mass spectrometry (GC/MS), and 17alpha-methyl-5alpha-androstan-3beta,17beta-diol, 17alpha-hydroxymethyl-5alpha-androstan-3beta,17beta-diol, 17alpha-methyl-5alpha-androstan-3beta,16beta,17beta-triol, and 17alpha-methyl-5alpha-androstan-3beta,16alpha,17beta-triol were detected as the common metabolites by comparison with synthesized reference standards. The urinary concentrations of these metabolites after dosing were determined by GC/MS. 17Alpha-methyl-5alpha-androstan-3beta,16beta,17beta-triol was mainly detected in the sulfate fractions of urine samples after administration. This compound was consistently detected for the longest time in the urine samples after dosing with both steroids. The results suggest that 17alpha-methyl-5alpha-androstan-3beta,16beta,17beta-triol is a very useful screening target for the doping test of MTS and MSL in racehorses.

  4. Regioselective azidotrimethylsilylation of carbohydrates and applications thereof.

    PubMed

    L, Mallikharjuna Rao; Yousuf, Syed Khalid; Mukherjee, Debaraj; Taneja, Subhash Chandra

    2012-12-07

    Azidotrimethylsilylation of carbohydrates (monosaccharides and disaccharides) has been achieved in high yields under Mitsunobu conditions. The azidation of carbohydrates is effected at 0 °C essentially only at the primary alcoholic position in mono, di- and triols in protected/unprotected glycosides, whereas the remaining secondary hydroxyl groups got silylated. Surprisingly, no azidation of the secondary hydroxyls was observed in all the carbohydrate substrates. Applications of the methodology for the synthesis of amino sugars, triazoles and azasugars are reported.

  5. New ceramide from Alocasia macrorrhiza.

    PubMed

    Tien, Nguyen Quyet; Ngoc, PhamHoang; Minh, Pham Hong; Van Kiem, Phan; Van Minh, Chau; Kim, Young Ho

    2004-10-01

    A new ceramide alomacrorrhiza A was isolated from the ethanolic extract of the plant Alocasia macrorrhiza (L.) Schott. Its chemical structure was elucidated as (2S,3S,4R)-2N-[(2'R)-2'-hydroxy-hexacosanoyl]-tetradecane-1,3,4-triol based on extensive 1D, 2D NMR, EI-MS, FAB-MS, HR-FAB-MS spectroscopic data and chemical degradation studies.

  6. Dihydrophenanthrenes from Bletilla formosana.

    PubMed

    Lin, Yun-Lian; Chen, Wan-Ping; Macabalang, Abdulgafor Datu

    2005-09-01

    Three new dihydrophenanthrenes, 4-methoxy-9,10-dihydrophenanthrene-1,2,7-triol (1), 1-(4-hydroxybenzyl)-4,7-dimethoxy-9,10-dihydrophenanthrene-2-ol (2), and 1,3,6-tri(4-hydroxybenzyl)-4-methoxydihydrophenanthrene-2,7-diol (3) together with seven known phenanthrene derivatives, six known flavonoids, a bibenzyl and three phenolic compounds were isolated from the whole plant of Bletilla formosana. Their structures were elucidated by spectroscopic, mainly 2D NMR spectrometry and chemical methods.

  7. A sub-decadal trend of diacids in atmospheric aerosols in East Asia

    NASA Astrophysics Data System (ADS)

    Kundu, S.; Kawamura, K.; Kobayashi, M.; Tachibana, E.; Lee, M.; Fu, P. Q.; Jung, J.

    2015-08-01

    The change of secondary organic aerosols (SOA) has been predicted to be highly uncertain in the future atmosphere in Asia. To better quantify the SOA change, we study a sub-decadal (2001-2008) trend of major surrogate compounds (C2-C10 diacids) of SOA in atmospheric aerosols from Gosan site in Jeju Island, South Korea. Gosan site is influenced by the pollution-outflows from East Asia. The molecular distribution of diacids was characterized by the predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids in each year. The seasonal variations of diacids in each year were characterized by the highest concentrations of saturated diacids in spring and unsaturated diacids in winter. The consistent molecular distribution and seasonal variations are indicative of similar pollution sources for diacids in East Asia over a sub-decadal scale. However, the intensity of the pollution sources has increased as evidenced by the increases of major diacids at the rate of 3.9-47.4 % year-1 particularly in April. The temporal variations of atmospheric tracer compounds (CO, levoglucosan, 2-methyltetrols, pinic acid, glyoxylic acid, glyoxal and methylglyoxal) suggest that the increases of diacids are due to an enhanced precursor emissions associated with more anthropogenic than biogenic activities followed by their chemical processing in the atmosphere. The trends of diacids are opposite to the reported decreases of sulfate, nitrate and ammonium in the recent years in East Asia. This study demonstrates that recent pollution control strategies in East Asia could not decrease organic acidic species in the atmosphere. If the current rates of increases continue, the organic acid- and water-soluble fractions of SOA could increase significantly in the future atmosphere in East Asia.

  8. A sub-decadal trend in diacids in atmospheric aerosols in eastern Asia

    NASA Astrophysics Data System (ADS)

    Kundu, S.; Kawamura, K.; Kobayashi, M.; Tachibana, E.; Lee, M.; Fu, P. Q.; Jung, J.

    2016-01-01

    Change in secondary organic aerosols (SOAs) has been predicted to be highly uncertain in the future atmosphere in Asia. To better quantify the SOA change, we examine the sub-decadal (2001-2008) trend in major surrogate compounds (C2-C10 diacids) of SOA in atmospheric aerosols from Gosan site on Cheju Island, South Korea. The Gosan site is influenced by pollution outflows from eastern Asia. The molecular distributions of diacids were characterized by the predominance of oxalic (C2) acid followed by malonic (C3) and succinic (C4) acids in each year. The seasonal variations in diacids in each year were characterized by the highest concentrations of saturated diacids in spring and unsaturated diacids in winter. The consistent molecular distributions and seasonal variations along with significantly similar air mass transport patterns are indicative of similar pollution sources for diacids in eastern Asia on a sub-decadal scale. However, the intensity of the pollution sources has increased as evidenced by the increases in major diacids at the rate of 3.9-47.4 % per year, particularly in April. The temporal variations in atmospheric tracer compounds (carbon monoxide, levoglucosan, 2-methyltetrols, pinic acid, glyoxylic acid, glyoxal and methylglyoxal) suggest that the increases in diacids are due to enhanced precursor emissions associated with more anthropogenic than biogenic activities followed by the compounds' chemical processing in the atmosphere. The trends in diacids contrast with the reported decreases in sulfate, nitrate and ammonium in recent years in eastern Asia. This study demonstrates that recent pollution control strategies in eastern Asia were not able to decrease organic acidic species in the atmosphere. The increases in water-soluble organic acid fraction could modify the aerosol organic composition and its sensitivity to climate relevant physical properties.

  9. Spatial and seasonal variations of biogenic tracer compounds in ambient PM 10 and PM 1 samples in Berlin, Germany

    NASA Astrophysics Data System (ADS)

    Wagener, Sandra; Langner, Marcel; Hansen, Ute; Moriske, Heinz-Jörn; Endlicher, Wilfried R.

    2012-02-01

    PM 10 and PM 1 aerosol samples were collected between February and October, 2010 at three sites in Berlin that were characterized by different vegetation influences. The aim of the study was to determine the spatial and seasonal variations of several, mainly biogenic secondary and primary tracers in an urban area. Selected tracers including isoprene and α-pinene markers, fatty acids and levoglucosan were detected with GC-MS. The highest median concentrations, up to 45.1 ng m -3, were found for the combustion product levoglucosan. The concentration range of the secondary compounds was 0.3 ng m -3 for the isoprene markers 2-methyltetrols up to 35.7 ng m -3 for malic acid. The occurrence of these compounds was mainly affected by the seasons, which could be described by three patterns. Whereas secondary compounds were mainly characterized by significantly higher concentrations during the warmer months, levoglucosan showed significantly higher concentrations during the colder months. No significant concentration differences between the two periods were rather observed for the primary compounds but also for the α-pinene degradation product pinonic acid. The secondary compounds and levoglucosan could be associated with the fine mode (particles with an aerodynamic diameter (AD) < 1 μm), while primary compounds are rather associated with the coarse mode (AD > 1 μm). Spatial variations were emphasized with a tendency toward higher concentrations for most compounds at sites that were influenced by vegetation, especially evident for the PM 10 fraction. Besides concentration differences, spatial variations could also be described by differences in seasonal behavior and the size distribution, indicating major complexity in the composition of biogenic PM within the city of Berlin.

  10. Assessing the oxidative potential of isoprene-derived epoxides and secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    Kramer, Amanda J.; Rattanavaraha, Weruka; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.; Lin, Ying-Hsuan

    2016-04-01

    Fine particulate matter (PM2.5) is known to contribute to adverse health effects, such as asthma, cardiopulmonary disease, and lung cancer. Secondary organic aerosol (SOA) is a major component of PM2.5 and can be enhanced by atmospheric oxidation of biogenic volatile organic compounds in the presence of anthropogenic pollutants, such as nitrogen oxides (NOx) and sulfur dioxide. However, whether biogenic SOA contributes to adverse health effects remains unclear. The objective of this study was to assess the potential of isoprene-derived epoxides and SOA for generating reactive oxygen species (ROS) in light of the recent recognition that atmospheric oxidation of isoprene in the presence of acidic sulfate aerosol is a major contributor to the global SOA burden. The dithiothreitol (DTT) assay was used to characterize the ROS generation by the isoprene-derived epoxides, trans-β-isoprene epoxydiol (trans-β-IEPOX) and methacrylic acid epoxide (MAE), and their hydrolysis products, the 2-methyltetrol diastereomers (2-MT), 2-methylglyceric acid (2-MG), their organosulfate derivatives, as well as an isoprene-derived hydroxyhydroperoxide (ISOPOOH). In addition, ROS generation potential was evaluated for total SOA produced from photooxidation of isoprene and methacrolein (MACR) as well as from the reactive uptake of trans-β-IEPOX and MAE onto acidified sulfate aerosol. The high-NOx regime, which yields 2-MG-, MAE- and MACR-derived SOA has a higher ROS generation potential than the low-NOx regime, which yields 2-MT, IEPOX- and isoprene-derived SOA. ISOPOOH has an ROS generation potential similar to 1,4-naphthoquinone (1,4-NQ), suggesting a significant contribution of aerosol-phase organic peroxides to PM oxidative potential. MAE- and MACR-derived SOA show equal or greater ROS generation potential than reported in studies on diesel exhaust PM, highlighting the importance of a comprehensive investigation of the toxicity of isoprene-derived SOA.

  11. Structural and Sensory Characterization of Bitter Tasting Steroidal Saponins from Asparagus Spears (Asparagus officinalis L.).

    PubMed

    Dawid, Corinna; Hofmann, Thomas

    2012-12-05

    Application of sequential solvent extraction and iterative chromatographic separation in combination with taste dilution analysis recently revealed a series of steroidal saponins as the key contributors to the typical bitter taste of white asparagus spears (Asparagus officinalis L.). Besides six previously reported saponins, (25R)-furost-5-en-3β,22,26-triol-3-O-[α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranoside]-26-O-β-D-glucopyranoside, (25R)-furostane-3β,22,26-triol-3-O-[α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranoside]-26-O-β-D-glucopyranoside, and (25S)-furostane-3β,22,26-triol-3-O-[α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranoside]-26-O-β-D-glucopyranoside, and 3-O-[{α-L-rhamnopyranosyl-(1→2)}{α-L-rhamnopyranosyl-(1→4)}-β-D-glucopyranosyl]-(25S)-spirost-5-ene-3β-ol were identified for the first time as key bitter compounds in the edible spears of white asparagus by means of LC-MS/MS, LC-TOF-MS, 1D/2D-NMR spectroscopy, and hydrolysis experiments. This paper presents the isolation, structure determination, and sensory activity of these saponins. Depending on their chemical structure, the saponins identified showed human bitter recognition thresholds between 10.9 and 199.7 μmol/L (water).

  12. Four new steroid constituents from the waste residue of fibre separation from Agave americana leaves.

    PubMed

    Jin, Jian-Ming; Zhang, Ying-Jun; Yang, Chong-Ren

    2004-06-01

    Three new steroidal saponins, named agamenosides H-J (1-3), and a new cholestane steroid agavegenin D (4) were isolated from the waste residue of fibre separation from Agave americana leaves, together with six known steroids. Structures of the new compounds 1-4 were deduced to be (22S,23S,24R,25S)-24-[(beta-D-glucopyranosyl)oxy]-5alpha-spirostane-3beta,6alpha,23-triol 6-O-beta-D-glucopyranoside (1), (22S,23S,24R,25S)-5alpha-spirostane-3beta,23,24-triol 24-O-beta-D-glucopyranoside (2), (22S,23S,25R,26S)-23,26-epoxy-5alpha-furostane-3beta,22,26-triol 26-O-beta-D-glucopyranoside (3), and (22S,25S)-5alpha-cholestane-3beta,16beta,22,26-tetrol (4), respectively, by means of spectroscopic analysis, including extensive 1D and 2D NMR data, and the results of hydrolytic cleavage.

  13. Metabolism of methyltestosterone in the greyhound.

    PubMed

    Biddle, S T B; O'Donnell, A; Houghton, E; Creaser, C

    2009-03-01

    Gas chromatography/mass spectrometry and selective derivatisation techniques have been used to identify urinary metabolites of methyltestosterone following oral administration to the greyhound. Several metabolites were identified including reduced, mono-, di- and trihydroxylated steroids. The major metabolites observed were 17alpha-methyl-5beta-androstane-3alpha-17beta-diol, 17alpha-methyl-5beta-androstane-3alpha,16alpha,17beta-triol, and a further compound tentatively identified as 17alpha-methyl-5z-androstane-6z,17beta-triol. The most abundant of these was the 17alpha-methyl-5beta-androstane-3alpha,16alpha,17beta-triol. This metabolite was identified by comparison with a reference standard synthesised using a Grignard procedure and characterised using trimethylsilyl (TMS) and acetonide-TMS derivatisation techniques. There did not appear to be any evidence for 16beta-hydroxylation as a phase I metabolic transformation in the greyhound. However, significant quantities of 16alpha-hydroxy metabolites were detected. Selective enzymatic hydrolysis procedures indicated that the major metabolites identified were excreted as glucuronic acid conjugates. Metabolic transformations observed in the greyhound have been compared with those of other mammalian species and are discussed here.

  14. Three new labdane-type diterpene glycosides from fruits of Rubus chingii and their cytotoxic activities against five humor cell lines.

    PubMed

    Zhong, Ruijian; Guo, Qing; Zhou, Guoping; Fu, Huizheng; Wan, Kaihua

    2015-04-01

    Three new labdane-type diterpene glycosides, 15,18-di-O-β-d-glucopyranosyl-13(E)-ent-labda-7(8),13(14)-diene-3β,15,18-triol (1), 15,18-di-O-β-d-glucopyranosyl-13(E)-ent-labda-8(9),13(14)-diene-3β,15,18-triol (2), and 15-O-β-d-apiofuranosyl-(1→2)-β-d-glucopyranosyl-18-O-β-d-glucopyranosyl-13(E)-ent-labda-8(9),13(14)-diene-3β,15,18-triol (3), were isolated from the fruits of Rubus chingii. Their structures were elucidated on the basis of spectroscopic data and chemical methods. The cytotoxic activities of compounds 1-3 were evaluated against five human tumor cell lines (HCT-8, BGC-823, A549, and A2780). Compounds 3 showed cytotoxic activity against A549 with an IC50 value of 2.32μM.

  15. Antibacterial Biphenanthrenes from the Fibrous Roots of Bletilla striata.

    PubMed

    Qian, Chao-Dong; Jiang, Fu-Sheng; Yu, Hang-Su; Shen, Yong; Fu, Yu-Hang; Cheng, Dong-Qing; Gan, Li-She; Ding, Zhi-Shan

    2015-04-24

    Four new 9',10'-dihydro-biphenanthrenes, including an unprecedented 1,2'-linked biphenanthrene, 4,7,3',5'-tetramethoxy-9',10'-dihydro(1,2'-biphenanthrene)-2,7'-diol (1), a new 1,3'-linked biphenanthrene, 4,7,7'-trimethoxy-9',10'-dihydro(1,3'-biphenanthrene)-2,2',5'-triol (2), and two new 1,1'-linked biphenanthrenes, 4,7,4'-trimethoxy-9',10'-dihydro(1,1'-biphenanthrene)-2,2',7'-triol (3) and 4,7,3',5'-tetramethoxy-9',10'-dihydro(1,1'-biphenanthrene)-2,2',7'-triol (4), as well as two known biphenanthrenes (5, 6), were isolated from a 95% ethanol extract of the fibrous roots of Bletilla striata. Their structures were determined by spectroscopic and spectrometric methods. Atropisomerism of these compounds was considered based on their chiral optical properties and potential energy surface scans at the ab initio HF/3-21G level, which revealed their racemic mixture form. Compounds 2-6 showed potent antibacterial activities against six Gram-positive bacterial strains.

  16. Chemical loss of volatile organic compounds and its impact on the source analysis through a two-year continuous measurement

    NASA Astrophysics Data System (ADS)

    Wang, H. L.; Chen, C. H.; Wang, Q.; Huang, C.; Su, L. Y.; Huang, H. Y.; Lou, S. R.; Zhou, M.; Li, L.; Qiao, L. P.; Wang, Y. H.

    2013-12-01

    Chemical loss of volatile organic compounds (VOCs) is more important than the observed VOCs, which is the real actor of the chemical process in the atmosphere. The chemical loss of VOCs might impact on the identification of VOCs sources in ambient. For this reason, VOCs with 56 species were continuously measured in the urban area of Shanghai from 2009 to 2010, and based on the measurement the chemical loss of VOCs was calculated. According to the result, the initial VOCs in Shanghai urban was (34.8 ± 20.7) ppbv, higher than the observed one by ˜35%, including alkanes (˜38%), aromatics (˜36%), alkenes (˜17%), and acetylene (˜8%). The chemical reactivity of VOCs would be underestimated by ˜60% if the chemical loss were ignored. The chemical loss of VOCs showed a good agreement with Ox (O3 + NO2). C7-C8 aromatics and C3-C5 alkenes contributed ˜60% of consumed VOCs. Seven sources were identified and quantified from positive matrix factorization (PMF) analysis. Vehicular emissions were the largest anthropogenic source of VOCs in Shanghai urban, accounting for 27.6% of VOCs, followed by solvent usage (19.4%), chemical industry (13.2%), petrochemical industry (9.1%), and coal burning (˜5%). The contribution of biogenic emissions to total VOCs was 5.8%. Besides the five local anthropogenic sources and one biogenic source, the regional transportation was identified as one important source, contributing about 20% of VOCs in Shanghai urban. Sources apportionment results from PMF analysis based on the initial VOCs showed some differences from those based on observed data and might be more appropriate to be applied into the formulation of air pollution control measures.

  17. Characterization of NOx, SO2, ethene, and propene from industrial emission sources in Houston, Texas

    NASA Astrophysics Data System (ADS)

    Washenfelder, R. A.; Trainer, M.; Frost, G. J.; Ryerson, T. B.; Atlas, E. L.; de Gouw, J. A.; Flocke, F. M.; Fried, A.; Holloway, J. S.; Parrish, D. D.; Peischl, J.; Richter, D.; Schauffler, S. M.; Walega, J. G.; Warneke, C.; Weibring, P.; Zheng, W.

    2010-08-01

    The Houston-Galveston-Brazoria urban area contains industrial petrochemical sources that emit volatile organic compounds and nitrogen oxides, resulting in rapid and efficient ozone production downwind. During September to October 2006, the NOAA WP-3D aircraft conducted research flights as part of the second Texas Air Quality Study (TexAQS II). We use measurements of NOx, SO2, and speciated hydrocarbons from industrial sources in Houston to derive source emission ratios and compare these to emission inventories and the first Texas Air Quality Study (TexAQS) in 2000. Between 2000 and 2006, NOx/CO2 emission ratios changed by an average of -29% ± 20%, while a significant trend in SO2/CO2 emission ratios was not observed. We find that high hydrocarbon emissions are routine for the isolated petrochemical facilities. Ethene (C2H4) and propene (C3H6) are the major contributors to ozone formation based on calculations of OH reactivity for organic species including C2-C10 alkanes, C2-C5 alkenes, ethyne, and C2-C5 aldehydes and ketones. Measured ratios of C2H4/NOx and C3H6/NOx exceed emission inventory values by factors of 1.4-20 and 1-24, respectively. We examine trends in C2H4/NOx and C3H6/NOx ratios between 2000 and 2006 for the isolated petrochemical sources and estimate a change of -30% ± 30%, with significant day-to-day and within-plume variability. Median ambient mixing ratios of ethene and propene in Houston show decreases of -52% and -48%, respectively, between 2000 and 2006. The formaldehyde, acetaldehyde, and peroxyacetyl nitrate products produced by alkene oxidation are observed downwind, and their time evolution is consistent with the rapid photochemistry that also produces ozone.

  18. Evaluation of incremental reactivity and its uncertainty in Southern California.

    PubMed

    Martien, Philip T; Harley, Robert A; Milford, Jana B; Russell, Armistead G

    2003-04-15

    The incremental reactivity (IR) and relative incremental reactivity (RIR) of carbon monoxide and 30 individual volatile organic compounds (VOC) were estimated for the South Coast Air Basin using two photochemical air quality models: a 3-D, grid-based model and a vertically resolved trajectory model. Both models include an extended version of the SAPRC99 chemical mechanism. For the 3-D modeling, the decoupled direct method (DDM-3D) was used to assess reactivities. The trajectory model was applied to estimate uncertainties in reactivities due to uncertainties in chemical rate parameters, deposition parameters, and emission rates using Monte Carlo analysis with Latin hypercube sampling. For most VOC, RIRs were found to be consistent in rankings with those produced by Carter using a box model. However, 3-D simulations show that coastal regions, upwind of most of the emissions, have comparatively low IR but higher RIR than predicted by box models for C4-C5 alkenes and carbonyls that initiate the production of HOx radicals. Biogenic VOC emissions were found to have a lower RIR than predicted by box model estimates, because emissions of these VOC were mostly downwind of the areas of primary ozone production. Uncertainties in RIR of individual VOC were found to be dominated by uncertainties in the rate parameters of their primary oxidation reactions. The coefficient of variation (COV) of most RIR values ranged from 20% to 30%, whereas the COV of absolute incremental reactivity ranged from about 30% to 40%. In general, uncertainty and variability both decreased when relative rather than absolute reactivity metrics were used.

  19. Biogenic Emissions of Light Alkenes from a Coniferous Forest

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Turnipseed, A. A.; Martinez, L.; Shen, S.; De Gouw, J. A.; Warneke, C.; Koss, A.; Lerner, B. M.; Miller, B. R.; Smith, J. N.; Guenther, A. B.

    2014-12-01

    Alkenes are reactive hydrocarbons that play important roles in the photochemical production of tropospheric ozone and in the formation of secondary organic aerosols. The light alkenes (C2-C4) originate from both biogenic and anthropogenic sources and include C2H4 (ethene), C3H6 (propene) and C4H8 (1-butene, 2-butene, 2-methylpropene). Light alkenes are used widely as chemical feedstocks because their double bond makes them versatile for industrial reactions. Their biogenic sources are poorly characterized, with most global emissions estimates relying on laboratory-based studies; net ecosystem emissions have been measured at only one site thus far. Here we report net ecosystem fluxes of light alkenes and isoprene from a semi-arid ponderosa pine forest in the Rocky Mountains of Colorado, USA. Canopy scale fluxes were measured using relaxed eddy accumulation (REA) techniques on the 28-meter NCAR tower in the Manitou Experimental Forest Observatory. Updrafts and downdrafts were determined by sonic anemometry and segregated into 'up' and 'down' reservoirs over the course of an hour. Samples were then measured on two separate automated gas chromatographs (GCs). The first GC measured light hydrocarbons (C2-C6 alkanes and C2-C5 alkenes) by flame ionization detection (FID). The second GC measured halocarbons (methyl chloride, CFC-12, and HCFC-22) by electron capture detection (ECD). Additional air measurements from the top of the tower included hydrocarbons and their oxidation products by Proton Transfer Reaction Mass Spectrometry (PTR-MS). Three field intensives were conducted during the summer of 2014. The REA flux measurements showed that ethene, propene and the butene emissions have significant diurnal cycles, with maximum emissions at midday. The light alkenes contribute significantly to the overall biogenic source of reactive hydrocarbons and have a temporal variability that may be associated with physical and biological parameters. These ecosystem scale measurements

  20. Source apportionment of ambient non-methane hydrocarbons in Hong Kong: application of a principal component analysis/absolute principal component scores (PCA/APCS) receptor model.

    PubMed

    Guo, H; Wang, T; Louie, P K K

    2004-06-01

    Receptor-oriented source apportionment models are often used to identify sources of ambient air pollutants and to estimate source contributions to air pollutant concentrations. In this study, a PCA/APCS model was applied to the data on non-methane hydrocarbons (NMHCs) measured from January to December 2001 at two sampling sites: Tsuen Wan (TW) and Central & Western (CW) Toxic Air Pollutants Monitoring Stations in Hong Kong. This multivariate method enables the identification of major air pollution sources along with the quantitative apportionment of each source to pollutant species. The PCA analysis identified four major pollution sources at TW site and five major sources at CW site. The extracted pollution sources included vehicular internal engine combustion with unburned fuel emissions, use of solvent particularly paints, liquefied petroleum gas (LPG) or natural gas leakage, and industrial, commercial and domestic sources such as solvents, decoration, fuel combustion, chemical factories and power plants. The results of APCS receptor model indicated that 39% and 48% of the total NMHCs mass concentrations measured at CW and TW were originated from vehicle emissions, respectively. 32% and 36.4% of the total NMHCs were emitted from the use of solvent and 11% and 19.4% were apportioned to the LPG or natural gas leakage, respectively. 5.2% and 9% of the total NMHCs mass concentrations were attributed to other industrial, commercial and domestic sources, respectively. It was also found that vehicle emissions and LPG or natural gas leakage were the main sources of C(3)-C(5) alkanes and C(3)-C(5) alkenes while aromatics were predominantly released from paints. Comparison of source contributions to ambient NMHCs at the two sites indicated that the contribution of LPG or natural gas at CW site was almost twice that at TW site. High correlation coefficients (R(2) > 0.8) between the measured and predicted values suggested that the PCA/APCS model was applicable for estimation

  1. Global comparison of VOC and CO observations in urban areas

    NASA Astrophysics Data System (ADS)

    von Schneidemesser, Erika; Monks, Paul S.; Plass-Duelmer, Christian

    2010-12-01

    Speciated volatile organic compound (VOC) and carbon monoxide (CO) measurements from the Marylebone Road site in central London from 1998 through 2008 are presented. Long-term trends show statistically significant decreases for all the VOCs considered, ranging from -3% to -26% per year. Carbon monoxide decreased by -12% per year over the measurement period. The VOC trends observed at the kerbside site in London showed greater rates of decline relative to trends from monitoring sites in rural England (Harwell) and a remote high-altitude site (Hohenpeissenberg), which showed decreases for individual VOCs from -2% to -13% per year. Over the same 1998 through 2008 period VOC to CO ratios for London remained steady, an indication that emissions reduction measures affected the measured compounds equally. Relative trends comparing VOC to CO ratios between Marylebone Road and Hohenpeissenberg showed greater similarities than absolute trends, indicating that emissions reductions measures in urban areas are reflected by regional background locations. A comparison of VOC mixing ratios and VOC to CO ratios was undertaken for London and other global cities. Carbon monoxide and VOCs (alkanes greater than C 5, alkenes, and aromatics) were found to be strongly correlated (>0.8) in the Annex I countries, whereas only ethene and ethyne were strongly correlated with CO in the non-Annex I countries. The correlation results indicate significant emissions from traffic-related sources in Annex I countries, and a much larger influence of other sources, such as industry and LPG-related sources in non-Annex I countries. Yearly benzene to ethyne ratios for London from 2000 to 2008 ranged from 0.17 to 0.29 and compared well with previous results from US cities and three global megacities.

  2. Characterization of Nonmethane Hydrocarbons during the NACHTT Campaign at the Boulder Atmospheric Observatory

    NASA Astrophysics Data System (ADS)

    Russo, R. S.; Sive, B. C.; Zhou, Y.; Swarthout, R.; Hart, A.

    2011-12-01

    Whole air samples were collected in 2-liter electropolished stainless steel canisters at the top of each hour between February 18-March 13, 2011 from a height of 20 meters on the tower at the Boulder Atmospheric Observatory (BAO) in Erie, Colorado during the NACHTT (Nitrogen, Aerosol Composition and Halogens on a Tall Tower) campaign. Canister samples were also collected 2-3 times per day at heights of 50, 100, 150, 200, and 250 meters on the tower to obtain vertical profiles of the trace gas distributions. The canister samples were analyzed for a suite of volatile organic compounds (VOCs) on a three gas chromatograph system in the laboratory at the University of New Hampshire. This work discusses the distribution of nonmethane hydrocarbons (NMHCs)(specifically C2-C10 alkanes, C2-C5 alkenes, C6-C9 aromatics, and ethyne) during the NACHTT campaign. This analysis has revealed a significant and persistent influence from a source of C2-C5 alkanes, which is likely associated with natural gas production and/or distribution. The mixing ratios of ethane(median = 13.6 ppbv), propane (8.7 ppbv), i-butane (1.5 ppbv), n-butane (3.5 ppbv), and n-pentane (1.1 ppbv) at the BAO tower were higher than observed in major North American cities, including Houston and Mexico City. Using the complete suite of VOC data (including halocarbons and alkyl nitrates) and complimentary measurements (i.e., reactive nitrogen compounds, ozone, halogens, aerosol composition, meteorology) made during the NACHTT campaign, the large alkane source(s) will be evaluated. Additional analyses will include examination of the NMHC time series and vertical profiles, correlations, NMHC reactivity, and the potential impact on ozone production, halogen chemistry and regional air quality.

  3. Comparison of bile salt/phosphatidylcholine mixed micelles in solubilization to sterols and stability

    PubMed Central

    Guo, Qin; Cai, Jie; Li, Pengyu; Xu, Dongling; Ni, Xiaomin; Wen, Hui; Liu, Dan; Lin, Suizhen; Hu, Haiyan

    2016-01-01

    Androst-3β,5α,6β-triol (Triol) is a promising neuroprotective agent, but its poor solubility restricts its development into parenteral preparations. In this study, Triol is significantly solubilized by bile salt/phosphatidylcholine mixed micelles (BS/PC-MM). All BS/PC-MM systems are tested to remarkably improve the drug solubility with various stabilities after drug loading. Among them, the sodium glycocholate (SGC)/egg phosphatidylcholine (EPC) system with 2:1 ratio in weight and the total concentration of SGC and EPC of 100 mg/mL is proved to produce stable mixed micelles with high drug loading. It is found that the stability of drug-loaded mixed micelles is quite different, which might be related to the change in critical micelle concentration (CMC) after incorporating drugs. SGC/EPC and SGC/soya phosphatidylcholine (SPC) remain transparent under accelerated conditions and manifest a decreased CMC (dropping from 0.105 to 0.056 mg/mL and from 0.067 to 0.024 mg/mL, respectively). In contrast, swine bile acid-sodium salt (SBA-Na)/PC and sodium deoxycholate (SDC)/PC are accompanied by drug precipitation and reached the maximum CMC on the first and the third days, respectively. Interestingly, the variation of CMC under accelerated testing conditions highly matches the drug-precipitating event in the primary stability experiment. In brief, the bile salt/phosphatidylcholine system exists as a potential strategy of improving sterol drug solubility. CMC variation under accelerated testing conditions might be a simple and easy method to predict the stability of drug-loaded mixed micelles. PMID:27895469

  4. Natural occurrence of 16 fusarium toxins in grains and feedstuffs of plant origin from Germany.

    PubMed

    Schollenberger, Margit; Müller, Hans-Martin; Rüfle, Melanie; Suchy, Sybille; Plank, Susanne; Drochner, Winfried

    2006-01-01

    A total of 220 samples comprising cereals, cereal byproducts, corn plants and corn silage as well as non-grain based feedstuffs was randomly collected during 2000 and 2001 from sources located in Germany and analysed for 16 Fusarium toxins. The trichothecenes scirpentriol (SCIRP), 15-monoacetoxyscirpenol (MAS), diacetoxyscirpenol (DAS), T-2 tetraol, T-2 triol, HT-2 and T-2 toxin (HT-2, T-2), neosolaniol (NEO), deoxynivalenol (DON), 3-acetyldeoxynivalenol (3-ADON), 15-acetyldeoxynivealenol (15-ADON), nivalenol (NIV) and fusarenon-X (FUS-X) were determined by gas chromatography/mass spectrometry. Zearalenone (ZEA) and alpha- and beta-zearalenol (alpha- and beta-ZOL) were analysed by high performance liquid chromatography with fluorescence and UV-detection. Detection limits ranged between 1 and 19 microg/kg. Out of 125 samples of a group consisting of wheat, oats, corn, corn byproducts, corn plants and corn silage only two wheat samples did not contain any of the toxins analysed. Based on 125 samples the incidences were at 2-11% for DAS, NEO, T-2 Triol, FUS-X, alpha- and beta-ZOL, at 20-22% for SCIRP, MAS, T-2 tetraol and 3-ADON, at 44-74% for HT-2, T-2, 15-ADON, NIV and ZEA, and at 94% for DON. Mean levels of positive samples were between 6 and 758 microg/kg. Out of 95 samples of a group consisting of hay, lupines, peas, soya meal, rapeseed meal and other oil-seed meals, 64 samples were toxin negative. DAS, T-2 triol, NEO and FUS-X were not detected in any sample. The incidences of DON and ZEA were at 14 and 23% respectively, those of the other toxins between 1-4%, mean levels of positive samples were between 5 and 95 microg/kg.

  5. Preparative isolation and purification of five steroid saponins from Dioscorea zingiberensis C.H.Wright by counter-current chromatography coupled with evaporative light scattering detector.

    PubMed

    Zhang, Xinxin; Ito, Yoichiro; Liang, Jinru; Su, Qi; Zhang, Yongmin; Liu, Jianli; Sun, Wenji

    2013-10-01

    A counter-current chromatography (CCC) method was successfully applied to separate and purify steroid saponins from the traditional Chinese medicine Dioscorea zingiberensis C.H.Wright for the first time. Ethyl acetate-n-butanol-methanol-water (4:1:2:4, v/v) was used as the two-phase solvent system, and evaporative light scattering detector (ELSD) was used as the detector in this method. The method separated in a single run the following five steroid saponins: 26-O-β-d-glucopyranosyl-(25R)-furost-5-en-3β, 22ζ, 26-triol-3-O-[β-d-glucopyranosyl-(1→3)-β-d-glucopyranol-(1→4)-α-l-rhamnopyranosyl-(1→2)]-β-d-glucopyranoside (Compound A); 26-O-β-d-glucopyranosyl-(25R)-furost-5-en-3β, 22ζ, 26-triol-3-O-[β-d-glucopyranosyl(1→3)-α-l-rhamnopyranosyl(1→2)]-β-d-glucopyranoside (Compound B); 26-O-β-d-glucopyranosyl-(25R)-furost-5-en-3β, 22ζ, 26-triol-3-O-[α-l-rhamnopyranosyl(1→4)]-β-d-glucopyranoside (Compound C); 26-O-β-d-glucopyranosyl-(25R)-furost-5, 20(22)-diene-3β, 26-diol-3-O-{α-l-rhamnopyranosyl-(1→4)-[β-d-glucopyranosyl-(1→3)-β-d-glucopyranosyl-(1→2)]}-β-d-glucopyranoside (Compound D); and 26-O-β-d-glucopyranosyl-(25R)-furost-5, 20(22)-diene-3β, 26-diol-3-O-[β-d-glucopyranosyl-(1→4)-α-l-rhamnopyranosyl(1→2)]-β-d-glucopyranoside (Compound E). Their structural identification of the five steroid saponins was performed by means of ESI-MS, and (13)C NMR.

  6. The Coast Artillery Journal. Volume 86, Number 1, January-February 1943

    DTIC Science & Technology

    1943-02-01

    Garden Encyclopedia. By E. L. D. Seymour 4.00 See Here, Private Hargrove. By ,\\I,triol1 Hargroz1e 2.00 Suez to Singapore. By Cecil BrOIl’l1 3.50 They...Strange Woman. By Ben Ames IPilliam 2.75 This Above All. By Eric Knight 2.50 The Fighting Littles. By Booth Tarkington 2.00 Storm. By George R...The commander of this regiment, Colonel Hubert A. i\\/IcMorrow, evidently believes in the JOUR- NALas a training aid for his unit. Undoubtedly more

  7. A new steroidal saponin, yuccalan, from the leaves of Yucca smalliana.

    PubMed

    Jin, Yu-Lan; Kuk, Ju-Hee; Oh, Kyung-Taek; Kim, Young-Ju; Piao, Xiang-Lan; Park, Ro-Dong

    2007-05-01

    An extract of the leaves of Yucca smalliana Fern. (Agavaceae) showed potential antimicrobial activity. Employing a bioassay linked fractionation method, one of the active principles, namely yuccalan, was isolated as a new steroidal saponin. The structure of the new steroidal saponin was elucidated as 3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(3beta, 5alpha, 6alpha, 25S)-spirostan-3,6,27-triol (1) using various spectroscopic techniques, including IR, MS, 1D and 2D 1H-NMR, and 13C-NMR. The purified yuccalan showed antifungal activities against both Rhizoctonia solani and Fusarium oxysporum.

  8. Cerebrosides and a monoacylmonogalactosylglycerol from Clinacanthus nutans.

    PubMed

    Tuntiwachwuttikul, Pittaya; Pootaeng-On, Yupa; Phansa, Photchana; Taylor, Walter Charles

    2004-01-01

    A mixture of nine cerebrosides and a monoacylmonogalactosylglycerol were separated from the leaves of Clinacanthus nutans. The structures of the cerebrosides were characterized as 1-O-beta-D-glucosides of phytosphingosines, which comprised a common long-chain base, (2S,3S,4R,8Z)-2-amino-8(Z)-octadecene-1,3,4-triol with nine 2-hydroxy fatty acids of varying chain lengths (C(16), C(18), C(20-26)) linked to the amino group. The glycosylglyceride was characterized as (2S)-1-O-linolenoyl-3-O-beta-D-galactopyranosylglycerol. The structures were established on the basis of the spectroscopic data and chemical reactions.

  9. Experimental (X-ray, IR and UV-vis.) and DFT studies on cocrystallization of two tautomers of a novel Schiff base compound

    NASA Astrophysics Data System (ADS)

    Temel, Ersin; Alaşalvar, Can; Eserci, Hande; Ağar, Erbil

    2017-01-01

    In this study, the structure of 4-(((2-methyl-3-nitrophenyl)imino)methyl)benzene-1,2,3-triol was investigated with experimental (X-ray single crystal technique, UV-vis. and FT-IR spectroscopic techniques) and theoretical (DFT) methods. X-ray studies show that there are two independent molecules in asymmetric unit and coexist both keto-amin and enol-imine tautomeric forms. Theoretical studies were carried out in B3LYP with CAM-631G(d,p). The data obtained from calculation were compared with experimental data.

  10. DFT molecular modeling and NMR conformational analysis of a new longipinenetriolone diester

    NASA Astrophysics Data System (ADS)

    Cerda-García-Rojas, Carlos M.; Guerra-Ramírez, Diana; Román-Marín, Luisa U.; Hernández-Hernández, Juan D.; Joseph-Nathan, Pedro

    2006-05-01

    The structure and conformational behavior of the new natural compound (4 R,5 S,7 S,8 R,9 S,10 R,11 R)-longipin-2-en-7,8,9-triol-1-one 7-angelate-9-isovalerate (1) isolated from Stevia eupatoria, were studied by molecular modeling and NMR spectroscopy. A Monte Carlo search followed by DFT calculations at the B3LYP/6-31G* level provided the theoretical conformations of the sesquiterpene framework, which were in full agreement with results derived from the 1H- 1H coupling constant analysis.

  11. Alkaloids with antioxidant activities from Aconitum handelianum.

    PubMed

    Yin, Tian-Peng; Cai, Le; Xing, Yun; Yu, Jing; Li, Xue-Jiao; Mei, Rui-Feng; Ding, Zhong-Tao

    2016-06-01

    A new C20-diterpenoid alkaloid handelidine (1) and twenty-seven known alkaloids (2-28) were isolated from the roots of Aconitum handelianum. Their structures were established on the basis of extensive spectroscopic analyses. The study indicated that denudatine-type C20-diterpenoid alkaloids with vicinal-triol system and benzyltetrahydroisoquinoline alkaloids exhibited significant antioxidant activities measured by three antioxidant test systems. The aconitine-type C19-diterpenoid alkaloids could serve as potential secondary antioxidants for their strong binding effects to metal ions.

  12. Three novel compounds from the leaves of Smallanthus sonchifolius.

    PubMed

    Qiu, Ying-Kun; Kang, Ting-Guo; Dou, De-Qiang; Liang, Li; Dong, Feng

    2008-01-01

    Three novel compounds, together with five known ingredients, octacosanol, 3',4',5-trihydroxy-3,7-dimethoxyflavone, 3,4-dihydroxybenzaldehyde, isorhamnetin, and ent-kaurane-3beta,16beta,17-triol, were obtained from the leaves of Smallanthus sonchifolius (yacon), and their structures were elucidated as ent-kaurane-3beta,16beta,17,18-tertol (1), 3R,7E-9-butoxyl-megastigma-3-ol-3-O-beta-D-glucopyranoside (2), and 3S,5R,6Z-megastigma-6-en-3,5,8,9-tertol (3) on the basis of spectroscopic and chemical methods.

  13. Total synthesis of fostriecin: via a regio- and stereoselective polyene hydration, oxidation, and hydroboration sequence.

    PubMed

    Gao, Dong; O'Doherty, George A

    2010-09-03

    A total synthesis of the fostriecin has been achieved in 24 steps from enyne 11. The lactone moiety was installed by a Leighton allylation and Grubbs ring-closing metathesis reaction. The highly reactive Z,Z,E-triene moiety was installed via a late-stage Suzuki-Miyaura cross-coupling of a remarkably stable Z-vinyl boronate. The relative and absolute stereocenters of the C-8,9,11 triol were generated with a regio- and stereoselective asymmetric hydration/oxidation sequence.

  14. Potential anti-allergic ent-kaurene diterpenes from the bark of Suregada multiflora.

    PubMed

    Cheenpracha, Sarot; Yodsaoue, Orapun; Karalai, Chatchanok; Ponglimanont, Chanita; Subhadhirasakul, Sanan; Tewtrakul, Supinya; Kanjana-opas, Akkharawit

    2006-12-01

    Two ent-kaurene diterpenes, ent-16-kaurene-3beta,15beta,18-triol (1) and ent-3-oxo-16-kaurene-15beta,18-diol (2), were isolated from a dichloromethane extract of the bark of Suregada multiflora along with five known diterpenes:ent-16-kaurene-3beta,15beta-diol (3), abbeokutone (4), helioscopinolide A (5), helioscopinolide C (6) and helioscopinolide I (7). Their structures were elucidated on the basis of spectroscopic analysis. Compounds 1-7 possessed appreciable anti-allergic activities in RBL-2H3 cells model with IC50 values ranging from 22.5 to 42.2 microM.

  15. Both estrogen receptor alpha and estrogen receptor beta agonists enhance cell proliferation in the dentate gyrus of adult female rats.

    PubMed

    Mazzucco, C A; Lieblich, S E; Bingham, B I; Williamson, M A; Viau, V; Galea, L A M

    2006-09-15

    This study investigated the involvement of estrogen receptors alpha and beta in estradiol-induced enhancement of hippocampal neurogenesis in the adult female rat. Subtype selective estrogen receptor agonists, propyl-pyrazole triol (estrogen receptor alpha agonist) and diarylpropionitrile (estrogen receptor beta agonist) were examined for each receptor's contribution, individual and cooperative, for estradiol-enhanced hippocampal cell proliferation. Estradiol increases hippocampal cell proliferation within 4 h [Ormerod BK, Lee TT, Galea LA (2003) Estradiol initially enhances but subsequently suppresses (via adrenal steroids) granule cell proliferation in the dentate gyrus of adult female rats. J Neurobiol 55:247-260]. Therefore, animals received s.c. injections of estradiol (10 microg), propyl-pyrazole triol and diarylpropionitrile alone (1.25, 2.5, 5.0 mg/0.1 ml dimethylsulfoxide) or in combination (2.5 mg propyl-pyrazole triol+2.5 mg diarylpropionitrile/0.1 ml dimethylsulfoxide) and 4 h later received an i.p. injection of the cell synthesis marker, bromodeoxyuridine (200 mg/kg). Diarylpropionitrile enhanced cell proliferation at all three administered doses (1.25 mg, P<0.008; 2.5 mg, P<0.003; 5 mg, P<0.005), whereas propyl-pyrazole triol significantly increased cell proliferation (P<0.0002) only at the dose of 2.5 mg. Our results demonstrate both estrogen receptor alpha and estrogen receptor beta are individually involved in estradiol-enhanced cell proliferation. Furthermore both estrogen receptor alpha and estrogen receptor beta mRNA was found co-localized with Ki-67 expression in the hippocampus albeit at low levels, indicating a potential direct influence of each receptor subtype on progenitor cells and their progeny. Dual receptor activation resulted in reduced levels of cell proliferation, supporting previous studies suggesting that estrogen receptor alpha and estrogen receptor beta may modulate each other's activity. Our results also suggest that a component

  16. Qualitative and quantitative analysis of atmospheric organosulfates in Centreville, Alabama

    NASA Astrophysics Data System (ADS)

    Hettiyadura, Anusha P. S.; Jayarathne, Thilina; Baumann, Karsten; Goldstein, Allen H.; de Gouw, Joost A.; Koss, Abigail; Keutsch, Frank N.; Skog, Kate; Stone, Elizabeth A.

