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Sample records for acid labile group

  1. Incorporation of Acid-Labile Masking Groups for the Traceless Synthesis of C-Terminal Peptide α-Ketoacids.

    PubMed

    Thuaud, Frédéric; Rohrbacher, Florian; Zwicky, André; Bode, Jeffrey W

    2016-08-01

    An optimized protocol for the masking of α-ketoacids with acid-labile cyclic acetal protecting groups is reported. Unlike prior approaches, these new conditions allow the synthesis of protected α-ketoacids bearing aromatic, hindered alkyl, and protected polar side chains. Attachment to a Wang-type linker and solid support provides a resin that delivers fully unprotected C-terminal peptide α-ketoacids upon resin cleavage. These peptides are the key starting materials for chemical protein synthesis using the α-ketoacid-hydroxylamine ligation. PMID:27439001

  2. Lability of copper bound to humic acid.

    PubMed

    Mao, Lingchen; Young, Scott D; Bailey, Elizabeth H

    2015-07-01

    Geochemical speciation models generally include the assumption that all metal bound to humic acid and fulvic acid (HA, FA) is labile. However, in the current study, we determined the presence of a soluble 'non-labile' Cu fraction bound to HA extracted from grassland and peat soils. This was quantified by determining isotopically-exchangeable Cu (E-value) and EDTA-extraction of HA-bound Cu, separated by size-exclusion chromatography (SEC) and assayed by coupled ICP-MS. Evidence of time-dependent Cu fixation by HA was found during the course of an incubation study (160 d); up to 50% of dissolved HA-bound Cu was not isotopically exchangeable. This result was supported by extraction with EDTA where approximately 40% of Cu remained bound to HA despite dissolution in 0.05 M Na2-EDTA. The presence of a substantial non-labile metal fraction held by HA challenges the assumption of wholly reversible equilibrium which is central to current geochemical models of metal binding to humic substances. PMID:25863164

  3. Removal of acid-labile protecting groups on carbohydrates using water-tolerant and recoverable vanadyl triflate catalyst.

    PubMed

    Yan, Ming-Chung; Chen, Yeng-Nan; Wu, Huan-Ting; Lin, Chang-Ching; Chen, Chien-Tien; Lin, Chun-Cheng

    2007-01-01

    Acetal, trityl, and TBDMS protecting groups on saccharides were subjected to alcoholysis using a catalytic amount of vanadyl triflate in an MeOH-CH2Cl2 solvent system. The configuration at the anomeric positions of saccharides was retained, and no glycosidic bond cleavage and oxidation of sulfides were observed. The presented method was easily implemented, compatible with diverse functional groups, and regioselective in some cases. PMID:17194117

  4. Evaluation of ascorbic acid in protecting labile folic acid derivatives.

    PubMed Central

    Wilson, S D; Horne, D W

    1983-01-01

    The use of ascorbic acid as a reducing agent to protect labile, reduced derivatives of folic acid has been evaluated by high-performance liquid chromatographic separations and Lactobacillus casei microbiological assay of eluate fractions. Upon heating for 10 min at 100 degrees C, solutions of tetrahydropteroylglutamic acid (H4PteGlu) in 2% sodium ascorbate gave rise to 5,10-methylene-H4PteGlu and 5-methyl-H4PteGlu. H2PteGlu acid gave rise to 5-methyl-H4PteGlu and PteGlu. 10-Formyl-H4PteGlu gave rise to 5-formyl-H4PteGlu and 10-formyl-PteGlu. 5-Formyl-H4-PteGlu gave rise to a small amount of 10-formyl-PteGlu. 5-Methyl-H4PteGlu and PteGlu appeared stable to these conditions. These interconversions were not seen when solutions of these folate derivatives were kept at 0 degrees C in 1% ascorbate. These observations indicate that elevated temperatures are necessary for the interconversions of folates in ascorbate solutions. Assays of ascorbic acid solutions indicated the presence of formaldehyde (approximately equal to 6 mM). This was confirmed by the identification of 3,5-diacetyl-1,4-dihydrolutidine by UV, visible, and fluorescence spectroscopy and by thin-layer chromatography of chloroform extracts of the reaction mixture of ascorbic acid solutions, acetylacetone, and ammonium acetate. These results indicate that solutions of sodium ascorbate used at elevated temperatures are not suitable for extracting tissue for the subsequent assay of the individual folic acid derivatives. PMID:6415653

  5. Enantiomeric Excesses of Acid Labile Amino Acid Precursors of the Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Pizzarello, Sandra

    1998-01-01

    Amino acids present in carbonaceous chondrite are extracted in water in part as free compounds and in approximately equal part as acid labile precursors. On the assumption that they would be free of contamination, the precursors of two Murchison amino acids that have terrestrial occurrence, alanine and glutamic acid, have been targeted for analysis of their enantiomeric ratios. Pyroglutamic acid, the precursor of glutamic acid, was found with an L-enantiomeric excess comparable to that of the free acid, while alanine's precursor, N-acetyl alanine, appears approximately racemic. Also alpha-imino propioacetic acid, a proposed end product of alanine synthesis in the meteorite, was analyzed and found racemic.