    2017-01-01

    Organosulfates are components of secondary organic aerosols (SOA) that form from oxidation of volatile organic compounds (VOCs) in the presence of sulfate. In this study, the composition and abundance of organosulfates were determined in fine particulate matter (PM2.5) collected from Centreville, AL, during the Southern Oxidant and Aerosol Study (SOAS) in summer 2013. Six organosulfates were quantified using hydrophilic interaction liquid chromatography (HILIC) with triple quadrupole mass spectrometry (TQD) against authentic standards. Among these, the three most abundant species were glycolic acid sulfate (0.5-52.5 ng m-3), lactic acid sulfate (0.5-36.7 ng m-3), and hydroxyacetone sulfate (0.5-14.3 ng m-3). These three species were strongly inter-correlated, suggesting similar precursors and/or formation pathways. Further correlations with sulfate, isoprene, and isoprene oxidation products indicate important roles for these precursors in organosulfate formation in Centreville. Positive filter sampling artifacts associated with these organosulfates due to gas adsorption or reaction of gas phase precursors of organosulfates with sulfuric acid were assessed for a subset of samples and were less than 7.8 % of their PM2.5 concentrations. Together, the quantified organosulfates accounted for < 0.3 % of organic carbon mass in PM2.5. To gain insights into other organosulfates in PM2.5 collected from Centreville, semi-quantitative analysis was employed by way of monitoring characteristic product ions of organosulfates (HSO4- at m/z 97 and SO4- ṡ at m/z 96) and evaluating relative signal strength by HILIC-TQD. Molecular formulas of organosulfates were determined by high-resolution time-of-flight (TOF) mass spectrometry. The major organosulfate signal across all samples corresponded to 2-methyltetrol sulfates, which accounted for 42-62 % of the total bisulfate ion signal. Conversely, glycolic acid sulfate, the most abundant organosulfate quantified in this study, was 0

  17. Synthesis and characterization of biodegradable polyurethane films based on HDI with hydrolyzable crosslinked bonds and a homogeneous structure for biomedical applications.

    PubMed

    Barrioni, Breno Rocha; de Carvalho, Sandhra Maria; Oréfice, Rodrigo Lambert; de Oliveira, Agda Aline Rocha; Pereira, Marivalda de Magalhães

    2015-01-01

    Synthetic biodegradable polymers are considered strategic in the biomaterials field and are used in various applications. Among the polymers used as biomaterials, polyurethanes (PUs) feature prominently due to their versatility and the ability to obtain products with a wide range of physical and mechanical properties. In this work, new biodegradable polyurethane films were developed based on hexamethylene diisocyanate (HDI) and glycerol as the hard segment (HS), and poly(caprolactone) triol (PCL triol) and low-molecular-weight poly(ethylene glycol) PEG as the soft segment (SS) without the use of a catalyst. The films obtained were characterized by structural, mechanical and biological testing. A highly connected network with a homogeneous PU structure was obtained due to crosslinked bonds. The films showed amorphous structures, high water uptake, hydrogel behavior, and susceptibility to hydrolytic degradation. Mechanical tests indicated that the films reached a high deformation at break of up to 425.4%, an elastic modulus of 1.6 MPa and a tensile strength of 3.6 MPa. The materials presented a moderate toxic effect on MTT assay and can be considered potential materials for biomedical applications.

  18. Poly(meth)acrylates obtained by cascade reaction.

    PubMed

    Popescu, Dragos; Keul, Helmut; Moeller, Martin

    2011-04-04

    Preparation, purification, and stabilization of functional (meth)acrylates with a high dipole moment are complex, laborious, and expensive processes. In order to avoid purification and stabilization of the highly reactive functional monomers, a concept of cascade reactions was developed comprising enzymatic monomer synthesis and radical polymerization. Transacylation of methyl acrylate (MA) and methyl methacrylate (MMA) with different functional alcohols, diols, and triols (1,2,6-hexanetriol and glycerol) in the presence of Novozyme 435 led to functional (meth)acrylates. After the removal of the enzyme by means of filtration, removal of excess (meth)acrylate and/or addition of a new monomer, e.g., 2-hydroxyethyl (meth)acrylate the (co)polymerization via free radical (FRP) or nitroxide mediated radical polymerization (NMP) resulted in poly[(meth)acrylate]s with predefined functionalities. Hydrophilic, hydrophobic as well as ionic repeating units were assembled within the copolymer. The transacylation of MA and MMA with diols and triols carried out under mild conditions is an easy and rapid process and is suitable for the preparation of sensitive monomers.

  19. Two new steroidal saponins from Selaginella uncinata (Desv.) Spring and their protective effect against anoxia.

    PubMed

    Zheng, Junxia; Zheng, Yang; Zhi, Hui; Dai, Yi; Wang, Naili; Wu, Liying; Fan, Ming; Fang, Yanxiong; Zhao, Suqing; Zhang, Kun

    2013-07-01

    Four steroidal saponins were isolated from the anti-anoxic fraction of the 60% EtOH extract of Selaginella uncinata, including two new compounds, (3β, 7β, 12β, 25R)-spirost-5-ene-3, 7, 12-triol-3-O-α-L-rhamnopyranosyl-(1→2)-O-[α-L-rhamnopyranosyl-(1→4)]-O-β-D-glucopyranoside (1), (2α, 3β, 12β, 25R)-spirost-5-ene-2, 3, 12-triol-3-O-α-L-rhamnopyranosyl-(1→2)-O-[α-L-rhamnopyranosyl-(1→4)]-O-β-D-glucopyranoside (2) and two known compounds, (3β, 12β, 25R)-spirost-5-ene-3,12-diol-3-O-α-L-rhamnopyranosyl-(1→2)-O-[α-L-rhamnopyranosyl-(1→4)]-O-β-D-glucopyranoside, (3), (1α, 3β, 25R)-spirost-5-ene-2-diol-3-O-α-L-rhamnopyranosyl-(1→2)-O-[α-L-rhamnopyranosyl(1→4)]-O-β-D-glucopyranoside (4). The four compounds showed potent protective effect against anoxia in the anoxic PC12 cells assay, among which compounds 1 and 2 were the most active. To our knowledge, this is the first study to report the steroidal saponins in the plant S. uncinata and demonstrate their protective effect against anoxia in PC12 cell assay.

  20. Levels of phytosterol oxides in enriched and nonenriched spreads: application of a thin-layer chromatography-gas chromatography methodology.

    PubMed

    Conchillo, Ana; Cercaci, Luisito; Ansorena, Diana; Rodriguez-Estrada, Maria Teresa; Lercker, Giovanni; Astiasarán, Iciar

    2005-10-05

    The content of phytosterol oxidation products (POPs) in enriched and nonenriched commercial spreads was evaluated by thin-layer chromatography-gas chromatography (TLC-GC). Oxides of beta-sitosterol, campesterol, and stigmasterol were produced by thermo-oxidation (7-hydroxy, 7-keto, and epoxy derivatives) and chemical synthesis (triol derivatives), which were then separated and identified by TLC-GC. Their identification was further confirmed by GC-mass spectrometry (GC-MS). The total amounts of phytosterols found were 6.07 and 0.33 g/100 g of sample in phytosterol-enriched and nonenriched spread, respectively, whereas the total POPs contents were 45.60 and 13.31 mg/kg of sample in the enriched and nonenriched products. The main POPs found were the 7-keto derivatives of all phytosterols analyzed; 7-ketositosterol was the most abundant one (14.96 and 5.93 mg/kg of sample in phytosterol-enriched and nonenriched spread). No beta-epoxy and triol derivatives were detected in both types of samples. The enriched spread presented a lower phytosterol oxidation rate (0.07%) than the nonenriched one (0.41%).

  1. A new SPE/GC-fid method for the determination of cholesterol oxidation products. Application to subcutaneous fat from Iberian dry-cured ham.

    PubMed

    Narváez-Rivas, Mónica; Pham, Alessandra J; Schilling, M Wes; León-Camacho, Manuel

    2014-05-01

    A new method for the isolation and analysis of cholesterol oxidation products (COPs) using solid phase extraction (SPE) and silica columns was developed using gas chromatography-flame ion detection (GC-FID). The method comprises of saponification and liquid-liquid extraction of the unsaponifiable fraction prior to the isolation and derivatization of the COPs to trimethylsilyl ethers. The COPs used in this study are cholestane-5α-6α-epoxide, cholestane-3β-5α-6β-triol, 25-hydroxycholesterol and 5-cholesten-3β-ol-7-one. In order to identify the COPs fraction a GC-ion-trap-mass spectrometry experiment were conducted using authentic standards to verify the presence of the COPs. The method was effective at rapidly separating the COPs (25 min run). Calibration curves were linear with the LODs and LOQs bellow 0.03 and 0.07 mgkg(-1) for all cases, respectively. This methodology gave a total recovery for every compound that was used in the study. Betulin was used as an internal standard to monitor the recovery. The method was validated with a standard mixture of COPs. The method has been applied to characterize the COP fraction of subcutaneous fat from Iberian dry-cured ham. Cholestane-5α-6α-epoxide, cholestane-3β-5α-6β-triol, 25-hydroxycholesterol and 5-cholesten-3β-ol-7-one have been identified for the first time in these samples.

  2. New lanostanes and naphthoquinones isolated from Antrodia salmonea and their antioxidative burst activity in human leukocytes.

    PubMed

    Shen, Chien-Chang; Shen, Yuh-Chiang; Wang, Yea-Hwey; Lin, Lie-Chwen; Don, Ming-Jaw; Liou, Kuo-Tong; Wang, Wen-Yen; Hou, Yu-Chang; Chang, Tun-Tschu

    2006-02-01

    Four new compounds were isolated from the basidiomata of the fungus Antrodia salmonea, a newly identified species of Antrodia (Aphyllophorales) in Taiwan. These new compounds are named as lanosta-8,24-diene-3beta,15alpha,21-triol (1), 24-methylenelanost-8-ene-3beta,15alpha,21-triol (2), 2,3-dimethoxy-5-(2',5'-dimethoxy-3',4'-methylenedioxyphenyl)-7-methyl-[1,4]-naphthoquinone (3), and 2,3-dimethoxy-6-(2',5'-dimethoxy-3',4'-methylenedioxyphenyl)-7-methyl-[1,4]-naphthoquinone (4), respectively. Their structures were elucidated by spectroscopic methods. An in vitro cellular functional assay was performed to evaluate their anti-oxidative burst activity in human leukocytes. They showed inhibitory effects against phorbol 12-myristate-13-acetate (PMA), a direct protein kinase C activator, induced oxidative burst in neutrophils (PMN) and mononuclear cells (MNC) with 50 % inhibitory concentration (IC(50)) ranging from 3.5 to 25.8 microM. The potency order of these compounds in PMA-activated leukocytes was as 1 > 3 > 4 > 2. They were relatively less effective in formyl-Met-Leu-Phe (fMLP), a G-protein coupled receptor agonist, induced oxidative burst, except for compounds 3 and 4 in fMLP-activated PMN. These results indicated that three (1, 3, and 4) of these four newly identified compounds displayed anti-oxidative effect in human leukocytes with different potency and might confer anti-inflammatory activity to these drugs.

  3. The ERα-PI3K Cascade in Proopiomelanocortin Progenitor Neurons Regulates Feeding and Glucose Balance in Female Mice.

    PubMed

    Zhu, Liangru; Xu, Pingwen; Cao, Xuehong; Yang, Yongjie; Hinton, Antentor Othrell; Xia, Yan; Saito, Kenji; Yan, Xiaofeng; Zou, Fang; Ding, Hongfang; Wang, Chunmei; Yan, Chunling; Saha, Pradip; Khan, Sohaib A; Zhao, Jean; Fukuda, Makoto; Tong, Qingchun; Clegg, Deborah J; Chan, Lawrence; Xu, Yong

    2015-12-01

    Estrogens act upon estrogen receptor (ER)α to inhibit feeding and improve glucose homeostasis in female animals. However, the intracellular signals that mediate these estrogenic actions remain unknown. Here, we report that anorexigenic effects of estrogens are blunted in female mice that lack ERα specifically in proopiomelanocortin (POMC) progenitor neurons. These mutant mice also develop insulin resistance and are insensitive to the glucose-regulatory effects of estrogens. Moreover, we showed that propyl pyrazole triol (an ERα agonist) stimulates the phosphatidyl inositol 3-kinase (PI3K) pathway specifically in POMC progenitor neurons, and that blockade of PI3K attenuates propyl pyrazole triol-induced activation of POMC neurons. Finally, we show that effects of estrogens to inhibit food intake and to improve insulin sensitivity are significantly attenuated in female mice with PI3K genetically inhibited in POMC progenitor neurons. Together, our results indicate that an ERα-PI3K cascade in POMC progenitor neurons mediates estrogenic actions to suppress food intake and improve insulin sensitivity.

  4. Sphingosines Derived from Marine Sponge as Potential Multi-Target Drug Related to Disorders in Cancer Development

    PubMed Central

    Biegelmeyer, Renata; Schröder, Rafael; Rambo, Douglas F.; Dresch, Roger R.; Carraro, João L. F.; Mothes, Beatriz; Moreira, José Cláudio F.; da Frota Junior, Mário L. C.; Henriques, Amélia T.

    2015-01-01

    Haliclona tubifera, marine sponge species abundant in Brazilian coastline, presents only a few papers published in the literature. Recently, we have reported the isolation of two modified C18 sphingoid bases: (2R,3R,6R,7Z)-2-aminooctadec-7-ene-1,3,6-triol and and (2R,3R,6R)-2-aminooctadec-1,3,6-triol. In order to continue our research, in this work aimed at the biological investigation of fractions that led to the isolation of these compounds. We evaluated the cytotoxic effect of marine sponge H. tubifera fractions in glioma (U87) and neuroblastoma (SH-SY5Y) human cell lines. In addition, considering the link between cancer, imbalance of reactive oxygen species and coagulation disorders, we also investigated the in vitro effects on blood coagulation and their redox properties. We showed that the ethyl acetate (EtOAc) fraction, rich in sphingoid bases, had important cytotoxic effects in both cancer cell lines with an IC50 < 15 μg/mL and also can inhibit the production of peroxyl radicals. Interestingly, this fraction increased the recalcification time of human blood, showing anticoagulant properties. The present study indicates the sphingosines fraction as a promising source of chemical prototypes, especially multifunctional drugs in cancer therapy. PMID:26308014

  5. The ERα-PI3K Cascade in Proopiomelanocortin Progenitor Neurons Regulates Feeding and Glucose Balance in Female Mice

    PubMed Central

    Zhu, Liangru; Xu, Pingwen; Cao, Xuehong; Yang, Yongjie; Hinton, Antentor Othrell; Xia, Yan; Saito, Kenji; Yan, Xiaofeng; Zou, Fang; Ding, Hongfang; Wang, Chunmei; Yan, Chunling; Saha, Pradip; Khan, Sohaib A.; Zhao, Jean; Fukuda, Makoto; Tong, Qingchun; Clegg, Deborah J.; Chan, Lawrence

    2015-01-01

    Estrogens act upon estrogen receptor (ER)α to inhibit feeding and improve glucose homeostasis in female animals. However, the intracellular signals that mediate these estrogenic actions remain unknown. Here, we report that anorexigenic effects of estrogens are blunted in female mice that lack ERα specifically in proopiomelanocortin (POMC) progenitor neurons. These mutant mice also develop insulin resistance and are insensitive to the glucose-regulatory effects of estrogens. Moreover, we showed that propyl pyrazole triol (an ERα agonist) stimulates the phosphatidyl inositol 3-kinase (PI3K) pathway specifically in POMC progenitor neurons, and that blockade of PI3K attenuates propyl pyrazole triol-induced activation of POMC neurons. Finally, we show that effects of estrogens to inhibit food intake and to improve insulin sensitivity are significantly attenuated in female mice with PI3K genetically inhibited in POMC progenitor neurons. Together, our results indicate that an ERα-PI3K cascade in POMC progenitor neurons mediates estrogenic actions to suppress food intake and improve insulin sensitivity. PMID:26375425

  6. Green engineering: Green composite material, biodiesel from waste coffee grounds, and polyurethane bio-foam

    NASA Astrophysics Data System (ADS)

    Cheng, Hsiang-Fu

    In this thesis we developed several ways of producing green materials and energy resources. First, we developed a method to fabricate natural fibers composites, with the purpose to develop green textile/woven composites that could potentially serve as an alternative to materials derived from non-renewable sources. Flax and hemp fabrics were chosen because of their lightweight and exceptional mechanical properties. To make these textile/woven composites withstand moist environments, a commercially available marine resin was utilized as a matrix. The tensile, three-point bending, and edgewise compression strengths of these green textile/woven composites were measured using ASTM protocols. Secondly, we developed a chemical procedure to obtain oil from waste coffee grounds; we did leaching and liquid extractions to get liquid oil from the solid coffee. This coffee oil was used to produce bio-diesel that could be used as a substitute for petroleum-based diesel. Finally, polyurethane Bio-foam formation utilized glycerol that is the by-product from the biodiesel synthesis. A chemical synthesis procedure from the literature was used as the reference system: a triol and isocynate are mixed to produce polyurethane foam. Moreover, we use a similar triol, a by-product from bio-diesel synthesis, to reproduce polyurethane foam.

  7. Key Phytochemicals Contributing to the Bitter Off-Taste of Oat (Avena sativa L.).

    PubMed

    Günther-Jordanland, Kirsten; Dawid, Corinna; Dietz, Maximilian; Hofmann, Thomas

    2016-12-28

    Sensory-directed fractionation of extracts prepared from oat flour (Avena sativa L.) followed by LC-TOF-MS, LC-MS/MS, and 1D/2D-NMR experiments revealed avenanthramides and saponins as the key phytochemicals contributing to the typical astringent and bitter off-taste of oat. Besides avenacosides A and B, two previously unreported bitter-tasting bidesmosidic saponins were identified, namely, 3-(O-α-l-rhamnopyranosyl(1→2)-[β-d-glucopyranosyl(1→3)-β-d-glucopyranosyl(1→4)]-β-d-glucopyranosid)-26-O-β-d-glucopyranosyl-(25R)-furost-5-ene-3β,22,26-triol, and 3-(O-α-l-rhamnopyranosyl(1→2)-[β-d-glucopyranosyl(1→4)]-β-d-glucopyranosid)-26-O-β-d-glucopyranosyl-(25R)-furost-5-ene-3β,22,26-triol. Depending on the chemical structure of the saponins and avenanthramides, sensory studies revealed human orosensory recognition thresholds of these phytochemicals to range between 3 and 170 μmol/L.

  8. New furostanol saponins from Smilax aspera L. and their in vitro cytotoxicity.

    PubMed

    Ivanova, Antoaneta; Mikhova, Bozhanka; Batsalova, Tsvetelina; Dzhambazov, Balik; Kostova, Ivanka

    2011-03-01

    The occurrence of the two new cis-fused A/B rings furostanol saponins (25S)-26-O-β-D-glucopyranosyl-5β-furostan-1β,3β,22α,26-tetraol-1-O-β-D-glucopyranoside and (25S)-26-O-β-D-glucopyranosyl-5β-furostan-1β,2β,3β,5β,22α,26-hexaol and the known compounds (25S)-26-O-β-D-glucopyranosyl-5β-furostan-3β,22α,26-triol-3-O-α-L-rhamnopyranosyl-(1 → 2)-O-β-D-glucopyranosyl-(1 → 2)-O-β-D-glucopyranoside and (25S)-26-O-β-D-glucopyranosyl-5β-furostan-3β,22α,26-triol-3-O-β-D-glucopyranosyl-(1 → 2)-O-β-D-glucopyranoside, trans-resveratrol, (+) catechin and (-) epicatechin in the rhizomes of Smilax aspera is reported. All saponins have been isolated as their 22-OMe derivatives, which were further subjected to extensive spectroscopic analysis. The isolated furostanol saponins were evaluated for cytotoxic activity against human normal amniotic and human lung carcinoma cell lines using neutral red and MTT assays. In vitro experiments showed significant cytotoxicity in a dose dependent manner with IC(50) values in the range of 32.98-94.53 µM.

  9. Chemosystematic investigations of irregular diterpenes in Anisotome and related New Zealand Apiaceae.

    PubMed

    Zidorn, Christian; Sturm, Sonja; Dawson, John W; van Klink, John W; Stuppner, Hermann; Perry, Nigel B

    2002-02-01

    A chemosystematic HPLC-UV and HPLC-MS investigation of New Zealand members of the Apiaceae was performed. Diterpenes were identified and quantified in methanolic extracts from subaerial parts of 28 taxa and 54 samples of Aciphylla, Anisotome, Apium, Gingidia, Lignocarpa, Oreomyrrhis, and Scandia. Six diterpenes (1-2, 4-7) and four polyacetylenes (8-11) were identified. The known compounds were the diterpenes anisotomenoic acid 1, anisotomene-1-ol 2, 16-acetoxyanisotomenoic acid 4 and anisotomene-1,12-diol 5; and the polyacetylenes falcarinol 8, falcarindiol 9, (+)-9(Z),17-octadecadiene-12,14-diyne-1,11,16-triol 10, and (+)-9(Z),17-octadecadiene-12,14-diyne-1,11,16-triol 1-acetate 11. New irregular diterpenes 13,14-dihydroanisotom-12E-ene-1,14-diol 6 and 14-methoxy-13,14-dihydroanisotom-12E-ene-1-ol 7 were isolated from A. haastii. Isomers of the new semi-synthetic diterpene 16-hydroxyanisotomenoic acid 3 were detected in extracts of Anisitone flexuosa. Structure elucidation was performed by HR mass spectrometry and 1D and 2D NMR spectroscopy. In crude extracts, compounds were identified by their HPLC retention times and their on-line HPLC-UV and MS spectra. Anisotomene diterpenes occurred in eight out of 16 species of the genus Anisotome, but were not detected in any of the other genera. In contrast, polyacetylenes were present in all the genera investigated.

  10. Synthesis of four carbon-13-labeled type a trichothecene mycotoxins and their application as internal standards in stable isotope dilution assays.

    PubMed

    Asam, Stefan; Rychlik, Michael

    2006-09-06

    The first stable isotope dilution assay (SIDA) for the simultaneous quantitation of the most abundant type A trichothecenes in foods and feeds was developed. Synthesis of carbon-13-labeled T2-toxin, HT2-toxin, diacetoxyscirpenol, and monoacetoxyscirpenol was accomplished by [13C2]-acetylation of T2-triol and scirpentriol, respectively. Scirpentriol was prepared from diacetoxyscirpenol by complete alkaline hydrolysis and subsequently was converted to [13C6]-triacetoxyscirpentriol by peracetylation with [13C4]-acetic anhydride. The latter compound was selectively hydrolyzed using ammonium hydroxide to give [13C4]-diacetoxyscirpenol and [13C2]-monoacetoxyscirpenol in reasonable yields. Analogously, [13C6]-T2-triacetate was prepared from T2-triol and subjected to controlled hydrolysis to yield [13C4]-T2-toxin and [13C2]-HT2-toxin. All synthesized products were characterized by NMR and MS experiments. Using the prepared isotopically labeled standards, SIDAs were developed for the quantitation of type A trichothecenes in food and feeds. The mycotoxins were quantified by LC-single and tandem MS after cleanup on multifunctional columns. The method revealed good sensitivity with low detection and quantification limits along with excellent recovery and good precision in interassay studies. Food samples were analyzed using the developed SIDA and showed substantial contamination of oat products with T2-toxin and HT2-toxin. Diacetoxyscirpenol was detected on potatoes, whereas monoacetoxyscirpenol was not present in the analyzed samples.

  11. Metabolic studies of formestane in horses.

    PubMed

    Leung, Gary N W; Kwok, W H; Wan, Terence S M; Lam, Kenneth K H; Schiff, Peter J

    2013-06-01

    Formestane (4-hydroxyandrost-4-ene-3,17-dione) is an irreversible steroidal aromatase inhibitor with reported abuse in human sports. In 2011, our laboratory identified the presence of formestane in a horse urine sample from an overseas jurisdiction. This was the first reported case of formestane in a racehorse. The metabolism of formestane in humans has been reported previously; however, little is known about its metabolic fate in horses. This paper describes the in vitro and in vivo metabolic studies of formestane in horses, with the objective of identifying the target metabolite with the longest detection time for controlling formestane abuse. In vitro metabolic studies of formestane were performed using homogenized horse liver. Seven in vitro metabolites, namely 4-hydroxytestosterone (M1), 3β,4α-dihydroxy-5β-androstan-17-one (M2a), 3β,4β-dihydroxy-5β-androstan-17-one (M2b), 3β,4α-dihydroxy-5α-androstan-17-one (M2c), androst-4-ene-3α,4,17β-triol (M3a), androst-4-ene-3β,4,17β-triol (M3b), and 5β-androstane-3β,4β,17β-triol (M4) were identified. For the in vivo studies, two thoroughbred geldings were each administered with 800 mg of formestane (32 capsules of Formadex) by stomach tubing. The results revealed that the parent drug and seven metabolites were detected in post-administration urine. The six in vitro metabolites (M1, M2a, M2b, M2c, M3a, and M3b) identified earlier were all detected in post-administration urine samples. In addition, 3α,4α-dihydroxy-5α-androstan-17-one (M2d), a stereoisomer of M2a/M2b/M2c, was also identified. This study has shown that the detection of formestane administration would be best achieved by monitoring 4-hydroxytestosterone (M1) in the glucuronide-conjugated fraction. M1 could be detected for up to 34 h post-administration. In blood samples, the parent drug could be detected for up to 34 h post administration.

  12. The Metabolic Fate of Tritium-Labeled T-2 Toxin, a Trichothecene Mycotoxin, in Swine.

    NASA Astrophysics Data System (ADS)

    Corley, Richard Allen

    The metabolic fate of T-2 toxin was determined in two female crossbred swine following the intravascular administration of one millicurie of tritium-labeled T-2 toxin at a nonlethal dose of 0.15 mg/kg body weight. The plasma elimination phase half-life was 90 minutes for total tritium residues. A total of 13.1 and 1.3 percent of the administered dose was found in the gall bladders in addition to 17.9 and 42.5 percent in the urine of the two pigs, S1 and S2, respectively, 4 hours after dosing. Free metabolites, identified by thin-layer chromatography, represented less than 20 and 30 percent of the metabolite residues in bile and urine, respectively, with the parent compound, T-2 toxin, never exceeding 0.25 percent. The major free metabolites were 3'-OH HT-2 and T-2 triol. Glucuronide conjugates represented 63 and 77 percent of the metabolite residues in urine and bile, respectively. The major conjugated metabolites were glucuronides of HT-2, 3'-OH T-2, 3'-OH HT-2 and T-2 toxin. Neosolaniol, 4-deacetyl-neosolaniol and T-2 tetraol were also identified in addition to 3 unknown metabolites. In the tissues, the greatest amount of radioactivity was located in the gastrointestinal tract (15.5 and 24.1 percent of the dose for the 2 pigs, S1 and S2, respectively). The remaining tissues sampled accounted for approximately 5 percent of the dose for the 2 pigs. Twenty-one metabolites were identified in tissues following reverse phase HPLC radiochromatography. Approximately 55 percent of the extractable radioactivity in the tissues, including the gastrointestinal tract, of both pigs corresponded to T-2 toxin, HT-2, deepoxy HT-2, T-2 triol, deepoxy T-2 triol, 3'-OH T-2, 3'-OH HT -2, T-2 tetraol and deepoxy T-2 tetraol. The major metabolite in tissues, PM-XV, did not correspond to any standard and represented an additional 27 percent of the extractable radioactivity.

  13. Comparative studies on performance of CCC and preparative RP-HPLC in separation and purification of steroid saponins from Dioscorea zingiberensis C.H.Wright.

    PubMed

    Zhang, Xinxin; Liang, Jinru; Zhang, Yongmin; Liu, Jianli; Sun, Wenji; Ito, Yoichiro

    2015-03-01

    Steroid saponins from Dioscorea zingiberensis C.H.Wright were separated for the first time using two chromatographic methods for comparison: counter-current chromatography (CCC) coupled with evaporative light scattering detector (ELSD) and preparative reversed phase high-performance liquid chromatography (RP-HPLC) with an ultraviolet detector. Ethyl acetate-n-butanol-methanol-water (4:1:2:4, v/v) was chosen as the two-phase solvent system for CCC, while the acetonitrile-water (25:75 for the first step and15:85 for the second step, v/v) was used as the mobile phase in the preparative RP-HPLC. The following five steroid saponins were purified by theses two chromatographic methods, in one-step operation by CCC and by two-step operation in preparative RP-HPLC: 1) 26-O-β-D- glucopyranosyl-(25R)-furost-5-en-3β, 22ζ, 26-triol-3-O-[β-D-glucopyranosyl-(1→3)-β-D-glucopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)]-β-D-glucopyranoside (compound A), 2) 26-O-β-D-glucopyranosyl-(25R)-furost-5-en-3β, 22ζ, 4) 26-triol-3-O-[β-D-glucopyranosyl-(1→3)-α-L-rhamnopyranosyl-(1→2)]-β-D-glucopyranoside (compound B), 3) 26-O-β-D-glucopyranosyl-(25R)-furost-5-en-3β, 22ζ, 26-triol-3-O-[α-L-rhamnopyranosyl-(1→4)]-β-D-glucopyranoside (compound C), 4) 26-O-β-D-glucopyranosyl-(25R)-furost-5, 20(22)-diene-3β, 26-diol-3-O-{α-L-rhamnopyranosyl-(1→4)-[β-D-glucopyranosyl-(1→3)-β-D-glucopyranosyl-(1→2)]}-β-D-glucopyranoside (compound D) and 5) 26-O-β-D-glucopyranosyl-(25R)-furost-5, 20(22)-diene-3β, 26-diol-3-O-[β-D-glucopyranosyl-(1→4)-α-L-rhamnopyranosy-(1→2)]-β-D-glucopyranoside (compound E). The purities of these five steroid saponins separated by both methods were over 95%, and structural identification of these compounds was performed by ESI-MS, and (13)C NMR. Comparison of these two established approaches revealed that CCC required a longer separation time but with less solvent consumption, whereas preparative RP-HPLC gave a shorter separation time

  14. Metabolism of 4-hydroxyandrostenedione and 4-hydroxytestosterone: Mass spectrometric identification of urinary metabolites.

    PubMed

    Kohler, Maxie; Parr, Maria K; Opfermann, Georg; Thevis, Mario; Schlörer, Nils; Marner, Franz-Josef; Schänzer, Wilhelm

    2007-03-01

    4-Hydroxyandrost-4-ene-3,17-dione is a second generation, irreversible aromatase inhibitor and commonly used as anti breast cancer medication for postmenopausal women. 4-Hydroxytestosterone is advertised as anabolic steroid and does not have any therapeutic indication. Both substances are prohibited in sports by the World Anti-Doping Agency, and, due to a considerable increase of structurally related steroids with anabolic effects offered via the internet, the metabolism of two representative candidates was investigated. Excretion studies were conducted with oral applications of 100mg of 4-hydroxyandrostenedione or 200mg of 4-hydroxytestosterone to healthy male volunteers. Urine samples were analyzed for metabolic products using conventional gas chromatography-mass spectrometry approaches, and the identification of urinary metabolites was based on reference substances, which were synthesized and structurally characterized by nuclear magnetic resonance spectroscopy and high resolution/high accuracy mass spectrometry. Identified phase-I as well as phase-II metabolites were identical for both substances. Regarding phase-I metabolism 4-hydroxyandrostenedione (1) and its reduction products 3beta-hydroxy-5alpha-androstane-4,17-dione (2) and 3alpha-hydroxy-5beta-androstane-4,17-dione (3) were detected. Further reductive conversion led to all possible isomers of 3xi,4xi-dihydroxy-5xi-androstan-17-one (4, 6-11) except 3alpha,4alpha-dihydroxy-5beta-androstan-17-one (5). Out of the 17beta-hydroxylated analogs 4-hydroxytestosterone (18), 3beta,17beta-dihydroxy-5alpha-androstan-4-one (19), 3alpha,17beta-dihydroxy-5beta-androstan-4-one (20), 5alpha-androstane-3beta,4beta,17beta-triol (21), 5alpha-androstane-3alpha,4beta,17beta-triol (26) and 5alpha-androstane-3alpha,4alpha,17beta-triol (28) were identified in the post administration urine specimens. Furthermore 4-hydroxyandrosta-4,6-diene-3,17-dione (29) and 4-hydroxyandrosta-1,4-diene-3,17-dione (30) were determined as

  15. Steroids from the leaves of Chinese Melia azedarach and their cytotoxic effects on human cancer cell lines.

    PubMed

    Wu, Shi-Biao; Ji, Yan-Ping; Zhu, Jing-Jing; Zhao, Yun; Xia, Gang; Hu, Ying-He; Hu, Jin-Feng

    2009-09-01

    Three new (1-3) and several known (4-6) steroids were isolated from the leaves of Chinese Melia azedarach. The structures of the new compounds were elucidated by means of spectroscopic methods including 2D NMR techniques and mass spectrometry to be (20S)-5,24(28)-ergostadiene-3beta,7alpha,16beta,20-tetrol (1), (20S)-5-ergostene-3beta,7alpha,16beta,20-tetrol (2), and 2alpha,3beta-dihydro-5-pregnen-16-one (3). The cytotoxicities of the isolated compounds against three human cancer cell lines (A549, H460, U251) were evaluated; only compounds 1, 2, and (20S)-5-stigmastene-3beta,7alpha,20-triol (4) were found to show significant cyctotoxic effects with IC(50)s from 12.0 to 30.1 microg/mL.

  16. Defective peroxisomal cleavage of the C27-steroid side chain in the cerebro-hepato-renal syndrome of Zellweger.

    PubMed Central

    Kase, B F; Björkhem, I; Hågå, P; Pedersen, J I

    1985-01-01

    Based on in vitro work with rat liver, we recently suggested that the peroxisomal fraction is most important for the oxidation of 3 alpha, 7 alpha, 12 alpha-trihydroxy-5 beta-cholestanoic acid (THCA) into cholic acid. The cerebro-hepato-renal syndrome of Zellweger is a fatal recessive autosomal disorder, the most characteristic histological feature of which is a virtual absence of peroxisomes in liver and kidneys. This disease offers a unique opportunity to evaluate the relative importance of peroxisomes in bile acid biosynthesis. A child with Zellweger syndrome was studied in the present work. In accordance with previous work, there was a considerable accumulation of THCA, 3 alpha, 7 alpha, 12 alpha, 24-tetrahydroxy-5 beta-cholestanoic acid (24-OH-THCA), 3 alpha, 7 alpha, 12 alpha-trihydroxy-27-carboxymethyl-5 beta-cholestan-26-oic acid (C29-dicarboxylic acid), and 3 alpha, 7 alpha-dihydroxy-5 beta-cholestanoic acid in serum. In addition, a tetrahydroxylated 5 beta-cholestanoic acid with all the hydroxyl groups in the steroid nucleus was found. 3H-Labeled 5 beta-cholestane-3 alpha, 7 alpha, 12 alpha-triol was administered intravenously together with 14C-labeled cholic acid. There was a rapid incorporation of 3H in THCA and a slow incorporation into cholic acid. The specific radioactivity of 3H in THCA was about one magnitude higher than that in cholic acid. The conversion was evaluated by following the increasing ratio between 3H and 14C in biliary cholic acid. The rate of incorporation of 3H in cholic acid was considerably less than previously reported in experiments with healthy subjects, and the maximal conversion of the triol into cholic acid was only 15-20%. About the same rate of conversion was found after oral administration of 3H-THCA. Both in the experiment with 3H-5 beta-cholestane-3 alpha, 7 alpha, 12 alpha-triol and with 3H-THCA, there was an efficient incorporation of 3H in the above unidentified tetrahydroxylated 5 beta-cholestanoic acid. There was

  17. Cholesterol Analogs with Degradation-resistant Alkyl Side Chains Are Effective Mycobacterium tuberculosis Growth Inhibitors.

    PubMed

    Frank, Daniel J; Zhao, Yan; Wong, Siew Hoon; Basudhar, Debashree; De Voss, James J; Ortiz de Montellano, Paul R

    2016-04-01

    Cholest-4-en-3-one, whether added exogenously or generated intracellularly from cholesterol, inhibits the growth ofMycobacterium tuberculosiswhen CYP125A1 and CYP142A1, the cytochrome P450 enzymes that initiate degradation of the sterol side chain, are disabled. Here we demonstrate that a 16-hydroxy derivative of cholesterol, which was previously reported to inhibit growth ofM. tuberculosis, acts by preventing the oxidation of the sterol side chain even in the presence of the relevant cytochrome P450 enzymes. The finding that (25R)-cholest-5-en-3β,16β,26-triol (1) (and its 3-keto metabolite) inhibit growth suggests that cholesterol analogs with non-degradable side chains represent a novel class of anti-mycobacterial agents. In accord with this, two cholesterol analogs with truncated, fluorinated side chains have been synthesized and shown to similarly block the growth in culture ofM. tuberculosis.

  18. Cholesterol Analogs with Degradation-resistant Alkyl Side Chains Are Effective Mycobacterium tuberculosis Growth Inhibitors*

    PubMed Central

    Frank, Daniel J.; Zhao, Yan; Wong, Siew Hoon; Basudhar, Debashree; De Voss, James J.; Ortiz de Montellano, Paul R.

    2016-01-01

    Cholest-4-en-3-one, whether added exogenously or generated intracellularly from cholesterol, inhibits the growth of Mycobacterium tuberculosis when CYP125A1 and CYP142A1, the cytochrome P450 enzymes that initiate degradation of the sterol side chain, are disabled. Here we demonstrate that a 16-hydroxy derivative of cholesterol, which was previously reported to inhibit growth of M. tuberculosis, acts by preventing the oxidation of the sterol side chain even in the presence of the relevant cytochrome P450 enzymes. The finding that (25R)-cholest-5-en-3β,16β,26-triol (1) (and its 3-keto metabolite) inhibit growth suggests that cholesterol analogs with non-degradable side chains represent a novel class of anti-mycobacterial agents. In accord with this, two cholesterol analogs with truncated, fluorinated side chains have been synthesized and shown to similarly block the growth in culture of M. tuberculosis. PMID:26833565

  19. Highly diastereoselective and stereodivergent dihydroxylations of acyclic allylic amines: application to the asymmetric synthesis of 3,6-dideoxy-3-amino-L-talose.

    PubMed

    Csatayová, Kristína; Davies, Stephen G; Lee, James A; Roberts, Paul M; Russell, Angela J; Thomson, James E; Wilson, David L

    2011-05-20

    Aminohydroxylation of tert-butyl sorbate [tert-butyl (E,E)-hexa-2,4-dienoate] using enantiopure lithium (R)-N-benzyl-N-(α-methylbenzyl)amide and (-)-camphorsulfonyloxaziridine gives tert-butyl (R,R,R,E)-2-hydroxy-3-[N-benzyl-N-(α-methylbenzyl)amino]hex-4-enoate in >99:1 dr. Subsequent dihydroxylation under Upjohn conditions (OsO(4)/NMO) gives tert-butyl (2R,3R,4S,5S,αR)-2,4,5-trihydroxy-3-[N-benzyl-N-(α-methylbenzyl)amino]hexanoate (in 95:5 dr) while dihydroxylation under Donohoe conditions (OsO(4)/TMEDA) proceeds with antipodal diastereofacial selectivity to give the (R,R,R,R,R)-diastereoisomer (in 95:5 dr). The amino triols resulting from these dihydroxylation reactions are useful for further elaboration, as demonstrated by the asymmetric synthesis of 3,6-dideoxy-3-amino-L-talose.

  20. Polyurethane waste recycling; glycolysis and hydroglycolysis of water-blown foams

    SciTech Connect

    Gerlock, J.; Braslaw, J.; Zinbo, M.

    1984-07-01

    In this paper, glycolysis of toluenediisocyanate based water-blown polyurethane foam has been examined by high performance liquid chromatography and gel permeation chromatography to determine the product distribution. Glycolysis with diethylene glycol (DEG) yields toluenediamine (TDA), TDA mono- and di- DEG carbamates, a series of urea-linked mono- and di- DEG carbamate TDA oligomers, and polyether triol (polyol). The complexity of the product mixture suggests problems in applying simple glycolysis to the recovery of mixed and/or contaminated polyurethane wastes. A simpler product mixture results when water and a base catalyst are added to the glycolysis reaction (hydroglycolysis). Hydroglycolysis yields TDA and polyol as principal products. Data for the rate of the hydroglycolysis reaction are presented in the temperature range of 150 to 190/sup 0/C. These results suggest that hydroglycolysis could be used to recover polyols from mixed and/or contaminated water-blown polyurethane wastes.

  1. Plant sterol oxides in functional beverages: influence of matrix and storage.

    PubMed

    González-Larena, Marina; Garcia-Llatas, Guadalupe; Clemente, Gonzalo; Barberá, Reyes; Lagarda, María Jesús

    2015-04-15

    Three plant sterol (PS)-enriched beverages, milk based fruit juice (MFJPS), fruit juice (FJPS) and milk beverage (MPS), were stored at 4, 24, or 37 °C and analysed at regular time intervals of 2 months until 6 months. PS stability was analysed from the production of phytosterol oxidation products (POPs). The β-sitosterol oxides (7α/7β-hydroxy, β/α-epoxy, triol, and 7-keto) and campesterol oxides (β/α-epoxy, and 7-keto) were detected in all beverages and at all storage times and temperatures. Total POP contents followed the order MPS≫FJPS>MFJPS. In general, the beverages showed low PS oxidation levels (<0.17%). Predictive models of POP content versus storage time were established. These models explain total POP content by over 75% and individual POP content by over 50%. We propose 7-ketositosterol and 7-ketocampesterol as PS oxidation markers during storage of beverages of this kind.

  2. Degradation of trichothecene mycotoxins by chicken intestinal microbes.

    PubMed

    Young, J Christopher; Zhou, Ting; Yu, Hai; Zhu, Honghui; Gong, Jianhua

    2007-01-01

    The degradation of 12 trichothecene mycotoxins by chicken intestinal microbes was monitored by liquid chromatography-ultraviolet-mass spectrometry under positive ion atmospheric pressure chemical ionization. Two pathways were observed: deacylation and deepoxidation. Essentially complete conversions to the deepoxy metabolites were observed for the non-acylated trichothecenes 4-deoxynivalenol, nivalenol, and verrucarol. However, deacetylation was the predominant pathway for the monoacetyl trichothecenes 3-acetyldeoxynivalenol, 15-acetyldeoxynivalenol (15ADON), and fusarenon X. Small amounts of the deepoxy metabolites were observed from 15ADON and large amounts from 15-monoacetoxyscirpenol where steric hindrance protected the C-15 acetyl groups from enzymatic attack. Diacetylated trichothecenes diacetoxyscirpenol and neosolaniol exhibited only deacetylation. The larger isovaleryl functionality was resistant to removal and deepoxidation was the prevalent reaction in HT-2 toxin and T-2 triol, whereas T2 toxin showed only deacetylation.

  3. Novel designed enediynes: molecular design, chemical synthesis, mode of cycloaromatization and guanine-specific DNA cleavage.

    PubMed

    Toshima, K; Ohta, K; Kano, T; Nakamura, T; Nakata, M; Kinoshita, M; Matsumura, S

    1996-01-01

    The molecular design and chemical synthesis of novel enediyne molecules related to the neocarzinostatin chromophore (1), and their chemical and DNA cleaving properties are described. The 10-membered enediyne triols 16-18 were effectively synthesized from xylitol (10) in a short step, and found to be quite stable when handled at room temperature. The representative and acylated enediyne 16 was cycloaromatized by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in cyclohexa-1,4-diene-benzene to give the benzenoid product 21 through a radical pathway. On the other hand, the enediyne 16 was cycloaromatized by diethylamine in dimethyl sulfoxide-Tris-HCl, pH 8.5 buffer to afford another benzenoid product 22 as a diethylamine adduct through a polar pathway. Furthermore, the enediynes 16-18 were found to exhibit guanine-specific DNA cleavage under weakly basic conditions with no additive.

  4. Design, synthesis and 1H NMR study of C3v-symmetric anion receptors with urethane-NH as recognition group

    NASA Astrophysics Data System (ADS)

    Park, Jin-Oh; Sahoo, Suban K.; Choi, Heung-Jin

    2016-01-01

    C3v-Symmetric anion receptors 3 and 4 with urethane groups were synthesized by using trindane triol as tripodal molecular framework. In 1H NMR titration study, the receptors showed noticeable downfield shift/disappearance of the urethane-NH peak in presence of H2PO4- and F- due to the host-guest complexation occurred through multiple hydrogen bonding and/or the deprotonation of urethane-NH groups. Other tested anions such as Cl-, Br-, HSO4-, and NO3- showed either no or negligible chemical shift of the urethane groups. The deprotonation event in 4 allowed selective detection of F- by perceptible color change from colorless to yellowish-red with the appearance of a new charge transfer absorption band at 450 nm.

  5. Triterpenoids from the stems of Schisandra grandiflora and their biological activity.

    PubMed

    Shi, Wei; Liu, Han-Wei; Guo, Xin; Hou, Lan; Gao, Jin-Ming

    2016-07-01

    One new ursane-type triterpenoid (1), named granditriol, along with 14 known compounds (2-15), was isolated from the organic extracts of Schisandra grandiflora stems. The structure of the new compound was elucidated by extensive spectroscopic methods as 28-norursa-12,17,19,21-tetraen-2α,3α,23-triol. These isolates were evaluated for anti-phytopathogenic fungi activity and cytotoxicity against human cancer cell line (HepG2). Asiatic acid (8) and 2α,3α,19α-trihydroxyurs-12-en-28-oic acid (9) inhibited the growth of two plant pathogens, Alternaria alternata and Alternaria solani. In addition, compounds 12, 15, and 11 displayed notable anti-proliferative activity against HepG2 cells. Compound 1 is the first report of 28-nortriterpenoid from the Schisandraceae family. All these were obtained from this plant for the first time.

  6. Glucosyltransferase from Streptococcus sobrinus Catalyzes Glucosylation of Catechin.

    PubMed

    Nakahara, K; Kontani, M; Ono, H; Kodama, T; Tanaka, T; Ooshima, T; Hamada, S

    1995-07-01

    We previously showed that the polymeric forms of polyphenols present in oolong tea extract exhibited strong inhibitory activities against glucosyltransferases (GTases) of mutans streptococci, while green tea extract, which is rich in catechins, did not show such GTase-inhibitory activities. In this study, (+)-catechin [2-(3,4-dihydroxyphenyl)-3,4-dihydro-2H-1-benzopyran-3,5,7-triol] was found to be glucosylated by the GTase of Streptococcus sobrinus 6715 with sucrose as the substrate, and the product was identified as 4(prm1)-O-(alpha)-d-glucopyranosyl-(+)-catechin, with a molecular weight of 452. The (alpha)-glucosylated (+)-catechin did not exhibit significant inhibition of glucan synthesis from sucrose by the GTase, which is in contrast to the polymeric polyphenols isolated from oolong tea leaves.

  7. Cucurbitane-type triterpenoids from the stems and leaves of Momordica charantia.

    PubMed

    Zhao, Gao-Ting; Liu, Jie-Qing; Deng, Yuan-Yuan; Li, Hai-Zhou; Chen, Jian-Chao; Zhang, Zhi-Run; Zhou, Lin; Qiu, Ming-Hua

    2014-06-01

    Six new cucurbitane-type triterpenoids, karavilagenin F (1), karavilosides XII and XIII (2, 3), momordicines VI, VII, and VIII (4, 5 and 6), along with four known ones, 5β,19-epoxy-25-methoxycucurbita-6,23-diene-3β,19-diol (7), 5β,19-epoxycucurbita-6, 23-diene-3β,19,25-triol (8), kuguacin R (9), and (19R,23E)-5β,19-epoxy-19-methoxycucurbita-6,23,25-trien-3β-ol (10), were isolated from the stems and leaves of Momordica charantia L. Their chemical structures were elucidated by extensive 1D NMR and 2D NMR (HSQC, HMBC, COSY, and ROESY), MS experiments, and CD spectrum. Compound 6 showed weak cytotoxicity against five human cancer cells lines with IC50 values of 14.3-20.5μmol/L.

  8. A new ceramide from Suillus luteus and its cytotoxic activity against human melanoma cells.

    PubMed

    León, Francisco; Brouard, Ignacio; Torres, Fernando; Quintana, José; Rivera, Augusto; Estévez, Francisco; Bermejo, Jaime

    2008-01-01

    A new phytosphingosine-type ceramide, suillumide (1), was isolated from the EtOH extract of the basidiomycete Suillus luteus (L.) S. F. Gray, along with ten known compounds: ergosta-4,6,8(14),22-tetraen-3-one, ergosterol, ergosterol peroxide, suillin, (E)-3,4,5-trimethoxycinnamic alcohol, 5 alpha,6 alpha-epoxyergosta-8,22-diene-3beta,7 beta-diol, (R)-1-palmitoylglycerol, ergosta-7,9(11),22-triene-3beta,5 alpha,6 beta-triol, cerevisterol, and 4-hydroxybenzoic acid. The structure of 1 was determined on the basis of spectroscopic and mass-spectrometric analyses, as well as by chemical methods. Compound 1 and its synthetic diacetyl derivative 2 were tested for their cytotoxic activities against the human melanoma cell line SK-MEL-1. Both drugs showed IC(50) values of ca. 10 microM after 72 h of exposure.

  9. A stereochemical examination of the equine metabolism of 17alpha-methyltestosterone.

    PubMed

    McKinney, Andrew R; Suann, Craig J; Stenhouse, Allen M

    2007-01-09

    An investigation was conducted into the stereochemistry of the equine urinary metabolites of 17alpha-methyltestosterone observed after oral administration. Standards of the complete range of C3/C5/C16 stereoisomeric 17alpha-methylandrostane-3,17beta-diols, 17alpha-methylandrostane-3,16,17beta-triols and 17alpha-hydroxymethylandrostane-3,17beta-diols were purchased or synthesised, and were used to unequivocally identify the absolute structures of the metabolites. Phase I metabolism was found to involve combinations of Delta(4)-3-ketone reduction with both 5alpha,3beta- and 5beta,3alpha-stereochemistry, hydroxylation at C16 with both 16alpha- and 16beta-stereochemistry and hydroxylation of the 17alpha-methyl substituent. Phase II metabolism involved mainly sulfation with a lesser degree of beta-glucuronidation.

  10. Large scale synthesis and regioselective protection schemes of ethyl 2-azido-2-deoxy-1-thio-α-d-cellobioside for preparation of heparin thiodisaccharide building blocks.

    PubMed

    Sheerin, Kevin; Guazzelli, Lorenzo; Oscarson, Stefan

    2017-02-22

    Crystalline acetylated ethyl 2-azido-2-deoxy-1-thio-α-d-cellobioside has been prepared on a multigram scale from cellobiose in an overall yield of 23% with no chromatography required and converted after deacetylation into the 4',6'-O-benzylidene and 4',6'-O-benzylidene-6-O-TBDMS protected derivatives. Applying a number of regioselective benzylation methods on these gave access to a variety of regioselectively protected derivatives, both mono-ols (2'- and 3-OH), diols (2',6-, 2',3-, and 3,6-di-OH), and triols (2',3,6- and 2',3',3-tri-OH). A number of these derivatives were further processed by benzoylation followed by removal or opening of the benzylidene acetal and selective oxidation of the exposed primary alcohol to give heparin building block intermediates comprising a range of possible sulfation patterns.

  11. Degradation of the synthetic dye amaranth by the fungus Bjerkandera adusta Dec 1: inference of the degradation pathway from an analysis of decolorized products.

    PubMed

    Gomi, Nichina; Yoshida, Shuji; Matsumoto, Kazutsugu; Okudomi, Masayuki; Konno, Hiroki; Hisabori, Toru; Sugano, Yasushi

    2011-11-01

    We examined the degradation of amaranth, a representative azo dye, by Bjerkandera adusta Dec 1. The degradation products were analyzed by high performance liquid chromatography (HPLC), visible absorbance, and electrospray ionization time-of-flight mass spectroscopy (ESI-TOF-MS). At the primary culture stage (3 days), the probable reaction intermediates were 1-aminonaphthalene-2,3,6-triol, 4-(hydroxyamino) naphthalene-1-ol, and 2-hydroxy-3-[2-(4-sulfophenyl) hydrazinyl] benzenesulfonic acid. After 10 days, the reaction products detected were 4-nitrophenol, phenol, 2-hydroxy-3-nitrobenzenesulfonic acid, 4-nitrobenzene sulfonic acid, and 3,4'-disulfonyl azo benzene, suggesting that no aromatic amines were created. Manganese-dependent peroxidase activity increased sharply after 3 days culture. Based on these results, we herein propose, for the first time, a degradation pathway for amaranth. Our results suggest that Dec 1 degrades amaranth via the combined activities of peroxidase and hydrolase and reductase action.

  12. Phomentrioloxin: A phytotoxic pentasubstituted geranylcyclohexentriol produced by Phomopsis sp., a potential mycoherbicide for Carthamus lanatus Biocontrol.

    PubMed

    Cimmino, Alessio; Andolfi, Anna; Zonno, Maria C; Troise, Ciro; Santini, Antonello; Tuzi, Angela; Vurro, Maurizio; Ash, Gavin; Evidente, Antonio

    2012-06-22

    A new phytotoxic geranylcyclohexenetriol, named phomentrioloxin, was isolated from the liquid culture of Phomopsis sp., a fungal pathogen proposed for the biological control of Carthamus lanatus, a widespread and troublesome thistle weed belonging to the Asteraceae family causing severe crop and pastures losses in Australia. The structure of phomentrioloxin was established by spectroscopic, X-ray, and chemical methods as (1S,2S,3S,4S)-3-methoxy-6-(7-methyl-3-methylene-oct-6-en-1-ynyl)cyclohex-5-ene-1,2,4-triol. At a concentration of 6.85 mM, the toxin causes the appearance of necrotic spots when applied to leaves of both host and nonhost plants. It also causes growth and chlorophyll content reduction of fronds of Lemna minor and inhibition of tomato rootlet elongation. Finally, in preliminary bioassays, phomentrioloxin did not show any antibacterial, fungicidal, or zootoxic activities.

  13. Cholesterol photosensitised oxidation of horse meat slices stored under different packaging films.

    PubMed

    Boselli, Emanuele; Rodriguez-Estrada, Maria Teresa; Ferioli, Federico; Caboni, Maria Fiorenza; Lercker, Giovanni

    2010-07-01

    The effect of the type of packaging film (transparent vs. light-protecting red film) was evaluated on the formation of cholesterol oxidation products (COPs) in refrigerated horse meat slices stored in retail conditions under light exposure for 8h. In meat wrapped with a transparent film, COPs increased from 233 (control) to 317 microg/g of fat, whereas the red film delayed cholesterol oxidation and offered protection against COPs formation, since COPs decreased from 173 (control) to 139 microg/g of fat after 8h of light exposure. In addition, light opened the epoxy ring and led to the formation of triol, which was actually absent at T(0.) A proper packaging film may represent a useful strategy to retard oxidative degradation in a light-sensitive, high pigment- and fat-containing food, such as horse meat.

  14. An expedient synthesis of linden ether.

    PubMed

    Serra, Stefano; Cominetti, Alessandra A

    2014-03-01

    We here describe a comprehensive study on the preparation of the intensive flavor 3,9-epoxy-p-mentha-1,4(8)-diene (1). Key steps of the presented synthesis are the selective addition of MeLi to the keto-ester 7, the regioselective cyclization of the obtained triol to give the ethers 4 and 8 and the selective dehydration of ether 4 through the use of POCI3 and pyridine. It is worth noting that the presented synthesis represents the first expedient and reliable entry to ether 1. Being present in linden honey, 1 is also known as linden ether and it has been regarded as a potential marker for the authentication of the linden honey origin. Therefore, ether 1 can be used as a useful reference standard for the analysis of the natural flavors, as we demonstrated by means of its identification in a sample ofunifloral linden honey.

  15. Assessing the impact of anthropogenic pollution on isoprene-derived secondary organic aerosol formation in PM2.5 collected from the Birmingham, Alabama, ground site during the 2013 Southern Oxidant and Aerosol Study

    NASA Astrophysics Data System (ADS)

    Rattanavaraha, Weruka; Chu, Kevin; Hapsari Budisulistiorini, Sri; Riva, Matthieu; Lin, Ying-Hsuan; Edgerton, Eric S.; Baumann, Karsten; Shaw, Stephanie L.; Guo, Hongyu; King, Laura; Weber, Rodney J.; Neff, Miranda E.; Stone, Elizabeth A.; Offenberg, John H.; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.

    2016-04-01

    forming this SOA type. However, the nighttime correlation of these tracers with nitrogen dioxide (NO2) (r2 = 0.26, n = 40) was weaker. Ozone (O3) correlated strongly with MAE/HMML-derived tracers (r2 = 0.72, n = 30) and moderately with 2-methyltetrols (r2 = 0.34, n = 15) during daytime only, suggesting that a fraction of SOA formation could occur from isoprene ozonolysis in urban areas. No correlation was observed between aerosol pH and isoprene-derived SOA. Lack of correlation between aerosol acidity and isoprene-derived SOA is consistent with the observation that acidity is not a limiting factor for isoprene SOA formation at the BHM site as aerosols were acidic enough to promote multiphase chemistry of isoprene-derived epoxides throughout the duration of the study. All in all, these results confirm previous studies suggesting that anthropogenic pollutants enhance isoprene-derived SOA formation.

  16. Seasonal variation of secondary organic aerosol tracers in Central Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Shen, R.-Q.; Ding, X.; He, Q.-F.; Cong, Z.-Y.; Yu, Q.-Q.; Wang, X.-M.

    2015-08-01

    Secondary organic aerosol (SOA) affects the earth's radiation balance and global climate. High-elevation areas are sensitive to global climate change. However, at present, SOA origins and seasonal variations are understudied in remote high-elevation areas. In this study, particulate samples were collected from July 2012 to July 2013 at the remote Nam Co (NC) site, Central Tibetan Plateau and analyzed for SOA tracers from biogenic (isoprene, monoterpenes and β-caryophyllene) and anthropogenic (aromatics) precursors. Among these compounds, isoprene SOA (SOAI) tracers represented the majority (26.6 ± 44.2 ng m-3), followed by monoterpene SOA (SOAM) tracers (0.97 ± 0.57 ng m-3), aromatic SOA (SOAA) tracer (2,3-dihydroxy-4-oxopentanoic acid, DHOPA, 0.25 ± 0.18 ng m-3) and β-caryophyllene SOA tracer (β-caryophyllenic acid, 0.09 ± 0.10 ng m-3). SOAI tracers exhibited high concentrations in the summer and low levels in the winter. The similar temperature dependence of SOAI tracers and isoprene emission suggested that the seasonal variation of SOAI tracers at the NC site was mainly influenced by the isoprene emission. The ratio of high-NOx to low-NOx products of SOAI (2-methylglyceric acid to 2-methyltetrols) was highest in the winter and lowest in the summer, due to the influence of temperature and relative humidity. The seasonal variation of SOAM tracers was impacted by monoterpenes emission and gas-particle partitioning. During the summer to the fall, temperature effect on partitioning was the dominant process influencing SOAM tracers' variation; while the temperature effect on emission was the dominant process influencing SOAM tracers' variation during the winter to the spring. SOAM tracer levels did not elevate with increased temperature in the summer, probably resulting from the counteraction of temperature effects on emission and partitioning. The concentrations of DHOPA were 1-2 orders of magnitude lower than those reported in the urban regions of the world

  17. Seasonal variation of secondary organic aerosol in Nam Co, Central Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Shen, R.-Q.; Ding, X.; He, Q.-F.; Cong, Z.-Y.; Yu, Q.-Q.; Wang, X.-M.

    2015-03-01

    Secondary organic aerosol (SOA) affects the earth's radiation balance and global climate. High-elevation areas are sensitive to global climate change. However, at present, SOA origins and seasonal variations are understudied in remote high-elevation areas. In this study, particulate samples were collected from July 2012 to July 2013 at the remote Nam Co (NC) site, Central Tibetan Plateau and analyzed for SOA tracers from biogenic (isoprene, monoterpenes and β-caryophyllene) and anthropogenic (aromatics) precursors. Among these compounds, isoprene SOA (SOAI) tracers represented the majority (26.6 ± 44.2 ng m-3), followed by monoterpene SOA (SOAM) tracers (0.97 ± 0.57 ng m-3), aromatic SOA (SOAA) tracer (2,3-dihydroxy-4-oxopentanoic acid, DHOPA, 0.25 ± 0.18 ng m-3) and β-caryophyllene SOA tracer (β-caryophyllenic acid, 0.09 ± 0.10 ng m-3). SOAI tracers exhibited high concentrations in the summer and low levels in the winter. The similar temperature dependence of SOAI tracers and isoprene emission suggested that the seasonal variation of SOAI at the NC site was mainly influenced by isoprene emission. The ratio of high-NOx to low-NOx products of isoprene (2-methylglyceric acid to 2-methyltetrols) was the highest in the winter and the lowest in the summer, due to the influence of temperature and relative humidity. The seasonal variation of SOAM tracers was impacted by monoterpenes emission and tracers partitioning. The similar temperature dependence of SOAM tracers and monoterpenes emission was only observed during winter to spring. SOAM tracer levels did not elevate with increased temperature in the summer, probably resulting from the counteraction of temperature effects on gas/particle partitioning and monoterpenes emission. The concentrations of DHOPA were 1-2 orders of magnitude lower than those reported in the urban regions of the world. Due to the transport of air pollutants from the adjacent Bangladesh and the eastern India, DHOPA presented relatively

  18. Secondary Pollutants in the Lake Tahoe Basin, USA

    NASA Astrophysics Data System (ADS)

    Zielinska, B.; Bytnerowicz, A.; Gertler, A.; McDaniel, M.; Burley, J. D.

    2013-12-01

    total VOC. The photooxidation reaction products of isoprene and α-pinene, 2-methyltetrols and pinonic acid, respectively, were measured in combined PM2.5 day and night samples from four sampling sites and their concentrations ranged from 16 to 47 ng/m3 for 2-methylthreitol, from 34 to 87 ng/m3 for 2-methylerythritol and from 14 to 42 ng/m3 for pinonic acid. In general, organic carbon (OC) constituted from 87 to 99.9% of total carbon. All four sites show maximum ozone concentrations in the range of 60 ppb. However, the lower sites show a pronounced diurnal pattern (i.e. maximum concentrations during the daytime hours, 0900 to 1700, with minimum values at night and in the early morning hours), whereas the upper sites show much less variability over the 24-hour diurnal period.

  19. Wild Bitter Melon Leaf Extract Inhibits Porphyromonas gingivalis-Induced Inflammation: Identification of Active Compounds through Bioassay-Guided Isolation.

    PubMed

    Tsai, Tzung-Hsun; Huang, Wen-Cheng; Ying, How-Ting; Kuo, Yueh-Hsiung; Shen, Chien-Chang; Lin, Yin-Ku; Tsai, Po-Jung

    2016-04-06

    Porphyromonas gingivalis has been identified as one of the major periodontal pathogens. Activity-directed fractionation and purification processes were employed to identify the anti-inflammatory active compounds using heat-killed P. gingivalis-stimulated human monocytic THP-1 cells in vitro. Five major fractions were collected from the ethanol/ethyl acetate extract of wild bitter melon (Momordica charantia Linn. var. abbreviata Ser.) leaves and evaluated for their anti-inflammatory activity against P. gingivalis. Among the test fractions, Fraction 5 effectively decreased heat-killed P. gingivalis-induced interleukin (IL)-8 and was subjected to separation and purification by using chromatographic techniques. Two cucurbitane triterpenoids were isolated from the active fraction and identified as 5β,19-epoxycucurbita-6,23-diene-3β,19,25-triol (1) and 3β,7β,25-trihydroxycucurbita-5,23-dien-19-al (2) by comparing spectral data. Treatments of both compounds in vitro potently suppressed P. gingivalis-induced IL-8, IL-6, and IL-1β levels and the activation of mitogen-activated protein kinase (MAPK) in THP-1 cells. Both compounds effectively inhibited the mRNA levels of IL-6, tumor necrosis factor (TNF)-α, and cyclooxygenase (COX)-2 in P. gingivalis-stimulated gingival tissue of mice. These findings imply that 5β,19-epoxycucurbita-6,23-diene-3β,19,25-triol and 3β,7β,25-trihydroxycucurbita-5,23-dien-19-al could be used for the development of novel therapeutic approaches against P. gingivalis infections.

  20. Determination of T-2 toxin, HT-2 toxin, and three other type A trichothecenes in layer feed by high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS)--comparison of two sample preparation methods.

    PubMed

    Bernhardt, Katrin; Valenta, Hana; Kersten, Susanne; Humpf, Hans-Ulrich; Dänicke, Sven

    2016-05-01

    A sensitive method for the simultaneous determination of T-2 toxin, HT-2 toxin, neosolaniol, T-2 triol, and T-2 tetraol in layer feed using high-performance liquid chromatography coupled to triple quadrupole mass spectrometry in the positive ionization mode (LC-ESI-MS/MS) is described. Two fast and easy clean-up methods-with BondElut Mycotoxin and MycoSep 227 columns, respectively-were tested. The separation of the toxins was conducted on a Pursuit XRs Ultra 2.8 HPLC column using 0.13 mM ammonium acetate as eluent A and methanol as eluent B. Detection of the mycotoxins was carried out in the multiple reaction monitoring (MRM) mode using ammonium adducts as precursor ions. Quantification of all analytes was performed with d3-T-2 toxin as an internal standard. The clean-up method with MycoSep 227 columns gave slightly better results for layer feed compared to the method using BondElut Mycotoxin columns (MycoSep 227: recovery between 50 and 63%, BondElut Mycotoxin: recovery between 32 and 67%) and was therefore chosen as the final method. The limits of detection ranged between 0.9 and 7.5 ng/g depending on the mycotoxin. The method was developed for the analysis of layer feed used at carry-over experiments with T-2 toxin in laying hens. For carry-over experiments, it is necessary that the method includes not only T-2 toxin but also the potential metabolites in animal tissues HT-2 toxin, neosolaniol, T-2 triol, and T-2 tetraol which could naturally occur in cereals used as feed stuff as well.

  1. Sources for sedimentary bacteriohopanepolyols as revealed by 16S rDNA stratigraphy.

    PubMed

    Coolen, Marco J L; Talbot, Helen M; Abbas, Ben A; Ward, Christopher; Schouten, Stefan; Volkman, John K; Damsté, Jaap S Sinninghe

    2008-07-01

    Bacteriohopanoids are widespread lipid biomarkers in the sedimentary record. Many aerobic and anaerobic bacteria are potential sources of these lipids which sometimes complicates the use of these biomarkers as proxies for ecological and environmental changes. Therefore, we applied preserved 16S ribosomal RNA genes to identify likely Holocene biological sources of bacteriohopanepolyols (BHPs) in the sulfidic sediments of the permanently stratified postglacial Ace Lake, Antarctica. A suite of intact BHPs were identified, which revealed a variety of structural forms whose composition differed through the sediment core reflecting changes in bacterial populations induced by large changes in lake salinity. Stable isotopic compositions of the hopanols formed from periodic acid-cleaved BHPs, showed that some were substantially depleted in (13)C, indicative of their methanotrophic origin. Using sensitive molecular tools, we found that Type I and II methanotrophic bacteria (respectively Methylomonas and Methylocystis) were unique to the oldest lacustrine sediments (> 9400 years BP), but quantification of fossil DNA revealed that the Type I methanotrophs, including methanotrophs related to methanotrophic gill symbionts of deep-sea cold-seep mussels, were the main precursors of the 35-amino BHPs (i.e. aminopentol, -tetrol and -triols). After isolation of the lake approximately 3000 years ago, one Type I methanotroph of the 'methanotrophic gill symbionts cluster' remained the most obvious source of aminotetrol and -triol. We, furthermore, identified a Synechococcus phylotype related to pelagic freshwater strains in the oldest lacustrine sediments as a putative source of 2-methylbacteriohopanetetrol (2-Me BHT). This combined application of advanced geochemical and paleogenomical tools further refined our knowledge about Holocene biogeochemical processes in Ace Lake.

  2. The neuro-steroid, 3beta androstene 17alpha diol exhibits potent cytotoxic effects on human malignant glioma and lymphoma cells through different programmed cell death pathways.

    PubMed

    Graf, M R; Jia, W; Loria, R M

    2007-09-03

    The neuro-steroids 3beta-androstene-17alpha-diol (17alpha-AED), 3beta-androstene-17beta-diol (17beta-AED), 3beta-androstene-7alpha,-17beta-triol (7alpha-AET) and 3beta-androstene-7beta,-17beta-triol (7beta-AET) are metabolites of dehydroepiandrosterone and are produced in neuro-ectodermal tissue. Both epimers of androstenediols (17alpha-AED and 17beta-AED) and androstenetriols (7alpha-AET and 7beta-AET) have markedly different biological functions of their chemical analogue. We investigated the cytotoxic activity of these neuro-steroids on human T98G and U251MG glioblastoma and U937 lymphoma cells. Proliferation studies showed that 17alpha-AED is the most potent inhibitor, with an IC(50) approximately 15 microM. For T98G glioma, 90% inhibition was achieved with 25 muM of 17alpha-AED. Other neuro-steroids tested only marginally suppressed cell proliferation. Reduced cell adherence and viability could be detected after 18 h of 17alpha-AED exposure. Treatment with 17alpha-AED induced a significant level of apoptosis in U937 lymphoma cells, but not in the glioma cells. Cytopathology of 17alpha-AED-treated T98G cells revealed the presence of multiple cytoplasmic vacuoles. Acridine orange staining demonstrated the formation of acidic vesicular organelles in 17alpha-AED-treated T98G and U251MG, which was inhibited by bafilomycin A1. These findings indicate that 17alpha-AED bears the most potent cytotoxic activity of the neuro-steroids tested, and the effectiveness may depend on the number of hydroxyls and their position on the androstene molecule. These cytotoxic effects may utilize a non-apoptotic pathway in malignant glioma cells.

  3. Synthesis and crystal structures of C24-epimeric 20(R)-ocotillol-type saponins.

    PubMed

    Xu, Yang Rong; Yang, Jing Jing; Liu, Juan; Hou, Gui Ge; Meng, Qing Guo

    2016-06-01

    Ocotillol-type saponins have a wide spectrum of biological activities. Previous studies indicated that the configuration at the C24 position may be responsible for their stereoselectivity in pharmacological action and pharmacokinetics. Natural ocotillol-type saponins share a 20(S)-form but it has been found that the 20(R)-stereoisomers have different pharmacological effects. The semisynthesis of 20(R)-ocotillol-type saponins has not been reported and it is therefore worthwhile clarifying their crystal structures. Two C24 epimeric 20(R)-ocotillol-type saponins, namely (20R,24S)-20,24-epoxydammarane-3β,12β,25-triol, C30H52O4, (III), and (20R,24R)-20,24-epoxydammarane-3β,12β,25-triol monohydrate, C30H52O4·H2O, (IV), were synthesized, and their structures were elucidated by spectral studies and finally confirmed by single-crystal X-ray diffraction. The (Me)C-O-C-C(OH) torsion angle of (III) is 146.41 (14)°, whereas the corresponding torsion angle of (IV) is -146.4 (7)°, indicating a different conformation at the C24 position. The crystal stacking in (III) generates an R4(4)(8) motif, through which the molecules are linked into a one-dimensional double chain. The chains are linked via nonclassical C-H...O hydrogen bonds into a two-dimensional network, and further stacked into a three-dimensional structure. In contrast to (III), epimer (IV) crystallizes as a hydrate, in which the water molecules act as hydrogen-bond donors linking one-dimensional chains into a two-dimensional network through intermolecular O-H...O hydrogen bonds. The hydrogen-bonded chains extend helically along the crystallographic a axis and generate a C4(4)(8) motif.

  4. The expression of aromatase in gonadotropes is regulated by estradiol and gonadotropin-releasing hormone in a manner that differs from the regulation of luteinizing hormone.

    PubMed

    Galmiche, Guillaume; Richard, Nicolas; Corvaisier, Sophie; Kottler, Marie-Laure

    2006-09-01

    The role of estrogens is dual: they suppress basal expression of gonadotropins and enhance GnRH responsiveness at the time of the LH surge. Estrogens are synthesized by cytochrome P450 aromatase (P450arom), encoded by the cyp19 gene. We focused on the cyp19 gene in rat and showed that it is expressed in gonadotropes through promoters PII and PI.f, using RT-PCR and dual fluorescence labeling with anti-P450arom and -LH antibodies. Real-time PCR quantification revealed that aromatase mRNA levels varied during the estrous cycle and were significantly increased after ovariectomy. This effect is prevented by estradiol (E2) as well as GnRH antagonist administration, suggesting that GnRH may mediate the steroid effect. Interestingly, the long-acting GnRH agonist that induces LH desensitization does not modify aromatase expression in ovariectomized rats. Administration of E2 in ovariectomized rats receiving either GnRH agonist or GnRH antagonist clearly demonstrated that E2 also reduces cyp19 expression at the pituitary level. The selective estrogen receptor-alpha ligand propyl pyrazole triol and the selective estrogen receptor-beta ligand diarylpropionitrile both mimic the E2 effects. By contrast, propyl pyrazole triol reduces LH beta expression whereas diarylpropionitrile does not. In addition, using transient transfection assays in an L beta T2 gonadotrope cell line, we provided evidence that GnRH agonist stimulated, in a dose-dependant manner, cyp19 promoters PII and PI.f and that E2 decreased the GnRH stimulation. In conclusion, our data demonstrate that GnRH is an important signal in the regulation of cyp19 in gonadotrope cells. Both common and specific intracellular factors were responsible for dissociated variations of LH beta and cyp19 expression.

  5. X-ray structures of 4-chlorocatechol 1,2-dioxygenase adducts with substituted catechols: new perspectives in the molecular basis of intradiol ring cleaving dioxygenases specificity.

    PubMed

    Ferraroni, Marta; Kolomytseva, Marina; Scozzafava, Andrea; Golovleva, Ludmila; Briganti, Fabrizio

    2013-03-01

    The crystallographic structures of 4-chlorocatechol 1,2-dioxygenase (4-CCD) complexes with 3,5-dichlorocatechol, protocatechuate (3,4-dihydroxybenzoate), hydroxyquinol (benzen-1,2,4-triol) and pyrogallol (benzen-1,2,3-triol), which act as substrates or inhibitors of the enzyme, have been determined and analyzed. 4-CCD from the Gram-positive bacterium Rhodococcus opacus 1CP is a Fe(III) ion containing enzyme specialized in the aerobic biodegradation of chlorocatechols. The structures of the 4-CCD complexes show that the catechols bind the catalytic iron ion in a bidentate mode displacing Tyr169 and the benzoate ion (found in the native enzyme structure) from the metal coordination sphere, as found in other adducts of intradiol dioxygenases with substrates. The analysis of the present structures allowed to identify the residues selectively involved in recognition of the diverse substrates. Furthermore the structural comparison with the corresponding complexes of catechol 1,2-dioxygenase from the same Rhodococcus strain (Rho-1,2-CTD) highlights significant differences in the binding of the tested catechols to the active site of the enzyme, particularly in the orientation of the aromatic ring substituents. As an example the 3-substituted catechols are bound with the substituent oriented towards the external part of the 4-CCD active site cavity, whereas in the Rho-1,2-CTD complexes the 3-substituents were placed in the internal position. The present crystallographic study shed light on the mechanism that allows substrate recognition inside this class of high specific enzymes involved in the biodegradation of recalcitrant pollutants.

  6. New esters of okadaic acid in seawater and blue mussels (Mytilus edulis).

    PubMed

    Torgersen, Trine; Miles, Christopher O; Rundberget, Thomas; Wilkins, Alistair L

    2008-10-22

    Marine algal toxins of the okadaic acid (OA) group can occur as diol esters and sulfated diol esters in algae and as fatty acid esters in shellfish. Several of these ester forms have been identified, but the most common procedure for detecting OA group toxin esters is by measuring the increase in parent toxin after alkaline hydrolysis. Use of this alkaline hydrolysis method led to the discovery of high levels of conjugates of OA and dinophysistoxins-2 (DTX2) in seawater and of OA, DTX1, and DTX2 in blue mussel hepatopancreas (HP) from Flødevigen, Norway, during a bloom of Dinophysis spp. In the water sample, a C 8-diol ester, a C 9-diol ester, and a previously undescribed C 8-triol ester of OA were characterized using HPLC-MS (2), -MS (3), and -MS (4) in combination with various derivatization procedures. Palmitic acid (16:0) ester derivatives of these diol/triol esters were found in mussel HP and characterized using HPLC-MS (2), -MS (3), and -MS (4). To the authors' knowledge, hybrid diol-fatty acid esters of OA have not been previously described. Mass spectral analysis showed the presence of two forms of hybrid esters: one with the fatty acid conjugated to the 7-OH of the OA moiety and the other with the fatty acid conjugated to the OH group in the "diol" moiety. In the water sample, the C 8-diol ester was the most abundant, whereas in the mussels, the 16:0-C 9-diol hybrid ester was most abundant, and only minor amounts of the 16:0-C 8-diol hybrid ester were detected, suggesting that C 8- and C 9-diol esters of OA may be metabolized differently in blue mussels. 7- O-acyl esters of OA, DTX1, and DTX2 are thought to contribute to shellfish toxicity by being hydrolyzed in the human stomach to the parent toxins, and the newly characterized hybrid esters are likely to contribute similarly.

  7. Survey of Fusarium toxins in foodstuffs of plant origin marketed in Germany.

    PubMed

    Schollenberger, Margit; Müller, H-M; Rüfle, Melanie; Suchy, Sybille; Planck, Susanne; Drochner, W

    2005-01-01

    A total of 219 samples of foodstuffs of plant origin, consisting of grain-based food, pseudocereals and gluten-free food as well as vegetables, fruits, oilseeds and nuts, were randomly collected during 2000 and 2001 in food and health food stores. A spectra of 13 trichothecene toxins including diacetoxyscirpenol (DAS), 15-monoacetoxyscirpenol (MAS), scirpentriol (SCIRP), T-2 and HT-2 toxins (T-2, HT-2), T-2 triol, T-2 tetraol, neosolaniol (NEO) of the A-type as well as deoxynivalenol (DON), 3- and 15-acetyl-DON (3-, 15-ADON), nivalenol (NIV), and fusarenon-X (FUS-X) of the B-type were determined by gas chromatography/mass spectrometry. Analysis of zearalenone (ZEA), alpha- and beta-zearalenol (alpha- and beta-ZOL) was made by high-performance liquid chromatography with fluorescence and UV-detection. Detection limits ranged between 1 and 19 microg/kg. Out of 84 samples of cereal-based including gluten-free foods, 60 samples were positive for at least one of the toxins DON, 15-ADON, 3-ADON, NIV, T-2, HT-2, T-2 tetraol and ZEA, with incidences at 57%, 13%, 1%, 10%, 12%, 37%, 4% and 38%, respectively, whereas SCIRP and its derivatives MAS and DAS, T-2 triol, Fus-X as well as alpha- and beta-ZOL were not detected in any sample of this subgroup. Contents of DON ranged between 8 and 389 microg/kg, for all other toxins determined concentrations were below 100 microg/kg. The pseudocereals amaranth, quinoa and buckwheat were free of the toxins investigated. Ten of 85 samples of vegetables and fruits were toxin positive. ZEA and the type A trichothecenes MAS, SCIRP, DAS, HT-2 were detected in 7, 3, 2, 1 and 1 samples, respectively. Out of 35 samples of oilseeds and nuts, 7 samples were toxin positive. HT-2, T-2 and ZEA were detected in 4, 3 and 4 samples, respectively. In vegetables and fruits as well as in oilseeds and nuts, toxin levels were below 50 microg/kg. None of the B-type trichothecenes analysed was found for both subgroups.

  8. Synthesis of Suberin during Wound-healing in Jade Leaves, Tomato Fruit, and Bean Pods 1

    PubMed Central

    Dean, Bill Bryan; Kolattukudy, P. E.

    1976-01-01

    The structure and composition of the aliphatic monomers of the polymeric material deposited during wound-healing of tomato fruit, bean pods, and Jade leaves were examined. After removing the cuticle-containing layer of tissue, the wounds were healed for 14 days and the resulting surface layer was excised, lyophilized, solvent-extracted, and depolymerized by hydrogenolysis with LiAlH4 or transesterified with BF3 in methanol. The products obtained by the chemical depolymerization were subjected to thin layer chromatography and combined gas chromatography and mass spectrometry. The major aliphatic components isolated from the hydrogenolysate of the wound polymer produced by tomato fruit were hexadecane-1,16-diol and octadec-9-ene-1,18-diol, which were shown to be derived from a 1:1 mixture of ω-hydroxy and dicarboxylic acids of the appropriate chain length by LiAlH4 reduction. Also identified in the wound polymer were long chain (>C20) fatty acids and alcohols. This monomer composition is typical of suberin polymers and is in sharp contrast with that of the cutin of tomato fruit which contains dihydroxy C16 acid as the major aliphatic component. The hydrogenolysis of the wound material from bean pods gave octadecene-1,18-diol as the major aliphatic component, and smaller amounts of hexadecane-1,16-diol and long chain alcohols. Similar treatment of the normal cuticular tissue of these pods gave hexadecane triol, as well as C16 and C18 alcohols. Hydrogenolysis of wound material from the Jade leaves gave octadecene-1,18-diol, C16 and C22 diols, as well as alcohols from C16 to C26, whereas similar treatment of the cutin-containing tissue from these leaves gave C16 triol as the major aliphatic component. Thus, the major aliphatic monomers of the polymeric material deposited during the wound-healing of bean pods and Jade leaves are very similar to those of suberin, although the natural protective polymer of these tissues is cutin. From these results, it is concluded that

  9. Phytotoxic steroidal saponins from Agave offoyana leaves.

    PubMed

    Pérez, Andy J; Simonet, Ana M; Calle, Juan M; Pecio, Łukasz; Guerra, José O; Stochmal, Anna; Macías, Francisco A

    2014-09-01

    A bioassay-guided fractionation of Agave offoyana leaves led to the isolation of five steroidal saponins (1-5) along with six known saponins (6-11). The compounds were identified as (25R)-spirost-5-en-2α,3β-diol-12-one 3-O-{α-l-rhamnopyranosyl-(1→3)-O-β-d-glucopyranosyl-(1→2)-O-[β-d-xylopyranosyl-(1→3)]-O-β-d-glucopyranosyl-(1→4)-O-β-d-galactopyranoside} (1), (25R)-spirost-5-en-3β-ol-12-one 3-O-{α-l-rhamnopyranosyl-(1→3)-O-β-d-glucopyranosyl-(1→2)-O-[β-d-xylopyranosyl-(1→3)]-O-β-d-glucopyranosyl-(1→4)-O-β-d-galactopyranoside} (2), (25R)-spirost-5-en-3β-ol-12-one 3-O-{β-d-xylopyranosyl-(1→3)-O-β-d-glucopyranosyl-(1→2)-O-[β-d-xylopyranosyl-(1→3)]-O-β-d-glucopyranosyl-(1→4)-O-β-d-galactopyranoside} (3), (25R)-26-O-β-d-glucopyranosylfurost-5-en-3β,22α,26-triol-12-one 3-O-{α-l-rhamnopyranosyl-(1→3)-O-β-d-glucopyranosyl-(1→2)-O-[β-d-xylopyranosyl-(1→3)]-O-β-d-glucopyranosyl-(1→4)-O-β-d-galactopyranoside} (4) and (25R)-26-O-β-d-glucopyranosylfurost-5-en-3β,22α,26-triol-12-one 3-O-{β-d-xylopyranosyl-(1→3)-O-β-d-glucopyranosyl-(1→2)-O-[β-d-xylopyranosyl-(1→3)]-O-β-d-glucopyranosyl-(1→4)-O-β-d-galactopyranoside} (5) by comprehensive spectroscopic analysis, including one- and two-dimensional NMR techniques, mass spectrometry and chemical methods. The phytotoxicity of the isolated compounds on the standard target species Lactuca sativa was evaluated.

  10. Cutaneous sensitization to some polyisocyanate prepolymers in guinea pigs.

    PubMed

    Zissu, D; Binet, S; Limasset, J C

    1998-11-01

    Isocyanates are used extensively in the polyurethane industry. Pulmonary and dermal sensitization resulting from exposure to diisocyanates has frequently been reported, but the potential effects of polyisocyanates on health are less well known. Thus, since 1978, occupational exposure limits have been established for diisocyanates only. Nevertheless, respiratory diseases and dermatitis have been reported in the polyurethane industry after accidental isocyanate contact during spills or splashes. The aim of this experimental work was to assess the dermal hypersensitivity of guinea pigs to some polyisocyanate prepolymers by means of a well-conducted standard predictive Buehler test. Our results showed that dicyclohexylmethane 4,4'-diisocyanate (HMDI), toluylene 2,4-diisocyanate (TDI), TDI adduct triol, TDI isocyanurate, 1,6-hexamethylene diisocyanate (HDI), HDI isocyanurate, HDI biuret and isophorone diisocyanate (IPDI) induced dermal sensitization while IPDI isocyanurate did not. In conclusion, the dermal hypersensitivity of guinea pigs to some polyisocyanates was similar to those of their corresponding monomers except for IPDI isocyanurate, suggesting that the results from diisocyanate monomers could not be a valuable approach for the detection of the sensitization potency of the corresponding prepolymers.

  11. Increased serum levels of C21 steroids in female patients with multiple sclerosis.

    PubMed

    Kanceva, R; Stárka, L; Kancheva, L; Hill, M; Veliková, M; Havrdová, E

    2015-01-01

    Multiple sclerosis (MS) is one of the most common neurological diseases. This neurodegenerative autoimmune disease manifests as inflammatory and demyelinating impairment of the central nervous system (CNS). Although some studies demonstrated associations between altered steroidogenesis and pathophysiology of MS as well as the importance of steroids in the pathophysiology of MS, the knowledge concerning the steroid metabolome in female patients is limited. Hence, 51 steroids and steroid polar conjugates were measured in the serum of 12 women with MS, untreated with steroids and 6 age-corresponding female controls with the use of gas chromatography - mass spectrometry (GC-MS). The data were processed using age adjusted ANCOVA, receiver operating characteristics (ROC) analysis and orthogonal projections to latent structures (OPLS). Our data show higher levels of circulating C21 steroids including steroid modulators of ionotropic type A gamma-aminobutyric acid (GABA A) receptors and glutamate receptors. Furthermore, the levels of GABAergic androsterone and 5-androsten-3beta,7alpha,17beta-triol were also higher in the female MS patients. In conclusion, the data demonstrate higher levels of circulating C21 steroids and their polar conjugates and some bioactive C19 steroids in women with MS, which may influence neuronal activity and affect the balance between neuroprotection and excitotoxicity.

  12. The effects of sex, age and commensal way of life on levels of fecal glucocorticoid metabolites in spiny mice (Acomys cahirinus).

    PubMed

    Nováková, M; Palme, R; Kutalová, H; Janský, L; Frynta, D

    2008-09-03

    We studied levels of fecal glucocorticoid metabolites (GCM) in a social rodent - Egyptian spiny mouse. As breeding adults are socially dominant over subadults, and adolescent males are driven away by the dominant males, we addressed the question whether animals within extended families are stressed differently depending upon their social category. In addition, we evaluated whether there are differences between non-commensal (outdoor) and commensal (adapted to human settlements) populations. Concentrations of fecal GCM were assessed from samples collected in a special cage that allowed continuous individual sampling of undisturbed mice housed as a semi-natural social unit. First we performed an ACTH challenge test to validate two enzyme immunoassays (EIA): a 5alpha-pregnane-3beta,11beta,21-triol-20-one EIA and an 11-oxoetiocholanolone EIA to measure a group of fecal GCM in this species. Next we monitored concentrations of fecal GCM in 68 individuals belonging to 10 family groups and two populations. Commensal spiny mice showed higher fecal GCM levels than non-commensal ones. No effect of age (i.e., social dominance) and only a small effect of sex (in the commensal population only, with males exhibiting lower values) on fecal GCM levels were found. On the other hand, considerable variations in measured fecal GCM between family groups were revealed, indicating that the social settings of the particular group play an important role.

  13. p21 and Notch signalings in the persistently altered vagina induced by neonatal diethylstilbestrol exposure in mice.

    PubMed

    Nakamura, Takeshi; Miyagawa, Shinichi; Katsu, Yoshinao; Mizutani, Takeshi; Sato, Tomomi; Takeuchi, Takashi; Iguchi, Taisen; Ohta, Yasuhiko

    2012-12-01

    Female reproductive organs show organ-specific morphological changes during estrous cycles. Perinatal exposure to natural and synthetic estrogens including diethylstilbestrol (DES) or estrogenic chemicals induces estrogen-independent persistent proliferation of vaginal epithelium in mice. To understand the underlying mechanism of the estrogen-independent persistent vaginal changes induced by perinatal DES exposure, we examined global gene expressions in the vaginae of ovariectomized adult mice exposed neonatally to DES using a microarray. The cell cycle-related gene, p21, a cyclin-dependent kinase inhibitor, showed upregulation in the vagina, and p21 protein was localized in the basal layer of the vaginal epithelium in mice exposed neonatally to DES and an estrogen receptor α agonist, propyl pyrazole triol (PPT). The expressions of Notch receptors and Notch ligands were unchanged; however, the mRNAs of hairy-related basic helix-loop-helix (bHLH) transcription factor genes, Hes1, Hey1 and Heyl were persistently downregulated in the vagina, indicating estrogen-independent epithelial cell proliferation in mice exposed neonatally to DES and PPT.