  6. The acid lability of the glycosidic bonds of L-iduronic acid residues in glycosaminoglycans.

    PubMed Central

    Conrad, H E

    1980-01-01

    Heparan sulphate, heparin and dermatan sulphate were hydrolysed in 0.5M-H2SO4 at 100 degrees C. At intervals portions of the hydrolysate were removed and treated with HNO2 at pH 4.0 to cleave the glycosidic bonds of the N-unsubstituted hexosamine residues and to convert both free and combined hexosamines into anhydrohexoses. These hydrolysis/deamination mixtures were reduced with NaB3H4 and analysed by radiochromatography for alpha-L-iduronosylanhydrohexose, beta-D-glucuronosylanhydrohexose, and the free uronic acids and anhydrohexose. These data gave a kinetic profile of the cleavage of the alpha-L-iduronosyl and the beta-D-glucuronosyl bonds in these glycosaminoglycans. The beta-D-glucuronosyl bonds showed the expected resistance to acid hydrolysis, but the alpha-L-iduronosyl bonds were found to be as labile to acid as some neutral sugar glycosides. This unusual lability of alpha-D-iduronosyl-anhydromannitol and beta-D-glucuronosylanhydromannitol. The procedures used to follow the kinetics of glycosaminoglycan hydrolysis can also be sued to obtain quantitative analyses of L-iduronic acid, D-glucuronic acid and hexosamine in these polymers. PMID:6453583

  7. Enzymatically- and Ultraviolet-labile Phosphorus in Humic Acid Fractions From Rice Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Humic acid is an important soil component which can improve nutrient availability and impact other important chemical, biological, and physical properties of soils. We investigated the lability of phosphorus (P) in the mobile humic acid (MHA) and calcium humate (CaHA) fractions of four rice soils as...

  8. Forms and Lability of Phosphorus in Humic Acid Fractions of Hord Silt Loam Soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Phosphorus (P) has long been known to be present in soil humic fractions, but little is known about specific P forms in humic fractions, or their lability. We extracted the mobile humic acid (MHA) and recalcitrant calcium humate (CaHA) fractions from a Nebraska Hord silt loam soil under continuous c...

  9. Acid-Labile Thermoresponsive Copolymers That Combine Fast pH-Triggered Hydrolysis and High Stability under Neutral Conditions.

    PubMed

    Zhang, Qilu; Hou, Zhanyao; Louage, Benoit; Zhou, Dingying; Vanparijs, Nane; De Geest, Bruno G; Hoogenboom, Richard

    2015-09-01

    Biodegradable polymeric materials are intensively used in biomedical applications. Of particular interest for drug-delivery applications are polymers that are stable at pH 7.4, that is, in the blood stream, but rapidly hydrolyze under acidic conditions, such as those encountered in the endo/lysosome or the tumor microenvironment. However, an increase in the acidic-degradation rate of acid-labile groups goes hand in hand with higher instability of the polymer at pH 7.4 or during storage, thus posing an intrinsic limitation on fast degradation under acidic conditions. Herein, we report that a combination of acid-labile dimethyldioxolane side chains and hydroxyethyl side chains leads to acid-degradable thermoresponsive polymers that are quickly hydrolyzed under slightly acidic conditions but stable at pH 7.4 or during storage. We ascribe these properties to high hydration of the hydroxy-containing collapsed polymer globules in conjunction with autocatalytic acceleration of the hydrolysis reactions by the hydroxy groups. PMID:26212481

  10. Facile synthesis of acid-labile polymers with pendent ortho esters.

    PubMed

    Cheng, Jing; Ji, Ran; Gao, Shi-Juan; Du, Fu-Sheng; Li, Zi-Chen

    2012-01-01

    This work presents a facile approach for preparation of acid-labile and biocompatible polymers with pendent cyclic ortho esters, which is based on the efficient and mild reactions between cyclic ketene acetal (CKA) and hydroxyl groups. Three CKAs, 2-ethylidene-1,3-dioxane (EDO), 2-ethylidene-1,3-dioxolane (EDL), and 2-ethylidene-4- methyl-1,3-dioxolane (EMD) were prepared from the corresponding cyclic vinyl acetals by catalytic isomerization of the double bond. The reaction of CKAs with different alcohols and diols was examined using trace of p-toluenesulfonic acid as a catalyst. For the monohydroxyl alcohols, cyclic ortho esters were formed by simple addition of the hydroxyl group toward CKAs with ethanol showing a much greater reactivity than iso-propanol. When 1,2- or 1,3-diols were used to react with the CKAs, we observed the isomerized cyclic ortho esters besides the simple addition products. Biocompatible polyols, that is, poly(2-hydroxyethyl acrylate) (PHEA) and poly(vinyl alcohol) (PVA) were then modified with CKAs, and the degree of substitution of the pendent ortho esters can be easily tuned by changing feed ratio. Both the small molecule ortho esters and the CKA-modified polymers demonstrate the pH-dependent hydrolysis profiles, which depend also on the chemical structure of the ortho esters as well as the polymer hydrophobicity. PMID:22176024