  14. New Anthraquinone Derivatives from Geosmithia lavendula

    PubMed Central

    Malak, Lourin G.; Bishay, Daoud W.; Abdel-Baky, Afaf M.; Moharram, Ahmed M.; Cutler, Stephen J.; Ross, Samir A.

    2016-01-01

    A phytochemical study of Geosmithia lavendula Pitt led to the isolation of three new anthraquinones: 1-acetyl-2,4,6,8-tetrahydroxy-9,10-anthraquinone (1), 2-acetyl-1,4,5,7-tetrahydroxy-9,10-anthraquinone (2), and 1-acetyl-2,4,5,6,7-pentahydroxy-9,10-anthraquinone (3), as well as another new compound named didodecyl thiodipropionate (propionic acid, 3,3-sulfinyl di-1,1′-didodecyl ester) (4), along with ten known compounds: 1-acetyl-2,4,5,7-tetrahydroxy-9,10-anthraquinone (rhodolamprometrin) (5), 1-acetyl-2,4,5,7,8-pentahydroxy-9,10-anthraquinone (6), (22E)-ergosta-6,22-diene-3β,5α,8α-triol, p-hydroxybenzyl alcohol, oleic acid, D-mannitol, palmitic acid, stearic acid, cis-vaccenic acid and 2-decenal. The structures of the isolated metabolites were elucidated based on NMR spectroscopic and mass spectrometric data. Compound 1 exhibited moderate activity against methicillin resistant Staphylococcus aureus with an IC50 value of 16.1 μg/mL. PMID:23513726

  15. Identification of UV-Induced Diterpenes Including a New Diterpene Phytoalexin, Phytocassane F, from Rice Leaves by Complementary GC/MS and LC/MS Approaches.

    PubMed

    Horie, Kiyotaka; Inoue, Yasuno; Sakai, Miki; Yao, Qun; Tanimoto, Yosuke; Koga, Jinichiro; Toshima, Hiroaki; Hasegawa, Morifumi

    2015-04-29

    Rice phytoalexins are regarded as one of the most important weapons against pathogenic microorganisms. We attempted to identify novel phytoalexins and their derivatives using GC/MS and LC/MS analyses. Diterpene derivatives, 9β-pimara-7,15-diene-3β,6β,19-triol, 1, stemar-13-en-2α-ol, 2, and 1α,2α-dihydroxy-ent-12,15-cassadiene-3,11-dione, 3, were isolated from UV-irradiated rice leaves by chromatographic methods. These structures were confirmed by 1D- and 2D-NMR and MS analyses. Interestingly, all three compounds were accumulated following an infection by the rice blast pathogen Magnaporthe oryzae. Compounds 1 and 2 exhibited weak antifungal activity and may be the biosynthetic intermediates of rice phytoalexins momilactones and oryzalexin S, respectively. Compound 3 exhibited relatively high inhibitory activity against the fungal mycelial growth of M. oryzae to the same extent as the known phytoalexin phytocassane A. We conclude that 3 is a member of the cassane-type phytoalexin family and propose the name phytocassane F.

  16. Artemisinin selectively decreases functional levels of estrogen receptor-alpha and ablates estrogen-induced proliferation in human breast cancer cells.

    PubMed

    Sundar, Shyam N; Marconett, Crystal N; Doan, Victor B; Willoughby, Jamin A; Firestone, Gary L

    2008-12-01

    MCF7 cells are an estrogen-responsive human breast cancer cell line that expresses both estrogen receptor (ER) alpha and ERbeta. Treatment of MCF7 cells with artemisinin, an antimalarial phytochemical from the sweet wormwood plant, effectively blocked estrogen-stimulated cell cycle progression induced by either 17beta-estradiol (E(2)), an agonist for both ERs, or by propyl pyrazole triol (PPT), a selective ERalpha agonist. Artemisinin strongly downregulated ERalpha protein and transcripts without altering expression or activity of ERbeta. Transfection of MCF7 cells with ERalpha promoter-linked luciferase reporter plasmids revealed that the artemisinin downregulation of ERalpha promoter activity accounted for the loss of ERalpha expression. Artemisinin treatment ablated the estrogenic induction of endogenous progesterone receptor (PR) transcripts by either E(2) or PPT and inhibited the estrogenic stimulation of a luciferase reporter plasmid driven by consensus estrogen response elements (EREs). Chromatin immunoprecipitation assays revealed that artemisinin significantly downregulated the level of endogeneous ERalpha bound to the PR promoter, whereas the level of bound endogeneous ERbeta was not altered. Treatment of MCF7 cells with artemisinin and the pure antiestrogen fulvestrant resulted in a cooperative reduction of ERalpha protein levels and enhanced G(1) cell cycle arrest compared with the effects of either compound alone. Our results show that artemisinin switches proliferative human breast cancer cells from expressing a high ERalpha:ERbeta ratio to a condition in which ERbeta predominates, which parallels the physiological state linked to antiproliferative events in normal mammary epithelium.

  17. Water-soluble derivatives of 25-OCH3-PPD and their anti-proliferative activities.

    PubMed

    Zhou, Wu-Xi; Sun, Yuan-Yuan; Yuan, Wei-Hui; Zhao, Yu-Qing

    2017-03-18

    (20R)-25-Methoxyl-dammarane-3β,12β,20-triol (25-OCH3-PPD, AD-1) is a dammarane-type sapogenin showing anti-tumor potential. In the search for new anti-tumor agents with higher potency than our previously identified compound 25-OCH3-PPD, 11 novel sulfamic acid and diacid derivatives that could improve water solubility and contribute to good drug potency and pharmacokinetic profiles were designed and synthesized. Their in vitro anti-tumor activities in MCF-7, A-549, HCT-116, and BGC-823 cell lines and one normal cell line were tested by standard MTT assay. Results showed that compared with compound 25-OCH3-PPD, compounds 1, 4, and 5 exhibited higher cytotoxic activity on almost all cell lines, together with lower toxicity in the normal cell. In particular, compound 1 exhibited the best anti-tumor activity in the in vitro assays. The water solubility of 25-OCH3-PPD and its derivatives was tested and the results showed that the solubility of 25-OCH3-PPD sulfamic acid and diacid derivatives were better than that of 25-OCH3-PPD in water, which may provide valuable data for the research and development of new anti-tumor agents.

  18. Effect of Transition Metal Ions on the B Ring Oxidation of Sterols and their Kinetics in Oil-in-Water Emulsions

    NASA Astrophysics Data System (ADS)

    Lu, Baiyi; Hu, Yinzhou; Huang, Weisu; Wang, Mengmeng; Jiang, Yuan; Lou, Tiantian

    2016-06-01

    This study investigated the effect of metal ions on the oxidation of sterols and their kinetics in oil-in-water emulsions. Sterol substrates were added with different metal ions (Cu2+, Fe2+, Mn2+, Zn2+, Na+, and Mg2+) of five concentrations and investigated after 2 h of heating at 90 °C. The substrates added with Fe2+ and Cu2+ were heated continuously to evaluate the kinetics of four sterols and their corresponding sterol oxidation products (SOPs). Sterol oxidation increased as the metal ion concentration increased and the heating time was prolonged. The capability of the metal ions oxidizing sterols ranked as followed: Fe2+ > Cu2+ > Mn2+ > Zn2+ > Mg2+ ≈ Na+. 7-Ketosterol, 7β/7α-Hydroxysterol, 5β,6β/5α,6α-Epoxysterol, and Triols were the main oxides on the B ring, whereas 6β-Hydroxysterol was not or only slightly influenced. The acceleration of sterol degradation induced by Fe2+ and Cu2+, as well as the formation of oxidation products, followed first-order formation/elimination kinetics. The acceleration effect may be partly ascribed to the increase in elimination rate constant and formation rate constant. Transition metal ions can significantly induce sterol oxidation, which reduces food nutritional quality and triggers the formation of undesirable compounds, such as SOPs.

  19. Low density biodegradable shape memory polyurethane foams for embolic biomedical applications

    PubMed Central

    Singhal, Pooja; Small, Ward; Cosgriff-Hernandez, Elizabeth; Maitland, Duncan J; Wilson, Thomas S

    2014-01-01

    Low density shape memory polymer foams hold significant interest in the biomaterials community for their potential use in minimally invasive embolic biomedical applications. The unique shape memory behavior of these foams allows them to be compressed to a miniaturized form, which can be delivered to an anatomical site via a transcatheter process, and thereafter actuated to embolize the desired area. Previous work in this field has described the use of a highly covalently crosslinked polymer structure for maintaining excellent mechanical and shape memory properties at the application-specific ultra low densities. This work is aimed at further expanding the utility of these biomaterials, as implantable low density shape memory polymer foams, by introducing controlled biodegradability. A highly covalently crosslinked network structure was maintained by use of low molecular weight, symmetrical and polyfunctional hydroxyl monomers such as Polycaprolactone triol (PCL-t, Mn 900 g), N,N,N0,N0-Tetrakis (hydroxypropyl) ethylenediamine (HPED), and Tris (2-hydroxyethyl) amine (TEA). Control over the degradation rate of the materials was achieved by changing the concentration of the degradable PCL-t monomer, and by varying the material hydrophobicity. These porous SMP materials exhibit a uniform cell morphology and excellent shape recovery, along with controllable actuation temperature and degradation rate. We believe that they form a new class of low density biodegradable SMP scaffolds that can potentially be used as “smart” non-permanent implants in multiple minimally invasive biomedical applications. PMID:24090987

  20. γ-Hydroxyethyl piperidine iminosugar and N-alkylated derivatives: a study of their activity as glycosidase inhibitors and as immunosuppressive agents.

    PubMed

    Markad, Pramod R; Sonawane, Dhiraj P; Ghosh, Sougata; Chopade, Balu A; Kumbhar, Navnath; Louat, Thierry; Herman, Jean; Waer, Mark; Herdewijn, Piet; Dhavale, Dilip D

    2014-11-01

    An efficient and practical strategy for the synthesis of (3R,4s,5S)-4-(2-hydroxyethyl) piperidine-3,4,5-triol and its N-alkyl derivatives 8a-f, starting from the D-glucose, is reported. The chiral pool methodology involves preparation of the C-3-allyl-α-D-ribofuranodialdose 10, which was converted to the C-5-amino derivative 11 by reductive amination. The presence of C-3-allyl group gives an easy access to the requisite hydroxyethyl substituted compound 13. Intramolecular reductive aminocyclization of C-5 amino group with C-1 aldehyde provided the γ-hydroxyethyl substituted piperidine iminosugar 8a that was N-alkylated to get N-alkyl derivatives 8b-f. Iminosugars 8a-f were screened against glycosidase enzymes. Amongst synthetic N-alkylated iminosugars, 8b and 8c were found to be α-galactosidase inhibitors while 8d and 8e were selective and moderate α-mannosidase inhibitors. In addition, immunomodulatory activity of compounds 8a-f was examined. These results were substantiated by molecular docking studies using AUTODOCK 4.2 programme.

  1. The Stoichiometry of the Conversion of Cholesterol and Hydroxycholesterols to Pregnenolone (3β-Hydroxypregn-5-en-20-one) Catalysed by Adrenal Cytochrome P-450

    PubMed Central

    Shikita, Mikio; Hall, Peter F.

    1974-01-01

    The stoichiometry of the side-chain cleavage of cholesterol (cholest-5-en-3β-ol), 20α-hydroxycholesterol (cholest-5-ene-3β,20α-diol), and 20α,22-dihydroxycholesterol (cholest-5-ene-3β,20α,22-triol) has been examined with respect to TPNH, oxygen and H+. Side-chain cleavage of cholesterol can be described by the following equation: Cholesterol + 3TPNH + 3H+ + 3O2 → Pregnenolone (3β-hydroxypregn-5-ene-20-one) + isocapraldehyde + 3 TPN+ 4H2O Stoichiometry of 20 α-hydroxycholesterol is 2TPNH and 2O2 per mole of cleavage and with 20α, 22-dihydroxycholesterol the values are 1:1:1. In addition 1 mole of H+ is consumed per mole of TPNH oxidized in each of these reactions. These observations are in keeping with a mechanism previously proposed in the literature, namely: Cholesterol → 20α-OH-Cholesterol → 20α, 22-di-OH-Cholesterol → pregnenolone Discordant observations are reviewed and it is concluded that insufficient data are available to sustain objections to this pathway. PMID:4151518

  2. Acetonitrile adduct formation as a sensitive means for simple alcohol detection by LC-MS.

    PubMed

    Bogseth, Roy; Edgcomb, Eric; Jones, Christopher M; Chess, Edward K; Hu, Peifeng

    2014-11-01

    Simple alcohols formed protonated acetonitrile adducts containing up to two acetonitrile molecules when analyzed by ESI or APCI in the presence of acetonitrile in the solvent. These acetonitrile adducts underwent dissociation to form a nitrilium ion, also referred to as the substitution ion. Diols and triols behaved differently. In ESI, they formed only one acetonitrile adduct containing one acetonitrile. The S ion was not observed in ESI and was only weakly observed from the dissociation of the (M + ACN + H)(+) ion. On the other hand, the S ion was abundantly formed from the diols in APCI. This formation of acetonitrile adducts and substitution ion from simple alcohols/diols offers an opportunity to detect simple alcohols/diols sensitively by LC-MS interfaced by ESI or APCI. The utility of this chemistry was demonstrated in a method developed for the quantification of cyclohexanol in rat plasma by monitoring the CID-induced fragmentation from the S ion to a fragment ion.

  3. Cholesterol autoxidation in phospholipid membrane bilayers

    SciTech Connect

    Sevanian, A.; McLeod, L.L.

    1987-09-01

    Lipid peroxidation in unilamellar liposomes of known cholesterol-phospholipid composition was monitored under conditions of autoxidation or as induced by a superoxide radical generating system, gamma-irradiation or cumene hydroperoxide. Formation of cholesterol oxidation products was indexed to the level of lipid peroxidation. The major cholesterol oxidation products identified were 7-keto-cholesterol, isomeric cholesterol 5,6-epoxides, isomeric 7-hydroperoxides and isomeric 3,7-cholestane diols. Other commonly encountered products included 3,5-cholestadiene-7-one and cholestane-3 beta, 5 alpha, 6 beta-triol. Superoxide-dependent peroxidation required iron and produced a gradual increase in 7-keto-cholesterol and cholesterol epoxides. Cholesterol oxidation was greatest in liposomes containing high proportions of unsaturated phospholipid to cholesterol (4:1 molar ratio), intermediate with low phospholipid to cholesterol ratios (2:1) and least in liposomes prepared with dipalmitoylphosphatidylcholine and cholesterol. This relationship held regardless of the oxidizing conditions used. Cumene hydroperoxide-dependent lipid peroxidation and/or more prolonged oxidations with other oxidizing systems yielded a variety of products where cholesterol-5 beta,6 beta-epoxide, 7-ketocholesterol and the 7-hydroperoxides were most consistently elevated. Oxyradical initiation of lipid peroxidation produced a pattern of cholesterol oxidation products distinguishable from the pattern derived by cumene hydroperoxide-dependent peroxidation.

  4. Crystal structure of canagliflozin hemihydrate.

    PubMed

    Liu, Kai-Hang; Gu, Jian-Ming; Hu, Xiu-Rong; Tang, Gu-Ping

    2016-05-01

    There are two canagliflozin mol-ecules (A and B) and one water mol-ecule in the asymmetric unit of the title compound, C24H25FO5S·0.5H2O [systematic name: (2S,3R,4R,5S,6R)-2-(3-{[5-(4-fluoro-phen-yl)thio-phen-2-yl]meth-yl}-4-methylphen-yl)-6-(hy-droxy-meth-yl)-3,4,5,6-tetra-hydro-2H-pyran-3,4,5-triol hemihydrate]. The dihedral angles between the methyl-benzene and thio-phene rings are 115.7 (4) and 111.7 (4)°, while the dihedral angles between the fluoro-benzene and thio-phene rings are 24.2 (6) and 20.5 (9)° in mol-ecules A and B, respectively. The hydro-pyran ring exhibits a chair conformation in both canagliflozin mol-ecules. In the crystal, the canagliflozin mol-ecules and lattice water mol-ecules are connected via O-H⋯O hydrogen bonds into a three-dimensional supra-molecular architecture.

  5. Crystal structure of canagliflozin hemihydrate

    PubMed Central

    Liu, Kai-Hang; Gu, Jian-Ming; Hu, Xiu-Rong; Tang, Gu-Ping

    2016-01-01

    There are two canagliflozin mol­ecules (A and B) and one water mol­ecule in the asymmetric unit of the title compound, C24H25FO5S·0.5H2O [systematic name: (2S,3R,4R,5S,6R)-2-(3-{[5-(4-fluoro­phen­yl)thio­phen-2-yl]meth­yl}-4-methylphen­yl)-6-(hy­droxy­meth­yl)-3,4,5,6-tetra­hydro-2H-pyran-3,4,5-triol hemihydrate]. The dihedral angles between the methyl­benzene and thio­phene rings are 115.7 (4) and 111.7 (4)°, while the dihedral angles between the fluoro­benzene and thio­phene rings are 24.2 (6) and 20.5 (9)° in mol­ecules A and B, respectively. The hydro­pyran ring exhibits a chair conformation in both canagliflozin mol­ecules. In the crystal, the canagliflozin mol­ecules and lattice water mol­ecules are connected via O—H⋯O hydrogen bonds into a three-dimensional supra­molecular architecture. PMID:27308030

  6. Inhibitor versus chaperone behaviour of d-fagomine, DAB and LAB sp(2)-iminosugar conjugates against glycosidases: A structure-activity relationship study in Gaucher fibroblasts.

    PubMed

    Mena-Barragán, Teresa; García-Moreno, M Isabel; Nanba, Eiji; Higaki, Katsumi; Concia, Alda Lisa; Clapés, Pere; García Fernández, José Manuel; Ortiz Mellet, Carmen

    2016-10-04

    A library of sp(2)-iminosugar conjugates derived from the piperidine iminosugar d-fagomine and the enantiomeric pyrrolidine iminosugars DAB and LAB has been generated in only two steps involving direct coupling of the fully unprotected polyhydroxylated heterocycles with isothiocyanates, to give monocyclic thiourea adducts, and further intramolecular nucleophilic displacement of the δ-located primary hydroxyl group by the thiocarbonyl sulphur atom, affording bicyclic isothioureas. These transformations led to a dramatic shift in the inhibitory selectivity from α- to β-glucosidases, with inhibition potencies that depended strongly on the nature of the aglycone-type moiety in the conjugates. Some of the new derivatives behaved as potent inhibitors of human β-glucocerebrosidase (GCase), the lysosomal enzyme whose dysfunction is responsible for Gaucher disease. Moreover, GCase inhibition was 10-fold weaker at pH 5 as compared to pH 7, which is generally considered as a good property for pharmacological chaperones. Surprisingly, most of the compounds strongly inhibited GCase in wild type fibroblasts at rather low concentrations, showing an unfavourable chaperone/inhibitor balance on disease-associated GCase mutants in cellulo. A structure-activity relationship analysis points to the need for keeping a contiguous triol system in the glycone moiety of the conjugates to elicit a chaperone effect. In any case, the results reported here represent a proof of concept of the utmost importance of implementing diversity-oriented strategies for the identification and optimization of potent and specific glycosidase inhibitors and chaperones.

  7. Identification of antibacterial constituents from the indigenous Australian medicinal plant Eremophila duttonii F. Muell. (Myoporaceae).

    PubMed

    Smith, Joshua E; Tucker, David; Watson, Kenneth; Jones, Graham Lloyd

    2007-06-13

    This paper reports on the isolation and identification of antibacterial constituents from the indigenous Australian medicinal plant Eremophila duttonii F. Muell. (Myoporaceae). Preparations derived from this plant are used by indigenous populations in the topical treatment of minor wounds, otitis and ocular complaints, and as a gargle for sore throat. Several authors have reported extracts of this plant to effect rapid bacteriolysis and inhibit growth of a wide range of Gram-positive micro-organisms. In other studies involving screening of native medicinal plants for antibacterial activity, extracts of Eremophila duttonii have been reported to consistently exhibit the highest potency amongst all species included. From a hexane extract, we identified two diterpenes of the serrulatane class, the principal constituents responsible for antibacterial activity and present as major constituents of the resinous leaf cuticle: serrulat-14-en-7,8,20-triol (1) and serrulat-14-en-3,7,8,20-tetraol (2). In addition, a hydroxylated furanosesquiterpene with mild antibacterial activity which appeared to be a novel compound was isolated from the extract and tentatively identified as 4-hydroxy-4-methyl-1-(2,3,4,5-tetrahydro-5-methyl[2,3'-bifuran]-5-yl) pentan-2-one. Minimum inhibitory concentrations for each of the compounds against three Gram-positive bacteria: Staphylococcus aureus (ATCC 29213), Staphylococcus epidermidis (ATCC 12228) and Streptococcus pneumoniae (ARL 10582), were determined using a micro-titre plate broth dilution assay.

  8. Inulin as a novel biocompatible coating: evaluation of surface affinities toward CaHPO4, α-Fe2O3, ZnO, CaHPO4@ZnO and α-Fe2O3@ZnO nanoparticles.

    PubMed

    Santillán-Urquiza, E; Arteaga-Cardona, F; Hernandez-Herman, E; Pacheco-García, P F; González-Rodríguez, R; Coffer, J L; Mendoza-Alvarez, M E; Vélez-Ruiz, J F; Méndez-Rojas, M A

    2015-12-15

    The introduction of biocompatible coatings onto nanoparticle surfaces can be synthetically challenging. In this work, calcium phosphate (brushite, CaHPO4⋅2H2O), iron oxide (hematite, α-Fe2O3), zinc oxide (ZnO), and CaHPO4@ZnO and α-Fe2O3@ZnO nanoparticles were synthesized and treated with the biocompatible, biodegradable, polysaccharide inulin {(2R,3S,4S,5R)-2-[[(2R,3S,4S,5R)-3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]oxymethyl]-5-(hydroxymethyl)oxolane-2,3,4-triol} under mild conditions. The products were fully characterized by Fourier transforms infrared (FTIR) spectroscopy, energy dispersive spectroscopy (EDS), dynamic light scattering (DLS), differential thermogravimetric/differential thermal analysis (TGA/DTA), transmission electron microscopy (TEM) and powder X-ray diffraction (XRD). Surface interactions among hematite and brushite with inulin are weak, but coating the nanoparticle surface with ZnO increased the affinity toward the polysaccharide. Inulin adsorption on the nanoparticle surface was confirmed by thermal and spectroscopic analyses. The nanoparticles had diameters ranging from 50 to 80nm, with nearly spherical morphology. The nanoparticles sizes, stability and solubility in water could make them useful as components for enriched foods.

  9. Diplopimarane, a 20-nor-ent-pimarane produced by the oak pathogen Diplodia quercivora.

    PubMed

    Andolfi, Anna; Maddau, Lucia; Basso, Sara; Linaldeddu, Benedetto T; Cimmino, Alessio; Scanu, Bruno; Deidda, Antonio; Tuzi, Angela; Evidente, Antonio

    2014-11-26

    In this study a new 20-nor-ent-pimarane, named diplopimarane, was isolated together with sphaeropsidins A (9) and C (10), and (+)-epiepoformin (11) from organic crude extracts of Diplodia quercivora, a recently described oak pathogen originally found on declining Quercus canariensis trees in Tunisia. Diplopimarane was characterized as (1S,2R)-2,8,8-trimethyl-2-vinyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-1,9,10-triol by spectroscopic, X-ray, optical, and chemical methods. It exhibited a wide range of activities including remarkable phytotoxicity on nonhost plants such as tomato cuttings, moderate antifungal activity against important plant pathogens, and moderate zootoxicity against Artemia salina. Its derivatives (2-4 and 6) were also tested for their phytotoxic and zootoxic activities. All these derivatives proved to be active against A. salina at 200 μg/mL, while 2 and 6 were also active on tomato cuttings. The other secondary metabolites (9, 10, and 11) herein reported for D. quercivora exhibited phytotoxic, antifungal, and zootoxic activity. This is the first report on the secondary metabolites secreted in vitro by this oak pathogen that could be key components of its adaptative strategies.

  10. Special susceptive aqueous ammonia chemi-sensor: extended applications of novel UV-curable polyurethane-clay nanohybrid.

    PubMed

    Khan, Sher Bahadar; Rahman, Mohammed M; Jang, Eui Soung; Akhtar, Kalsoom; Han, Haksoo

    2011-05-30

    In this contribution, chemical sensor for the detection of aqueous ammonia has been fabricated using UV-curable polyurethane acrylate (PU) and nanohybrids (NH-1, NH-3 and NH-5). PU has been prepared by reacting polycaprolactone triol (PCLT) and isophorone diisocyanate (IPDI) while the nanohybrids, NH-1, NH-3, and NH-5 have been synthesized by solution blending method using PU with 1, 3, and 5 wt% loading levels of C-20B. PU and their nanohybrids showed higher sensitivity investigated by I-V technique using aqueous ammonia as a target chemical. All the nanohybrids showed higher sensitivity as compared to neat PU. The sensitivity increased with increase in clay content and the nanohybrid containing 5 wt% of clay showed the highest sensitivity (8.5254 μA cm(-2) mM(-1)) with the limit of detection (LOD) of 0.0175 ± 0.001 μM, being 7.8 times higher than pure PU. The calibration plot for all the sensors was linear over the large range of 0.05 μM to 0.05 M. The response time of the fabricated sensor was <10.0 s. Therefore, one can fabricate efficient aqueous ammonia sensor by utilization of nanohybrid as an efficient electron mediator.

  11. Local Proton Source in Electrocatalytic CO2 Reduction with [Mn(bpy-R)(CO)3 Br] Complexes.

    PubMed

    Franco, Federico; Cometto, Claudio; Nencini, Luca; Barolo, Claudia; Sordello, Fabrizio; Minero, Claudio; Fiedler, Jan; Robert, Marc; Gobetto, Roberto; Nervi, Carlo

    2017-01-20

    The electrochemical behavior of fac-[Mn(pdbpy)(CO)3 Br] (pdbpy=4-phenyl-6-(phenyl-2,6-diol)-2,2'-bipyridine) (1) in acetonitrile under Ar, and its catalytic performances for CO2 reduction with added water, 2,2,2-trifluoroethanol (TFE), and phenol are discussed in detail. Preparative-scale electrolysis experiments, carried out at -1.5 V versus the standard calomel electrode (SCE) in CO2 -saturated acetonitrile, reveal that the process selectivity is extremely sensitive to the acid strength, producing CO and formate in different faradaic yields. A detailed spectroelectrochemical (IR and UV/Vis) study under Ar and CO2 atmospheres shows that 1 undergoes fast solvolysis; however, dimer formation in acetonitrile is suppressed, resulting in an atypical reduction mechanism in comparison with other reported Mn(I) catalysts. Spectroscopic evidence of Mn hydride formation supports the existence of different electrocatalytic CO2 reduction pathways. Furthermore, a comparative investigation performed on the new fac-[Mn(ptbpy)(CO)3 Br] (ptbpy=4-phenyl-6-(phenyl-3,4,5-triol)-2,2'-bipyridine) catalyst (2), bearing a bipyridyl derivative with OH groups in different positions to those in 1, provides complementary information about the role that the local proton source plays during the electrochemical reduction of CO2 .

  12. Microbial-catalysed derivatization of anti-cancer drug exemestane and cytotoxicity of resulting metabolites against human breast adenocarcinoma cell line (MCF-7) in vitro.

    PubMed

    Baydoun, Serine; Wahab, Atia-Tul; Bano, Saira; Imad, Rehan; Choudhary, M Iqbal

    2016-11-01

    Structural transformation of anticancer drug exemestane (1) with fungi Cunninghamella blakesleeana (ATCC 8688A), Curvularia lunata (ATCC 12017), Aspergillus niger (ATCC 10549), and Gibberella fujikuroi (ATCC 10704) yielded eleven metabolites 2-12, in which 2 and 8 were identified as new. Their structures were characterized as 6-methylene-5α-androstane-3β,16β,17β-triol (2), 17β-hydroxy-6-methyleneandrosta-4-ene-3-one (3), 6α-spiroxirandrost-4-ene-3,17-dione (4), 6-methyleneandrosta-4-ene-3,17-dione (5), 6β,17β-dihydroxyandrost-4-en-3-one (6), 17β-hydroxy-6α-spiroxirandrost-1,4-diene-3-one (7), 17β-hydroxy-6α-hydroxymethylandrosta-1,4-dien-3-one (8), 6α-hydroxymethylandrosta-1,4-diene-3,17-dione (9), 17β-hydroxy-6-methyleneandrosta-1,4-diene-3,16-dione (10), 6α-hydroxy-4-androstene-3,17-dione (11), and 6α-hydroxymethylandrost-4-ene-3,17-dione (12). Substrate 1, and its transformed products were evaluated for their cytotoxicity against breast cancer cell line (MCF-7). Compound 3 was found to be moderately active with an IC50 of 33.43±4.01μM, in comparison to the standard anti-cancer drug, doxorubicin (IC50=0.92±0.1μM).

  13. Resin-bound chiral derivatizing agents for assignment of configuration by NMR spectroscopy.

    PubMed

    Porto, Silvia; Seco, José Manuel; Espinosa, Juan Félix; Quiñoá, Emilio; Riguera, Ricardo

    2008-08-01

    A general methodology for assigning the configuration of chiral mono- and polyfunctional compounds by NMR is presented. The approach is based on the use of polystyrene-bound chiral derivatizing agents (CDA-resins) specifically designed to achieve the high-yield formation of the covalent linkages (amide or ester bonds) between the substrate and the chiral auxiliary within the NMR tube, without the need for other manipulations, on a microscale level and in a short time. The deuterated NMR solvents (CDCl3, CD3CN, CS2/CD2Cl2) are also the reaction solvents and separations, purifications or workups of any kind are not necessary prior to recording the spectra. The CDA-resins prepared included MPA, 9-AMA, BPG, MTPA, and 2-NTBA as auxiliary agents incorporated either as single enantiomers or as mixed combinations of the (R)- and the (S)-enantiomers at unequal and known ratios. The high versatility of these systems was successfully demonstrated in a variety of ways based on double and single derivatization, low temperature experiments, or the formation of metal complexes. The approach allowed the absolute configurations of chiral primary amines, primary and secondary alcohols, cyanohydrins, thiols, diols, triols, and amino alcohols to be determined. Extensive high-resolution magic angle spinning (HR-MAS) NMR experiments allowed the characterization of the new CDA-resins and enabled the study of their stability and regioselectivity.

  14. Effects of nanoporous anodic titanium oxide on human adipose derived stem cells.

    PubMed

    Malec, Katarzyna; Góralska, Joanna; Hubalewska-Mazgaj, Magdalena; Głowacz, Paulina; Jarosz, Magdalena; Brzewski, Pawel; Sulka, Grzegorz D; Jaskuła, Marian; Wybrańska, Iwona

    The aim of current bone biomaterials research is to design implants that induce controlled, guided, successful, and rapid healing. Titanium implants are widely used in dental, orthopedic, and reconstructive surgery. A series of studies has indicated that cells can respond not only to the chemical properties of the biomaterial, but also, in particular, to the changes in surface topography. Nanoporous materials remain in focus of scientific queries due to their exclusive properties and broad applications. One such material is nanostructured titanium oxide with highly ordered, mutually perpendicular nanopores. Nanoporous anodic titanium dioxide (TiO2) films were fabricated by a three-step anodization process in propan-1,2,3-triol-based electrolyte containing fluoride ions. Adipose-derived stem cells offer many interesting opportunities for regenerative medicine. The important goal of tissue engineering is to direct stem cell differentiation into a desired cell lineage. The influence of nanoporous TiO2 with pore diameters of 80 and 108 nm on cell response, growth, viability, and ability to differentiate into osteoblastic lineage of human adipose-derived progenitors was explored. Cells were harvested from the subcutaneous abdominal fat tissue by a simple, minimally invasive, and inexpensive method. Our results indicate that anodic nanostructured TiO2 is a safe and nontoxic biomaterial. In vitro studies demonstrated that the nanotopography induced and enhanced osteodifferentiation of human adipose-derived stem cells from the abdominal subcutaneous fat tissue.

  15. Effect of Transition Metal Ions on the B Ring Oxidation of Sterols and their Kinetics in Oil-in-Water Emulsions

    PubMed Central

    Lu, Baiyi; Hu, Yinzhou; Huang, Weisu; Wang, Mengmeng; Jiang, Yuan; Lou, Tiantian

    2016-01-01

    This study investigated the effect of metal ions on the oxidation of sterols and their kinetics in oil-in-water emulsions. Sterol substrates were added with different metal ions (Cu2+, Fe2+, Mn2+, Zn2+, Na+, and Mg2+) of five concentrations and investigated after 2 h of heating at 90 °C. The substrates added with Fe2+ and Cu2+ were heated continuously to evaluate the kinetics of four sterols and their corresponding sterol oxidation products (SOPs). Sterol oxidation increased as the metal ion concentration increased and the heating time was prolonged. The capability of the metal ions oxidizing sterols ranked as followed: Fe2+ > Cu2+ > Mn2+ > Zn2+ > Mg2+ ≈ Na+. 7-Ketosterol, 7β/7α-Hydroxysterol, 5β,6β/5α,6α-Epoxysterol, and Triols were the main oxides on the B ring, whereas 6β-Hydroxysterol was not or only slightly influenced. The acceleration of sterol degradation induced by Fe2+ and Cu2+, as well as the formation of oxidation products, followed first-order formation/elimination kinetics. The acceleration effect may be partly ascribed to the increase in elimination rate constant and formation rate constant. Transition metal ions can significantly induce sterol oxidation, which reduces food nutritional quality and triggers the formation of undesirable compounds, such as SOPs. PMID:27328709

  16. The antigluconeogenic activity of cucurbitacins from Momordica charantia.

    PubMed

    Chen, Jian-Chao; Lau, Clara Bik-San; Chan, Judy Yuet-Wa; Fung, Kwok-Pui; Leung, Ping-Chung; Liu, Jie-Qing; Zhou, Lin; Xie, Ming-Jin; Qiu, Ming-Hua

    2015-03-01

    Five new cucurbitacins, kuguacins II-VI (1-5), along with five known analogues (6-10), were obtained from the fruit of Momordica charantia. Structures of the new compounds were elucidated as 5β,19-epoxycucurbit-23-en-7-on-3β,25-diol (1), 5β,19-epoxycucurbit-7,23-dion-3β,25-diol (2), 5β,19-epoxycucurbit-6-en-19,23-dion-3β,25-diol (3), 5β,19-epoxy-23,24,25,26,27-pentanorcucurbit-6-en-7,19-dion-3β,22-diol (4), and cucurbit-5-en-7,23-dion-3β,19,25-triol (5) by extensive spectroscopic and single-crystal X-ray diffraction analyses. Some cucurbitane compounds from this species were screened for their potential antidiabetic properties in terms of antigluconeogenic activity. As a result, compounds 1, 10, 11, and 12 (at 25-100 µM) showed concentration-dependent inhibition on glucose production from liver cells. In addition, compounds 11 and 12 (at 100 µM) showed around 20-30 % inhibition on PEPCK activity.

  17. A Single Molecular Diels-Alder Crosslinker for Achieving Recyclable Cross-Linked Polymers.

    PubMed

    Chen, Shengli; Wang, Fenfen; Peng, Yongjin; Chen, Tiehong; Wu, Qiang; Sun, Pingchuan

    2015-09-01

    A triol-functional crosslinker combining the thermoreversible properties of Diels-Alder (DA) adducts in one molecule is designed, synthesized, and used as an ideal substitute of a traditional crosslinker to prepare thermal recyclable cross-linked polyurethanes with excellent mechanical properties and recyclability in a very simple and efficient way. The recycle property of these materials achieved by the DA/retro-DA reaction at a suitable temperature is verified by differential scanning calorimetry and in situ variable temperature solid-state NMR experiments during the cyclic heating and cooling processes. The thermal recyclability and remending ability of the bulk polyurethanes is demonstrated by three polymer processing methods, including hot-press molding, injection molding, and solution casting. It is notable that all the recycled cross-linked polymers display nearly invariable elongation/stress at break compared to the as-synthesized samples. Further end-group functionalization of this single molecular DA crosslinker provides the potential in preparing a wide range of recyclable cross-linked polymers.

  18. Correlations for Adsorption of Oxygenates onto Zeolites from Aqueous Solutions

    SciTech Connect

    Mallon, Elizabeth E.; Babineau, Ian J.; Kranz, Joshua I.; Guefrachi, Yasmine; Siepmann, J. Ilja; Bhan, Aditya; Tsapatsis, Michael

    2011-10-06

    Henry’s constants (K{sub ads}) for adsorption of C₃ polyfunctional molecules onto zeolites from aqueous solutions at 278 K were obtained and compared with the octanol–water partition coefficients, K{sub ow}, which were calculated using the prevalent ClogP group contribution method. K{sub ads} increases linearly with K{sub ow} for these adsorbates on H–ZSM-5 (MFI), FAU, BEA, and ITQ-1 (MWW). K{sub ads} values for C₂–C₆ diol adsorption at 278 K are also linearly correlated with K{sub ow} regardless of interactions in the bulk phase as measured by the solution activity coefficient. Exceptions to the correlation established between K{sub ads} and K{sub ow} are the adsorption of 1,2,ω-triols with carbon number greater than three on H–ZSM-5 and adsorption of all oxygenates studied on FER, which we postulate to be due to the effect of changing adsorption configuration with adsorbate/zeolite structure which cannot be captured by K{sub ow} alone. These results enable the prediction of separation selectivities of biomass-derived compounds on zeolite adsorbents.

  19. Antifungal activity of flavonoids isolated from mango (Mangifera indica L.) leaves.

    PubMed

    Kanwal, Qudsia; Hussain, Ishtiaq; Latif Siddiqui, Hamid; Javaid, Arshad

    2010-12-01

    Five flavonoids, namely (-)-epicatechin-3-O-β-glucopyranoside (1), 5-hydroxy-3-(4-hydroxylphenyl)pyrano[3,2-g]chromene-4(8H)-one (2), 6-(p-hydroxybenzyl)taxifolin-7-O-β-D-glucoside (tricuspid) (3), quercetin-3-O-α-glucopyranosyl-(1 → 2)-β-D-glucopyranoside (4) and (-)-epicatechin(2-(3,4-dihydroxyphenyl)-3,4-dihydro-2H-chromene-3,5,7-triol (5), were isolated from the leaves of mango (Mangifera indica L.). Antifungal activity of these compounds was evaluated against five fungal species, namely Alternaria alternata (Fr.) Keissler, Aspergillus fumigatus Fresenius, Aspergillus niger van Tieghem, Macrophomina phaseolina (Tassi) Goid. and Penicillium citrii. Six concentrations, namely 100, 300, 500, 700, 900 and 1000 ppm of each of the five flavonoids were employed by means of the poisoned medium technique. All concentrations of the five test flavonoids significantly suppressed fungal growth. However, the specificity of different test compounds was evident against different fungal species. In general, antifungal activity of the flavonoids was gradually increased by increasing their concentrations. The highest concentration (of 1000 ppm) of compounds 1-5 reduced the growth of different target fungal species by 63-97%, 56-96%, 76-99%, 76-98% and 82-96%, respectively.

  20. Herbicidal activity of flavonoids of mango leaves against Parthenium hysterophorus L.

    PubMed

    Javaid, Arshad; Shafique, Shazia; Kanwal, Qudsia; Shafique, Sobiya

    2010-11-01

    This study was undertaken to investigate the herbicidal activity of mango (Mangifera indica L.) leaves against parthenium weed (Parthenium hysterophorus L.). The aqueous leaf extract at 15% concentration (on fresh weight basis) significantly reduced germination, shoot length and the shoot and root biomasses of parthenium seedlings. In a leaf residue incorporation pot trial, 2% residue incorporation treatment significantly suppressed the root and shoot biomasses of parthenium, while a 5% residue treatment completely stopped the growth of the weed. Five flavonoids, namely (-)-epicatechin-3-O-β-glucopyranoside (1), 5-hydroxy-3-(4-hydroxyphenyl)pyrano[3,2-g]chromene-4(8H)-one (2), 6-(p-hydroxybenzyl)taxifolin-7-O-β-D-glucoside (tricuspid) (3), quercetin-3-O-α-glucopyranosyl-(1 → 2)-β-D-glucopyranoside (4) and (-)-epicatechin(2-(3,4-dihydroxyphenyl)-3,4-dihydro-2H chromene-3,5,7-triol (5) were isolated from mango leaves. In a laboratory bioassay, 50 ppm solution of compounds 3 and 4 caused yellowing of the parthenium seedlings. A 250 ppm solution of compound 4 also significantly reduced germination and the root and shoot lengths of parthenium seedlings. This study concludes that compound 4 exhibits herbicidal activity against parthenium weed.

  1. Lignan derivatives from the stem bark of Syzygium cumini (L.) Skeels.

    PubMed

    Mir, Qurat Y; Ali, M; Alam, Prawez

    2009-01-01

    Phytochemical investigation of the stem bark of Syzygium cumini (L.) Skeels (Myrtaceae) yielded four new lignan derivatives characterised as (7alpha,8alpha,2'alpha)-3,4,5-trimethoxy-7,3',1',9'-diepoxylignan (cuminiresinol), (7alpha,7'alpha,8alpha,8'alpha)-3,4-dioxymethylene-3',4'-dimethoxy-7,9',7',9-diepoxylignan-5'-ol (5'-hydroxy-methyl-piperitol), (7alpha,7'alpha,8alpha,8'alpha)-3'-methoxy-9-oxo-7,9',7',9-diepoxylignan-3,4,4'-triol or 3-demethyl-9-oxo-pinoresinol (syzygiresinol A), (7alpha,7'alpha,8alpha,8'alpha)-9-oxo-7,9',7',9-diepoxylignan-3,4,3',4',5'-pentaol or 3,3'-didemethyl-9-oxo-pinoresinol (syzygiresinol B) along with the known lignans di-demethyl-5-hydroxypinoresinol, dimethylpinoresinol, didemethoxypinoresinol, pinoresinol and 4'-methyl-5'-hydroxypinoresinol. The structures of these lignans were elucidated on the basis of structural data analysis and chemical reactions.

  2. Phytotoxic and Nematicidal Components of Lavandula luisieri.

    PubMed

    Julio, Luis F; Barrero, Alejandro F; Herrador del Pino, M Mar; Arteaga, Jesús F; Burillo, Jesús; Andres, Maria Fe; Díaz, Carmen E; González-Coloma, Azucena

    2016-02-26

    Several preparations were obtained from the aerial parts of predomesticated Lavandula luisieri, including the essential oil and ethanolic, hexane, and ethyl acetate extractives. Additionally, pilot plant vapor pressure extraction was carried out at a pressure range of 0.5-1.0 bar to give a vapor pressure oil and an aqueous residue. A chemical study of the hexane extract led to the isolation of six necrodane derivatives (1, 2, and 4-7), with four of these (1, 2, 5, and 7) being new, as well as camphor, a cadinane sesquiterpene (9), tormentic acid, and ursolic acid. The EtOAc and EtOH extracts contained a mixture of phenolic compounds with rosmarinic acid being the major component. Workup of the aqueous residue resulted in the isolation of the necrodane 3 and (1R*,2S*,4R*)-p-menth-5-ene-1,2,8-triol (8), both new natural compounds. The structures of the new compounds were established based on their spectroscopic data. The phytotoxic and nematicidal activities of these compounds were evaluated.

  3. Effects of additives on surfactant phase behavior relevant to bacteriorhodopsin crystallization

    PubMed Central

    Berger, Bryan W.; Gendron, Colleen M.; Lenhoff, Abraham M.; Kaler, Eric W.

    2006-01-01

    The interactions leading to crystallization of the integral membrane protein bacteriorhodopsin solubilized in n-octyl-β-D-glucoside were investigated. Osmotic second virial coefficients (B22) were measured by self-interaction chromatography using a wide range of additives and precipitants, including polyethylene glycol (PEG) and heptane-1,2,3-triol (HT). In all cases, attractive protein–detergent complex (PDC) interactions were observed near the surfactant cloud point temperature, and there is a correlation between the surfactant cloud point temperatures and PDC B22 values. Light scattering, isothermal titration calorimetry, and tensiometry reveal that although the underlying reasons for the patterns of interaction may be different for various combinations of precipitants and additives, surfactant phase behavior plays an important role in promoting crystallization. In most cases, solution conditions that led to crystallization fell within a similar range of slightly negative B22 values, suggesting that weakly attractive interactions are important as they are for soluble proteins. However, the sensitivity of the cloud point temperatures and resultant coexistence curves varied significantly as a function of precipitant type, which suggests that different types of forces are involved in driving phase separation depending on the precipitant used. PMID:17088325

  4. Anti-inflammatory and anti-melanogenic steroidal saponin glycosides from Fenugreek (Trigonella foenum-graecum L.) seeds.

    PubMed

    Kawabata, Tetsuro; Cui, Ming-Yue; Hasegawa, Tatsuya; Takano, Fumihide; Ohta, Tomihisa

    2011-05-01

    Fenugreek seed ( Trigonella foenum-graecum L.) is used as an herbal medicine for treating metabolic and nutritive dysfunctions. To determine if this plant has other beneficial effects, we tested the inhibitory activities of a methanol (MeOH) extract of fenugreek seed on the production of inflammatory cytokines and melanin synthesis in cultured cell lines in vitro. The MeOH extract inhibited the production of phorbol-12-myristate-13-acetate-induced inflammatory cytokines such as tumor necrosis factor (TNF)-α in cultured THP-1 cells, and also restrained the intracellular synthesis of melanin in murine melanoma B16F1 cells. We isolated three active constituents from fenugreek seed extracts. These were identified as the steroidal saponins 26- O-β-D-glucopyranosyl-(25 R)-furost-5(6)-en-3 β,22 β,26-triol-3- O-α-L-rhamno-pyranosyl-(1'' → 2')-O-[β-D-glucopyranosyl-(1''' → 6')- O]-β-D-glucopyranoside 1, minutoside B 2, and pseudoprotodioscin 3. Compounds 1 and 2 strongly suppressed the production of inflammatory cytokines, whereas 3 showed a weaker suppressing effect. Melanogenesis in B16F1 cells was significantly suppressed by 1 and 3, and weakly suppressed by 2. All three compounds showed moderate cytotoxicities. These results indicate that fenugreek extract and its active constituents could protect against skin damage.

  5. Biodegradable sizing agents from soy protein via controlled hydrolysis and dis-entanglement for remediation of textile effluents.

    PubMed

    Yang, Maiping; Xu, Helan; Hou, Xiuliang; Zhang, Jie; Yang, Yiqi

    2017-03-01

    Fully biodegradable textile sizes with satisfactory performance properties were developed from soy protein with controlled hydrolysis and dis-entanglement to tackle the intractable environmental issues associated with the non-biodegradable polyvinyl alcohol (PVA) in textile effluents. PVA derived from petroleum is the primary sizing agent due to its excellent sizing performance on polyester-containing yarns, especially in increasingly prevailing high-speed weaving. However, due to the poor biodegradability, PVA causes serious environmental pollution, and thus, should be substituted with more environmentally friendly polymers. Soy protein treated with high amount of triethanolamine was found with acceptable sizing properties. However, triethanolamine is also non-biodegradable and originated from petroleum, therefore, is not an ideal additive. In this research, soy sizes were developed from soy protein treated with glycerol, the biodegradable triol that could also be obtained from soy. The soy sizes had good film properties, adhesion to polyester and abrasion resistance close to PVA, rendering them qualified for sizing applications. Regarding desizing, consumption of water and energy for removal of soy size could be remarkably decreased, comparing to removal of PVA. Moreover, with satisfactory degradability, the wastewater containing soy sizes was readily dischargeable after treated in activated sludge for two days. In summary, the fully biodegradable soy sizes had potential to substitute PVA for sustainable textile processing.

  6. Effects of nanoporous anodic titanium oxide on human adipose derived stem cells

    PubMed Central

    Malec, Katarzyna; Góralska, Joanna; Hubalewska-Mazgaj, Magdalena; Głowacz, Paulina; Jarosz, Magdalena; Brzewski, Pawel; Sulka, Grzegorz D; Jaskuła, Marian; Wybrańska, Iwona

    2016-01-01

    The aim of current bone biomaterials research is to design implants that induce controlled, guided, successful, and rapid healing. Titanium implants are widely used in dental, orthopedic, and reconstructive surgery. A series of studies has indicated that cells can respond not only to the chemical properties of the biomaterial, but also, in particular, to the changes in surface topography. Nanoporous materials remain in focus of scientific queries due to their exclusive properties and broad applications. One such material is nanostructured titanium oxide with highly ordered, mutually perpendicular nanopores. Nanoporous anodic titanium dioxide (TiO2) films were fabricated by a three-step anodization process in propan-1,2,3-triol-based electrolyte containing fluoride ions. Adipose-derived stem cells offer many interesting opportunities for regenerative medicine. The important goal of tissue engineering is to direct stem cell differentiation into a desired cell lineage. The influence of nanoporous TiO2 with pore diameters of 80 and 108 nm on cell response, growth, viability, and ability to differentiate into osteoblastic lineage of human adipose-derived progenitors was explored. Cells were harvested from the subcutaneous abdominal fat tissue by a simple, minimally invasive, and inexpensive method. Our results indicate that anodic nanostructured TiO2 is a safe and nontoxic biomaterial. In vitro studies demonstrated that the nanotopography induced and enhanced osteodifferentiation of human adipose-derived stem cells from the abdominal subcutaneous fat tissue. PMID:27789947

  7. Bacteriohopanepolyol signatures as markers for methanotrophic bacteria in peat moss

    NASA Astrophysics Data System (ADS)

    van Winden, Julia F.; Talbot, Helen M.; Kip, Nardy; Reichart, Gert-Jan; Pol, Arjan; McNamara, Niall P.; Jetten, Mike S. M.; Op den Camp, Huub J. M.; Sinninghe Damsté, Jaap S.

    2012-01-01

    Bacteriohopanepolyols (BHPs) are bacterial biomarkers with a likely potential to identify present and past methanotrophic communities. To unravel the methanotrophic community in peat bogs, we report the BHP signatures of type I and type II methanotrophs isolated from Sphagnum mosses and of an extreme acidophilic verrucomicrobial methanotroph. A type I Methylovulum-like strain (M200) contains a remarkable combination of BHPs, including a complete suite of mono-unsaturated aminobacteriohopanepentol, -tetrol and -triol. The Methylomonas-like strain (M5) mainly produces aminobacteriohopanepentol, characteristic for type I methanotrophs, and the Methylosinus-like strain (29) contains both aminobacteriohopanetetrol and aminobacteriohopanetriol, typical for a type II methanotroph. The type II methanotroph Methylocella palustris and the verrucomicrobial Methylacidiphilum fumariolicum strain SolV primarily produce aminotriol, which is also produced by many other bacteria. In Sphagnum mosses and underlying peat from a peat bog from Moorhouse, UK, the only detectable BHPs indicative of methanotrophs are aminobacteriohopanepentol (aminopentol) and aminobacteriohopanetetrol (aminotetrol), although both are relatively low in abundance compared to other BHPs. Aminopentol serves as a marker for type I methanotrophs, while aminotetrol may reflect the presence of both type I and type II methanotrophs. The similar quantities of aminotetrol and aminopentol indicate that the methanotrophic community in Sphagnum peat probably consist of a combination of both type I and type II methanotrophs, which is in line with previously published pmoA-based micro-array results.

  8. Synthesis of Oxylipin Mimics and Their Antifungal Activity against the Citrus Postharvest Pathogens.

    PubMed

    Ma, Jimei; Li, Yupeng; Chen, Hangwei; Zeng, Zhen; Li, Zi-Long; Jiang, Hong

    2016-02-22

    Nine oxylipin mimics were designed and synthesized starting from d-mannose. Their antifungal activity against three citrus postharvest pathogens was evaluated by spore germination assay. The results indicated that all the compounds significantly inhibited the growth of Penicillium digitatum, Penicillium italicum and Aspergillus niger. The compound (3Z,6Z,8S,9R,10R)-octadeca-3,6-diene-8,9,10-triol (3) exhibited excellent inhibitory effect on both Penicillium digitatum (IC50 = 34 ppm) and Penicillium italicum (IC50 = 94 ppm). Their in vivo antifungal activities against citrus postharvest blue mold were tested with fruit inoculated with the pathogen Penicillium italicum. The compound (3R,4S)-methyl 3,4-dihydroxy-5-octyltetrahydrofuran-2-carboxylate (9) demonstrated significant efficacy by reducing the disease severity to 60%. The antifungal mechanism of these oxylipin mimics was postulated in which both inhibition of pathogenic mycelium and stimuli of the host oxylipin-mediated defense response played important roles.

  9. A dual purpose cell line of an Indian congener of ginseng--Panax sikkimensis with distinct ginsenoside and anthocyanin production profiles.

    PubMed

    Biswas, Tanya; Singh, Manju; Mathur, Ajay Kumar; Mathur, Archana

    2015-03-01

    The age-dependent production kinetics of ginsenosides and an anthocyanin pigment in a cell suspension line of Panax sikkimensis was followed in vitro. Highest total saponin content [7.37 mg/g dry weight (DW)] and biomass accumulation (% biomass increase = 209.67) in this line occurred after 3 and 5 weeks of culture, respectively. Accumulation of individual protopanaxatriol (Re, Rg1, and Rg2) and protopanaxadiol (Rb1, Rb2, and Rc) ginsenosides showed a variable pattern of accumulation independent of cell biomass buildup during the 7-week culture cycle. However, total content of triol ginsenosides was always significantly more than the diol group of ginsenosides, being 183.2-, 63.5-, and 72.1-folds at third, fourth, and fifth week stage of cell growth. Interestingly, in addition to these ginsenosides, the cell line also co-accumulated an anthocyanin pigment in vitro. The pigment content increased gradually from 8.66 to 14.29 mg/g DW after first to fifth week followed by a marginal fall to 12.79 and 10.95 mg/g DW during next 2 weeks. Therefore, in terms of total recovery of saponins (77.4 mg/l) and anthocyanin (199.16 mg/l), harvesting of cells after 3 and 5 weeks of growth was most profitable, respectively. The possible utility of this dual purpose cell line in nutraceutical industry is discussed.

  10. Natural product ginsenoside 25-OCH3-PPD inhibits breast cancer growth and metastasis through down-regulating MDM2.

    PubMed

    Wang, Wei; Zhang, Xu; Qin, Jiang-Jiang; Voruganti, Sukesh; Nag, Subhasree Ashok; Wang, Ming-Hai; Wang, Hui; Zhang, Ruiwen

    2012-01-01

    Although ginseng and related herbs have a long history of utility for various health benefits, their application in cancer therapy and underlying mechanisms of action are not fully understood. Our recent work has shown that 20(S)-25-methoxyl-dammarane-3β, 12β, 20-triol (25-OCH(3)-PPD), a newly identified ginsenoside from Panax notoginseng, exerts activities against a variety of cancer cells in vitro and in vivo. This study was designed to investigate its anti-breast cancer activity and the underlying mechanisms of action. We observed that 25-OCH(3)-PPD decreased the survival of breast cancer cells by induction of apoptosis and G1 phase arrest and inhibited the growth of breast cancer xenografts in vivo. We further demonstrated that, in a dose- and time-dependent manner, 25-OCH(3)-PPD inhibited MDM2 expression at both transcriptional and post-translational levels in human breast cancer cells with various p53 statuses (wild type and mutant). Moreover, 25-OCH(3)-PPD inhibited in vitro cell migration, reduced the expression of epithelial-to-mesenchymal transition (EMT) markers, and prevented in vivo metastasis of breast cancer. In summary, 25-OCH(3)-PPD is a potential therapeutic and anti-metastatic agent for human breast cancer through down-regulating MDM2. Further preclinical and clinical development of this agent is warranted.

  11. Evaluation of mycotoxins and their metabolites in human breast milk using liquid chromatography coupled to high resolution mass spectrometry.

    PubMed

    Rubert, Josep; León, Nuria; Sáez, Carmen; Martins, Claudia P B; Godula, Michal; Yusà, Vicent; Mañes, Jordi; Soriano, José Miguel; Soler, Carla

    2014-04-11

    Humans can be exposed to mycotoxins through the food chain. Mycotoxins are mainly found as contaminants in food and could be subsequently excreted via biological fluids such as urine or human breast milk in native or metabolised form. Since breast milk is usually supposed as the only food for new-borns, the occurrence of mycotoxins in thirty-five human milk samples was evaluated by a newly developed method based on QuEChERS extraction and UHPLC-HRMS detection. The method described here allows the detection of target mycotoxins in order to determine the quality of this initial feeding. The method has been fully validated, with recoveries ranging from 64% to 93% and relative standard deviations (RSD, %) being lower than 20%. Using the method described, non-metabolised mycotoxins such as ZEA, NEO, NIV, ENA, ENA1, ENB, ENB1 and metabolites, such as ZEA metabolites, HT-2, DOM and T-2 triol were detected in human milk samples. Results obtained help to estimate the exposure of mothers and infants to mycotoxins. Moreover, to the best of our knowledge, this is the first work describing the simultaneous detection, quantification and screening of mycotoxins and their metabolites in human mature milk.

  12. Structural characterization of phytotoxic terpenoids from Cestrum parqui.

    PubMed

    D'Abrosca, Brigida; Dellagreca, Marina; Fiorentino, Antonio; Monaco, Pietro; Natale, Angela; Oriano, Palma; Zarrelli, Armando

    2005-11-01

    Isolation, chemical characterization and phytotoxicity of nine polyhydroxylated terpenes (five C13nor-isoprenoids, two sesquiterpenes, a spirostane and a pseudosapogenin) from Cestrum parqui L'Herr are reported. In this work we completed the phytochemical investigation of the terpenic fraction of the plant and described the structural elucidation of polar isoprenoids using NMR methods. All the configurations of the compounds have been assigned by NOESY experiments. Four new structures have been identified as (3S,5R,6R,7E,9R)-5,6,9-trihydroxy-3-isopropyloxy-7-megastigmene, 5alpha-spirostan-3beta,12beta,15alpha-triol, and 26-O-(3'-isopentanoyl)-beta-d-glucopyranosyl-5alpha-furost-20(22)-ene-3beta,26-diol, and as an unusual tricyclic sesquiterpene. The compounds have been assayed for their phytotoxicity on lettuce at the concentrations ranging between 10(-4) and 10(-7)M. The activities of some compounds were similar to that of the herbicide pendimethalin.

  13. Focal toxicity of oxysterols in vascular smooth muscle cell culture. A model of the atherosclerotic core region.

    PubMed Central

    Guyton, J. R.; Black, B. L.; Seidel, C. L.

    1990-01-01

    Cell necrosis and reactive cellular processes in and near the atherosclerotic core region might result from short-range interactions with toxic lipids. To model these interactions in cell culture, focal crystalline deposits of cholestane-3 beta,5 alpha,6 beta-triol, 25-OH cholesterol, and cholesterol were overlaid by a collagen gel, on which canine aortic smooth muscle cells were seeded. Oxysterols, but not cholesterol, caused focally decreased plating efficiency and cell death, leading to the formation of a persistent circular gap in the cell culture. Cholestanetriol was largely removed from the culture dishes over 3 to 4 weeks, whereas cholesterol and 25-OH cholesterol were largely retained. Smooth muscle cells were motile even in proximity to oxysterol crystals, with occasional suicidal migration toward the crystals. Chemoattraction, however, could not be demonstrated. Despite toxicity, cholestanetriol did not appear to alter the fraction of cells exhibiting 3H-thymidine uptake, even in areas close to the crystals. Thus, oxysterols may be toxic to some cells, without causing major impairment of the migration and proliferation of nearby cells. This would allow the simultaneous occurrence of cell death and proliferation evident in atherosclerosis. Images Figure 2 Figure 4 Figure 5 PMID:2201200

  14. Anti-Inflammatory Constituents from Bidens frondosa.

    PubMed

    Le, Jiamei; Lu, Wenquan; Xiong, Xiaojuan; Wu, Zhijun; Chen, Wansheng

    2015-10-09

    A new polyacetylene glucoside (3E,5E,11E)-tridecatriene-7,9-diyne-1,2,13-triol-2-O-β-D-glucopyranoside (1), a new phenylpropanoid glucoside 2'-butoxyethylconiferin (2), and a new flavonoid glycoside 8,3',4'-trihydroxyflavone-7-O-(6''-O-p-coumaroyl)-β-D-glucopyranoside (3), have been isolated from Bidens frondosa together with fifty-three known compounds 4-56. The structures of these compounds were established by spectroscopic methods. mainly ESIMS, 1D- and 2D-NMR spectroscopic data. and comparison with literature data. Compounds 1-34, 36, 39, 43, 47, 51, and 52 were tested for inhibition of nuclear factor kappa B (NF-κB) in 293-NF-κB-luciferase report cell line induced by lipopolysaccharide (LPS), and compounds 1, 2, 3, 9, 15, 21, 24 and 51 were tested for the production of TNF-α, IL-1β, IL-6, IL-10 in RAW 264.7 macrophages induced by LPS. In conclusion, the isolated compounds 1, 2, 3, 9, 15, 21, 24 and 51 exhibited significant activity in anti-inflammatory activity assays.

  15. Indole-diterpenoids with anti-H1N1 activity from the aciduric fungus Penicillium camemberti OUCMDZ-1492.

    PubMed

    Fan, Yaqin; Wang, Yi; Liu, Peipei; Fu, Peng; Zhu, Tonghan; Wang, Wei; Zhu, Weiming

    2013-07-26

    An aciduric fungal strain, Penicillium camemberti OUCMDZ-1492, was isolated from an acidic marine niche, mangrove soil and mud, around the roots of Rhizophora apiculata. Six new indole-diterpenoids (1-6), along with five known analogues, emindole SB (7), 21-isopentenylpaxilline (8), paspaline (9), paxilline (10), and dehydroxypaxilline (11), were isolated from the fermentation broth of P. camemberti OUCMDZ-1492 grown at pH 5.0. On the basis of spectroscopic analyses, CD spectra, quantum ECD calculations, and chemical methods, new structures 1-6 were established as 3-deoxo-4b-deoxypaxilline, 4a-demethylpaspaline-4a-carboxylic acid, 4a-demethylpaspaline-3,4,4a-triol, 2'-hydroxypaxilline, 9,10-diisopentenylpaxilline, and (6S,7R,10E,14E)-16-(1H-indol-3-yl)-2,6,10,14-tetramethylhexadeca-2,10,14-triene-6,7-diol, respectively. Compounds 1-3 and 5-10 exhibited significant activity against the H1N1 virus with IC50 values of 28.3, 38.9, 32.2, 73.3, 34.1, 26.2, 6.6, 77.9, and 17.7 μM, respectively. The results showed that 3-oxo, 4b-hydroxy, and 9-isopentenyl substitutions tend to increase the anti-H1N1 activity of hexacyclic indole-diterpenoids.

  16. Chemical Constituents and Antimicrobial Activity of Indian Green Leafy Vegetable Cardiospermum halicacabum.

    PubMed

    Jeyadevi, R; Sivasudha, T; Ilavarasi, A; Thajuddin, N

    2013-06-01

    The present study was carried out to analyze chemical constituents and antibacterial activity of ethanolic leaf extract of Cardiospermum halicacabum (ECH). The FT-IR spectrum confirmed the presence of alcohols, phenols, alkanes, alkynes, aliphatic ester and flavonoids in ECH. The GC-MS analysis revealed that ECH contained about twenty four compounds. The major chemical compounds identified were cyclohexane-1, 4, 5-triol-3-one-1-carboxylic acid, benzene acetic acid, caryophyllene, phytol and neophytadiene. The ECH was screened for its antibacterial activity against different bacterial strains and anti fungal activity against Candida albicans by agar well diffusion and minimum inhibitory concentration (MIC) assay. ECH exhibited antibacterial and antifungal activity. All the tested bacterial strains showed MIC values ranging from 80 to 125 μg of extract/ml and C. albicans showed 190 μg of extract/ml as a MIC. The maximum activity ECH was observed against human pathogen Staphylococcus aureus followed by Escherichia coli and the fish pathogen Aeromonas hydrophila. ECH exhibited moderate activity against some of the tested multidrug resistant strains.

  17. Anti-inflammatory activity of different agave plants and the compound cantalasaponin-1.

    PubMed

    Monterrosas-Brisson, Nayeli; Ocampo, Martha L Arenas; Jiménez-Ferrer, Enrique; Jiménez-Aparicio, Antonio R; Zamilpa, Alejandro; Gonzalez-Cortazar, Manases; Tortoriello, Jaime; Herrera-Ruiz, Maribel

    2013-07-10

    Species of the agave genus, such as Agave tequilana, Agave angustifolia and Agave americana are used in Mexican traditional medicine to treat inflammation-associated conditions. These plants' leaves contain saponin compounds which show anti-inflammatory properties in different models. The goal of this investigation was to evaluate the anti-inflammatory capacity of these plants, identify which is the most active, and isolate the active compound by a bio-directed fractionation using the ear edema induced in mice with 12-O-tetradecanoylphorbol-13-acetate (TPA) technique. A dose of 6 mg/ear of acetone extract from the three agave species induced anti-inflammatory effects, however, the one from A. americana proved to be the most active. Different fractions of this species showed biological activity. Finally the F5 fraction at 2.0 mg/ear induced an inhibition of 85.6%. We identified one compound in this fraction as (25R)-5α-spirostan-3β,6α,23α-triol-3,6-di-O-β-D-glucopyranoside (cantalasaponin-1) through 1H- and 13C-NMR spectral analysis and two dimensional experiments like DEPT NMR, COSY, HSQC and HMBC. This steroidal glycoside showed a dose dependent effect of up to 90% of ear edema inhibition at the highest dose of 1.5 mg/ear.

  18. Synthesis and thermal studies of boron-containing heterosiloxanes, and their relevance to ceramic formation

    NASA Astrophysics Data System (ADS)

    Behebehani, Haider S. J.

    -heptasiloxane-l,6,7-triol, [(c-C6H11)7Si7O9(OH)3], were prepared by controlled hydrolysis of cyclohexyltrichlorosilane. The triol was used to synthesise a boron containing silsesquioxane, [(c-C6H1])7Si7O12B]2, by reaction with BI3. Thermolysis of c-Cy6Si6O9 up to 1700C under an inert atmosphere forms crystalline silica, whereas under similar conditions (Ph2SiO)n (where n = 3 or 4) volatilises. For comparative purposes a phenylmethylsilane-dimethylsilane copolymer was thermolysed under similar conditions in order to prepare silicon carbide from an oxygen free polymeric source. Compound 3, Ph2(HO)SiOSi(Ph2)OSi(OH)Ph2, compound 6, c-Cy6Si6O9, compound 16, PhB(Ph3SiO)2 and compound 19 Me2Si(PhBNH)2NH, were all characterised for the first time by single crystal x-ray diffraction studies, and their main structural features were discussed in relation to their chemical reactivity.

  19. Estrogen receptor-β in the paraventricular nucleus and rostroventrolateral medulla plays an essential protective role in aldosterone/salt-induced hypertension in female rats.

    PubMed

    Xue, Baojian; Zhang, Zhongming; Beltz, Terry G; Johnson, Ralph F; Guo, Fang; Hay, Meredith; Johnson, Alan Kim

    2013-06-01

    The identification of the specific estrogen receptor (ER) subtypes that are involved in estrogen protection from hypertension and their specific locations in the central nervous system is critical to our understanding and design of effective estrogen replacement therapies in women. Using selective ER agonists and recombinant adeno-associated virus (AAV) carrying small interference (si) RNA to silence either ERα (AAV-siRNA-ERα) or ERβ (AAV-siRNA-ERβ), the present study investigated regional specificity of different ER subtypes in the protective actions of estrogen in aldosterone (Aldo)-induced hypertension. Intracerebroventricular infusions of either diarylpropionitrile, a selective ERβ agonist, or propyl-pyrazole-triol, a selective ERα agonist, attenuated Aldo/NaCl-induced hypertension in ovariectomized rats. In contrast, intracerebroventricular injections of siRNA-ERα or siRNA-ERβ augmented Aldo-induced hypertension in intact females. Site-specific paraventricular nucleus (PVN) or rostroventrolateral medulla (RVLM) injections of siRNA-ERβ augmented Aldo-induced hypertension. However, rats with PVN or RVLM injections of siRNA-ERα did not significantly increase blood pressure induced by Aldo. Real-time polymerase chain reaction analyses of the PVN and RVLM of siRNA-injected rat confirmed a marked reduction in the expression of ERα and ERβ. In cultured PVN neurons, silencing either ERα or ERβ by culturing PVN neurons with siRNA-ERα or siRNA-ERβ enhanced Aldo-induced reactive oxygen species production. Ganglionic blockade after Aldo infusion showed an increase in sympathetic activity in ERβ knockdown rats. These results indicate that both PVN and RVLM ERβ, but not ERα in these nuclei, contribute to the protective effects of estrogen against Aldo-induced hypertension. The brain regions responsible for the protective effects of estrogen interaction with ERα in Aldo-induced hypertension still need to be determined.

  20. Identification of catechin as one of the flavonoids from Combretum albiflorum bark extract that reduces the production of quorum-sensing-controlled virulence factors in Pseudomonas aeruginosa PAO1.

    PubMed

    Vandeputte, Olivier M; Kiendrebeogo, Martin; Rajaonson, Sanda; Diallo, Billo; Mol, Adeline; El Jaziri, Mondher; Baucher, Marie

    2010-01-01

    Quorum-sensing (QS) regulates the production of key virulence factors in Pseudomonas aeruginosa and other important pathogenic bacteria. In this report, extracts of leaves and bark of Combretum albiflorum (Tul.) Jongkind (Combretaceae) were found to quench the production of QS-dependent factors in P. aeruginosa PAO1. Chromatographic fractionation of the crude active extract generated several active fractions containing flavonoids, as shown by their typical spectral features. Purification and structural characterization of one of the active compounds led to the identification of the flavan-3-ol catechin [(2R,3S)-2-(3,4-dihydroxyphenyl)-3,4-dihydro-1(2H)-benzopyran-3,5,7-triol]. The identity of catechin as one of the active molecules was confirmed by comparing the high-pressure liquid chromatography profiles and the mass spectrometry spectra obtained for a catechin standard and for the active C. albiflorum fraction. Moreover, standard catechin had a significant negative effect on pyocyanin and elastase productions and biofilm formation, as well as on the expression of the QS-regulated genes lasB and rhlA and of the key QS regulatory genes lasI, lasR, rhlI, and rhlR. The use of RhlR- and LasR-based biosensors indicated that catechin might interfere with the perception of the QS signal N-butanoyl-l-homoserine lactone by RhlR, thereby leading to a reduction of the production of QS factors. Hence, catechin, along with other flavonoids produced by higher plants, might constitute a first line of defense against pathogenic attacks by affecting QS mechanisms and thereby virulence factor production.

  1. Structure-activity relationship (SAR) analysis of a family of steroids acutely controlling steroidogenesis.

    PubMed

    Midzak, Andrew; Rammouz, Georges; Papadopoulos, Vassilios

    2012-11-01

    Steroids metabolically derive from lipid cholesterol, and vertebrate steroids additionally derive from the steroid pregnenolone. Pregnenolone is derived from cholesterol by hydrolytic cleavage of the aliphatic tail by mitochondrial cytochrome P450 enzyme CYP11A1, located in the inner mitochondrial membrane. Delivery of cholesterol to CYP11A1 comprises the principal control step of steroidogenesis, and requires a series of proteins spanning the mitochondrial double membranes. A critical member of this cholesterol translocation machinery is the integral outer mitochondrial membrane translocator protein (18kDa, TSPO), a high-affinity drug- and cholesterol-binding protein. The cholesterol-binding site of TSPO consists of a phylogenetically conserved cholesterol recognition/interaction amino acid consensus (CRAC). Previous studies from our group identified 5-androsten-3β,17,19-triol (19-Atriol) as drug ligand for the TSPO CRAC motif inhibiting cholesterol binding to CRAC domain and steroidogenesis. To further understand 19-Atriol's mechanism of action as well as the molecular recognition by the TSPO CRAC motif, we undertook structure-activity relationship (SAR) analysis of the 19-Atriol molecule with a variety of substituted steroids oxygenated at positions around the steroid backbone. We found that in addition to steroids hydroxylated at carbon C19, hydroxylations at C4, C7, and C11 contributed to inhibition of cAMP-mediated steroidogenesis in a minimal steroidogenic cell model. However, only substituted steroids with C19 hydroxylations exhibited specificity to TSPO, its CRAC motif, and mitochondrial cholesterol transport, as the C4, C7, and C11 hydroxylated steroids inhibited the metabolic transformation of cholesterol by CYP11A1. We thus provide new insights into structure-activity relationships of steroids inhibiting mitochondrial cholesterol transport and steroidogenic cholesterol metabolic enzymes.

  2. Identification of Catechin as One of the Flavonoids from Combretum albiflorum Bark Extract That Reduces the Production of Quorum-Sensing-Controlled Virulence Factors in Pseudomonas aeruginosa PAO1 ▿

    PubMed Central

    Vandeputte, Olivier M.; Kiendrebeogo, Martin; Rajaonson, Sanda; Diallo, Billo; Mol, Adeline; El Jaziri, Mondher; Baucher, Marie

    2010-01-01

    Quorum-sensing (QS) regulates the production of key virulence factors in Pseudomonas aeruginosa and other important pathogenic bacteria. In this report, extracts of leaves and bark of Combretum albiflorum (Tul.) Jongkind (Combretaceae) were found to quench the production of QS-dependent factors in P. aeruginosa PAO1. Chromatographic fractionation of the crude active extract generated several active fractions containing flavonoids, as shown by their typical spectral features. Purification and structural characterization of one of the active compounds led to the identification of the flavan-3-ol catechin [(2R,3S)-2-(3,4-dihydroxyphenyl)-3,4-dihydro-1(2H)-benzopyran-3,5,7-triol]. The identity of catechin as one of the active molecules was confirmed by comparing the high-pressure liquid chromatography profiles and the mass spectrometry spectra obtained for a catechin standard and for the active C. albiflorum fraction. Moreover, standard catechin had a significant negative effect on pyocyanin and elastase productions and biofilm formation, as well as on the expression of the QS-regulated genes lasB and rhlA and of the key QS regulatory genes lasI, lasR, rhlI, and rhlR. The use of RhlR- and LasR-based biosensors indicated that catechin might interfere with the perception of the QS signal N-butanoyl-l-homoserine lactone by RhlR, thereby leading to a reduction of the production of QS factors. Hence, catechin, along with other flavonoids produced by higher plants, might constitute a first line of defense against pathogenic attacks by affecting QS mechanisms and thereby virulence factor production. PMID:19854927

  3. In vivo and vitro studies on formation of bile acids in patients with Zellweger syndrome. Evidence that peroxisomes are of importance in the normal biosynthesis of both cholic and chenodeoxycholic acid.

    PubMed Central

    Kase, B F; Pedersen, J I; Strandvik, B; Björkhem, I

    1985-01-01

    The last step in bile acid formation involves conversion of 3 alpha,7 alpha,12 alpha-trihydroxy-5 beta-cholestanoic acid (THCA) into cholic acid and 3 alpha,7 alpha-dihydroxy-5 beta-cholestanoic acid (DHCA) into chenodeoxycholic acid. The peroxisomal fraction of rat and human liver has the highest capacity to catalyze these reactions. Infants with Zellweger syndrome lack liver peroxisomes, and accumulate 5 beta-cholestanoic acids in bile and serum. We recently showed that such an infant had reduced capacity to convert a cholic acid precursor, 5 beta-cholestane-3 alpha,7 alpha,12 alpha-triol into cholic acid. 7 alpha-Hydroxy-4-cholesten-3-one is a common precursor for both cholic acid and chenodeoxycholic acid. Intravenous administration of [3H]7 alpha-hydroxy-4-cholesten-3-one to an infant with Zellweger syndrome led to a rapid incorporation of 3H into biliary THCA but only 10% of 3H was incorporated into cholic acid after 48 h. The incorporation of 3H into DHCA was only 25% of that into THCA and the incorporation into chenodeoxycholic acid approximately 50% of that in cholic acid. The conversion of intravenously administered [3H]THCA into cholic acid in another infant with Zellweger syndrome was only 7%. There was a slow conversion of THCA into 3 alpha,7 alpha,12 alpha-trihydroxy-5 beta-C29-dicarboxylic acid. The pool size of both cholic- and chenodeoxycholic acid was markedly reduced. Preparations of liver from two patients with Zellweger syndrome had no capacity to catalyze conversion of THCA into cholic acid. There was, however, a small conversion of DHCA into chenodeoxycholic acid and into THCA. It is concluded that liver peroxisomes are important both for the conversion of THCA into cholic acid and DHCA into chenodeoxycholic acid. PMID:4077985

  4. Development of a pH-responsive drug delivery system for enantioselective-controlled delivery of racemic drugs.

    PubMed

    Suedee, Roongnapa; Jantarat, Chutima; Lindner, Wolfgang; Viernstein, Helmut; Songkro, Sarunyoo; Srichana, Teerapol

    2010-02-25

    This study aimed to develop enantioselective-controlled drug delivery systems for selective release of the required (S)-enantiomer in a dose formulation containing a racemic drug in response to pH stimuli. The recognition system was obtained from a nanoparticle-on-microsphere (NOM) molecularly imprinted polymer (MIP) with a multifunctional chiral cinchona anchor synthesised by suspension polymerisation using ethylene glycol dimethacrylate as a cross-linker. (S)-omeprazole was used as an imprinting molecule conferring stereoselectivity upon the polymers. The ability of the prepared recognition polymers to selectively rebind (S)-omeprazole was evident at different pH levels (the highest being at pH 7.4). The partial selective-release phenomenon of the (S)-enantiomer in MIP-containing composite cellulose membranes with increased vehicular racemic omeprazole concentrations was highly pH-dependent. Cinchona-bonded polymers imprinted with (S)-omeprazole could recognise the moldable contact site of (S)-omeprazole independently of its chirality; this is responsible for the delivery of (S)-enantiomer from racemic omeprazole. The controlled-release drug devices were fabricated with synthesised composite latex, and consisted of a pH stimuli-responsive poly(hydroxyethyl methacrylate) (HEMA) and polycaprolactone-triol (PCL-T) blend, and a MIP with preloaded drug, along with pH 7.4 buffer in the device's interior. The results demonstrate that drug delivery systems containing (S)-omeprazole imprinted cinchona-polymer nanoparticle-on-microspheres may maximise efficacy while minimising dose frequency.

  5. Skin of the male African catfish, Clarias gariepinus: a source of steroid glucuronides

    SciTech Connect

    Ali, S.A.; Schoonen, W.G.; Lambert, J.G.; Van den Hurk, R.; Van Oordt, P.G.

    1987-06-01

    Steroid metabolism in the skin of mature male African catfish, Clarias gariepinus, reared in the laboratory, was studied in vitro by tissue incubations with (/sup 3/H)pregnenolone, (/sup 3/H)dehydroepiandrosterone, (/sup 3/H)17 alpha-hydroxyprogesterone, (/sup 3/H)androstenedione, (/sup 14/C)11 beta-hydroxyandrostenedione, and (/sup 3/H)testosterone as precursors. While pregnenolone was not converted to any other steroid, dehydroepiandrosterone was transformed mainly to 5-androstene-3 beta, 17 beta-diol. The products of 17 alpha-hydroxyprogesterone incubations were 5 beta-pregnane-3 alpha,17 alpha-diol-20-one, 5 beta-pregnane-3 alpha,17 alpha, 20 beta-triol, and 5 beta-pregnan-17 alpha-o1-3,20-dione. The major steroids of androstenedione incubations were etiocholanolone, testosterone, and androsterone. Testosterone was converted mainly to etiocholanolone and androstenedione, and only small quantities of 11 beta-hydroxytestosterone, 11-ketotestosterone, and 11-ketoandrostenedione were the metabolites found in 11 beta-hydroxyandrostenedione incubation. These results demonstrated the presence of the enzymes 5 alpha- and 5 beta-reductases and 3 alpha-, 11 beta-, 17 beta-, and 20 beta-hydroxysteroid dehydrogenases in the skin. From enzymehistochemical results it appeared that the steroid conversions take place in the epithelial cells. Moreover, the presence of UDP-glucose dehydrogenase, an enzyme involved in the synthesis of glucuronic acid, in these cells indicates the possibility of steroid glucuronide formation. Indeed significant amounts of water-soluble steroid conjugates, particularly 5 beta-dihydrotestosterone- and testosterone-glucuronide, were found in the incubations with androstenedione and testosterone, indicating the presence of the UDP-glucuronosyl transferase in the catfish skin.

  6. From tamoxifen to dendrogenin A: The discovery of a mammalian tumor suppressor and cholesterol metabolite.

    PubMed

    Silvente-Poirot, Sandrine; de Medina, Philippe; Record, Michel; Poirot, Marc

    2016-11-01

    Tamoxifen (Tam) was developed as a ligand and modulator of estrogen receptor α (ERα) and is one of the main drugs used globally for the hormonotherapy of breast cancers. Besides ERα, Tam also binds with high affinity to the microsomal antiestrogen binding site (AEBS). The AEBS is a hetero-oligomeric proteinaceous complex with cholesterol-5,6-epoxide hydrolase (ChEH) activity that is associated with an intracellular histamine (HA) binding site. The enzymatic activities of the ChEH subunits control developmental programs in mammals and transform cholesterol-5,6-epoxides (5,6-EC) into cholestane-3β,5α,6β-triol. Inhibition of the ChEH activity by pharmacological agents such as Tam induce cancer cell re-differentiation through the accumulation of 5,6-EC. A few years ago, the putative chemical reactivity of the 5,6-EC epoxide group towards nucleophiles led our group to hypothesize that 5,6-EC could react with HA that was co-localized at the AEBS to give a new molecule involved in cell differentiation. This hypothesis was chemically tested and the conjugation of 5,6α-EC: with HA was found possible but only under catalytic conditions. It gave a stereo-selective single product of transformation which was named dendrogenin A (DDA). DDA was found to display potent cancer cell differentiation and anticancer properties in vitro and in vivo, suggesting that it was a tumor suppressor metabolite. The presence of DDA was then established in several mammalian tissues, providing the first evidence of a steroidal alkaloid metabolite in mammals. The discovery of DDA highlights a new metabolic pathway in mammals which lies at the crossroads of cholesterol and histamine metabolism and produces this tumor suppressor metabolite.

  7. Quantitation and bitter taste contribution of saponins in fresh and cooked white asparagus (Asparagus officinalis L.).

    PubMed

    Dawid, Corinna; Hofmann, Thomas

    2014-02-15

    A sensitive HPLC-MS/MS method was developed enabling the simultaneous quantification of bitter-tasting mono- and bidesmosidic saponins in fresh and processed asparagus (Asparagus officinalis L.). Based on quantitative data and bitter taste recognition thresholds, dose-over-threshold factors were determined for the first time to determine the bitter impact of the individual saponins. Although 3-O-[α-L-rhamnopyranosyl-(1→2)-α-L-rhamnopyranosyl-(1 → 4)-β-D-glucopyranosyl]-(25R/S)-spirost-5-ene-3β-ol was found based on dose-over-threshold factors to be the predominant bitter saponin in raw asparagus spears, 3-O-[α-L-rhamnopyranosyl-(1 → 2)-{α-L-rhamnopyranosyl-(1 → 4)}-β-D-glucopyranosyl]-26-O-[β-D-glucopyranosyl]-(25R)-22-hydroxyfurost-5-ene-3β,26-diol, 3-O-[α-L-rhamnopyranosyl-(1 → 2)-{α-L-rhamnopyranosyl-(1 → 4)}-β-D-glucopyranosyl]-26-O-[β-D-glucopyranosyl]-(25S)-22-hydroxyfurost-5-ene-3β,26-diol, and (25R)- and (25S)-furost-5-en-3β,22,26-triol-3-O-[α-L-rhamnopyranosyl-(1 → 4)-β-D-glucopyranoside]-26-O-β-D-glucopyranoside were found as key bitter contributors after cooking. Interestingly, the monodesmosidic saponins 5a/b were demonstrated for the first time to be the major contributor to the bitter taste of fresh asparagus spears, while the bidesmosides 1a/b and 2a/b may be considered the primary determinants for the bitter taste of cooked asparagus.

  8. Estradiol modulates effort-based decision making in female rats.

    PubMed

    Uban, Kristina A; Rummel, Julia; Floresco, Stan B; Galea, Liisa A M

    2012-01-01

    Disorders of the dopamine system, such as schizophrenia or stimulant addiction, are associated with impairments in different forms of cost/benefit decision making. The neural circuitry (ie amygdala, prefrontal cortex, nucleus accumbens) underlying these functions receives dopamine input, which is thought to have a central role in mediating cost/benefit decisions. Estradiol modulates dopamine activity, and estrogen receptors (ERs) are found within this neurocircuitry, suggesting that decision making may be influenced by estradiol. The present study examined the contribution of estradiol and selective ERα and β agonists on cost/benefit decision making in adult female Long-Evans rats. An effort-discounting task was utilized, where rats could either emit a single response on a low-reward lever to receive two pellets, or make 2, 5, 10, or 20 responses on a high-reward lever to obtain four pellets. Ovariectomy increased the choice on the high-reward lever, whereas replacement with high (10 μg), but not low (0.3 μg), levels of estradiol benzoate reduced the choice on the high-reward lever. Interestingly, both an ERα agonist (propyl-pyrazole triol (PPT)) and an ERβ agonist (diarylpropionitrile (DPN)) increased choice on the high-reward lever when administered independently, but when these two agonists were combined, a decrease in choice for the high-reward lever was observed. The effects of estradiol, PPT, and DPN were more pronounced 24 h post-administration, suggesting that these effects may be genomic in nature. Together, these results demonstrate that estradiol modulates cost/benefit decision making in females, whereby concomitant activation of ERα and β receptors shifts the decision criteria and reduces preference for larger, yet more costly rewards.

  9. Dynamics of Immune Cell Types Within the Macaque Corpus Luteum During the Menstrual Cycle: Role of Progesterone1

    PubMed Central

    Bishop, Cecily V.; Xu, Fuhua; Molskness, Theodore A.; Stouffer, Richard L.; Hennebold, Jon D.

    2015-01-01

    The goal of the current study was to characterize the immune cell types within the primate corpus luteum (CL). Luteal tissue was collected from rhesus females at discrete intervals during the luteal phase of the natural menstrual cycle. Dispersed cells were incubated with fluorescently labeled antibodies specific for the immune cell surface proteins CD11b (neutrophils and monocytes/macrophages), CD14 (monocytes/macrophages), CD16 (natural killer [NK] cells), CD20 (B-lymphocytes), and CD3epsilon (T-lymphocytes) for analysis by flow cytometry. Numbers of CD11b-positive (CD11b+) and CD14+ cells increased significantly 3 to 4 days after serum progesterone (P4) concentrations declined below 0.3 ng/ml. CD16+ cells were the most abundant immune cell type in CL during the mid and mid-late luteal phases and were 3-fold increased 3 to 4 days after serum P4 decreased to baseline levels. CD3epsilon+ cells tended to increase 3 to 4 days after P4 decline. To determine whether immune cells were upregulated by the loss of luteotropic (LH) support or through loss of LH-dependent steroid milieu, monkeys were assigned to 4 groups: control (no treatment), the GnRH antagonist Antide, Antide plus synthetic progestin (R5020), or Antide plus the estrogen receptor agonists diarylpropionitrile (DPN)/propyl-pyrazole-triol (PPT) during the mid-late luteal phase. Antide treatment increased the numbers of CD11b+ and CD14+ cells, whereas progestin, but not estrogen, replacement suppressed the numbers of CD11b+, CD14+, and CD16+ cells. Neither Antide nor steroid replacement altered numbers of CD3epsilon+ cells. These data suggest that increased numbers of innate immune cells in primate CL after P4 synthesis declines play a role in onset of structural regression of primate CL. PMID:26400401

  10. High performance liquid chromatography time of flight electrospray ionization mass spectrometry for quantification of sesquiterpenes in Chrysanthemi indici Flos active extract

    PubMed Central

    Fu, Ling; Wang, Pan; Sun, Yiqun; Wang, Yangyang; Zhao, Jing; Ye, Yuting; Zhang, Yanbin; Bi, Yuefeng

    2015-01-01

    Background: Chrysanthemi indici Flos, a traditional herbal medicine is used to clearing heat–toxicity, removing the liver fire, and improving eyesight. In our preliminary work, an active extract of CTC in C. An indici Flos with anti-hepatitis B virus and liver protective activity was found by HepG2.2.1.5 test and experiment of protein synthesis in mice's injured liver. In this work, we aimed to study the active faction CTC further by qualitative and quantitative analysis method. Materials and Methods: High performance liquid chromatography time of flight electrospray ionization mass spectrometry (HPLC TOF ESI-MS) analysis method of the CTC was established. Cumambrin A and angeloylcumambrin B in CTC were analyzed by high performance liquid chromatography-ultraviolet-evaporative light scattering detector (HPLC-UV-ELSD) analysis methods. A binary gradient elution program was conducted for chromatographic separation with acetonitrile (A) and ultrapure water (B) as follows: 0–10 min, 42–46% A; 10–20 min, 46–55% A; 20–25 min, 55–60% A; and 25–35 min, 60–75% A. The column temperature and UV wavelength were set at 30°C and 205 nm. Result: Ten constituents including (3R, 5R, 6S, 7S, 10R)-7-(2-hydroxy-2-propyl)-10-methyl-4-methyleneperhy, dronaphthal-ene-3, 5, 6-triol acetone solvate; (+)-edusmance-4, (14)-ene-11, 13-diol; linarin; luteolin; apigenin; tricin; 5, 3’,4’- trimethyl-6,7-dimethoxy flavones; cumambrin A; acacetin; and angeloylcumambrin B in CTC were identified by HPLC TOF ESI-MS. The contents of sesquiterpenes in CTC were decreased by storing years. Conclusions: The results showed that both UV and ELSD methods were feasible, accurate, and the determination results were in good consistency. The contents of two sesquiterpenes decreased with storing years. Two sesquiterpenes could be used as quality control for C. indici flos CTC. PMID:26600718

  11. Four process-related potential new impurities in ticagrelor: Identification, isolation, characterization using HPLC, LC/ESI-MS(n), NMR and their synthesis.