  11. Acid-Labile Poly(glycidyl methacrylate)-Based Star Gene Vectors.

    PubMed

    Yang, Yan-Yu; Hu, Hao; Wang, Xing; Yang, Fei; Shen, Hong; Xu, Fu-Jian; Wu, De-Cheng

    2015-06-10

    It was recently reported that ethanolamine-functionalized poly(glycidyl methacrylate) (PGEA) possesses great potential applications in gene therapy due to its good biocompatibility and high transfection efficiency. Importing responsivity into PGEA vectors would further improve their performances. Herein, a series of responsive star-shaped vectors, acetaled β-cyclodextrin-PGEAs (A-CD-PGEAs) consisting of a β-CD core and five PGEA arms linked by acid-labile acetal groups, were proposed and characterized as therapeutic pDNA vectors. The A-CD-PGEAs owned abundant hydroxyl groups to shield extra positive charges of A-CD-PGEAs/pDNA complexes, and the star structure could decrease charge density. The incorporation of acetal linkers endowed A-CD-PGEAs with pH responsivity and degradation. In weakly acidic endosome, the broken acetal linkers resulted in decomposition of A-CD-PGEAs and morphological transformation of A-CD-PGEAs/pDNA complexes, lowering cytotoxicity and accelerating release of pDNA. In comparison with control CD-PGEAs without acetal linkers, A-CD-PGEAs exhibited significantly better transfection performances. PMID:25993557

  12. Acid-Labile Amphiphilic PEO-b-PPO-b-PEO Copolymers: Degradable Poloxamer Analogs.

    PubMed

    Worm, Matthias; Kang, Biao; Dingels, Carsten; Wurm, Frederik R; Frey, Holger

    2016-05-01

    Poly ((ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid-labile acetal moieties in the backbone of poloxamers to generate acid-cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate-protected vinyl ether to introduce acetal units. Three cleavable PEO-PPO-PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol(-1) ; Mn,PEO = 2200, 3600, 4750 g·mol(-1) ) have been synthesized using anionic ring-opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06-1.08). Surface tension measurements reveal surface-active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid-triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation "on demand." PMID:27000789

  13. CD44 Binding to Hyaluronic Acid Is Redox Regulated by a Labile Disulfide Bond in the Hyaluronic Acid Binding Site

    PubMed Central

    Kellett-Clarke, Helena; Stegmann, Monika; Barclay, A. Neil; Metcalfe, Clive

    2015-01-01

    CD44 is the primary leukocyte cell surface receptor for hyaluronic acid (HA), a component of the extracellular matrix. Enzymatic post translational cleavage of labile disulfide bonds is a mechanism by which proteins are structurally regulated by imparting an allosteric change and altering activity. We have identified one such disulfide bond in CD44 formed by Cys77 and Cys97 that stabilises the HA binding groove. This bond is labile on the surface of leukocytes treated with chemical and enzymatic reducing agents. Analysis of CD44 crystal structures reveal the disulfide bond to be solvent accessible and in the–LH hook configuration characteristic of labile disulfide bonds. Kinetic trapping and binding experiments on CD44-Fc chimeric proteins show the bond is preferentially reduced over the other disulfide bonds in CD44 and reduction inhibits the CD44-HA interaction. Furthermore cells transfected with CD44 no longer adhere to HA coated surfaces after pre-treatment with reducing agents. The implications of CD44 redox regulation are discussed in the context of immune function, disease and therapeutic strategies. PMID:26379032

  14. Acid-Labile Subunit Deficiency and Growth Failure: Description of Two Novel Cases

    PubMed Central

    David, A; Rose, S.J.; Miraki-Moud, F.; Metherell, L.A.; Savage, M.O.; Clark, A.J.L.; Camacho-Hübner, C.

    2010-01-01

    Background/Aims Mutations in the acid-labile subunit (ALS) gene (IGFALS) have been associated with circulating insulin-like growth factor I (IGF-I) deficiency and short stature. Whether severe pubertal delay is also part of the phenotype remains controversial due to the small number of cases reported. We report 2 children with a history of growth failure due to novel IGFALS mutations. Methods The growth hormone receptor gene (GHR) and IGFALS were analyzed by direct sequencing. Ternary complex formation was studied by size exclusion chromatography. Results Two boys of 13.3 and 10.6 years, with pubertal stages 2 and 1, had mild short stature (−3.2 and −2.8 SDS, respectively) and a biochemical profile suggestive of growth hormone resistance. No defects were identified in the GHR. Patient 1 was homozygous for the IGFALS missense mutation P73L. Patient 2 was a compound heterozygote for the missense mutation L134Q and a novel GGC to AG substitution at position 546–548 (546–548delGGCinsAG). The latter causes a frameshift and the appearance of a premature stop codon. Size exclusion chromatography showed no peaks corresponding to ternary and binary complexes in either patient. Conclusion Screening of the IGFALS is important in children with short stature associated with low serum IGF-I, IGFBP-3 and ALS. PMID:20389102

  15. Variable effects of labile carbon on the carbon use of different microbial groups in black slate degradation

    NASA Astrophysics Data System (ADS)

    Seifert, Anne-Gret; Trumbore, Susan; Xu, Xiaomei; Zhang, Dachung; Kothe, Erika; Gleixner, Gerd