    PubMed

    Kumar, Neeraj; Devineni, Subba Rao; Gajjala, Prasad Reddy; Gupta, Dharmendra Kumar; Bhat, Sandesh; Kumar, Rajesh; Dubey, Shailendra Kumar; Kumar, Pramod

    2016-02-20

    Five process-related impurities were detected in the range of 0.08-0.22% in ticagrelor laboratory batches by HPLC and LC-MS methods. These impurities were named as TIC Imp-I, -II, -III, -IV and -V. Four of these impurities, TIC Imp-I to -IV were unknown and have not been reported previously. Based on LC-ESI/MS(n) study, the chemical structures of new impurities were presumed as (1S,2S,3S,5S)-3-(2-hydroxyethoxy)-5-(7-amino-5-(propylthio)-3H-[1,2,3]triazolo[4,5-d] pyrimidin-3-yl)cyclopentane-1,2-diol (TIC Imp-I), (1S,2S,3S,5S)-3-(7-((1R,2S)-2-(3,4-difluorophenyl)cyclopropylamino)-5-(propylsulfinyl)-3H-[1,2,3]triazolo [4,5-d]pyrimidin-3-yl)-5-(2-hydroxyethoxy)cyclopentane-1,2-diol (TIC Imp-II), (1S,2R,3S,4S)-4-(7-((1R,2S)-2-(3,4-difluorophenyl)cyclopropylamino)-5-(propylthio)-3H-[1,2,3]triazolo[4,5-d]pyrimidin-3-yl)cyclopentane-1,2,3-triol (TIC Imp-III) and (3S,5S)-3-(7-((1R,2S)-2-(3,4-difluorophenyl)cyclopropylamino)-5-(propylthio)-3H-[1,2,3]triazolo[4,5-d]pyrimidin-3-yl)-5-(2-hydroxyethoxy)cyclopentane-1,2-diol (TIC Imp-IV). The unknown impurities were isolated from enriched crude sample by column chromatography and preparative HPLC. The complete spectral analysis, MS, 1D NMR ((1)H, (13)C and DEPT), 2D NMR (HSQC and HMBC) and IR confirmed the proposed chemical structures of impurities. Identification, isolation, structural characterization, prospects for the formation of impurities and their synthesis were first reported in this paper.

  12. A Transient Cell-Shielding Method for Viable MSC Delivery within Hydrophobic Scaffolds Polymerized In Situ

    PubMed Central

    Guo, Ruijing; Ward, Catherine L.; Davidson, Jeffrey M.; Duvall, Craig L.; Wenke, Joseph C.

    2015-01-01

    Cell-based therapies have emerged as promising approaches for regenerative medicine. Hydrophobic poly(ester urethane)s offer the advantages of robust mechanical properties, cell attachment without the use of peptides, and controlled degradation by oxidative and hydrolytic mechanisms. However, the application of injectable hydrophobic polymers to cell delivery is limited by the challenges of protecting cells from reaction products and creating a macroporous architecture post-cure. We designed injectable carriers for cell delivery derived from reactive, hydrophobic polyisocyanate and polyester triol precursors. To overcome cell death caused by reaction products from in situ polymerization, we encapsulated bone marrow-derived stem cells (BMSCs) in fast-degrading, oxidized alginate beads prior to mixing with the hydrophobic precursors. Cells survived the polymerization at >70% viability, and rapid dissolution of oxidized alginate beads after the scaffold cured created interconnected macropores that facilitated cellular adhesion to the scaffold in vitro. Applying this injectable system to deliver BMSCs to rat excisional skin wounds showed that the scaffolds supported survival of transplanted cells and infiltration of host cells, which improved new tissue formation compared to both implanted, pre-formed scaffolds seeded with cells and acellular controls. Our design is the first to enable injectable delivery of settable, hydrophobic scaffolds where cell encapsulation provides a mechanism for both temporary cytoprotection during polymerization and rapid formation of macropores post-polymerization. This simple approach provides potential advantages for cell delivery relative to hydrogel technologies, which have weaker mechanical properties and require incorporation of peptides to achieve cell adhesion and degradability. PMID:25907036

  13. The effect of female sexual hormones on the intestinal and serum cytokine response after traumatic brain injury: different roles for estrogen receptor subtypes.

    PubMed

    Khaksari, Mohammad; Keshavarzi, Zakieh; Gholamhoseinian, Ahmad; Bibak, Bahram

    2013-09-01

    The purpose of this study was to evaluate the effect of female sexual hormones on intestinal and serum cytokines following traumatic brain injury (TBI). Adult female rats were ovariectomized and distributed among the following 9 groups: (i) sham trauma, (ii) TBI (Marmarou's method), (iii) vehicle (dimethylsulfoxide) treated, (iv) estrogen (E2) treated, (v) progesterone (P) treated, (vi) treated with E2+P, (vii) propylpyrazole triol (PPT) treated, (viii) diarylpropionitrile (DPN) treated, and (ix) control. PPT and DPN are estrogen receptor αand β agonists, respectively. Serum and intestinal levels of interleukin (IL)-1β were increased by TBI (P < 0.001). The level of intestinal IL-1β was increased in the group treated with E2 (P < 0.001). There was a reduction in serum IL-1β (P < 0.01) and an increase in intestinal IL-1β level (P < 0.001) in the PPT-treated group compared with the vehicle-treated group. TBI reduced serum IL-6 (P < 0.01) and increased intestinal IL-6 (P < 0.001). Serum IL-6 was increased in the group treated with E2 (P < 0.001), P (P < 0.001), E2+P (P < 0.01), and DPN (P < 0.001) after TBI; however, intestinal IL-6 was higher in the E2-treated group compared with the vehicle-treated group (P < 0.01). Intestinal tumor necrosis factor α (TNF-α) was increased by TBI (P < 0.001). Progesterone decreased serum TNF-α (P < 0.01). Intestinal TNF-α in the E2 (P < 0.01), E2+P (P < 0.001), and PPT (P < 0.001) treatment groups was less than in the vehicle-treated group. In conclusion, estrogen influences the intestinal levels of proinflammatory cytokines, in particular TNF-α, mediated through estrogen receptor α.

  14. SELF-ASSEMBLY CE OXIDE/ORGANOPOLYSILOXANE COMPOSITE COATINGS.

    SciTech Connect

    SUGAMA,T.; SABATINI,R.; GAWLIK,K.

    2005-01-01

    A self-assembly composite synthesis technology was used to put together a Ce(OH){sub 3}-dispersed poly-acetamide-acetoxyl methyl-propylsiloxane (PAAMPA) organometallic polymer. Three spontaneous reactions were involved; condensation, amidation, and acetoxylation, between the Ce acetate and aminopropylsilane triol (APST) at 150 C. An increase in temperature to 200 C led to the in-situ phase transformation of Ce(OH){sub 3} into Ce{sub 2}O{sub 3} in the PAAMPA matrix. A further increase to 250 C caused oxidative degradation of the PAAMPA, thereby generating copious fissures in the composite. We assessed the potential of Ce(OH){sub 3}/ and Ce{sub 2}O{sub 3}/ PAAMPA composite materials as corrosion-preventing coatings for carbon steel and aluminum. The Ce{sub 2}O{sub 3} composite coating displayed better performance in protecting both metals against NaCl-caused corrosion than did the Ce(OH){sub 3} composite. Using this coating formed at 200 C, we demonstrated that the following four factors played an essential role in further mitigating the corrosion of the metals: First was a minimum susceptibility of coating's surface to moisture; second was an enhanced densification of the coating layer; third was the retardation of the cathodic oxygen reduction reaction at the metal's corrosion sites due to the deposition of Ce{sub 2}O{sub 3} as a passive film over the metal's surface; and, fourth was its good adherence to metals. The last two factors contributed to minimizing the cathodic delamination of coating film from the metal's surface. We also noted that the affinity of the composite with the surface of aluminum was much stronger than that with steel. Correspondingly, the rate of corrosion of aluminum was reduced as much as two orders of magnitude by a nanoscale thick coating. In contrast, its ability to reduce the corrosion rate of steel was lower than one order of magnitude.

  15. Renoprotective chemical constituents from an edible mushroom, Pleurotus cornucopiae in cisplatin-induced nephrotoxicity.

    PubMed

    Lee, Seoung Rak; Lee, Dahae; Lee, Hae-Jeung; Noh, Hyung Jun; Jung, Kiwon; Kang, Ki Sung; Kim, Ki Hyun

    2017-01-19

    Pleurotus cornucopiae (Pleurotaceae) is an edible and medicinal mushroom widely distributed in Korea, China, and Japan. The MeOH extract of the fruiting bodies of P. cornucopiae showed renoprotective effects against cisplatin-induced kidney cell damage. Chemical investigation of the MeOH extract led to the isolation and identification of 12 compounds including noransine (1), uridine (2), uracil (3), (3β, 5α, 6β, 22E, 24S) -ergosta-7, 22-diene-3, 5, 6, 9-tetrol (4), (22E,24S)-ergosta-7,22-diene-3β,5α,6β-triol (5), (22E,24R)-ergosta-8(14),22-diene-3β,5α,6β,7α-tetrol (6), cerebroside B (7), (2R) -N- [(1S, 2R, 3E, 7E) -1- [(β-d-glucopyranosyloxy) methyl] -2-hydroxy-8-methyl-3, 7-heptadecadien-1-yl] -2-hydroxy-heptadecanamide (8), cerebroside D (9), nicotinamide (10), 1,2-bis(hydroxymethyl)-4,5-dimethoxybenzene (11), and benzoic acid (12). Among them, compounds 1 and 11 were isolated as naturally occurring products for the first time, though they were reported as synthetic products in previous papers. All of the compounds (except 8 and 11) abrogated cisplatin-induced LLC-PK1 cell damage in a dose-dependent manner. Of special note, compounds 2, 5, 6, and 12 ameliorated cisplatin-induced nephrotoxicity to 80% of the control value at 10μM. The protective effects of compounds 2, 5, 6, and 12 were mediated via the deactivation of JNK-caspase 3 apoptotic cascade. This study is the first to demonstrate that the chemical constituents of P. cornucopiae display renoprotective effects against anticancer drug-induced damage in kidney cells.

  16. Xenobiotic biotransformation in unicellular green algae. Involvement of cytochrome P450 in the activation and selectivity of the pyridazinone pro-herbicide metflurazon.

    PubMed Central

    Thies, F; Backhaus, T; Bossmann, B; Grimme, L H

    1996-01-01

    The N-demethylation of the pyridazinone pro-herbicide metflurazon into norflurazon implies a toxification in photosynthetic organisms. This is confirmed by quantitative structure activity relationships determined for two unicellular green algae, Chlorella sorokiniana and Chlorella fusca; however, the latter is 25 to 80 times more sensitive to metflurazon. This sensitivity is linked to differences in the N-demethylase activity of both algae, as determined by an optimized in vivo biotransformation assay. Apparent K(m) values of the metflurazon-N-demethylase indicate a 10-fold higher affinity for this xenobiotic substrate for Chlorella fusca. Furthermore, algal metflurazon-N-demethylation is characterized by distinct variations in activity, depending on the stage of cell development within the cell cycle. Several well-established inhibitors of cytochrome P450-mediated reactions, including piperonylbutoxide, 1-aminobenzotriazole, 1-phenoxy-3-(1H-1,2,4-triol-1yl)-4-hydroxy-5,5-dimethylhexane++ +, and tetcyclacis, as well as cinnamic acid, a potential endogenous substrate, inhibited the N-demethylation of metflurazon. The results suggest that the N-demethylation of metflurazon by both algae is mediated by a cytochrome P450 monooxygenase. The determination of antigenic cross-reactivity of algal proteins with heterologous polyclonal antibodies originally raised against plant P450s, anti-cinnamic acid 4-hydroxylase (CYP73A1), anti-ethoxycoumarin-O-dealkylase, anti-tulip allene oxidase (CYP74), and an avocado P450 (CYP71A1) or those of bacterial origin, CYP105A1 and CYP105B1, suggests the presence of distinct P450 isoforms in both algae. PMID:8819332

  17. Identification and characterization of novel long term metabolites of oxymesterone and mesterolone in human urine by application of SRM GC-CI-MS/MS.

    PubMed

    Polet, Michael; Van Gansbeke, Wim; Geldof, Lore; Deventer, Koen; Van Eenoo, Peter

    2017-03-11

    The search for metabolites with longer detection times remains an important task in for example toxicology and doping control. The impact of these long term metabolites is highlighted by the high number of positive cases after reanalysis of samples that were stored for several years, e.g. samples of previous Olympic Games. A substantial number of previously alleged negative samples have now been declared positive due to the detection of various long term steroid metabolites of which the existence was unknown during the Olympic Games of 2008 and 2012. In this work, the metabolism of oxymesterone and mesterolone, two anabolic androgenic steroids (AAS), was investigated by application of a selected reaction monitoring (SRM) gas chromatography - chemical ionization - triple quadrupole mass spectrometry (GC-CI-MS/MS) protocol for metabolite detection and identification. Correlations between AAS structure and GC-CI-MS/MS fragmentation behaviour enabled the search for previously unknown but expected AAS metabolites by selection of theoretical transitions for expected metabolites. Use of different hydrolysis protocols allowed for evaluation of the detection window of both phase I and phase II metabolites. For oxymesterone, a new metabolite 18-nor-17β-hydroxymethyl-17α-methyl-4-hydroxy-androst-4,13-diene-3-one was identified. It was detectable up to 46 days by using GC-CI-MS/MS, whereas with a traditional screening (detection of metabolite 17-epioxymesterone with electron ionization GC-MS/MS) the oxymesterone administration was only detectable for 3.5 days. A new metabolite was also found for mesterolone. It was identified as 1α-methyl-5α-androstan-3,6,16-triol-17-one and its sulfate form after hydrolysis with Helix pomatia resulted in a prolonged detection time (up to 15 days) for mesterolone abuse.

  18. Excretion and measurement of corticosterone and testosterone metabolites in bank voles (Myodes glareolus).

    PubMed

    Sipari, Saana; Ylönen, Hannu; Palme, Rupert

    2017-03-01

    The bank vole is a commonly used model species in behavioral and ecophysiological studies. Thus, presenting a validated method for noninvasive monitoring of corticosterone and testosterone secretion is of high relevance. Here, we evaluated the effect of time of day and an ACTH challenge test on measured fecal corticosterone (FCM) and testosterone (FTM) metabolites in both sexes. Furthermore, we performed radiometabolism experiments for both steroids and sexes to study metabolism and excretion of (3)H-corticosterone and (3)H-testosterone. FCM and FTM were analysed with a 5α-pregnane-3β,11β,21-triol-20-one enzyme immunoassay (EIA) and a testosterone (measuring 17β-hydroxyandrostanes) EIA, respectively. Males had significantly higher FCM levels than females and their main excretion route was via the feces (∼72%), whereas females excreted nearly equal portions in both feces and urine. For testosterone the main excretion route was via the feces in both sexes (∼80%). The time course of excretion was similar in both sexes, but for the first time a significant difference between injected steroids was found: Corticosterone was excreted faster than testosterone, both in urine (median of peak levels: 4h vs 6h) and feces (6h vs 8h). Several metabolites were present in the feces and the tested EIAs reacted with some of them. Time of day had a significant effect on measured fecal steroid metabolites. As expected, males had significantly higher FTM levels than females. ACTH administration significantly increased FCM values; peaks were observed 4-8h after injection. In conclusion, both tested EIAs proved suited for a noninvasive measurement of glucocorticoids and androgens in bank voles.

  19. Four-Dimensional Printing Hierarchy Scaffolds with Highly Biocompatible Smart Polymers for Tissue Engineering Applications.

    PubMed

    Miao, Shida; Zhu, Wei; Castro, Nathan J; Leng, Jinsong; Zhang, Lijie Grace

    2016-10-01

    The objective of this study was to four-dimensional (4D) print novel biomimetic gradient tissue scaffolds with highly biocompatible naturally derived smart polymers. The term "4D printing" refers to the inherent smart shape transformation of fabricated constructs when implanted minimally invasively for seamless and dynamic integration. For this purpose, a series of novel shape memory polymers with excellent biocompatibility and tunable shape changing effects were synthesized and cured in the presence of three-dimensional printed sacrificial molds, which were subsequently dissolved to create controllable and graded porosity within the scaffold. Surface morphology, thermal, mechanical, and biocompatible properties as well as shape memory effects of the synthesized smart polymers and resultant porous scaffolds were characterized. Fourier transform infrared spectroscopy and gel content analysis confirmed the formation of chemical crosslinking by reacting polycaprolactone triol and castor oil with multi-isocyanate groups. Differential scanning calorimetry revealed an adjustable glass transition temperature in a range from -8°C to 35°C. Uniaxial compression testing indicated that the obtained polymers, possessing a highly crosslinked interpenetrating polymeric networks, have similar compressive modulus to polycaprolactone. Shape memory tests revealed that the smart polymers display finely tunable recovery speed and exhibit greater than 92% shape fixing at -18°C or 0°C and full shape recovery at physiological temperature. Scanning electron microscopy analysis of fabricated scaffolds revealed a graded microporous structure, which mimics the nonuniform distribution of porosity found within natural tissues. With polycaprolactone serving as a control, human bone marrow-derived mesenchymal stem cell adhesion, proliferation, and differentiation greatly increased on our novel smart polymers. The current work will significantly advance the future design and development of

  20. Synthesis of linear Geranylphenols and their effect on mycelial growth of plant pathogen Botrytis cinerea.

    PubMed

    Espinoza, Luis; Taborga, Lautaro; Díaz, Katy; Olea, Andrés F; Peña-Cortés, Hugo

    2014-01-27

    Natural geranyl compounds are known to exhibit important biological activities. In this work a series of geranylphenols were synthesized to evaluate their effect on the mycelial growth of Botrytis cinerea. Geranyl derivatives were synthesized by direct geranylation reactions between the corresponding phenol derivatives and geraniol, using BF3.OEt2 as catalyst and AgNO3 as secondary catalyst. Previously reported molecules [geranylhydroquinone (2), geranylhydroquinone diacetate (6) and geranylphloroglucinol (9)], and new substances [(E)-4-(3,7-dimethylocta-2,6-dienyl)benzene-1,2,3-triol (geranyl-pyrogallol, 7), (E)-4-(3,7-dimethylocta-2,6-dienyl)benzene-1,2,3-triyl triacetate (8), (E)-2-(3,7-dimethylocta-2,6-dienyl)benzene-1,3,5-triyl triacetate geranylphloroglucinol triacetate (10), 2,4-bis((E)-3,7-dimethylocta-2,6-dienyl)benzene-1,3,5-triyl triacetate (11), 2,6-bis((E)-3,7-dimethylocta-2,6-dienyl)-3,5-dihydroxyphenyl acetate (12)], were obtained. All compounds were characterized by IR, HRMS and NMR spectroscopic data. The inhibitory effect of the synthesized compounds on the mycelial growth of Botrytis cinerea was tested in vitro. Excepting compound 11, all substances constrained the mycelial growth of Botrytis cinerea. The antifungal activity depends on the chemical structure of geranylphenol derivatives. Compounds 2 and 9 were the more effective substances showing inhibition degrees higher than those obtained with the commercial fungicide Captan, even at lower concentrations. Monosubstitution on the aromatic nucleus by a geranyl chain seems to be more effective for the inhibition of mycelial growth than a double substitution. These results suggest that the new derivatives of geranylphenols have the ability to block the mycelial development of the plant pathogen B. cinerea and that this capacity depends strongly on the structural features and lipophilicity of the compounds.

  1. Effect of the CRAC Peptide, VLNYYVW, on mPTP Opening in Rat Brain and Liver Mitochondria

    PubMed Central

    Azarashvili, Tamara; Krestinina, Olga; Baburina, Yulia; Odinokova, Irina; Akatov, Vladimir; Beletsky, Igor; Lemasters, John; Papadopoulos, Vassilios

    2016-01-01

    The translocator protein (TSPO; 18 kDa) is a high-affinity cholesterol-binding protein located in the outer membrane of mitochondria. A domain in the C-terminus of TSPO was characterized as the cholesterol recognition/interaction amino acid consensus (CRAC). The ability of the CRAC domain to bind to cholesterol led us to hypothesize that this peptide may participate in the regulation of mitochondrial membrane permeability. Herein, we report the effect of the synthetic CRAC peptide, VLNYYVW, on mitochondrial permeability transition pore (mPTP) opening. It was found that the CRAC peptide alone prevents the mPTP from opening, as well as the release of apoptotic factors (cytochrome c, AIF, and EndoG) in rat brain mitochondria (RBM). Co-incubation of CRAC, together with the TSPO drug ligand, PK 11195, resulted in the acceleration of mPTP opening and in the increase of apoptotic factor release. VLNYYVW did not induce swelling in rat liver mitochondria (RLM). 3,17,19-androsten-5-triol (19-Atriol; an inhibitor of the cholesterol-binding activity of the CRAC peptide) alone and in combination with the peptide was able to stimulate RLM swelling, which was Ca2+- and CsA-sensitive. Additionally, a combination of 19-Atriol with 100 nM PK 11195 or with 100 µM PK 11195 displayed the opposite effect: namely, the addition of 19-Atriol with 100 µM PK 11195 in a suspension of RLM suppressed the Ca2+-induced swelling of RLM by 40%, while the presence of 100 nM PK 11195 with 19-Atriol enhanced the swelling of RLM by 60%. Taken together, these data suggest the participation of the TSPO’s CRAC domain in the regulation of permeability transition. PMID:27983605

  2. Epimerization of tea catechins and O-methylated derivatives of (-)-epigallocatechin-3-O-gallate: relationship between epimerization and chemical structure.

    PubMed

    Suzuki, Masazumi; Sano, Mitsuaki; Yoshida, Risa; Degawa, Masakuni; Miyase, Toshio; Maeda-Yamamoto, Mari

    2003-01-15

    Epimerization at C-2 of O-methylated catechin derivatives and four major tea catechins were investigated. The epimeric isomers of (-)-epicatechin (I), (-)-epicatechin-3-O-gallate (II), (-)-epigallocatechin (III), (-)-epigallocatechin-3-O-gallate (IV), and (-)-epigallocatechin-3-O-(3-O-methyl)gallate (V) in green tea extracts increased time-dependently at 90 degrees C. The epimerization rates of authentic tea catechins in distilled water are much lower than those in tea infusion or in pH 6.0 buffer solution. The addition of tea infusion to the authentic catechin solution accelerated the epimerization, and the addition of ethylenediaminetetraacetic acid, disodium salt (Na(2)EDTA) decreased the epimerization in the pH 6.0 buffer solution. Therefore, the metal ions in tea infusion may affect the rate of epimerization. The proportions of the epimers to authentic tea catechins [III, IV, V, and (-)-epigallocatechin-3-O-(4-O-methyl)gallate (VI)] in pH 6.0 buffer solution after heating at 90 degrees C for 30 min were 42.4%, 37.0%, 41.7%, and 30.4%, respectively. These values were higher than those of I and II (23.5% and 23.6%, respectively). The O-methylated derivatives at the 4'-position on the B ring of IV and VI were hardly epimerized. These results suggest that the hydroxyl moiety on the B ring of catechins plays an important role in the epimerization in the order 3',4',5'-triol type > 3',4'-diol type > 3',5'-diol type.

  3. Interfacial molecular interactions based on the conformation recognition between the insoluble antitumor drug AD-1 and DSPC.

    PubMed

    Yin, Tian; Cao, Xiuxiu; Liu, Xiaolin; Wang, Jian; Shi, Caihong; Su, Jia; Zhang, Yu; Gou, Jingxin; He, Haibing; Guo, Haiyan; Tang, Xing; Zhao, Yuqing

    2016-10-01

    In this study, molecular interactions between the anti-cancer agent 20(R)-25-methoxyl-dammarane-3β, 12β, 20-triol (AD-1) and phospholipid 1,2-Distearoyl-sn-glycero-3-phosphocholine (DSPC) were investigated using the Langmuir film balance technique. The characteristics of binary Langmuir monolayers consisting of DSPC and AD-1 were conducted on the basis of the surface pressure-area per molecule (π-A) isotherms. It was found that the drug was able to become efficiently inserted into preformed DSPC monolayers, indicating a preferential interaction between AD-1 and DSPC. For the examined lateral pressure at 20mN/m, the largest negative values of ΔGex were found for the AD-1/DSPC monolayer, which should be the most stable. Based on the calculated values of ΔGex, we found that the AD-1/DSPC systems exhibited the best mixed characteristics when the molar fraction of the AD-1 was 0.8; at that relative concentration, the AD-1 molecules can mix better and interact with the phospholipid molecules. In addition, the drug-DSPC binary supramolecular structure was also deposited on the mica plates as shown by atomic force microscopy (AFM). Finally, molecular docking calculations explained satisfactorily that, based on the conformations interactions (conformation recognition), even at an AD-1/DSPC molar ratio as high as 8:2, the interfacial stabilization of the AD-1/DSPC system was fairly strong due to hydrophobic interactions. A higher loading capacity of DSPC might be possible, as it is associated with a more flexible geometrical environment, which allows these supramolecular structures to accept larger increases in drug loading upon steric binding.

  4. Sex-specific response of rat costochondral cartilage growth plate chondrocytes to 17β-estradiol involves differential regulation of plasma membrane associated estrogen receptors.

    PubMed

    Elbaradie, Khairat B Y; Wang, Yun; Boyan, Barbara D; Schwartz, Zvi

    2013-05-01

    Both male and female rat growth plate chondrocytes express estrogen receptors (ERs); however 17β-estradiol (E2) induces membrane responses leading to activation of phospholipase A2 (PLA2), phospholipase C (PLC), prostaglandin E2 (PGE2) production, protein kinase C (PKC), and ultimately mitogen protein kinase (MAPK) only in female cells. This study investigated if these sex-specific responses are due to differences in the actual ERs or in downstream signaling. Western blots and flow cytometry of costochondral cartilage resting zone chondrocytes (RCs) showed 2-3 times more ERα in plasma membranes (PMs) from female cells than male cells. Tunicamycin blocked E2-dependent ER-translocation to the PM, indicating palmitoylation was required. Co-immunoprecipitation showed E2 induced complex formation between ER isoforms only in female RCs. To examine if the lack of response in PKC and PGE2 in males is due to differences in signaling, we examined involvement of ERs and the role of PLC and PLA2. Selective ERα (propylpyrazole triol, PPT) and ERβ (diarylproprionitrile, DPN) agonists activated PKC in female RCs only. The PLC inhibitor, U73122 blocked E2's effect on PKC and the cytosolic PLA2 inhibitor, AACOCF3 inhibited the effect on PGE2 in female RCs, confirming involvement of PLC and PLA2 in the mechanism. The PLC activator, m-3M3FβS activated PKC and PLAA peptide increased PGE2 levels in male and female RCs, showing that the signaling pathways are present. These data indicate that differences in membrane ER amount, localization, translocation and interaction are responsible for the sexual dimorphic response to E2.

  5. PLDLA/PCL-T Scaffold for Meniscus Tissue Engineering

    PubMed Central

    Moda, Marlon; Cattani, Silvia Mara de Melo; de Santana, Gracy Mara; Barbieri, Juliana Abreu; Munhoz, Monique Moron; Cardoso, Túlio Pereira; Barbo, Maria Lourdes Peris; Russo, Teresa; D'Amora, Ugo; Gloria, Antonio; Ambrosio, Luigi; Duek, Eliana Aparecida de Rezende

    2013-01-01

    Abstract The inability of the avascular region of the meniscus to regenerate has led to the use of tissue engineering to treat meniscal injuries. The aim of this study was to evaluate the ability of fibrochondrocytes preseeded on PLDLA/PCL-T [poly(L-co-D,L-lactic acid)/poly(caprolactone-triol)] scaffolds to stimulate regeneration of the whole meniscus. Porous PLDLA/PCL-T (90/10) scaffolds were obtained by solvent casting and particulate leaching. Compressive modulus of 9.5±1.0 MPa and maximum stress of 4.7±0.9 MPa were evaluated. Fibrochondrocytes from rabbit menisci were isolated, seeded directly on the scaffolds, and cultured for 21 days. New Zealand rabbits underwent total meniscectomy, after which implants consisting of cell-free scaffolds or cell-seeded scaffolds were introduced into the medial knee meniscus; the negative control group consisted of rabbits that received no implant. Macroscopic and histological evaluations of the neomeniscus were performed 12 and 24 weeks after implantation. The polymer scaffold implants adapted well to surrounding tissues, without apparent rejection, infection, or chronic inflammatory response. Fibrocartilaginous tissue with mature collagen fibers was observed predominantly in implants with seeded scaffolds compared to cell-free implants after 24 weeks. Similar results were not observed in the control group. Articular cartilage was preserved in the polymeric implants and showed higher chondrocyte cell number than the control group. These findings show that the PLDLA/PCL-T 90/10 scaffold has potential for orthopedic applications since this material allowed the formation of fibrocartilaginous tissue, a structure of crucial importance for repairing injuries to joints, including replacement of the meniscus and the protection of articular cartilage from degeneration. PMID:23593566

  6. Resveratrol and estradiol rapidly activate MAPK signaling through estrogen receptors alpha and beta in endothelial cells.

    PubMed

    Klinge, Carolyn M; Blankenship, Kristy A; Risinger, Kelly E; Bhatnagar, Shephali; Noisin, Edouard L; Sumanasekera, Wasana K; Zhao, Lei; Brey, Darren M; Keynton, Robert S

    2005-03-04

    Vascular endothelial cells (EC) are an important target of estrogen action through both the classical genomic (i.e. nuclear-initiated) activities of estrogen receptors alpha and beta (ERalpha and ERbeta) and the rapid "non-genomic" (i.e. membrane-initiated) activation of ER that stimulates intracellular phosphorylation pathways. We tested the hypothesis that the red wine polyphenol trans-resveratrol activates MAPK signaling via rapid ER activation in bovine aortic EC, human umbilical vein EC, and human microvascular EC. We report that bovine aortic EC, human umbilical vein EC, and human microvascular EC express ERalpha and ERbeta. We demonstrate that resveratrol and estradiol (E(2)) rapidly activated MAPK in a MEK-1, Src, matrix metalloproteinase, and epidermal growth factor receptor-dependent manner. Importantly, resveratrol activated MAPK and endothelial nitric-oxide synthase (eNOS) at nm concentrations (i.e. an order of magnitude less than that required for ER genomic activity) and concentrations possibly achieved transiently in serum following oral red wine consumption. Co-treatment with ER antagonists ICI 182,780 or 4-hydroxytamoxifen blocked resveratrol- or E(2)-induced MAPK and eNOS activation, indicating ER dependence. We demonstrate for the first time that ERalpha-and ERbeta-selective agonists propylpyrazole triol and diarylpropionitrile, respectively, stimulate MAPK and eNOS activity. A red but not a white wine extract also activated MAPK, and activity was directly correlated with the resveratrol concentration. These data suggest that ER may play a role in the rapid effects of resveratrol in EC and that some of the atheroprotective effects of resveratrol may be mediated through rapid activation of ER signaling in EC.

  7. Potential food additives from Carex distachya roots: identification and in vitro antioxidant properties.

    PubMed

    Fiorentino, Antonio; Ricci, Andreina; D'Abrosca, Brigida; Pacifico, Severina; Golino, Annunziata; Letizia, Marianna; Piccolella, Simona; Monaco, Pietro

    2008-09-10

    In the present study, the chemical composition and antioxidant properties of root methanol extract of Carex distachya Desf. (Cyperaceae) were assessed to use this plant as sources of food additives and nutraceuticals. The IC50 of the extract (4.2 microg/mL), derived from the DPPH radical scavenging capacity assay, was similar to those of ascorbic acid, alpha-tocopherol, and BHT. These results revealed a strong antioxidant activity because of the presence of an extraordinary quantity of bioactive phytochemicals. The phytochemical study of the root extract led to the isolation and identification of new and known polyphenols, most of them common constituents of plant foods. A total of 16 polyphenols, identified on the basis of spectroscopic data as 7 lignans, 4 phenylethanoids, 3 resveratrol derivatives, a monolignol, and a secoiridoid glucoside, were isolated. The tentative structural elucidation of the new metabolites 5'-O-beta-D-glucopyranosyloxy-3,3'-dimethoxy-7,9'-epoxylignan-4,8',9-triol and 3,5-bis-O-beta-D-glucopyranosyloxy-3'-methoxy-trans-stilben-4'-ol have been performed by a combined approach using ESI/TQ/MS techniques and 1D and 2D NMR experiments. All of the compounds have been tested for their antioxidant activity using six different antioxidant and radical scavenging tests. Interestingly, the extract contained high quantities of polyphenols, most of them reported as constituents of edible plants, such as grape and olive, suggesting that the methanol root extract of this plant could be used as a source of natural antioxidants useful as potential food additives.

  8. Biodegradable shape-memory block co-polymers for fast self-expandable stents.

    PubMed

    Xue, Liang; Dai, Shiyao; Li, Zhi

    2010-11-01

    Block co-polymers PCTBVs (M(n) of 36,300-65,300 g/mol, T(m) of 39-40 and 142 degrees C) containing hyperbranched three-arm poly(epsilon-caprolactone) (PCL) as switching segment and microbial polyester PHBV as crystallizable hard segment were designed as biodegradable shape-memory polymer (SMP) for fast self-expandable stent and synthesized in 96% yield by the reaction of three-arm PCL-triol (M(n) of 4200 g/mol, T(m) of 47 degrees C) with methylene diphenyl 4,4'-diisocyanate isocynate (MDI) to form the hyperbrached MDI-linked PCL (PTCM; M(n) of 25,400 g/mol and a T(m) of 38 degrees C), followed by further polymerization with PHBV-diol (M(n) of 2200 g/mol, T(m) of 137 and 148 degrees C). The polymers were characterized by (1)H NMR, GPC, DSC, tensile test, and cyclic thermomechanical tensile test. PCTBVs showed desired thermal properties, mechanical properties, and ductile nature. PCTBV containing 25 wt% PHBV (PCTBV-25) demonstrated excellent shape-memory property at 40 degrees C, with R(f) of 94%, R(r) of 98%, and shape recovery within 25s. PCTBV-25 was also shown as a safe material with good biocompatibility by cytotoxicity tests and cell growth experiments. The stent made from PCTBV-25 film showed nearly complete self-expansion at 37 degrees C within only 25 s, which is much better and faster than the best known self-expandable stents.

  9. Chemical constituents of Papulaspora immersa, an endophyte from Smallanthus sonchifolius (Asteraceae), and their cytotoxic activity.

    PubMed

    Gallo, Margareth Borges Coutinho; Cavalcanti, Bruno Coêlho; Barros, Francisco Washington Araújo; Odorico de Moraes, Manoel; Costa-Lotufo, Letícia Veras; Pessoa, Cláudia; Bastos, Jairo Kenupp; Pupo, Mônica Tallarico

    2010-12-01

    Papulaspora immersa H. H. Hotson was isolated from roots and leaves of Smallanthus sonchifolius (Poepp. and Endl.) H. Rob. (Asteraceae), traditionally known as Yacon. The fungus was cultured in rice, and, from the AcOEt fraction, 14 compounds were isolated. Among them, (22E,24R)-8,14-epoxyergosta-4,22-diene-3,6-dione (4), 2,3-epoxy-1,2,3,4-tetrahydronaphthalene-c-1,c-4,8-triol (10), and the chromone papulasporin (13) were new secondary metabolites. The spectral data of the known natural products were compared with the literature data, and their structures were established as the (24R)-stigmast-4-en-3-one (1), 24-methylenecycloartan-3β-ol (2), (22E,24R)-ergosta-4,6,8(14),22-tetraen-3-one (3), (-)-(3R,4R)-4-hydroxymellein (5), (-)-(3R)-5-hydroxymellein (6), 6,8-dihydroxy-3-methylisocoumarin (7), (-)-(4S)-4,8-dihydroxy-α-tetralone (8), naphthalene-1,8-diol (9), 6,7,8-trihydroxy-3-methylisocoumarin (11), 7-hydroxy-2,5-dimethylchromone (12), and tyrosol (14). Compound 4 showed the highest cytotoxic activity against the human tumor cell lines MDA-MB435 (melanoma), HCT-8 (colon), SF295 (glioblastoma), and HL-60 (promyelocytic leukemia), with IC₅₀ values of 3.3, 14.7, 5.0 and 1.6 μM, respectively. Strong synergistic effects were also observed with compound 5 and some of the isolated steroidal compounds.

  10. Thermal stability of plant sterols and formation of their oxidation products in vegetable oils and margarines upon controlled heating.

    PubMed

    Lin, Yuguang; Knol, Diny; Valk, Iris; van Andel, Vincent; Friedrichs, Silvia; Lütjohann, Dieter; Hrncirik, Karel; Trautwein, Elke A

    2017-02-02

    Fat-based products like vegetable oils and margarines are commonly used for cooking, which may enhance oxidation of plant sterols (PS) present therein, leading to the formation of PS oxidation products (POP). The present study aims to assess the kinetics of POP formation in six different fat-based products. Vegetable oils and margarines without and with added PS (7.5-7.6% w/w) in esterified form were heated in a Petri-dish at temperatures of 150, 180 and 210°C for 8, 12 and 16min. PS and POP were analysed using GC-FID and GC-MS-SIM, respectively. Increasing PS content, temperature and heating time led to higher POP formation in all tested fat-based products. PS (either naturally occurring or added) in margarines were less susceptible to oxidation as compared to PS in vegetable oils. The susceptibility of sitosterol to oxidation was about 20% lower than that of campesterol under all the applied experimental conditions. During heating, the relative abundance of 7-keto-PS (expressed as% of total POP) decreased in all the fat-based products regardless of their PS contents, which was accompanied by an increase in the relative abundance of 7-OH-PS and 5,6-epoxy-PS, while PS-triols were fairly unchanged. In conclusion, heating time, temperature, initial PS content and the matrix of the fat-based products (vegetable oil vs. margarine) showed distinct effects on POP formation and composition of individual POP formed.

  11. Human hepatoblastoma cells (HepG2) and rat hepatoma cells are defective in important enzyme activities in the oxidation of the C27 steroid side chain in bile acid formation.

    PubMed

    Farrants, A K; Nilsson, A; Pedersen, J I

    1993-12-01

    We have examined the ability of HepG2 human hepatoblastoma cells and 7800 C1 Morris rat hepatoma cells to convert 3 alpha, 7 alpha, 12 alpha-trihydroxy-5 beta-cholestanoic acid (THCA) and 3 alpha, 7 alpha-dihydroxy-5 beta-cholestanoic acid (DHCA) to cholic acid and chenodeoxycholic acid, respectively. Cell extracts from both these cell lines could neither form cholic acid from THCA nor from the activated form, THCA-CoA. This suggests that both cell lines are defective in two enzyme activities involved in the pathway, the microsomal THCA-CoA ligase and the peroxisomal THCA-CoA oxidase. Furthermore, we show that the subsequent enzymes are active in the conversion to bile acids, because the product of the THCA-CoA oxidase, 3 alpha, 7 alpha, 12 alpha-trihydroxy-5 beta-cholest-24-enoyl-coenzyme A (delta 24-THCA-CoA) or delta 24-THCA in the presence of THCA-CoA ligase, are converted to cholic acid by both cell lines. HepG2 cells were able to slowly form chenodeoxycholic acid and cholic acid from 5 beta-cholestane-3 alpha, 7 alpha-diol and 5 beta-cholestane-3 alpha, 7 alpha, 12 alpha-triol, respectively, in 24- and 96-h incubations. The rate of cholic acid formation was lower than the rate for chenodeoxycholic acid and there was a clear accumulation of THCA. 7800 C1 Morris cells had no ability to form cholic acid or chenodeoxycholic acid after 96 h incubation. We conclude that these two cell lines have defects in two enzyme activities involved in the peroxisomal oxidation in bile acid formation, the microsomal THCA-CoA ligase and the peroxisomal THCA-CoA oxidase.

  12. Drug ligand-induced activation of translocator protein (TSPO) stimulates steroid production by aged brown Norway rat Leydig cells.

    PubMed

    Chung, J Y; Chen, H; Midzak, A; Burnett, A L; Papadopoulos, V; Zirkin, B R

    2013-06-01

    Translocator protein (TSPO; 18 kDA) is a high-affinity cholesterol-binding protein that is integrally involved in cholesterol transfer from intracellular stores into mitochondria, the rate-determining step in steroid formation. Previous studies have shown that TSPO drug ligands are able to activate steroid production by MA-10 mouse Leydig tumor cells and by mitochondria isolated from steroidogenic cells. We hypothesized herein that the direct, pharmacological activation of TSPO might induce aged Leydig cells, which are characterized by reduced T production, to produce significantly higher levels of T both in vitro and in vivo. To test this, we first examined the in vitro effects of the TSPO selective and structurally distinct drug ligands N,N-dihexyl-2-(4-fluorophenyl)indole-3-acetamide (FGIN-1-27) and benzodiazepine 4'-chlorodiazepam (Ro5-4864) on steroidogenesis by Leydig cells isolated from aged (21-24 months old) and young adult (3-6 months old) Brown Norway rats. The ligands stimulated Leydig cell T production significantly, and equivalently, in cells of both ages, an effect that was significantly inhibited by the specific TSPO inhibitor 5-androsten-3,17,19-triol (19-Atriol). Additionally, we examined the in vivo effects of administering FGIN-1-27 to young and aged rats. In both cases, serum T levels increased significantly, consistent with the in vitro results. Indeed, serum T levels in aged rats administered FGIN-1-27 were equivalent to T levels in the serum of control young rats. Taken together, these results indicate that although there are reduced amounts of TSPO in aged Leydig cells, its direct activation is able to increase T production. We suggest that this approach might serve as a therapeutic means to increase steroid levels in vivo in cases of primary hypogonadism.

  13. Are motorways potential stressors of roadside wood mice (Apodemus sylvaticus) populations?

    PubMed

    Navarro-Castilla, Álvaro; Mata, Cristina; Ruiz-Capillas, Pablo; Palme, Rupert; Malo, Juan E; Barja, Isabel

    2014-01-01

    Linear infrastructures represent one of the most important human impacts on natural habitats and exert several effects on mammal populations. Motorways are recognized as a major cause of habitat fragmentation and degradation and of biodiversity loss. However, it is unknown whether motorways lead to increased physiological stress reactions in wild animal populations. We analysed faecal corticosterone metabolites (FCM) in wild populations of wood mice (Apodemus sylvaticus) living in a well-preserved Mediterranean agro-pastoral woodland at different distances (verge, 500 m and 1000 m) from the AP-51 motorway in Spain. Wood mice were captured with Sherman live traps, and fresh faecal samples from 424 individuals were collected and analyzed in the laboratory. The quantification of FCM was performed by a 5α-pregnane-3β,11β, 21-triol-20-one enzyme immunoassay. Results showed that females had higher FCM levels than males, and these levels were higher in breeding females. In addition, FCM levels were positively correlated with body weight of individuals. Wood mice captured where cattle were present showed higher FCM levels than individuals living where cattle were not detected. FCM levels were higher in non-breeding individuals living close to the motorway compared with FCM levels in those individuals captured further from the motorway. This is the first study showing evidence of the motorways' impact on physiological stress reactions in wild wood mice populations. Understanding how free-living animals are influenced by human interventions could help to understand other subtle changes observed in wild animal populations. Since mice are used world-wide as research models these results could open new perspectives testing human influence on the natural environment and trade-offs of species in degraded ecosystems.

  14. Are Motorways Potential Stressors of Roadside Wood Mice (Apodemus sylvaticus) Populations?

    PubMed Central

    Navarro-Castilla, Álvaro; Mata, Cristina; Ruiz-Capillas, Pablo; Palme, Rupert; Malo, Juan E.; Barja, Isabel

    2014-01-01

    Linear infrastructures represent one of the most important human impacts on natural habitats and exert several effects on mammal populations. Motorways are recognized as a major cause of habitat fragmentation and degradation and of biodiversity loss. However, it is unknown whether motorways lead to increased physiological stress reactions in wild animal populations. We analysed faecal corticosterone metabolites (FCM) in wild populations of wood mice (Apodemus sylvaticus) living in a well-preserved Mediterranean agro-pastoral woodland at different distances (verge, 500 m and 1000 m) from the AP-51 motorway in Spain. Wood mice were captured with Sherman live traps, and fresh faecal samples from 424 individuals were collected and analyzed in the laboratory. The quantification of FCM was performed by a 5α-pregnane-3β,11β, 21-triol-20-one enzyme immunoassay. Results showed that females had higher FCM levels than males, and these levels were higher in breeding females. In addition, FCM levels were positively correlated with body weight of individuals. Wood mice captured where cattle were present showed higher FCM levels than individuals living where cattle were not detected. FCM levels were higher in non-breeding individuals living close to the motorway compared with FCM levels in those individuals captured further from the motorway. This is the first study showing evidence of the motorways' impact on physiological stress reactions in wild wood mice populations. Understanding how free-living animals are influenced by human interventions could help to understand other subtle changes observed in wild animal populations. Since mice are used world-wide as research models these results could open new perspectives testing human influence on the natural environment and trade-offs of species in degraded ecosystems. PMID:24637740

  15. Anti-TB Polyynes from the roots of Angelica sinensis

    PubMed Central

    Deng, Shixin; Wang, Yuehong; Inui, Taichi; Chen, Shao-Nong; Farnsworth, Norman R.; Cho, Sanghyun; Franzblau, Scott G.; Pauli, Guido F.