    2011-05-01

    Weathering of ancient organic matter contributes significantly to biogeochemical carbon cycles over geological times. The principle role of microorganisms in this process is well recognized. However, information is lacking on the contribution of individual groups of microorganisms and on the effect of labile carbon sources to the degradation process. Therefore, we investigated the contribution of fungi, Gram-positive and Gram-negative bacteria in the degradation process using a column experiment. Investigations were performed on low metamorphic black slates. All columns contained freshly crushed, sieved (0.63-2 mm), not autoclaved black slates. Two columns were inoculated with the lignite-degrading fungus Schizophyllum commune and received a culture medium containing 13C labeled glucose, two columns received only this culture medium and two control columns received only water. The total mass balance was calculated from all carbon added to the slate and the CO 2 and DOC losses. Phospholipid fatty acids (PLFA) were extracted to investigate microbial communities. We used both the compound specific 14C and 13C signal of the PLFA to quantify carbon uptake from black slates and the glucose of the culture medium, respectively. The total carbon loss in these columns exceeded the amount of added carbon by approximately 60%, indicating that black slate carbon has been used. PLFA associated with Gram-positive bacteria dominated the indigenous community and took up 22% of carbon from black slate carbon, whereas PLFA of Gram-negative bacteria used only 8% of carbon from the slates. PLFA of Gram-negative bacteria and fungi were both mostly activated by the glucose addition. The added Schizophyllum did not establish well in the columns and was overgrown by the indigenous microbial community. Our results suggest that especially Gram-positive bacteria are able to live on and degrade black slate material. They also benefit from easy degradable carbon from the nutrient broth. In

  16. Synthesis of Acid-Labile PEG and PEG-Doxorubicin-Conjugate Nanoparticles via Brush-First ROMP

    PubMed Central

    2015-01-01

    A panel of acid-labile bis-norbornene cross-linkers was synthesized and evaluated for the formation of acid-degradable brush-arm star polymers (BASPs) via the brush-first ring-opening metathesis polymerization (ROMP) method. An acetal-based cross-linker was identified that, when employed in conjunction with a poly(ethylene glycol) (PEG) macromonomer, provided highly controlled BASP formation reactions. A combination of this new cross-linker with a novel doxorubicin (DOX)-branch-PEG macromonomer provided BASPs that simultaneously degrade and release cytotoxic DOX in vitro. PMID:25243099

  17. Enrichment adsorption of a labile substance to the surface of particular mineral particles in river water as investigated by SEM-EDX and dilute-acid extraction/ICP-MS.

    PubMed

    Kyotani, Tomohiro; Koshimizu, Satoshi

    2003-06-01

    The selective enrichment behavior of a labile substance, such as hydroxides, to the surface of particular mineral particles in river water was clarified by scanning electron microscopy/energy dispersive X-ray microanalysis (SEM-EDX). Individual particles other than diatom collected on a 0.45 microm filter from the Fuji and Sagami rivers, central Japan, were analyzed by SEM-EDX and classified into seventeen groups according to the chemical composition and shape. Phosphorus, sulfur, chlorine, manganese and copper detected in each particle collected on the 0.45 microm filter could be successfully used as effective indicators of labile substance secondarily formed and adsorbed afresh in river water, because the detection frequencies of such elements are quite low, or negligible, in fresh mineral particles derived from igneous rocks. The labile substance adsorbed on mineral particles collected on the 0.45 microm filter was also evaluated by dilute-acid leaching, followed by inductively coupled plasma mass spectrometry (ICP-MS). Almost all parts of the manganese detected in individual particles were those adsorbed afresh as hydroxides together with iron and aluminum. Also, anionic elements, such as phosphorus, sulfur and chlorine, formed complexes with the hydroxides and/or were incorporated in them. Mg and/or Ca-rich aluminosilicate groups were the most effective adsorbers of such labile species. However, Si-rich and Na-, K- and Na-Ca rich aluminosilicates did not significantly adsorb the labile substance. Consequently, the remarkable selectivity was clarified in the adsorption process of labile substance to individual mineral particles in river water. PMID:12834221

  18. Determination of enantiomers by FESI-sweeping with an acid-labile sweeper in nonaqueous capillary electrophoresis.

    PubMed

    Wang, Wei-feng; Zhang, Hui-ge; Qi, Sheng-da; Chen, Hong-li; Chen, Xing-guo

    2015-06-21

    In this work, a facile and highly efficient on-line concentration strategy based on a coupling of field enhanced sample injection (FESI) and sweeping was developed for the determination of trace enantiomers (propranolol, PL) by nonaqueous capillary electrophoresis (NACE). In this FESI-sweeping method, the use of a sample of high acidity and low conductivity (pH* = 2.5, 4.0 μS cm(-1)) allowed for a large amount of analyte injection. Then, the concentration of the analytes was carried out by sweeping based on the interaction of an acid-labile anionic selector, di-n-butyl L-tartrate-boric acid complex acid, and cationic analytes. Simultaneously, the concentrated analytes were released and focused at the boundary of the acid sample solution and separation buffer due to the decomposition of the selector in the acid sample solution. Under the optimum conditions, a 21,000-fold sensitivity enhancement upon normal capillary zone electrophoresis (CZE) was achieved for PL enantiomers. The detection limits of R-propranolol and S-propranolol were 0.26 ng mL(-1) and 0.31 ng mL(-1), respectively. Eventually, the FESI-sweeping method was applied to detect PL enantiomers in plasma, saliva, and urine. PMID:25923176

  19. Dialkylenecarbonate-Bridged Polysilsesquioxanes. Hybrid Organic Sol-Gels with a Thermally Labile Bridging Group

    SciTech Connect

    Loy, D.A.; Beach, J.V.; Baugher, B.M.; Assink, R.A.; Shea, K.J.; Tran, J.; Small, J.H.

    1999-04-21

    In this paper, we introduce a new approach for altering the properties of bridged polysilsesquioxane xerogels using post-processing modification of the polymeric network. The bridging organic group contains latent functionalities that can be liberated thermally, photochemically, or by chemical means after the gel has been processed to a xerogel. These modifications can produce changes in density, volubility, porosity, and or chemical properties of the material. Since every monomer possesses two latent functional groups, the technique allows for the introduction of high levels of functionality in hybrid organic-inorganic materials. Dialkylenecarbonate-bridged polysilsesquioxane gels were prepared by the sol-gel polymerization of bis(triethoxysilylpropyl)carbonate (1) and bis(triethoxysilylisobutyl)-carbonate (2). Thermal treatment of the resulting non-porous xerogels and aerogels at 300-350 C resulted in quantitative decarboxylation of the dialkylenecarbonate bridging groups to give new hydroxyalkyl and olefinic substituted polysilsesquioxane monolithic xerogels and aerogels that can not be directly prepared through direct sol-gel polymerization of organotrialkoxysilanes.

  20. Labile sulfide and sulfite in phytochelatin complexes

    SciTech Connect

    Eannetta, N.T.; Steffens, J.C. )

    1989-04-01

    Heavy metals such as cadmium induce tomato cell cultures to synthesize the metal binding polypeptides ({gamma}-Glu-Cys){sub 3} and ({gamma}-Glu-Cys){sub 4}-Gly (phytochelatins). Tomato cells selected for growth on normally lethal concentrations of CdCl{sub 2} synthesize higher quantities of these polypeptides. Cd{sup r} cells are not cross-resistant to other heavy metals, and recent work suggests that metal detoxification by these peptides may be Cd-specific. The occurrence of labile sulfur as a component of the metal complex raises questions concerning possible functions of phytochelatins besides that of Cd binding. The presence of acid-labile sulfide ion in phytochelatin complexes has been reported by several groups. We report the additional finding that labile sulfite is also present in these complexes and in higher amounts than sulfide. Sulfide and sulfite are both released from the metal binding complex by acidification or by treatment with EDTA.

  1. A Simple and Efficient Synthesis of an Acid-labile Polyphosphoramidate by Organobase-catalyzed Ring-Opening Polymerization and Transformation to Polyphosphoester Ionomers by Acid Treatment

    PubMed Central

    Zhang, Shiyi; Wang, Hai; Shen, Yuefei; Zhang, Fuwu; Seetho, Kellie; Zou, Jiong; Taylor, John-Stephen A.; Dove, Andrew P.; Wooley, Karen L.

    2013-01-01

    The direct synthesis of an acid-labile polyphosphoramidate by organobase-catalyzed ring-opening polymerization and an overall two-step preparation of polyphosphodiester ionomers (PPEI) by acid-assisted cleavage of the phosphoramidate bonds along the backbone of the polyphosphoramidate were developed in this study. The ultrafast organobase-catalyzed ring-opening polymerization of a cyclic phospholane methoxyethyl amidate monomer initiated by benzyl alcohol allowed for the preparation of well-defined polyphosphoramidates (PPA) with predictable molecular weights, narrow molecular weight distributions (PDI<1.10), and well-defined chain ends. Cleavage of the acid-labile phosphoramidate bonds on the polyphosphoramidate repeat units was evaluated under acidic conditions over a pH range of 1–5, and the complete hydrolysis produced polyphosphodiesters. The thermal properties of the resulting polyphosphoester ionomer acid and polyphosphoester ionomer sodium salt exhibited significant thermal stability. The parent PPA and both forms of the PPEIs showed low cytotoxicities toward HeLa cells and RAW 264.7 mouse macrophage cells. The synthetic methodology developed here has enriched the family of water-soluble polymers prepared by rapid and convenient organobase-catalyzed ring-opening polymerizations and straightforward chemical medication reactions, which are designed to be hydrolytically degradable and have promise for numerous biomedical and other applications. PMID:23997276

  2. High desolvation temperature facilitates the ESI-source H/D exchange at non-labile sites of hydroxybenzoic acids and aromatic amino acids.