    2008-01-01

    Following chemotaxonomic evidence, the PE and CHCl3 extracts of the roots of the botanical Angelica sinensis (Oliv.) Diels (Dang Gui) were investigated for in vitro anti-TB activity, in parallel to studying their serotonergic and GABAergic potential. The activities were confirmed to chemically overlap with the neurotropic active principles present in medium lipophilic fractions. Phytochemical investigations led to the isolation of five polyynes: falcarindiol (1), 9Z,17-octadecadiene-12,14-diyne-1,11,16-triol,1-acetate (2), oplopandiol (3), heptadeca-1-ene-9,10-epoxy-4,6-diyne-3,8-diol (4), and the new polyyne 8-hydroxy-1-methoxy-(Z)-9-heptadecene-4,6-diyn-3-one (5), as characterized by spectroscopic techniques including 1D, 2D NMR and HR-MS. All compounds were tested against two pathogenic strains of Mycobacterium tuberculosis (H37Rv and Erdman) in vitro in a microplate Alamar Blue assay (MABA). The most potent anti-TB constituents were 1 and 2, exhibiting MIC values of 1.4-26.7 μg/ml; 3 showed moderate MICs (49.5 and 50.2 μg/ml, respectively) while 4 and 5 were weakly active (MIC> 60 μg/ml). Notably, none of the five compounds exhibited significant cytotoxicity against VERO cells. These findings not only reveal a new potential area of therapeutic value for A. sinensis, but also underline the role of polyynes as anti-TB active principles in ethnobotanical preparations, and as lead compounds. PMID:18567055

  16. Activation of the G protein-coupled estrogen receptor, but not estrogen receptor α or β, rapidly enhances social learning.

    PubMed

    Ervin, Kelsy Sharice Jean; Mulvale, Erin; Gallagher, Nicola; Roussel, Véronique; Choleris, Elena

    2015-08-01

    Social learning is a highly adaptive process by which an animal acquires information from a conspecific. While estrogens are known to modulate learning and memory, much of this research focuses on individual learning. Estrogens have been shown to enhance social learning on a long-term time scale, likely via genomic mechanisms. Estrogens have also been shown to affect individual learning on a rapid time scale through cell-signaling cascades, rather than via genomic effects, suggesting they may also rapidly influence social learning. We therefore investigated the effects of 17β-estradiol and involvement of the estrogen receptors (ERs) using the ERα agonist propyl pyrazole triol, the ERβ agonist diarylpropionitrile, and the G protein-coupled ER 1 (GPER1) agonist G1 on the social transmission of food preferences (STFP) task, within a time scale that focused on the rapid effects of estrogens. General ER activation with 17β-estradiol resulted in a modest facilitation of social learning, with mice showing a preference up to 30min of testing. Specific activation of the GPER1 also rapidly enhanced social learning, with mice showing a socially learned preference up to 2h of testing. ERα activation instead shortened the expression of a socially learned food preference, while ERβ activation had little to no effects. Thus, rapid estrogenic modulation of social learning in the STFP may be the outcome of competing action at the three main receptors. Hence, estrogens' rapid effects on social learning likely depend on the specific ERs present in brain regions recruited during social learning.

  17. Steroid Transformations by Species of Cephalosporium and Other Fungi1

    PubMed Central

    Sardinas, Joseph L.; Pisano, Michael A.

    1967-01-01

    A total of 58 cultures, tentatively identified as species of the genus Cephalosporium, were screened in flask fermentations for their ability to effect conversions of progesterone (Δ4-pregnene-3,20-dione) and Reichstein's Substance S (Δ4-pregnene-17α,21-diol-3,20-dione). A large number of transformations were observed by means of a series of five paper chromatography systems rated for analysis of steroid compounds ranging in polarity from progesterone to polyhydroxylated steroids. Five different transformation products were selected for isolation and identification. For purposes of recovery, conversions were conducted under submerged conditions in either 4- or 200-liter fermentors in which the broth was agitated and aerated. The steroid substrate was dissolved in acetone and added aseptically to the growing culture in a final concentration of 0.025%. After the conversions were effected, the whole broth was extracted with chloroform, and the transformation products were recovered, either by direct crystallization from solvents or through the use of silica gel columns. It was determined that C. ciferrii 21C converted progesterone to Δ4-androstene-3,17-dione. Kendall's Compound F (Δ4-pregnene-11β,17α,21-triol-3,20-dione) was converted to its 20β-ol analogue by Geotrichum sp. 51C (during these studies, a number of cultures were taxonomically reclassified). Cephalosporium sp. 27C formed the Δ1-analogue of Reichstein's Substance S, and Cephalosporium sclerotigenum 31C and Verticillium aphidum both converted Substance S to the 6β-hydroxy derivative. Paecilomyces persicinus 22C converted Substance S to a product believed to be a dihydroxylated derivative. PMID:6029828

  18. PLDLA/PCL-T Scaffold for Meniscus Tissue Engineering.

    PubMed

    Esposito, Andrea Rodrigues; Moda, Marlon; Cattani, Silvia Mara de Melo; de Santana, Gracy Mara; Barbieri, Juliana Abreu; Munhoz, Monique Moron; Cardoso, Túlio Pereira; Barbo, Maria Lourdes Peris; Russo, Teresa; D'Amora, Ugo; Gloria, Antonio; Ambrosio, Luigi; Duek, Eliana Aparecida de Rezende

    2013-04-01

    The inability of the avascular region of the meniscus to regenerate has led to the use of tissue engineering to treat meniscal injuries. The aim of this study was to evaluate the ability of fibrochondrocytes preseeded on PLDLA/PCL-T [poly(L-co-D,L-lactic acid)/poly(caprolactone-triol)] scaffolds to stimulate regeneration of the whole meniscus. Porous PLDLA/PCL-T (90/10) scaffolds were obtained by solvent casting and particulate leaching. Compressive modulus of 9.5±1.0 MPa and maximum stress of 4.7±0.9 MPa were evaluated. Fibrochondrocytes from rabbit menisci were isolated, seeded directly on the scaffolds, and cultured for 21 days. New Zealand rabbits underwent total meniscectomy, after which implants consisting of cell-free scaffolds or cell-seeded scaffolds were introduced into the medial knee meniscus; the negative control group consisted of rabbits that received no implant. Macroscopic and histological evaluations of the neomeniscus were performed 12 and 24 weeks after implantation. The polymer scaffold implants adapted well to surrounding tissues, without apparent rejection, infection, or chronic inflammatory response. Fibrocartilaginous tissue with mature collagen fibers was observed predominantly in implants with seeded scaffolds compared to cell-free implants after 24 weeks. Similar results were not observed in the control group. Articular cartilage was preserved in the polymeric implants and showed higher chondrocyte cell number than the control group. These findings show that the PLDLA/PCL-T 90/10 scaffold has potential for orthopedic applications since this material allowed the formation of fibrocartilaginous tissue, a structure of crucial importance for repairing injuries to joints, including replacement of the meniscus and the protection of articular cartilage from degeneration.

  19. Neuroprotective effects of R,R-tetrahydrochrysene against glutamate-induced cell death through anti-excitotoxic and antioxidant actions involving estrogen receptor-dependent and -independent pathways.

    PubMed

    Xia, Y; Xing, J Z; Krukoff, T L

    2009-08-18

    Glutamate-induced neural cell death is mediated by excitotoxicity and oxidative stress. Treatment of glutamate toxicity with estrogen and its related compounds for neuroprotection remains controversial. In this study, we examined the effects of selective estrogen receptor (ER) ligands on glutamate toxicity and found that R,R-tetrahydrochrysene (R,R-THC), an antagonist of ERbeta and agonist of ERalpha, has neuroprotective effects against glutamate-induced death in primary rat cortical cells and mouse N29/4 hypothalamic cells. The protective effect of R,R-THC was dose-dependent and was maintained even when added several hours after the initial glutamate exposure. R,R-THC blocked glutamate-induced depletion of intracellular glutathione, increased superoxide dismutase activity, and protected cells from hydrogen peroxide-induced death. R,R-THC also prevented glutamate-induced nuclear translocation of apoptotic inducing factor and release of mitochondrial cytochrome c. The protective effect of R,R-THC was blocked by methyl-piperidino-pyrazole (MPP; an ERalpha antagonist) in glutamate-treated cortical cells, and pretreatment with MK-801 (an NMDA receptor antagonist) but not CNQX (an AMPA/kainate receptor antagonist) increased cell survival. On the other hand, MPP did not block the protective effect of R,R-THC in glutamate-treated N29/4 cells, and neither MK-801 nor CNQX conferred protection. Activation of ERalpha and/or ERbeta with 17beta-estradiol (E2), propyl-pyrazole-triol or diarylpropionitrile did not provide effective neuroprotection, and pretreatment with ICI 182,780 did not inhibit the protective effect of R,R-THC in either type of cell. These results suggest that the use of ER agonists (including E2) has limited beneficial effects when both excitotoxicity and oxidative stress occur. In contrast to agonists of ERs, R,R-THC, which possesses anti-excitotoxic and antioxidant actions via ER-dependent and -independent pathways, provides significant neuroprotection.

  20. Catechol 1,2-dioxygenase from the Gram-positive Rhodococcus opacus 1CP: quantitative structure/activity relationship and the crystal structures of native enzyme and catechols adducts.

    PubMed

    Matera, Irene; Ferraroni, Marta; Kolomytseva, Marina; Golovleva, Ludmila; Scozzafava, Andrea; Briganti, Fabrizio

    2010-06-01

    The first crystallographic structures of a catechol 1,2-dioxygenase from a Gram-positive bacterium Rhodococcus opacus 1CP (Rho 1,2-CTD), a Fe(III) ion containing enzyme specialized in the aerobic biodegradation of catechols, and its adducts with catechol, 3-methylcatechol, 4-methylcatechol, pyrogallol (benzene-1,2,3-triol), 3-chlorocatechol, 4-chlorocatechol, 3,5-dichlorocatechol, 4,5-dichlorocatechol and protocatechuate (3,4-dihydroxybenzoate) have been determined and analyzed. This study represents the first extensive characterization of catechols adducts of 1,2-CTDs. The structural analyses reveal the diverse modes of binding to the active metal iron ion of the tested catechols thus allowing to identify the residues selectively involved in recognition of the diverse substrates by this class of enzymes. The comparison is further extended to the structural and functional characteristics of the other 1,2-CTDs isolated from Gram-positive and Gram-negative bacteria. Moreover the high structural homology of the present enzyme with the 3-chlorocatechol 1,2-dioxygenase from the same bacterium are discussed in terms of their different substrate specificity. The catalytic rates for Rho 1,2-CTD conversion of the tested compounds are also compared with the calculated energies of the highest occupied molecular orbital (E(HOMO)) of the substrates. A quantitative relationship (R=0.966) between the ln k(cat) and the calculated electronic parameter E(HOMO) was obtained for catechol, 3-methylcatechol, 4-methylcatechol, pyrogallol, 3-chlorocatechol, 4-chlorocatechol. This indicates that for these substrates the rate-limiting step of the reaction cycle is dependent on their nucleophilic reactivity. The discrepancies observed in the quantitative relationship for 3,5-dichlorocatechol, 4,5-dichlorocatechol and protocatechuate are ascribed to the sterical hindrances leading to the distorted binding of such catechols observed in the corresponding structures.

  1. Alpha-Estrogen and Progesterone Receptors Modulate Kisspeptin Effects on Prolactin: Role in Estradiol-Induced Prolactin Surge in Female Rats.

    PubMed

    Aquino, Nayara S S; Araujo-Lopes, Roberta; Henriques, Patricia C; Lopes, Felipe E F; Gusmao, Daniela O; Coimbra, Candido C; Franci, Celso R; Reis, Adelina M; Szawka, Raphael E

    2017-04-06

    Kisspeptin regulates prolactin (PRL) in an estradiol-dependent manner. We investigated the interaction between ovarian-steroid receptors and kisspeptin in the control of PRL secretion. Intracerebroventricular injections of kisspeptin-10 (Kp-10) or kisspeptin-234 (Kp-234) were performed in ovariectomized (OVX) rats under different hormonal treatments. Kp-10 increased PRL release and decreased 3,4-dihydroxyphenylacet acid (DOPAC) levels in the median eminence (ME) of OVX rats treated with estradiol (OVX+E), which was prevented by tamoxifen. Whereas these effects of Kp-10 were absent in OVX rats, they were replicated in OVX rats treated with selective agonist of estrogen receptor (ER)α, propylpyrazole triol (PPT), but not of ERβ, diarylpropionitrile (DPN). Furthermore, the Kp-10-induced increase in PRL was 2-fold higher in OVX+E rats further treated with progesterone (OVX+EP), which was associated with a reduced expression of both tyrosine hydroxylase (TH) and Ser40-phosphorylated TH in the ME. Kp-10 also reduced dopamine levels in the ME of OVX+EP rats, an effect blocked by the progesterone receptor (PR) antagonist, RU486. We also determined the effect of kisspeptin antagonism with Kp-234 on the estradiol-induced surges of PRL and luteinizing hormone (LH), using tail-tip blood sampling combined with ultrasensitive ELISA. Kp-234 impaired the early phase of the PRL surge and prevented the LH surge in OVX+E rats. Thus, we provide evidence for the first time that kisspeptin stimulation of PRL release requires ERα and is potentiated by progesterone via PR activation. Moreover, alongside its essential role in the LH surge, kisspeptin seems to play a role in the peak phase of the estradiol-induced PRL surge.

  2. In silico analysis sheds light on the structural basis underlying the ribotoxicity of trichothecenes-A tool for supporting the hazard identification process.

    PubMed

    Dellafiora, Luca; Galaverna, Gianni; Dall'Asta, Chiara

    2017-03-15

    Deoxynivalenol is a food borne mycotoxin belonging to the trichothecenes family that may cause severe injuries in human and animals. The inhibition of protein synthesis via the interaction with the ribosome has been identified as a crucial mechanism underlying toxic action. However, it is not still fully understood how and to what extent compounds belonging to trichothecenes family affect human and animal health. In turn, this scenario causes delay in managing the related health risk. Aimed at supporting the hazard identification process, the in silico analysis may be a straightforward tool to investigate the structure-activity relationship of trichothecenes, finding out molecules of possible concern to carry forth in the risk assessment process. In this framework, this work investigated through a molecular modeling approach the structural basis underlying the interaction with the ribosome under a structure-activity relationship perspective. To identify further forms possibly involved in the total trichothecenes-dependent ribotoxic load, the model was challenged with a set of 16 trichothecene modified forms found in plants, fungi and animals, including also compounds never tested before for the capability to bind and inhibit the ribosome. Among them, only the regiospecific glycosylation in the position 3 of the sesquiterpenoid scaffold (i.e. T-2 toxin-3-glucuronide, α and β isomers of T-2 toxin-3-glucoside and deoxynivalenol-3-glucuronide) was found impairing the interaction with the ribosome, while the other compounds tested (i.e. neosolaniol, nivalenol, fusarenon-X, diacetoxyscirpenol, NT-1 toxin, HT-2 toxin, 19- and 20-hydroxy-T-2 toxin, T-2 toxin triol and tetraol, and 15-deacetyl-T-2 toxin), were found potentially able to inhibit the ribosome. Accordingly, they should be included with high priority in further risk assessment studies in order to better characterize the trichothecenes-related hazard.

  3. Asymmetric Synthesis of Spirocyclic 2-Benzopyrans for Positron Emission Tomography of σ1 Receptors in the Brain

    PubMed Central

    Holl, Katharina; Schepmann, Dirk; Fischer, Steffen; Ludwig, Friedrich-Alexander; Hiller, Achim; Donat, Cornelius K.; Deuther-Conrad, Winnie; Brust, Peter; Wünsch, Bernhard

    2014-01-01

    Sharpless asymmetric dihydroxylation of styrene derivative 6 afforded chiral triols (R)-7 and (S)-7, which were cyclized with tosyl chloride in the presence of Bu2SnO to provide 2-benzopyrans (R)-4 and (S)-4 with high regioselectivity. The additional hydroxy moiety in the 4-position was exploited for the introduction of various substituents. Williamson ether synthesis and replacement of the Boc protective group with a benzyl moiety led to potent σ1 ligands with high σ1/σ2-selectivity. With exception of the ethoxy derivative 16, the (R)-configured enantiomers represent eutomers with eudismic ratios of up to 29 for the ester (R)-18. The methyl ether (R)-15 represents the most potent σ1 ligand of this series of compounds, with a Ki value of 1.2 nM and an eudismic ratio of 7. Tosylate (R)-21 was used as precursor for the radiosynthesis of [18F]-(R)-20, which was available by nucleophilic substitution with K[18F]F K222 carbonate complex. The radiochemical yield of [18F]-(R)-20 was 18%–20%, the radiochemical purity greater than 97% and the specific radioactivity 175–300 GBq/µmol. Although radiometabolites were detected in plasma, urine and liver samples, radiometabolites were not found in brain samples. After 30 min, the uptake of the radiotracer in the brain was 3.4% of injected dose per gram of tissue and could be reduced by coadministration of the σ1 antagonist haloperidol. [18F]-(R)-20 was able to label those regions of the brain, which were reported to have high density of σ1 receptors. PMID:24451404

  4. Hydrophobic constituents and their potential anticancer activities from Devil’s Club Oplopanax horridus

    PubMed Central

    Sun, Shi; Du, Guang-Jian; Qi, Lian-Wen; Williams, Stainley; Wang, Chong-Zhi; Yuan, Chun-Su

    2011-01-01

    Ethnopharmacological relevance Devil’s Club Oplopanax horridus (Sm.) Miq. is a widely used folk medicine in the Pacific Northwest such as Alaska and British Columbia for treating a variety of ailments including arthritis, cold, fever, infections, diabetes and cancer. Aim of the study To investigate hydrophobic constituents and their potential anticancer activity from Devil’s Club O. horridus. Materials and methods The root bark of O. horridus (Sm.) Miq was isolated by chromatographic techniques. Structures of isolated compounds were identified by spectroscopic methods and comparison with published data. The anti-proliferation of isolated hydrophobic constituents in human breast cancer MCF-7 cells, human colon cancer SW-480 and HCT-116 cells were tested. The potential mechanism of anti-proliferation was also investigated using cell cycle and apoptosis assays. Results and discussion Six compounds were isolated and structurally identified as 9,17-octadecadiene-12,14-diyne-1,11,16-triol, 1-acetate (1), oplopandiol acetate (2), falcarindiol (3), oplopandiol (4), trans-nerolidol (5) and t-cadinol (6). These compounds showed potential anticancer activities on human breast cancer and colon cancer cells, of which compound 3 possesses the strongest activity. Further cell cycle and apoptosis test by flow cytometry showed the polyacetylenes 1–4 induced HCT-116 cell arresting in G2/M phase and inhibited proliferation by the induction of apoptosis at both earlier and later stage. Conclusion These results provide promising baseline information for the potential use of O. horridus as well as some of the isolated compounds in the treatment of cancer. PMID:20723598

  5. Relationships between Genetic Diversity and Fusarium Toxin Profiles of Winter Wheat Cultivars

    PubMed Central

    Góral, Tomasz; Stuper-Szablewska, Kinga; Buśko, Maciej; Boczkowska, Maja; Walentyn-Góral, Dorota; Wiśniewska, Halina; Perkowski, Juliusz

    2015-01-01

    Fusarium head blight is one of the most important and most common diseases of winter wheat. In order to better understanding this disease and to assess the correlations between different factors, 30 cultivars of this cereal were evaluated in a two-year period. Fusarium head blight resistance was evaluated and the concentration of trichothecene mycotoxins was analysed. Grain samples originated from plants inoculated with Fusarium culmorum and naturally infected with Fusarium species. The genetic distance between the tested cultivars was determined and data were analysed using multivariate data analysis methods. Genetic dissimilarity of wheat cultivars ranged between 0.06 and 0.78. They were grouped into three distinct groups after cluster analysis of genetic distance. Wheat cultivars differed in resistance to spike and kernel infection and in resistance to spread of Fusarium within a spike (type II). Only B trichothecenes (deoxynivalenol, 3-acetyldeoxynivalenol and nivalenol) produced by F. culmorum in grain samples from inoculated plots were present. In control samples trichothecenes of groups A (H-2 toxin, T-2 toxin, T-2 tetraol, T-2 triol, scirpentriol, diacetoxyscirpenol) and B were detected. On the basis of Fusarium head blight assessment and analysis of trichothecene concentration in the grain relationships between morphological characters, Fusarium head blight resistance and mycotoxins in grain of wheat cultivars were examined. The results were used to create of matrices of distance between cultivars – for trichothecene concentration in inoculated and naturally infected grain as well as for FHB resistance Correlations between genetic distance versus resistance/mycotoxin profiles were calculated using the Mantel test. A highly significant correlation between genetic distance and mycotoxin distance was found for the samples inoculated with Fusarium culmorum. Significant but weak relationships were found between genetic distance matrix and FHB resistance or

  6. Oestrogen receptors enhance dopamine neurone survival in rat midbrain.

    PubMed

    Johnson, M L; Ho, C C; Day, A E; Walker, Q D; Francis, R; Kuhn, C M

    2010-04-01

    Previous findings in our laboratory and elsewhere have shown that ovariectomy of rats in adulthood attenuates cocaine-stimulated locomotor behaviour. Ovarian hormones enhance both cocaine-stimulated behaviour and increase dopamine overflow after psychomotor stimulants. The present study aimed to determine whether ovarian hormones have these effects in part by maintaining dopamine neurone number in the substantia nigra pars compacta (SNpc) and ventral tegmental area (VTA) and to investigate the roles of specific oestrogen receptors (ERs) in the maintenance of mesencephalic dopamine neurones. To accomplish this goal, we used unbiased stereological techniques to estimate the number of tyrosine hydroxylase-immunoreactive (TH-IR) cell bodies in midbrain regions of intact, ovariectomised and hormone-replaced female rats and mice. Animals received active or sham gonadectomy on postnatal day 60 and received vehicle, 17beta-oestradiol (E(2)) or selective ER agonists propyl-pyrazole-triol (PPT, ERalpha) or diarylpropionitrile (DPN, ERbeta) for 1 month post-surgery. In both rats and mice, ovariectomy reduced the number of TH-IR cells in the SNpc and VTA. Replacement with E(2), PPT or DPN prevented or attenuated the loss observed with ovariectomy in both rats and mice. An additional study using ER knockout mice revealed that adult female mice lacking ERalpha had fewer TH-IR cells in midbrain regions than wild-type mice, whereas mice lacking ERbeta had TH-IR cell counts comparable to wild-type. These findings suggest that, although both ER subtypes play a role in the maintenance of TH-IR cell number in the SNpc and VTA, ERalpha may play a more significant role.

  7. Chemistry and cancer preventing activities of ginseng saponins and some related triterpenoid compounds.

    PubMed Central

    Shibata, S

    2001-01-01

    More than 25 dammarane-type tetracyclic triterpenoid saponins have been isolated from ginseng, the root and rhizome of Panax ginseng C.A. Meyer (Araliaceae). The genuine sapogenins of those saponins, 20(S)-protopanaxa-diol and -triol, were identified as 20(S) 12beta-hydroxy-and 20(S) 6alpha,12beta-dihydroxy-dammarenediol-II, respectively. There are two types of preparations from ginseng: white ginseng prepared by drying after peelling off and red ginseng prepared by steaming and drying. Some partly deglycosylated saponins such as ginsenoside Rh-1, Rh-2, and Rg-3 are obtained from red ginseng as artifacts produced during steaming. Several workers studied the metabolic transformation by human intestinal bacteria after oral administration of ginsenoside Rb-1 and Rb-2 and found that the stepwise deglyco-sylation yielded compound K and finally 20(S)-protopanaxadiol. Ginsenoside Rg-1 was converted into 20(S)-protopanaxatriol via ginsenoside Rh-1. Yun et al. in Korea conducted the epidemiological case-control studies of ginseng and suggested its cancer preventing activities. Kitagawa et al. demonstrated in vitro that ginsenosides, especially 20(R)-ginsenoside Rg-3, specifically inhibited cancer cell invasion and metastasis. Azuma et al. found that ginsenoside Rb-2 inhibited tumor angiogenesis, and Kikuchi et al. reported that ginsenoside Rh-2 inhibited the human ovarian cancer growth in nude mice. Recently, ginsenoside Rg-3 was produced as an anti-angiogenic anti-cancer drug in China. The aforementioned reports suggest that less glycosylated protopanaxadiol derivatives are effective in cancer prevention. Apart from Ginseng tetracyclic triterpenoid saponins, some oleanane-type pentacyclic triterpenoid compounds showed the anti-carcinogenic activity in the two-stage anti-cancer-promotion experiments in vitro and in vivo. PMID:11748374

  8. Oestradiol decreases colonic permeability through oestrogen receptor β-mediated up-regulation of occludin and junctional adhesion molecule-A in epithelial cells

    PubMed Central

    Braniste, Viorica; Leveque, Mathilde; Buisson-Brenac, Claire; Bueno, Lionel; Fioramonti, Jean; Houdeau, Eric

    2009-01-01

    Oestradiol modulates paracellular permeability and tight junction (TJ) function in endothelia and reproductive tissues, but whether the ovarian hormones and cycle affect the paracellular pathway in the intestinal epithelium remains unclear. Oestrogen receptors (ERs) are expressed in intestinal epithelial cells, and oestradiol regulates epithelium formation. We examined the effects of oestrous cycle stage, oestradiol benzoate (EB), and progesterone (P) on colonic paracellular permeability (CPP) in the female rat, and whether EB affects expression of the TJ proteins in the rat colon and the human colon cell line Caco-2. In cyclic rats, CPP was determined through lumen-to-blood 51Cr-labelled EDTA clearance, and in Ussing chambers for dextran permeability. CPP was also examined in ovariectomized (OVX) rats treated with P or EB, with and without the ER antagonist ICI 182,780, or with the selective agonists for ERα (propyl pyrazole triol; PPT) or ERβ (diarylpropionitrile; DPN). In oestrus rats, CPP was reduced (P < 0.01) relative to dioestrus. In OVX rats, EB dose-dependently decreased CPP, an effect mimicked by DPN and blocked by ICI 182,780, whereas P had no effect. Oestradiol increased occludin mRNA and protein in the colon (P < 0.05), but not zona occludens (ZO)-1. Further, EB and DPN enhanced occludin and junctional adhesion molecule (JAM)-A expression in Caco-2 cells without change in ZO-1, an effect blocked by ICI 182,780. These data show that oestrogen reinforces intestinal epithelial barrier through ERβ-mediated up-regulation of the transmembrane proteins occludin and JAM-A determining paracellular spaces. These findings highlight the importance of the ERβ pathway in the control of colonic paracellular transport and mucosal homeostasis. PMID:19433574

  9. ERalpha, but not ERbeta, mediates the expression of sexual behavior in the female rat.

    PubMed

    Mazzucco, Christine A; Walker, Hope A; Pawluski, Jodi L; Lieblich, Stephanie E; Galea, Liisa A M

    2008-08-05

    Estrogen has well known effects on sexual behavior, however the role of the estrogen receptors (ER) alpha and beta on sexual behavior remains to be fully determined. This study investigated the individual and co-operative involvement of ERalpha and beta on sexual behaviors in the adult female rat. Subtype selective ER agonists, propyl-pyrazole triol (PPT; ERalpha agonist) and diarylpropionitrile (DPN; ERbeta agonist) were utilized to examine each receptor subtype's contribution, individual and co-operative, for both receptive (lordosis) and proceptive (hopping/darting, 'ear wiggling') female sexual behaviors. Ovariectomized female rats received subcutaneous injections of either: sesame oil (OIL), dimethylsulfoxide (DMSO), estradiol benzoate (EB; 10 microg/0.1 ml OIL), one of three doses of the ERalpha agonist PPT (1.25mg, 2.5mg or 5.0mg/0.1 ml DMSO), one of three doses of the ERbeta agonist DPN (1.25mg, 2.5mg or 5.0mg/0.1 ml DMSO) or a combination dose of PPT and DPN (2.5mg PPT+2.5mg DPN/0.1 ml DMSO) for two consecutive days, 48 and 24h prior to testing followed by a progesterone injection (500 microg/0.1 ml OIL) 4h prior to testing in order to elicit sexual behavior. The ERalpha agonist PPT, but not the ERbeta agonist DPN, elicited both proceptive and receptive behavior. PPT at doses of 2.5 and 5.0mg significantly elicited lordosis and proceptive behavior ('ear wiggling', hopping and darting). Intriguingly, the administration of both agonists together at the 2.5mg dose resulted in reduced levels of proceptivity and receptivity, suggesting that ERbeta modulates ERalpha's ability to elicit receptive and proceptive sexual behavior.

  10. The expression of Hedgehog genes (Ihh, Dhh) and Hedgehog target genes (Ptc1, Gli1, Coup-TfII) is affected by estrogenic stimuli in the uterus of immature female rats

    SciTech Connect

    Katayama, Seiichi . E-mail: katayama@ankaken.co.jp; Ashizawa, Koji; Gohma, Hiroshi; Fukuhara, Tadahiro; Narumi, Kazunori; Tsuzuki, Yasuhiro; Tatemoto, Hideki; Nakada, Tadashi; Nagai, Kenji

    2006-12-15

    The objective of this study was to investigate the effects of estrogen receptor (ER) agonists and an ER antagonist on the expression of Hedgehog genes (Indian hedgehog: Ihh; Desert hedgehog: Dhh) and Hedgehog target genes (Patched 1: Ptc1; glioma-associated oncogene homolog 1: Gli1; chicken ovalbumin upstream promoter transcription factor II: Coup-TfII) in the rat uterus. Immature female rats were administered once with 17{alpha}-ethynyl estradiol (EE, an ER agonist), propyl pyrazole triole (PPT, an ER{alpha}-selective agonist), diarylpropionitrile (DPN, an ER{beta}-selective agonist), or ICI 182,780 (an ER antagonist). Expression of mRNA for Ihh, Dhh, and Ptc1 was dose-dependently downregulated by EE in the uterus of immature rats, mediated by ER as confirmed by coadministration of ICI 182,780. The mRNA expression levels of Ptc1, Gli1, and Coup-TfII were simultaneously downregulated during the period in which the mRNA expression levels of Ihh and Dhh were downregulated in the uterus after administration of EE. PPT downregulated the transcription of Ihh, Dhh, Ptc1, Gli1, and Coup-TfII, indicating that expression of these genes was regulated by the ER{alpha}-dependent pathway. DPN also downregulated the transcription of Ihh and Dhh, although the effect was weaker than that of PPT, indicating that the regulation of uterine Ihh and Dhh transcription was also affected by the ER{beta}-dependent pathway. These results suggest that the expression of Hedgehog genes (Ihh, Dhh) and Hedgehog target genes (Ptc1, Gli1, Coup-TfII) is affected by estrogenic stimuli in the uterus of immature female rats.

  11. Temporary inactivation of plasma amine oxidase by alkylhydrazines. A combined enzyme/model study implicates cofactor reduction/reoxidation but cofactor deoxygenation and subsequent reoxygenation in the case of hydrazine itself.

    PubMed

    Lee, Y; Jeon, H B; Huang, H; Sayre, L M

    2001-03-23

    It has been known for some time that hydrazine and its methyl and 1,1-dimethyl analogues induce inactivation of the copper-containing quinone-dependent plasma amine oxidase but that the activity recovers over time, suggesting metabolism of all three inhibitors. However, the mechanism responsible for loss and regain of activity has not been investigated. In this study a combination of enzyme studies under a controlled atmosphere along with model studies using 5-tert-butyl-2-hydroxy-1,4-benzoquinone to mimic the 2,4,5-trihydroxyphenylalanine quinone (TPQ) cofactor of the enzyme suggest that regain of enzyme activity represents two different O(2)-dependent processes. In the case of methylhydrazine and 1,1-dimethylhydrazine, we propose that the inactive methylhydrazone/azo form of the enzyme slowly rehydrates and eliminates MeN=NH to give the triol cofactor form, which instantly reoxidizes to the catalytically active quinone form in the presence of O(2). Metabolism of methylhydrazine represents its conversion to CH(4) and N(2), and of 1,1-dimethylhydrazine to CH(2)=O, CH(4), and N(2). In the case of hydrazine itself, however, we propose that the inactive hydrazone/azo form of the enzyme instead undergoes a slow decomposition, probably facilitated by the active-site copper, to give N(2) and a novel 5-desoxy resorcinol form of the cofactor. The latter undergoes a rapid, but noninstantaneous reoxygenation at C5 to restore the active cofactor form, also probably mediated by the active-site copper.

  12. Identifying new lignin bioengineering targets: 1. Monolignol-substitute impacts on lignin formation and cell wall fermentability

    PubMed Central

    2010-01-01

    Background Recent discoveries highlighting the metabolic malleability of plant lignification indicate that lignin can be engineered to dramatically alter its composition and properties. Current plant biotechnology efforts are primarily aimed at manipulating the biosynthesis of normal monolignols, but in the future apoplastic targeting of phenolics from other metabolic pathways may provide new approaches for designing lignins that are less inhibitory toward the enzymatic hydrolysis of structural polysaccharides, both with and without biomass pretreatment. To identify promising new avenues for lignin bioengineering, we artificially lignified cell walls from maize cell suspensions with various combinations of normal monolignols (coniferyl and sinapyl alcohols) plus a variety of phenolic monolignol substitutes. Cell walls were then incubated in vitro with anaerobic rumen microflora to assess the potential impact of lignin modifications on the enzymatic degradability of fibrous crops used for ruminant livestock or biofuel production. Results In the absence of anatomical constraints to digestion, lignification with normal monolignols hindered both the rate and extent of cell wall hydrolysis by rumen microflora. Inclusion of methyl caffeate, caffeoylquinic acid, or feruloylquinic acid with monolignols considerably depressed lignin formation and strikingly improved the degradability of cell walls. In contrast, dihydroconiferyl alcohol, guaiacyl glycerol, epicatechin, epigallocatechin, and epigallocatechin gallate readily formed copolymer-lignins with normal monolignols; cell wall degradability was moderately enhanced by greater hydroxylation or 1,2,3-triol functionality. Mono- or diferuloyl esters with various aliphatic or polyol groups readily copolymerized with monolignols, but in some cases they accelerated inactivation of wall-bound peroxidase and reduced lignification; cell wall degradability was influenced by lignin content and the degree of ester group hydroxylation

  13. Mastering analytical challenges for the characterization of pentacyclic triterpene mono- and diesters of Calendula officinalis flowers by non-aqueous C30 HPLC and hyphenation with APCI-QTOF-MS.

    PubMed

    Nicolaus, Christoph; Sievers-Engler, Adrian; Murillo, Renato; D'Ambrosio, Michele; Lämmerhofer, Michael; Merfort, Irmgard

    2016-01-25

    Pentacyclic triterpene mono- and diesters have been isolated from Calendula officinalis flowers. GC-MS, APCI-Exactive Orbitrap HR-MS and NMR allowed to identify the triterpene skeleton in various samples (different triterpene mixtures from Calendula n-hexane extract). NMR provided evidence that triterpene diesters are present in the samples as well. However, the corresponding quasi-molecular ions could not be detected by APCI-Exactive Orbitrap HR-MS. Instability of triterpene diesters and loss of a fatty acid residue, respectively, in the ion-source made their MS detection challenging. Thus, a set of new APCI-QTOF-MS methods (using the TripleTOF 5600+ mass spectrometer) were developed which made it eventually possible to solve this problem and confirm the diester structures by MS via quasi-molecular ion [M+H](+) detection. Direct infusion APCI-QTOF MS experiments in MS/MS high sensitivity scan mode with low collision energy and multi-channel averaging acquisition (MCA) allowed the detection of quasi-molecular ions of triterpene diesters for the first time and unequivocally confirmed the presence of faradiol 3,16-dimyristate and -dipalmitate, as well as the corresponding mixed diesters faradiol 3-myristate,16-palmitate and faradiol 3-palmitate,16-myristate. Preferential loss of the fatty acid in 16-position made it possible to distinguish the mixed diesters by MS/MS spectra. Their chromatographic separations turned out to be challenging due to their bulkiness and extended molecular dimensions. However, separation could be achieved by an uncommon non-aqueous RPLC mode with an in-house synthesized C30 phase. Finally, two (U)HPLC-APCI-QTOF-MS methods with C18- and C30-based non-aqueous RPLC provided suitable, sensitive assays to monitor the presence of monoesters and diesters of various triterpenes (faradiol, maniladiol, arnidiol, arnitriol A and lupane-3β,16β,20-triol esters) in the n-hexane extract of C. officinalis with high mass resolution and good mass accuracy.

  14. Functional characterization of estrogen receptor subtypes, ER{alpha} and ER{beta}, mediating vitellogenin production in the liver of rainbow trout

    SciTech Connect

    Leanos-Castaneda, Olga Kraak, Glen van der

    2007-10-15

    The estrogen-dependent process of vitellogenesis is a key function on oviparous fish reproduction and it has been widely used as an indicator of xenoestrogen exposure. The two estrogen receptor (ER) subtypes, ER{alpha} and ER{beta}, are often co-expressed in the liver of fish. The relative contribution of each ER subtype to modulate vitellogenin production by hepatocytes was studied using selected compounds known to preferentially interact with specific ER subtypes: propyl-pyrazole-triol (PPT) an ER{alpha} selective agonist, methyl-piperidino-pyrazole (MPP) an ER{alpha} selective antagonist, and diarylpropionitrile (DPN) an ER{beta} selective agonist. First, the relative binding affinity of the test compounds to estradiol for rainbow trout hepatic nuclear ER was determined using a competitive ligand binding assay. All the test ligands achieved complete displacement of specific [{sup 3}H]-estradiol binding from the nuclear ER extract. This indicates that the test ligands have the potential to modify the ER function in the rainbow trout liver. Secondly, the ability of the test compounds to induce or inhibit vitellogenin production by primary cultures of rainbow trout hepatocytes was studied. Estradiol and DPN were the only compounds that induced a dose-dependent increase on vitellogenin synthesis. The lack of vitellogenin induction by PPT indicates that ER{alpha} could not have a role on this reproductive process whereas the ability of DPN to induce vitellogenin production supports the participation of ER{beta}. In addition, this hypothesis is reinforced by the results obtained from MPP plus estradiol. On one hand, the absence of suppressive activity of MPP in the estradiol-induced vitellogenin production does not support the participation of ER{alpha}. On the other hand, once blocked ER{alpha} with MPP, the only manifestation of agonist activity of estradiol would be achieved via ER{beta}. In conclusion, the present results indicate that vitellogenin production is

  15. Seasonal lake surface water temperature trends reflected by heterocyst glycolipid-based molecular thermometers

    NASA Astrophysics Data System (ADS)

    Bauersachs, T.; Rochelmeier, J.; Schwark, L.

    2015-06-01

    It has been demonstrated that the relative distribution of heterocyst glycolipids (HGs) in cultures of N2-fixing heterocystous cyanobacteria is largely controlled by growth temperature, suggesting a potential use of these components in paleoenvironmental studies. Here, we investigated the effect of environmental parameters (e.g., surface water temperatures, oxygen concentrations and pH) on the distribution of HGs in a natural system using water column filtrates collected from Lake Schreventeich (Kiel, Germany) from late July to the end of October 2013. HPLC-ESI/MS (high-performance liquid chromatography coupled to electrospray ionization-mass spectrometry) analysis revealed a dominance of 1-(O-hexose)-3,25-hexacosanediols (HG26 diols) and 1-(O-hexose)-3-keto-25-hexacosanol (HG26 keto-ol) in the solvent-extracted water column filtrates, which were accompanied by minor abundances of 1-(O-hexose)-3,27-octacosanediol (HG28 diol) and 1-(O-hexose)-3-keto-27-octacosanol (HG28 keto-ol) as well as 1-(O-hexose)-3,25,27-octacosanetriol (HG28 triol) and 1-(O-hexose)-3-keto-25,27-octacosanediol (HG28 keto-diol). Fractional abundances of alcoholic and ketonic HGs generally showed strong linear correlations with surface water temperatures and no or only weak linear correlations with both oxygen concentrations and pH. Changes in the distribution of the most abundant diol and keto-ol (e.g., HG26 diol and HG26 keto-ol) were quantitatively expressed as the HDI26 (heterocyst diol index of 26 carbon atoms) with values of this index ranging from 0.89 in mid-August to 0.66 in mid-October. An average HDI26 value of 0.79, which translates into a calculated surface water temperature of 15.8 ± 0.3 °C, was obtained from surface sediments collected from Lake Schreventeich. This temperature - and temperatures obtained from other HG indices (e.g., HDI28 and HTI28) - is similar to the one measured during maximum cyanobacterial productivity in early to mid-September and suggests that HGs

  16. Seasonal lake surface water temperature trends reflected by heterocyst glycolipid based molecular thermometers

    NASA Astrophysics Data System (ADS)

    Bauersachs, T.; Rochelmeier, J.; Schwark, L.

    2015-01-01

    It has been demonstrated that the relative distribution of heterocyst glycolipids (HGs) in cultures of N2-fixing heterocystous cyanobacteria is largely controlled by growth temperature, suggesting a potential use of these components in paleoenvironmental studies. Here, we investigated the effect of environmental parameters (e.g. surface water temperatures, oxygen concentrations and pH) on the distribution of HGs in a natural system using water column filtrates collected from Lake Schreventeich (Kiel, Germany) from late July to the end of October 2013. HPLC-ESI/MS analysis revealed a dominance of 1-(O-hexose)-3,25-hexacosanediols (HG26 diols) and 1-(O-hexose)-3-keto-25-hexacosanol (HG26 keto-ol) in the solvent extracted water column filtrates, which were accompanied by minor abundances of 1-(O-hexose)-3,27-octacosanediol (HG28 diol) and 1-(O-hexose)-3-keto-27-octacosanol (HG28 keto-ol) as well as 1-(O-hexose)-3,25,27-octacosanetriol (HG28 triol) and 1-(O-hexose)-3-keto-25,27-octacosanediol (HG28 keto-diol). Fractional abundances of alcoholic and ketonic HGs generally showed strong linear correlations with surface water temperatures and no or only weak linear correlations with both oxygen concentrations and pH. Changes in the distribution of the most abundant diol and keto-ol (e.g., HG26 diol and HG26 keto-ol) were quantitatively expressed as the HDI26 (heterocyst diol index of 26carbon atoms) with values of this index ranging from 0.89 in mid-August to 0.66 in mid-October. An average HDI26 value of 0.79, which translates into a calculated surface water temperature of 15.8 ± 0.3 °C, was obtained from surface sediments collected from Lake Schreventeich. This temperature - and temperatures obtained from other HG indices (e.g., HDI28 and HTI28) - is similar to the one measured during maximum cyanobacterial productivity in early to mid-September and suggests that HGs preserved in Lake Schreventeich sediments record summer surface water temperatures. As N2-fixing

  17. Antiproliferative and anti-inflammatory polyhydroxylated spirostanol saponins from Tupistra chinensis

    PubMed Central

    Xiang, Limin; Yi, Xiaomin; Wang, Yihai; He, Xiangjiu

    2016-01-01

    Tupistra chinensis is widely distributed in southwestern China and its rhizome is a famous folk medicine for the treatment of carbuncles and pharyngitis. Its chemical identity of potent antiproliferative and anti-inflammatory constituents has been carried out in this study. Twenty-three polyhydroxylated spirostanol saponins, including nine novels, were isolated and identified. The new spirostanol saponins were elucidated as spirost-25(27)-en-1β,2β,3β,4β,5β-pentol-2-O-β-D-xylopyranoside (1), spirost-25(27)- en-1β,2β,3β,4β,5β-pentol-2-O-α-L-arabinopyranoside (2), spirost-25(27)-en- 1β,3α,5β-triol (12), spirost-25(27)-en-1β,3α,4β,5β,6β-pentol (13), spirost-25(27)-en- 1β,2β,3β,5β-tetraol-5-O-β-D-glucopyranoside (16), 5β-spirost-25(27)-en-1β,3β-diol- 3-O-β-D-glucopyranosyl-(1 → 4)-β-D-glucopyranoside (17), (25R)-5β-spirostan- 1β,3β-diol-3-O-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranoside (18), (25R)-5β- spirostan-1β,3β-diol-3-O-β-D-fructofuranosyl-(2 → 6)-β-D-glucopyranoside (19), 5β-spirost-25(27)-en-3β-ol-3-O-β-D-glucopyranosyl-(1 → 4)-β-D-glucopyranoside (20). The antiproliferative effects against seven human cancer cell lines and inhibitory activities on nitric oxide (NO) production induced by lipopolysaccharide (LPS) in a macrophage cell line RAW 264.7 were assayed for all the isolated compounds. Compounds 17, 19 and 21 exhibited potential antiproliferative activities against all of human cancer cell lines tested. Compounds 21 showed significant inhibition on NO production with IC50 values of 11.5 μM. These results showed that the spirostanol saponins isolated from the dried rhizomes of T. chinensis have potent antiproliferative and anti-inflammatory activities and T. chinensis might be used as anticancer and.anti-inflammatory supplement. PMID:27530890

  18. Glucose- and Hormone-Induced cAMP Oscillations in α- and β-Cells Within Intact Pancreatic Islets

    PubMed Central

    Tian, Geng; Sandler, Stellan; Gylfe, Erik; Tengholm, Anders

    2011-01-01

    OBJECTIVE cAMP is a critical messenger for insulin and glucagon secretion from pancreatic β- and α-cells, respectively. Dispersed β-cells show cAMP oscillations, but the signaling kinetics in cells within intact islets of Langerhans is unknown. RESEARCH DESIGN AND METHODS The subplasma-membrane cAMP concentration ([cAMP]pm) was recorded in α- and β-cells in the mantle of intact mouse pancreatic islets using total internal reflection microscopy and a fluorescent translocation biosensor. Cell identification was based on the opposite effects of adrenaline on cAMP in α- and β-cells. RESULTS In islets exposed to 3 mmol/L glucose, [cAMP]pm was low and stable. Glucagon and glucagon-like peptide-1(7-36)-amide (GLP-1) induced dose-dependent elevation of [cAMP]pm, often with oscillations synchronized among β-cells. Whereas glucagon also induced [cAMP]pm oscillations in most α-cells, <20% of the α-cells responded to GLP-1. Elevation of the glucose concentration to 11–30 mmol/L in the absence of hormones induced slow [cAMP]pm oscillations in both α- and β-cells. These cAMP oscillations were coordinated with those of the cytoplasmic Ca2+ concentration ([Ca2+]i) in the β-cells but not caused by the changes in [Ca2+]i. The transmembrane adenylyl cyclase (AC) inhibitor 2′5′-dideoxyadenosine suppressed the glucose- and hormone-induced [cAMP]pm elevations, whereas the preferential inhibitors of soluble AC, KH7, and 1,3,5(10)-estratrien-2,3,17-β-triol perturbed cell metabolism and lacked effect, respectively. CONCLUSIONS Oscillatory [cAMP]pm signaling in secretagogue-stimulated β-cells is maintained within intact islets and depends on transmembrane AC activity. The discovery of glucose- and glucagon-induced [cAMP]pm oscillations in α-cells indicates the involvement of cAMP in the regulation of pulsatile glucagon secretion. PMID:21444924

  19. Identification of plasma glucocorticoids in pallid sturgeon in response to stress

    USGS Publications Warehouse

    Webb, M.A.H.; Allert, J.A.; Kappenman, K.M.; Marcos, J.; Feist, G.W.; Schreck, C.B.; Shackleton, C.H.