    PubMed

    Zherebker, Alexander; Kostyukevich, Yury; Kononikhin, Alexey; Roznyatovsky, Vitaliy A; Popov, Igor; Grishin, Yuri K; Perminova, Irina V; Nikolaev, Eugene

    2016-04-21

    Hydrogen/deuterium exchange coupled with high-resolution mass spectrometry has become a powerful analytical approach for structural investigations of complex organic matrices. Here we report the feasibility of the site-specific H/D exchange of non-labile hydrogens directly in the electrospray ionization (ESI) source, which was facilitated by an increase in the desolvation temperature from 200 °C up to 400 °C. We have found that the exchanges at non-labile sites were observed only for the model compounds capable of keto-enol tautomeric transformations (e.g., 2,3-, 2,4-dihydroxybenzoic acids, gallic acid, DOPA), and only when water was used as a solvent. We hypothesized that the detected additional exchanges were induced by the presence of hydroxyls in the sprayed water droplets generated in the negative ESI mode. It was indicative of the exchange reactions taking place in the sprayed droplets rather than in the gas phase. To support this hypothesis, the H/D exchange experiments were run in deuterated water under base-catalyzed conditions for three model compounds, which showed the most intensive exchanges in the MS experiments: DOPA, 2,4-DHB, and 5-acetylsalicylic acid. (2)H NMR spectroscopy has confirmed keto-enolic transformations of the model compounds leading to the specific labeling of the corresponding non-labile sites. We believe that the proposed technique will be useful for structural investigations of natural complex mixtures (e.g. proteins, humic substances) using site-specific H/D exchange. PMID:27002310

  3. Effect of oxalic acid treatment on sediment arsenic concentrations and lability under reducing conditions.

    PubMed

    Sun, Jing; Bostick, Benjamin C; Mailloux, Brian J; Ross, James M; Chillrud, Steven N

    2016-07-01

    Oxalic acid enhances arsenic (As) mobilization by dissolving As host minerals and competing for sorption sites. Oxalic acid amendments thus could potentially improve the efficiency of widely used pump-and-treat (P&T) remediation. This study investigates the effectiveness of oxalic acid on As mobilization from contaminated sediments with different As input sources and redox conditions, and examines whether residual sediment As after oxalic acid treatment can still be reductively mobilized. Batch extraction, column, and microcosm experiments were performed in the laboratory using sediments from the Dover Municipal Landfill and the Vineland Chemical Company Superfund sites. Oxalic acid mobilized As from both Dover and Vineland sediments, although the efficiency rates were different. The residual As in both Dover and Vineland sediments after oxalic acid treatment was less vulnerable to microbial reduction than before the treatment. Oxalic acid could thus improve the efficiency of P&T. X-ray absorption spectroscopy analysis indicated that the Vineland sediment samples still contained reactive Fe(III) minerals after oxalic acid treatment, and thus released more As into solution under reducing conditions than the treated Dover samples. Therefore, the efficacy of enhanced P&T must consider sediment Fe mineralogy when evaluating its overall potential for remediating groundwater As. PMID:26970042

  4. PEG-detachable and acid-labile cross-linked micelles based on orthoester linked graft copolymer for paclitaxel release

    NASA Astrophysics Data System (ADS)

    Yuan, Zhefan; Huang, Jingyi; Liu, Jing; Cheng, Sixue; Zhuo, Renxi; Li, Feng

    2011-08-01

    Polyethylene glycol detachable graft copolymer, mPEG-g-p(NAS-co-BMA), was synthesized by grafting 2-(ω-methoxy)PEGyl-1,3-dioxan-5-ylamine onto poly(N-(acryloyloxy)succinimide-co-butyl methacrylate). Pseudo in situ cross-linking of the mPEG-g-p(NAS-co-BMA) was performed in dimethylformamide phosphate buffer (v/v = 1/1) by an acid-labile diamine cross-linker bearing two symmetrical cyclic orthoesters. The cross-linked (CL) micelles with different contents of mPEG segments represented different morphologies. The CL micelles containing approximately one mPEG segment exhibited 'echini' morphology whereas the CL micelle with approximately three mPEG segments formed nanowires. The hydrolysis rate of the CL micelles is highly pH-dependent and much more rapid at mild acid than physiological conditions. Hydrolyzates of the CL micelles formed vesicles because new amphiphilic copolymers were formed. Paclitaxel (PTX) was successfully loaded into the CL micelles and a controlled and pH-dependent release behavior was observed. No obvious cytotoxicity was found for the CL micelles at concentration as high as 800 mg l - 1.

  5. Preparation and characterization of poly(lactic-co-glycolic acid) microspheres loaded with a labile antiparkinson prodrug.

    PubMed

    D'Aurizio, E; van Nostrum, C F; van Steenbergen, M J; Sozio, P; Siepmann, F; Siepmann, J; Hennink, W E; Di Stefano, A

    2011-05-16

    L-dopa-α-lipoic acid (LD-LA) is a new multifunctional prodrug for the treatment of Parkinson's disease. In human plasma, LD-LA catechol esters and amide bonds are chemically and enzymatically cleaved, respectively, resulting in a half-life time of about fifty minutes. In the present work, the unstable LD-LA was entrapped into biodegradable poly(lactic-co-glycolic acid) (PLGA) microspheres designed as depot systems to protect this prodrug against degradation and to obtain a sustained release of the intact compound. The microspheres were prepared by an oil-in-water emulsion/solvent evaporation technique and the effect of formulation and processing parameters (polymer concentration in the organic solvent, volumes ratio of the phases, rate of the organic solvent evaporation) on microspheres characteristics (size, loading, morphology, release) was investigated. Also emphasis was given on the stability of the drug before and after release as well as on the underlying mass transport mechanisms controlling LD-LA release. Interestingly, when encapsulated in appropriate conditions into PLGA microspheres, the labile prodrug was stabilized and released via Fickian diffusion up to more than one week. PMID:21356295

  6. Warming Alters the Routing of Labile and Slower-Turnover Carbon Through Distinct Microbial Groups in Boreal Forest Organic Soils

    NASA Astrophysics Data System (ADS)

    Ziegler, S. E.; Billings, S. A.; Lane, C. S.; Li, J.; Fogel, M. L.

    2012-12-01

    Increased temperature has been linked to greater losses of soil organic carbon (SOC) via microbial respiration and potentially greater relative increases in mineralization of more complex, slow-turnover SOC pools. Though critical for predicting climate feedbacks, our mechanistic understanding of these temperature responses remains limited. Here we report results from a warming experiment using organic horizon soils from two mesic, boreal forest sites with contrasting climate regimes. We replaced extant Oi soil sub-horizons with another coniferous Oi possessing a distinct δ13C signature, and tracked incorporation of the replaced Oi-C and, by difference, the more humified Oea sub-horizon C into microbial phospholipid fatty acids (PLFA) following 120 day incubations at 15C and 20C. We demonstrate how regional climate (site effects) and experimental warming (temperature effects) influence microbial incorporation of Oi versus slower-turnover Oea SOC pools. Congruent with increased mineralization in these soils, the quantity of total PLFA, a proxy for microbial biomass, increased by 32-60% with experimental warming and was 20-42% higher within soils from the warmer versus cooler site. The proportion of Gram-positive bacterial PLFA-C derived from Oi-C more than doubled and coincided with a reduction in the incorporation of Oi-C into fungal relative to bacterial PLFA with laboratory warming and in soils from the warmer site. In conjunction with the relative decrease in fungal incorporation of Oi-C, warming led to an increase of 22-31% in the proportion of fungal PLFA-C derived from the Oea-C. This is consistent with site effects and an increased incorporation of this slower-turnover SOC pool in soils from the warmer site. The increase in microbial biomass and shift in routing of Oi and Oea pools through PLFA indicate that warming increases fungal mineralization of more slow-turnover C pools in these boreal organic soils. This increased exploitation of low C:N Oea by fungi

  7. Fmoc-Sec(Xan)-OH: synthesis and utility of Fmoc selenocysteine SPPS derivatives with acid-labile sidechain protection.

    PubMed

    Flemer, Stevenson

    2015-01-01

    We report here the synthesis of the first selenocysteine SPPS derivatives which bear TFA-labile sidechain protecting groups. New compounds Fmoc-Sec(Xan)-OH and Fmoc-Sec(Trt)-OH are presented as useful and practical alternatives to the traditional Fmoc-Sec-OH derivatives currently available to the peptide chemist. From a bis Fmoc-protected selenocystine precursor, multiple avenues of diselenide reduction were attempted to determine the most effective method for subsequent attachment of the protecting group electrophiles. Our previously reported one-pot reduction methodology was ultimately chosen as the optimal approach toward the synthesis of these novel building blocks, and both were easily obtained in high yield and purity. Fmoc-Sec(Xan)-OH was discovered to be bench-stable for extended timeframes while the corresponding Fmoc-Sec(Trt)-OH derivative appeared to detritylate slowly when not stored at -20 °C. Both Sec derivatives were incorporated into single- and multiple-Sec-containing test peptides in order to ascertain the peptides' deprotection behavior and final form upon TFA cleavage. Single-Sec-containing test peptides were always isolated as their corresponding diselenide dimers, while dual-Sec-containing peptide sequences were afforded exclusively as their intramolecular diselenides. PMID:25504629

  8. Development of pH-sensitive self-nanoemulsifying drug delivery systems for acid-labile lipophilic drugs.

    PubMed

    Zhao, Tianjing; Maniglio, Devid; Chen, Jie; Chen, Bin; Migliaresi, Claudio

    2016-03-01

    Oral administration is the most convenient way of all the drug delivery routes. Orally administered bioactive compounds must resist the harsh acidic fluids or enzyme digestion in stomach, to reach their absorbed destination in small intestine. This is the case for silibinin, a drug used to protect liver cells against toxins that has also been demonstrated in vitro to possess anti-cancer effects. However, as many other drugs, silibinin can degrade in the stomach due to the action of the gastric fluid. The use of pH-sensitive self-nanoemulsifying drug delivery systems (pH-SNEDDS) could overcome the drawback due to degradation of the drug in the stomach while enhancing its solubility and dissolution rate. In this paper we have investigated pH-sensitive self-nanoemulsifying formulations containing silibinin as model drug. Pseudo-ternary phase diagrams have been constructed in order to identify the self-emulsification regions under different pH. Solubility of silibinin in selected formulations has been assessed and stability of the pure drug and of the silibinin loaded pH-SNEDDS formulations in simulated gastric fluid had been compared. Droplet size of the optimized pH-SNEDDS has been correlated to pH, volume of dilution medium and silibinin loading amount. TEM (transmission electron microscopy) studies have shown that emulsion droplets had spherical shape and narrow size distribution. In vitro drug release studies of the optimal pH-SNEDDS indicated substantial increase of the drug release and release rate in comparison to pure silibinin and to the commercial silibinin tablet. The results indicated that pH-SNEDDS have potential to improve the biopharmaceutics properties of acid-labile lipophilic drugs. PMID:26923270