    2007-01-01

    Compared to teleosts, little is known about the stress response in chondrosteans, and the glucocorticoid(s) most responsive to stress have never been definitively determined in sturgeon. In terms of cortisol production, pallid sturgeon (Scaphirhynchus albus) have a low physiological response to stress compared to other sturgeons (Acipenser sp.). Because of this, our null hypothesis was that cortisol is not the predominant glucocorticoid secreted in response to stress in pallid sturgeon. Our objective was to identify the putative glucocorticoids present in the plasma of pallid sturgeon during the stress response. Pallid sturgeon were subjected to a severe confinement stress (12 h) with an additional handling stressor for the first 6 h. Control fish were not subjected to confinement but were handled only to collect blood. Blood plasma was collected at time 0, 6, and 12 h. Gas chromatography/mass spectrometry was used to screen the plasma for the spectrum of glucocorticoids and determine the putative steroid secreted during the stress response. Cortisol was the primary glucocorticoid detected in stressed pallid sturgeon. In addition, the cortisol metabolites cortisone, alloTHE (5??-pregnane-3??,17??,21-triol-11,20-dione), allo-??-cortolone (3??,17??,20??,21-tetrahydro-5??-pregnan-11-one), and allo-??-cortolone (3??,17??,20??,21-tetrahydro-5??-pregnan-11-one) were detected. Plasma cortisol increased from a resting concentration of 0.67 ng/ml to 10.66 ng/ml at 6 h followed by a decrease to 6.78 ng/ml by 12 h. Plasma glucose increased significantly by time 6 and 12 h in both stressed and unstressed groups and remained elevated at time 12 h, while resting lactate concentrations were low to non-detectable and did not increase significantly with the stressor over time. Cortisol was the primary glucocorticoid synthesized and secreted in response to a stressor in pallid sturgeon. Though the proportional increase in plasma cortisol in stressed pallid sturgeon was lower than

  20. Catalysis based on reversible covalent interactions of organoboron compounds.

    PubMed

    Taylor, Mark S

    2015-02-17

    CONSPECTUS: An Account of the development of organoboron-catalyzed methods for chemo- or regioselective activation of pyruvic acids, diols, and carbohydrate derivatives is presented. These methods are based on reversible, covalent interactions that have been exploited extensively in host-guest chemistry, but were comparatively underutilized in catalysis. Important differences between the established properties of organboron compounds in molecular recognition and their behavior as catalysts emerged over the course of this work: for instance, borinic acids, which have largely been ignored in molecular recognition, proved to be a particularly useful class of catalysts. Nonetheless, the high selectivity that has enabled applications of organoboron compounds in molecular recognition (e.g., the selective binding of cis-1,2-diol groups in carbohydrates) also appears to play a key role in the outcomes of catalytic reactions. This research program began as a modest, narrowly defined project aimed at developing direct aldol reactions based on established interactions between pyruvic acids and boronic acids. While this goal was achieved, it was unexpected observations related to the nature of the nucleophile in this transformation (a putative tetracoordinate boron enolate) that attracted our attention and pointed toward broader applications in the catalyst-controlled, regioselective functionalization of polyols. This line of research proved to be fruitful: diarylborinic-acid-based precatalysts were found to promote efficient monoalkylations, sulfonylations, and alkylations of a range of diol substrates, as well as cis-1,2-diol motifs in pyranoside-derived triols. Extension of this chemistry to glycosyl donors as electrophiles enabled the regioselective, catalyst-controlled synthesis of disaccharides from readily accessible feedstocks, and was also employed to modify the oligosaccharide component of a complex, glycosylated natural product. Mechanistic studies have played an

  1. Induction of apoptosis by c9, t11-CLA in human endometrial cancer RL 95-2 cells via ERα-mediated pathway.

    PubMed

    Wang, Jihui; Liu, Xiao; Zhang, Xiaojuan; Liu, Jing; Ye, Shuhong; Xiao, Shan; Chen, Hongzhou; Wang, Han

    2013-01-01

    Numerous studies have shown that conjugated linoleic acid (CLA) can inhibit cancer cells growth and induce apoptosis in vitro and in vivo. The aim of the present study was to investigate the effects of CLA, including cis9, trans11-conjugated linoleic acid (c9, t11-CLA) and trans10, cis12-conjugated linoleic acid (t10, c12-CLA), on apoptosis of human endometrial cancer RL 95-2 cells and its related mechanisms. The MTT analysis was used to evaluate the effect of CLA isomers on the viability of endometrial cancer RL 95-2 cells. We then estimated the apoptosis by Morphological observation and Annexin V-FITC/PI staining and flow cytometry. We also used Western blot analysis to assess the expression of caspase-3, Bax, Bcl-2 proteins and the activation of Akt/p-Akt and ERα/p-ERα. Propylpyrazole-triol (PPT), a selective ERα agonist was used to confirm the induction of apoptosis by c9, t11 CLA may relate to ERα-mediated pathway. In CLA-treated RL 95-2 cells, we found that c9, t11-CLA inhibited viability and trigged apoptosis, as judged from nuclear morphology and flow cytometric analysis. The expression of caspase-3 and the ratio of Bax/Bcl-2 were significant increased, but no obvious change was observed about Akt and p-Akt in c9, t11-CLA-treated cells. However, the expression of total ERα level in RL 95-2 cells-treated with c9, t11-CLA was unchanged, while in the concentration of 80 mM, c9, t11-CLA down-regulated the protein expression level of p-ERα. Then PPT has the antagonistic action on growth inhibitory effect in RL 95-2 cells incubated with c9, t11-CLA. This study demonstrated that c9, t11- CLA could induce apoptosis in RL 95-2 cells, and may involve in ERα-mediated pathway. These results indicated that c9, t11- CLA could induce apoptosis of endometrial cancer cells and may be potential agents for the treatment of endometrial cancer.

  2. Preanalytical standardization for reactive oxygen species derived oxysterol analysis in human plasma by liquid chromatography-tandem mass spectrometry.

    PubMed

    Helmschrodt, C; Becker, S; Thiery, J; Ceglarek, U

    2014-04-11

    The analysis of the oxysterols 7-keto-, 7-α/β-hydroxy-, 5α,6α-epoxy-, 5β,6β-epoxycholesterol and cholestane-3β,5α,6β-triol derived from reactive oxygen species (ROS) is of interest as biomarkers in the field of atherosclerosis. Preanalytical validation is a crucial point to minimize the susceptibility of oxysterols to in vitro autoxidation. The aim of this study was to standardize a preanalytical protocol for ROS-derived oxysterol analysis by liquid chromatography-tandem mass spectrometry in human plasma. Sample matrices were compared and stability of free oxysterols in whole blood and EDTA-plasma was investigated with regard to short-term storage until sample preparation, freeze-thaw cycles, addition of butylated hydroxytoluene and long-term storage up to 1 year at different temperatures (-20 °C, -80 °C and -130 °C) as well as different storage containers (safe-lock tubes, cryo tubes and straws). Sample preparation prior LC-MS/MS analysis was reduced to a simple concentration and protein precipitation step. Storing EDTA-whole blood for 30 min at room temperature resulted in <25% concentration changes, within acceptable change limits (ACL). In freshly prepared plasma samples, free oxysterols were stable for 90 min stored at 4 °C with concentration changes <23.5% (within ACL). Up to nine freeze-thaw cycles did not affect analyte concentrations (concentration change -8.5% to +5.0%). 7-Ketocholesterol was stable for 2 years stored <-80 °C; concentration changes below 20.5% (within ACL). The remaining oxysterols were stored for a maximum of 2-4 weeks without exceeding ACL. The addition of BHT did not reveal improvement in analyte stability for storage at -80 or -130 °C. We developed a standardized preanalytical protocol for oxysterol analysis based on LC-MS/MS, compared cryobanking conditions for each oxysterol and present data for long-term storage up to 2 years.

  3. In vivo oestrogenic modulation of Egr1 and Pitx1 gene expression in female rat pituitary gland.

    PubMed

    Gajewska, Alina; Herman, Andrzej P; Wolińska-Witort, Ewa; Kochman, Kazimierz; Zwierzchowski, Lech

    2014-12-01

    EGR1 and PITX1 are transcription factors required for gonadotroph cell Lhb promoter activation. To determine changes in Egr1 and Pitx1 mRNA levels in central and peripheral pituitary stimulations, an in vivo model based on i.c.v. pulsatile (1 pulse/0.5 h over 2 h) GnRH agonist (1.5 nM buserelin) or antagonist (2 nM antide) microinjections was used. The microinjections were given to ovariectomised and 17β-oestradiol (E2) (3×20 μg), ERA (ESR1) agonist propyl pyrazole triol (PPT) (3×0.5 mg), ERB (ESR2) agonist diarylpropionitrile (DPN) (3×0.5 mg) s.c. pre-treated rats 30 min after last pulse anterior pituitaries were excised. Relative mRNA expression was determined by quantitative RT-PCR (qRT-PCR). Results revealed a gene-specific response for GnRH and/or oestrogenic stimulations in vivo. Buserelin pulses enhanced Egr1 expression by 66% in ovariectomised rats, whereas the oestradiol-supplemented+i.c.v. NaCl-microinjected group showed a 50% increase in Egr1 mRNA expression. The oestrogenic signal was transmitted via ERA (ESR1) and ERB (ESR2) activation as administration of PPT and DPN resulted in 97 and 62%, respectively, elevation in Egr1 mRNA expression. A synergistic action of GnRH agonist and 17β-oestradiol (E2) stimulation of the Egr1 gene transcription in vivo were found. GnRHR activity did not affect Pitx1 mRNA expression; regardless of NaCl, buserelin or antide i.c.v. pulses, s.c. oestrogenic supplementation (with E2, PPT or DPN) consistently decreased (by -46, -48 and -41% respectively) the Pitx1 mRNA in the anterior pituitary gland. Orchestrated Egr1 and Pitx1 activities depending on specific central and peripheral regulatory inputs could be responsible for physiologically variable Lhb gene promoter activation in vivo.

  4. Biodegradable hyperbranched amphiphilic polyurethane multiblock copolymers consisting of poly(propylene glycol), poly(ethylene glycol), and polycaprolactone as in situ thermogels.

    PubMed

    Li, Zibiao; Zhang, Zhongxing; Liu, Kerh Li; Ni, Xiping; Li, Jun

    2012-12-10

    This paper reports the synthesis and characterization of new hyperbranched amphiphilic polyurethane multiblock copolymers consisting of poly(propylene glycol) (PPG), poly(ethylene glycol) (PEG), and polycaprolactone (PCL) segments as in situ thermogels. The hyperbranched poly(PPG/PEG/PCL urethane)s, termed as HBPEC copolymers, were synthesized from PPG-diol, PEG-diol, and PCL-triol by using 1,6-hexamethylene diisocyanate (HMDI) as a coupling agent. The compositions and structures of HBPEC copolymers were determined by GPC and 1H NMR spectroscopy. We carried out comparative studies of the new hyperbranched copolymers with their linear counterparts, the linear poly(PPG/PEG/PCL urethane) (LPEC) copolymer and Pluronic F127 PEG-PPG-PEG block copolymer, in terms of their self-assembly and aggregation behaviors and thermoresponsive properties. HBPEC copolymers were found to show thermoresponsive micelle formation and aggregation behaviors. Particularly, the lower critical solution temperature (LCST) of the copolymers was significantly affected by the copolymer architecture. HBPEC copolymers showed much lower LCST than LPEC, the linear counterpart. Our studies revealed that the effect of hyperbranch architecture was more prominent in the gelation of the copolymers. The aqueous solutions of HBPEC copolymers exhibited thermogelling behaviors at critical gelation concentrations (CGCs) ranging from 4.3 to 7.4 wt %. These values are much lower than those reported on other PCL-contained linear thermogelling copolymers and Pluronic F127 copolymer. In addition, the CGC of HBPEC copolymers is much lower than the control LPEC copolymer. More interestingly, at high temperatures, while LPEC and other linear thermogelling copolymers formed turbid sol, HBPEC formed a dehydrated gel. Our data suggest that these phenomena are caused by the hyperbranched structure of HBPEC copolymers, which could increase the interaction of copolymer branches and enhance the chain association through

  5. Report from SCOOP task 3.2.10 "collection of occurrence data of Fusarium toxins in food and assessment of dietary intake by the population of EU member states". Subtask: trichothecenes.

    PubMed

    Schothorst, Ronald C; van Egmond, Hans P

    2004-10-10

    In 2001 the SCOOP (SCOOP: Scientific Co-operation on Questions relating to Food) task 3.2.10 "Collection of occurrence data of Fusarium toxins in food and assessment of dietary intake by the population of EU Member States" was established. The task was divided in three subtasks (zearalenone, fumonisins and trichothecenes). Results of the subtask trichothecenes, which is co-ordinated by The Netherlands, will be presented. About 35,000 results were received about occurrence of 12 different trichothecenes (deoxynivalenol (DON), nivalenol (NIV), 3 and 15 acetyl-deoxynivalenol (3/15-AcDON), fusarenon-X (FUS-X), T-2 and HT-2 toxin, T2-triol, diacetoxyscirpenol (DAS), neosolaniol (NEOSOL, monoacetoxyscirpenol (MAS) and verrucarol (VOL)) in various food and food raw materials from 12 countries. Only the results of DON, NIV, T-2 and HT-2 toxin are included in this paper, because most of the data refer to these toxins and only for these trichothecenes the Scientific Committee for Food sets (temporary)-Tolerable Daily Intakes (t-TDIs). Occurrence data: By far most of the occurrence data were obtained for DON in wheat. Among cereals, corn showed the highest level of contamination with trichothecenes. Consumption data: There is a significant lack of consumption data in some countries. In particular information on baby's and children's food is generally not available. Intake data: Wheat and wheat containing products (like bread and pasta) represent the major source of intake for the four trichothecenes. The mean intakes for DON are below the TDI, however for the young children groups the mean intakes are sometimes (very) close to the TDI. By comparing the high intake levels for DON with the TDI, it is clear that especially for the young children groups most of the intakes are above the TDI. For NIV, the (mean and high level) intakes are far below the TDI. The summarised T-2 and HT-2 toxin intakes are in most cases (for the mean as well as the high level intake) above the t-TDI.

  6. Effects of temperature on the properties of glycerol: a computer simulation study of five different force fields.

    PubMed

    Jahn, David A; Akinkunmi, Frederick O; Giovambattista, Nicolas

    2014-09-25

    We perform molecular dynamics simulations of glycerol (propane-1,2,3-triol) at normal pressure and a wide range of temperatures (300-460 K) and study the sensitivity of simulation results to the force field (FF) considered. We employ five commonly used FFs: (i) AMBER, (ii) CHARMM22, and (iii) three versions of the OPLS-AA FF (OPLS1, OPLS2, and OPLS3). We study thermodynamic (density ρ(T), thermal expansion coefficient αP(T), isobaric specific heat cP(T)), dynamic (diffusion coefficient D(T)), as well as structural properties (molecular conformations and hydrogen-bond statistics). In comparison with experiments, FFs i and iii provide reasonable estimations of ρ(T) with deviations of ≤4.5%; for FF ii, deviations in density are more pronounced, ≤9%. Values of αP(T) vary considerably among the FFs; e.g., deviations are ≤9% for OPLS1-FF and ≤60% for FF ii. For all models studied, values of cP(T) are approximately twice the corresponding experimental values. Diffusion coefficients are very sensitive to the FFs considered. Specifically, for FFs i and ii and OPLS3, the values of D(T) are remarkably close to the experimental values over the whole range of temperatures studied. Instead, in the cases of OPLS1 and OPLS2-FFs, D(T) is underestimated by approximately 2 orders of magnitude. Interestingly, in all cases, D(T) can be well described by a Vogel-Tamman-Fulcher equation, as observed in experiments. We present a detailed characterization of glycerol backbone conformation based on the traditional classification introduced by Bastiansen, defined in terms of glycerol's OCCC dihedral angles. All FFs indicate that the conformer population varies smoothly with temperature. However, the FFs provide very different conformer distributions. This implies that, from the microscopic point of view, these glycerol models may provide very different liquid environments for, for example, guest biomolecules and hence may play a relevant role in interpreting simulation results

  7. Effects of genistein and estrogen receptor subtype-specific agonists in ArKO mice following different administration routes.

    PubMed

    Bliedtner, Anja; Zierau, Oliver; Albrecht, Steffen; Liebhaber, Steffi; Vollmer, Günter

    2010-01-15

    We have scrutinized the effects of the phytoestrogen genistein and three synthetic estrogen receptor agonists, 17 alpha-ethynylestradiol (EE), propylpyrazole-triol (PPT) and diarylpropionitrile (DPN) in the completely estrogen-free background of aromatase knockout (ArKO) mice by means of two routes of substance administration: oral via diet (per os; po) or subcutaneous injection (sc) with the intention to evaluate the ArKO mice as sensitive model organism for uterotrophic assays. Additionally, we were aiming to qualitatively analyze effects resulting from oral administration path, in particular for PPT and DPN. Therefore, we analyzed the resulting uterine wet weights (UWW) and epithelial heights as physiological endpoints of function as well as the gonadotropin levels. Moreover, the gene expression profiles of estrogen receptors as well as important uterine and ovarian estrogen-response genes were investigated by real-time PCR. The uterus of ArKO mice responded very sensitive upon the substitution with EE (sc 5 microg/kg BW; po 50 microg/kg BW) in a proliferative manner. This was evaluated inter alia by increased UWW and by up-regulation of the expression of proliferation-associated and estrogen-response genes. It is important to note, that ER alpha and ER beta-agonist, PPT and DPN respectively (po 5mg/kg BW and sc 0.5mg/kg BW), have only been used for sc applications so far. Here, effects resulting from oral application were qualitatively described and evaluated for their applicability. The UWW and expression of proliferation-associated genes were increased following both po and sc treatment with PPT. In contrast, DPN did not exert an increase of the UWW, but a significant decrease of proliferation-associated gene and protein expression. Additionally, a substantial hypoplasia was detectable in the uterine cross-sections of DPN-treated mice. On the other hand, the phytoestrogen genistein (sc 10mg/kg BW; po 70 mg/kg BW) did not cause detectable uterotrophic

  8. Atomic and Molecular Layer Deposition for Enhanced Lithium Ion Battery Electrodes and Development of Conductive Metal Oxide/Carbon Composites

    NASA Astrophysics Data System (ADS)

    Travis, Jonathan

    The performance and safety of lithium-ion batteries (LIBs) are dependent on interfacial processes at the positive and negative electrodes. For example, the surface layers that form on cathodes and anodes are known to affect the kinetics and capacity of LIBs. Interfacial reactions between the electrolyte and the electrodes are also known to initiate electrolyte combustion during thermal runaway events that compromise battery safety. Atomic layer deposition (ALD) and molecular layer deposition (MLD) are thin film deposition techniques based on sequential, self-limiting surface reactions. ALD and MLD can deposit ultrathin and conformal films on high aspect ratio and porous substrates such as composite particulate electrodes in lithium-ion batteries. The effects of electrode surface modification via ALD and MLD are studied using a variety of techniques. It was found that sub-nm thick coatings of Al2O 3 deposited via ALD have beneficial effects on the stability of LIB anodes and cathodes. These same Al2O3 ALD films were found to improve the safety of graphite based anodes through prevention of exothermic solid electrolyte interface (SEI) degradation at elevated temperatures. Ultrathin and conformal metal alkoxide polymer films known as "metalcones" were grown utilizing MLD techniques with trimethylaluminum (TMA) or titanium tetrachloride (TiCl4) and organic diols or triols, such as ethylene glycol (EG), glycerol (GL) or hydroquinone (HQ), as the reactants. Pyrolysis of these metalcone films under inert gas conditions led to the development of conductive metal oxide/carbon composites. The composites were found to contain sp2 carbon using micro-Raman spectroscopy in the pyrolyzed films with pyrolysis temperatures ≥ 600°C. Four point probe measurements demonstrated that the graphitic sp2 carbon domains in the metalcone films grown using GL and HQ led to significant conductivity. The pyrolysis of conformal MLD films to obtain conductive metal oxide/carbon composite films

  9. Accelerated sample treatment for screening of banned doping substances by GC-MS: ultrasonication versus microwave energy.

    PubMed

    Galesio, M; Mazzarino, M; de la Torre, X; Botrè, F; Capelo, J L

    2011-01-01

    (mesterolone metabolite 1), 17α-ethyl-5β-estrane-3α,17β,21-triol (norethandrolone metabolite 1), epioxandrolone, 4-chloro-6β,17β-dihydroxy-17α-methyl-1,4-androstadien-3-one (chlormetandienone metabolite 1), carphedon, esmolol and bambuterol the same results were obtained after 5 min under microwave irradiation.

  10. Aliphatic β-Nitroalcohols for Therapeutic Corneoscleral Cross-linking: Chemical Mechanisms and Higher Order Nitroalcohols

    PubMed Central

    Solomon, Marissa R.; Wen, Quan; Turro, Nicholas J.; Trokel, Stephen L.

    2010-01-01

    Purpose. The recent tissue cross-linking studies indicate that aliphatic β-nitroalcohols (BNAs) may be useful as pharmacologic corneoscleral cross-linking agents. The present study was performed to identify the specific chemistry involved under physiologic conditions, with the intent of identifying more effective agents. Methods. The mechanism of chemical cross-linking at pH 7.4 and 37°C was studied using three techniques. The colorimetric Griess assay was used to follow the release of nitrite from three mono-nitroalcohols (2-nitroethanol [2ne], 2-nitro-1-propanol [2nprop]), and 3-nitro-2-pentanol [3n2pent]). Second, the evolution of 2nprop in 0.2 M NaH2PO4/Na2HPO4/D2O was studied using 1H-NMR. Third, thermal shrinkage temperature analysis (Ts), a measure of tissue cross-linking, was used to support information from 1the H-NMR studies. Results. A time-dependent release of nitrite was observed for all three mono-nitroalcohols studied. The maximum levels were comparable using either 2ne or 2nprop (∼30%). However, much less (∼10%) was observed from 3n2pent. Using 1H-NMR, 2nprop evolved into a unique splitting pattern. No match was observed with reference spectra from three possible products of denitration. In contrast, 2-methyl-2-nitro-1,3-propanediol (MNPD), a nitro-diol, was identified, implying the formation of formaldehyde from a retro-nitroaldol (i.e., reverse Henry) reaction. In support of this mechanism, Ts shifts induced by the nitro-triol 2-hydroxymethyl-2-nitro-1,3-propanediol (HNPD) were superior to the nitro-diol MNPD which were superior to the mono nitroalcohol 2nprop. Conclusions. BNAs function as both formaldehyde and nitrite donors under physiologic conditions to cross-link collagenous tissue. Higher order BNAs are more effective than mono nitroalcohols, raising the possibility of using these agents for therapeutic corneoscleral cross-linking. PMID:19797229

  11. Mechanisms by Which 17β-Estradiol (E2) Suppress Neuronal cox-2 Gene Expression

    PubMed Central

    Stacey, Winfred; Bhave, Shreyas; Uht, Rosalie M.

    2016-01-01

    E2 attenuates inflammatory responses by suppressing expression of pro-inflammatory genes. Given that inflammation is increasingly being associated with neurodegenerative and psychiatric processes, we sought to elucidate mechanisms by which E2 down-regulates a component of an inflammatory response, cyclooxygenase– 2 (COX-2) expression. Although inflammatory processes in the brain are usually associated with microglia and astrocytes, we found that the COX-2 gene (cox-2) was expressed in a neuronal context, specifically in an amygdalar cell line (AR-5). Given that COX-2 has been reported to be in neurons in the brain, and that the amygdala is a site involved in neurodegenerative and neuropsychiatric processes, we investigated mechanisms by which E2 could down-regulate cox-2 expression in the AR-5 line. These cells express estrogen receptors alpha (ERα) and beta (ERβ), and as shown here cox-2. At the level of RNA, E2 and the ERβ selective ligand diarylpropionitrile (DPN) both attenuated gene expression, whereas the ERα selective ligand propyl pyrazole triol (PPT) had no effect. Neither ligand increased ERβ at the cox-2 promoter. Rather, DPN decreased promoter occupancy of NF-κB p65 and histone 4 (H4) acetylation. Treatment with the non-specific HDAC inhibitor Trichostatin A (TSA) counteracted DPN’s repressive effects on cox-2 expression. In keeping with the TSA effect, E2 and DPN increased histone deacetylase one (HDAC1) and switch-independent 3A (Sin3A) promoter occupancy. Lastly, even though E2 increased CpG methylation, DPN did not. Taken together, the pharmacological data indicate that ERβ contributes to neuronal cox-2 expression, as measured by RNA levels. Furthermore, ER ligands lead to increased recruitment of HDAC1, Sin3A and a concomitant reduction of p65 occupancy and Ac-H4 levels. None of the events, however, are associated with a significant recruitment of ERβ at the promoter. Thus, ERβ directs recruitment to the cox-2 promoter, but does so in

  12. Reproductive Experience Alters Neural and Behavioural Responses to Acute Oestrogen Receptor α Activation

    PubMed Central

    Byrnes, E. M.; Casey, K.; Carini, L. M.; Bridges, R. S.

    2014-01-01

    Reproductive experience (i.e. parturition and lactation) leads to persistent alterations in anxietylike behaviour that are influenced by the oestrous cycle. We recently found that repeated administration of the selective oestrogen receptors (ER)α agonist propyl-pyrazole triol (PPT) results in anxiolytic-like behaviours on the elevated plus maze (EPM) in primiparous (but not nulliparous) female rats. The present study examined the effects of the acute administration of PPT on EPM behaviour in primiparous and aged-matched, nulliparous female rats. In addition, corticosterone secretion, corticotrophin-releasing hormone (CRH) gene expression and expression of the immediate early gene product Fos in the paraventricular nucleus (PVN) and amygdala were measured either after EPM testing or in home cage controls. Acute PPT administration significantly modified EPM behaviour as a function of reproductive experience, with nulliparous females tending toward increased anxiety-like behaviours and primiparous females tending toward decreased anxiety-like behaviours. In home cage controls, PPT increased corticosterone secretion in all females; however, both vehicle- and PPT-treated, primiparous females had reduced corticosterone levels compared to their nulliparous counterparts. Significant effects of PPT on CRH mRNA within the PVN were observed after the administration of PPT but only in primiparous females tested on the EPM. PPT also increased Fos expression within the PVN of EPM-exposed females; however, both vehicle- and PPT-treated primiparous females had reduced Fos expression compared to nulliparous females. In the amygdala, PPT increased Fos immunore-activity in the central but not the medial or basolateral amygdala, although these effects were only observed in home cage females. Additionally, both vehicle- and PPT-treated home cage, primiparous females had increased Fos in the central nucleus of the amygdala compared to nullip-arous controls. Overall, these data

  13. Estrogen regulates the localization and expression of calbindin-D9k in the pituitary gland of immature male rats via the ERalpha-pathway.

    PubMed

    Tinnanooru, Pushpalatha; Dang, Vu Hoang; Nguyen, Thi Hoa; Lee, Geun-Shik; Choi, Kyung-Chul; Jeung, Eui-Bae

    2008-03-26

    Estrogen (E2; estradiol) plays a key role in the regulation of many pituitary hormones. It exerts its effects by binding to the intracellular estrogen receptor (ER), which then functions as a transcription factor. Although E2 has been shown to regulate calbindin-D(9k) (CaBP-9k) in the female reproductive system of rodents, the effects of E2 on the regulation of CaBP-9k in male rats remain to be elucidated. To investigate E2-induced regulation of the pituitary CaBP-9k gene, immature male rats were injected with E2 daily for 3 consecutive days with a dose of 40 microg/kg body weight (BW). The expression levels of CaBP-9k mRNA and protein were analyzed by RT-PCR and Western blot analysis, respectively, in the absence and presence of ICI 182,780 (ICI), an E2 antagonist. In addition, the tissue localization of CaBP-9k was determined by immunohistochemistry. CaBP-9k was localized in the cytoplasm of a specific cell type (acidophils) in the anterior lobe of the pituitary gland and highly expressed in the intermediate lobe. Exposure to E2 increased the number of cells that stained positive for CaBP-9k. To determine which ER subtype is involved in CaBP-9k regulation in the pituitary, the immature rats were treated with propyl pyrazole triol (PPT, an ERalpha-selective ligand) or diarylpropionitrile (DPN, an ERbeta-selective ligand) for 3 days. Pituitary CaBP-9k expression was mainly mediated by PPT in immature male rats, whereas no significant alteration of pituitary CaBP-9k gene expression was observed after DPN treatment. In addition, the estrogenicity of PPT in the induction of CaBP-9k expression was completely blocked by an estrogen antagonist, ICI, indicating that pituitary CaBP-9k expression is solely induced by ERalpha. Taken together, these results suggest that pituitary CaBP-9k is induced by E2 in male rats and its expression is predominantly regulated by ERalpha, but not ERbeta.

  14. Bioactive steroidal saponins from Agave offoyana flowers.

    PubMed

    Pérez, Andy J; Calle, Juan M; Simonet, Ana M; Guerra, José O; Stochmal, Anna; Macías, Francisco A

    2013-11-01

    Bioguided studies of flowers of Agave offoyana allowed the isolation of five steroidal saponins never described previously, Magueyosides A-E (1-5), along with six known steroidal saponins (6-11). The structures of compounds were determined as (25R)-spirost-5-en-2α,3β-diol-12-one 3-O-{β-d-xylopyranosyl-(1→3)-O-β-d-glucopyranosyl-(1→2)-O-[β-d-xylopyranosyl-(1→3)]-O-β-d-glucopyranosyl-(1→4)-O-β-d-galactopyranoside} (1), (25R)-spirost-5-en-2α,3β-diol-12-one 3-O-{β-d-glucopyranosyl-(1→2)-O-[β-d-xylopyranosyl-(1→3)]-O-β-d-glucopyranosyl-(1→4)-O-β-d-galactopyranoside} (2), (25R)-spirost-5-en-2α,3β,12β-triol 3-O-{β-d-glucopyranosyl-(1→2)-O-[β-d-xylopyranosyl-(1→3)]-O-β-d-glucopyranosyl-(1→4)-O-β-d-galactopyranoside} (3), (25R)-5α-spirostan-2α,3β-diol-12-one 3-O-{β-d-xylopyranosyl-(1→3)-O-β-d-glucopyranosyl-(1→2)-O-[β-d-xylopyranosyl-(1→3)]-O-β-d-glucopyranosyl-(1→4)-O-β-d-galactopyranoside} (4), and (25R)-5α-spirostan-2α,3β-diol-9(11)-en-12-one 3-O-{β-d-xylopyranosyl-(1→3)-O-β-d-glucopyranosyl-(1→2)-O-[β-d-xylopyranosyl-(1→3)]-O-β-d-glucopyranosyl-(1→4)-O-β-d-galactopyranoside} (5), by comprehensive spectroscopic analysis, including one- and two-dimensional NMR techniques, mass spectrometry and chemical methods. The bioactivities of the isolated compounds on the standard target species Lactuca sativa were evaluated. A dose-dependent phytotoxicity and low dose stimulation were observed.

  15. Structure Identification and Anti-Cancer Pharmacological Prediction of Triterpenes from Ganoderma lucidum.

    PubMed

    Shao, Yanyan; Qiao, Liansheng; Wu, Lingfang; Sun, Xuefei; Zhu, Dan; Yang, Guanghui; Zhang, Xiaoxue; Mao, Xin; Chen, Wenjing; Liang, Wenyi; Zhang, Yanling; Zhang, Lanzhen

    2016-05-21

    Ganoderma triterpenes (GTs) are the major secondary metabolites of Ganoderma lucidum, which is a popularly used traditional Chinese medicine for complementary cancer therapy. In the present study, systematic isolation, and in silico pharmacological prediction are implemented to discover potential anti-cancer active GTs from G. lucidum. Nineteen GTs, three steroids, one cerebroside, and one thymidine were isolated from G. lucidum. Six GTs were first isolated from the fruiting bodies of G. lucidum, including 3β,7β,15β-trihydroxy-11,23-dioxo-lanost-8,16-dien-26-oic acid methyl ester (1), 3β,7β,15β-trihydroxy-11,23-dioxo-lanost-8,16-dien-26-oic acid (2), 3β,7β,15α,28-tetrahydroxy-11,23-dioxo-lanost-8,16-dien-26-oic acid (3), ganotropic acid (4), 26-nor-11,23-dioxo-5α-lanost-8-en-3β,7β,15α,25-tetrol (5) and (3β,7α)-dihydroxy-lanosta-8,24-dien- 11-one (6). (4E,8E)-N-d-2'-hydroxypalmitoyl-l-O-β-d-glucopyranosyl-9-methyl-4,8-spingodienine (7), and stigmasta-7,22-dien-3β,5α,6α-triol (8) were first reported from the genus Ganodema. By using reverse pharmacophoric profiling of the six GTs, thirty potential anti-cancer therapeutic targets were identified and utilized to construct their ingredient-target interaction network. Then nineteen high frequency targets of GTs were selected from thirty potential targets to construct a protein interaction network (PIN). In order to cluster the pharmacological activity of GTs, twelve function modules were identified by molecular complex detection (MCODE) and gene ontology (GO) enrichment analysis. The results indicated that anti-cancer effect of GTs might be related to histone acetylation and interphase of mitotic cell cycle by regulating general control non-derepressible 5 (GCN5) and cyclin-dependent kinase-2 (CDK2), respectively. This research mode of extraction, isolation, pharmacological prediction, and PIN analysis might be beneficial to rapidly predict and discover pharmacological activities of novel compounds.

  16. Chemical constituents from branch of Fraxinus sieboldiana.

    PubMed

    Lin, Sheng; Zhang, Yan-ling; Liu, Ming-tao; Zi, Jia-chen; Gan, Mao-luo; Song, Wei-xia; Fan, Xiao-na; Wang, Xiao-na; Yang, Yong-chun; Shi, Jian-gong

    2015-07-01

    ,5-dimethoxyphenyl)-1-propanone(34), 2,3-dihydroxy-1-(4-hydroxy-3-methoxyphenyl)-1-propanone (35), 3-hydroxy-l-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone(36), omega-hydroxypropioguaiacone(37), sinapyladehyde(38), trans-p-hydroxycinnamaldehyde(39), syringic acid(40), vanilic acid(41), vanillin(42), 4-hydroxy-benzaldehyde (43), (24R)-24-ethyl-5alpha-cholestane-3beta,5,6beta-triol(44), beta-sitosterol(45), daucosterol(46), 2,6-dimethoxy-I,4-benzoquinone(47), 2,6-dimethoxy-pyran-4-one(48), 1-(beta-D-ribofuranosyl)uracil(49), and mannitol(50). Compouds 1-7,12,18,28-37,44 and 48 were obtained from the genus Fraxinus for the first time.

  17. Determination of thermal stability of specific biomarker lipids of the freshwater fern Azolla through hydrous pyrolysis

    NASA Astrophysics Data System (ADS)

    Sap, Merel; Speelman, Eveline N.; Lewan, Michael D.; Sinninghe Damsté, Jaap S.; Reichart, Gert-Jan

    2010-05-01

    Enormous blooms of the free-floating freshwater fern Azolla occurred within the Arctic Basin during an extended period of ~1.2 Ma during the middle Eocene (Brinkhuis et al. 2006; Speelman et al., GB, 2009). The sustained growth of Azolla, currently ranking among the fastest growing plants on Earth, in a major anoxic basin may have substantially contributed to decreasing atmospheric CO2 levels by burial of Azolla-derived organic matter. Speelman et al. (OG, 2009) reported biomarkers for Azolla (1,w20 C32 - C36 diols, structurally related C29 ω20,ω21 diols, C29 1,20,21 triols, C29 dihydroxy fatty acids as well as a series of wax esters containing these mono- and dihydroxy lipids), which can be used to reconstruct palaeo-environmental conditions. Here we assess the thermal stability of these compounds, to extend their biomarker potential. We specifically focused on the thermal stability of the Azolla biomarkers using hydrous pyrolysis in order to determine which burial conditions allow reconstruction of past occurrences of Azolla. In addition, hydrous pyrolysis was also performed on samples from the Eocene Arctic Ocean (ACEX core), to test if and how the biomarkers change under higher temperatures and pressures in situ. During hydrous pyrolysis, the biomass was heated under high pressure at temperatures ranging between 220 and 365°C for 72 hours. Four experiments were also run using different durations to explore the kinetics of biomarker degradation at specific temperatures. First results indicate that the Azolla specific diols are still present at 220°C, while the corresponding wax esters are already absent. At 300°C all Azolla specific biomarkers are destroyed. More specific determination of the different biomarkers' stability and kinetics would potentially allow the reconstruction of the temperature and pressure history of Azolla deposits. Literature: • Brinkhuis, H., Schouten, S., Collinson, M. E., Sluijs, A., Sinninghe Damste, J. S., Dickens, G. R., Huber

  18. Total synthesis of epothilones using functionalised allylstannanes for remote stereocontrol.

    PubMed

    Martin, Nathaniel; Thomas, Eric J

    2012-10-21

    Two syntheses of the C(7)–C(16)-fragment 41 of epothilone D 2 were developed that were based on tin(IV) bromide mediated reactions of 5,6-difunctionalised hex-2-enylstannanes with aldehydes. In the first synthesis, (5S)-6-tert-butyldimethylsilyloxy-5-hydroxy-2-methylhex-2-enyl(tributyl)stannane 20 was reacted with (E)-but-2-enal to give (2S,7R,4Z,8E)-1-tert-butyldimethylsilyloxy-5-methyldeca-4,8-diene-2,7-diol 26 containing ca. 20% of its (7S)-epimer. Following desilylation, the crystalline (2S,7R)-triol 32 was protected as its acetonide 33 and esterified to give the (4-methoxybenzyloxy)acetate 34. An Ireland–Claisen rearrangement of this ester gave methyl (2R,3S,10S,4E,7Z)-3,7-dimethyl-10,11-(dimethylmethylene)dioxy-2-(4-methoxybenzyloxy)undeca-4,7-dienoate 35 that was converted into (2S,9S,6Z)-2,6-dimethyl-9,10-(dimethylmethylene)dioxydec-6-en-1-ol 41 by regioselective alkene manipulation, ester reduction and cleavage of the resulting terminal diol 40 with a reductive work-up. The second synthesis involved the tin(IV) bromide mediated reaction between the stannane 20 and (3S)-4-(4-methoxybenzyloxy)-3-methylbutanal 44 that gave (2S,7S,9S,4Z)-1-tert-butyldimethylsilyloxy-5,9-dimethyl-10-(4-methoxybenzyloxy)dec-4-ene-2,7-diol 45 containing ca. 20% of its (7R)-epimer. After desilylation and protection of the vicinal diol as its acetonide 46, a Barton–McCombie reductive removal of the remaining hydroxyl group gave the (2S,9S,6Z)-2,6-dimethyl-9,10-(dimethylmethylene)dioxydec-6-en-1-ol 41 after oxidative removal of the PMB-ether. The first of these syntheses uses just one chiral starting material, but the second is shorter and more convergent. It was therefore modified by the use of (5S)-6-tert-butyldimethylsilyloxy-5-(2-trimethylsilylethoxy)methoxy-2-methylhex-2-enyl(tributyl)stannane 49 that reacted with (3S)-4-(4-methoxybenzyloxy)-3-methylbutanal 44 to give a 50:50 mixture of the C(4)-epimers of (2S,9S,6Z)-10-tert-butyldimethylsilyloxy-1-(4-methoxybenzyloxy)-2

  19. NTP Toxicology and Carcinogenesis Studies of Trichloroethylene (CAS No. 79-01-6) in Four Strains of Rats (ACI, August, Marshall, Osborne-Mendel) (Gavage Studies).

    PubMed

    1988-04-01

    in Marshall rats exposed to trichloroethylene. Synonyms: acetylene trichloride; 1-chloro-2,2-dichloroethylene; 1,1-dichloro-2-chloroethylene; ethinyl trichloride; ethylene trichloride; 1,1,2-trichloroethylene; trichloroethene Trade names of formulations: Algylen; Anamenth; Benzinol; Blacosolv; Blancosolv; Cecolene; Chlorilen; Chlorylea; Chorylen; Circosolv; Crawhaspol; Densinfluat; Dow-Tri; Dukeron; Fleck-Flip; Flock Flip; Fluate; Gemalgene; Germalgene; Lanadin; Lethurin; Narcogen; Narkogen; Narkosoid; Nialk; Perma-A-Chlor; Perm-A-Clor; Petzinol; Philex; Threthylen; Threthylene; Trethylene; Tri; Triad; Trial; Triasol; Trichloran; Trichloren; Triclene; Tri-Clene; Trielene; Trielin; Triklone; Trilen; Trilene; Triline; Trimar; Triol; TRI-plus; TRI-plus M; Vestrol; Vitran; Westrosol Target Organs & Incidences from 2-year Studies

  20. Solid State Ionics Advanced Materials for Emerging Technologies

    NASA Astrophysics Data System (ADS)

    Chowdari, B. V. R.; Careem, M. A.; Dissanayake, M. A. K. L.; Rajapakse, R. M. G.; Seneviratne, V. A.

    2006-06-01

    spectroscopic analysis of thin film LiNiVO[symbol] prepared by pulsed laser deposition technique / S. Selvasekarapandian ... [et al.]. Synthesis and characterization of LiFePO[symbol] cathode materials by microwave processing / J. Zhou ... [et al.]. Characterization of Nd[symbol]Sr[symbol]CoO[symbol] including Pt second phase as the cathode material for low-temperature SOFCs / J. W. Choi ... [et al.]. Thermodynamic behavior of lithium intercalation into natural vein and synthetic graphite / N. W. B. Balasooriya, P. W. S. K. Bandaranayake, Ph. Touzain -- pt. III. Electroactive polymers. Invited papers. Organised or disorganised? looking at polymer electrolytes from both points of view / Y.-P. Liao ... [et al.]. Polymer electrolytes - simple low permittivity solutions? / I. Albinsson, B.-E. Mellander. Dependence of conductivity enhancement on the dielectric constant of the dispersoid in polymer-ferroelectric composite electrolytes / A. Chandra, P. K. Singh, S. Chandra. Design and application of boron compounds for high-performance polymer electrolytes / T. Fujinami. Structural, vibrational and AC impedance analysis of nano composite polymer electrolytes based on PVAC / S. Selvasekarapandian ... [et al.]. Absorption intensity variation with ion association in PEO based electrolytes / J. E. Furneaux ... [et al.]. Study of ion-polymer interactions in cationic and anionic ionomers from the dependence of conductivity on pressure and temperature / M. Duclot ... [et al.]. Triol based polyurethane gel electrolytes for electrochemical devices / A. R. Kulkarni. Contributed papers. Accurate conductivity measurements to solvation energies in nafion / M. Maréchal, J.-L Souquet. Ion conducting behaviour of composite polymer gel electrolyte: PEG-PVA-(NH[symbol]CH[symbol]CO[symbol])[symbol] system / S. L. Agrawal, A. Awadhia, S. K. Patel. Impedance spectroscopy and DSC studies of poly(vinylalcohol)/ silicotungstic acid crosslinked composite membranes / A. Anis, A. K. Banthia. (PEO