  9. A new structural model of the acid-labile subunit: pathogenetic mechanisms of short stature-causing mutations.

    PubMed

    David, Alessia; Kelley, Lawrence A; Sternberg, Michael J E

    2012-12-01

    The acid-labile subunit (ALS) is the main regulator of IGF1 and IGF2 bioavailability. ALS deficiency caused by mutations in the ALS (IGFALS) gene often results in mild short stature in adulthood. Little is known about the ALS structure-function relationship. A structural model built in 1999 suggested a doughnut shape, which has never been observed in the leucine-rich repeat (LRR) superfamily, to which ALS belongs. In this study, we built a new ALS structural model, analysed its glycosylation and charge distribution and studied mechanisms by which missense mutations affect protein structure. We used three structure prediction servers and integrated their results with information derived from ALS experimental studies. The ALS model was built at high confidence using Toll-like receptor protein templates and resembled a horseshoe with an extensively negatively charged concave surface. Enrichment in prolines and disulphide bonds was found at the ALS N- and C-termini. Moreover, seven N-glycosylation sites were identified and mapped. ALS mutations were predicted to affect protein structure by causing loss of hydrophobic interactions (p.Leu134Gln), alteration of the amino acid backbone (p.Leu241Pro, p.Leu172Phe and p.Leu244Phe), loss of disulphide bridges (p.Cys60Ser and p.Cys540Arg), change in structural constrains (p.Pro73Leu), creation of novel glycosylation sites (p.Asp440Asn) or alteration of LRRs (p.Asn276Ser). In conclusion, our ALS structural model was identified as a highly confident prediction by three independent methods and disagrees with the previously published ALS model. The new model allowed us to analyse the ALS core and its caps and to interpret the potential structural effects of ALS mutations. PMID:22991227

  10. Peracetic acid: a practical agent for sterilizing heat-labile polymeric tissue-engineering scaffolds.

    PubMed

    Yoganarasimha, Suyog; Trahan, William R; Best, Al M; Bowlin, Gary L; Kitten, Todd O; Moon, Peter C; Madurantakam, Parthasarathy A

    2014-09-01

    Advanced biomaterials and sophisticated processing technologies aim at fabricating tissue-engineering scaffolds that can predictably interact within a biological environment at the cellular level. Sterilization of such scaffolds is at the core of patient safety and is an important regulatory issue that needs to be addressed before clinical translation. In addition, it is crucial that meticulously engineered micro- and nano- structures are preserved after sterilization. Conventional sterilization methods involving heat, steam, and radiation are not compatible with engineered polymeric systems because of scaffold degradation and loss of architecture. Using electrospun scaffolds made from polycaprolactone, a low melting polymer, and employing spores of Bacillus atrophaeus as biological indicators, we compared ethylene oxide, autoclaving and 80% ethanol to a known chemical sterilant, peracetic acid (PAA), for their ability to sterilize as well as their effects on scaffold properties. PAA diluted in 20% ethanol to 1000 ppm or above sterilized electrospun scaffolds in 15 min at room temperature while maintaining nano-architecture and mechanical properties. Scaffolds treated with PAA at 5000 ppm were rendered hydrophilic, with contact angles reduced to 0°. Therefore, PAA can provide economical, rapid, and effective sterilization of heat-sensitive polymeric electrospun scaffolds that are used in tissue engineering. PMID:24341350

  11. Peracetic Acid: A Practical Agent for Sterilizing Heat-Labile Polymeric Tissue-Engineering Scaffolds

    PubMed Central

    Yoganarasimha, Suyog; Trahan, William R.; Best, Al M.; Bowlin, Gary L.; Kitten, Todd O.; Moon, Peter C.

    2014-01-01

    Advanced biomaterials and sophisticated processing technologies aim at fabricating tissue-engineering scaffolds that can predictably interact within a biological environment at the cellular level. Sterilization of such scaffolds is at the core of patient safety and is an important regulatory issue that needs to be addressed before clinical translation. In addition, it is crucial that meticulously engineered micro- and nano- structures are preserved after sterilization. Conventional sterilization methods involving heat, steam, and radiation are not compatible with engineered polymeric systems because of scaffold degradation and loss of architecture. Using electrospun scaffolds made from polycaprolactone, a low melting polymer, and employing spores of Bacillus atrophaeus as biological indicators, we compared ethylene oxide, autoclaving and 80% ethanol to a known chemical sterilant, peracetic acid (PAA), for their ability to sterilize as well as their effects on scaffold properties. PAA diluted in 20% ethanol to 1000 ppm or above sterilized electrospun scaffolds in 15 min at room temperature while maintaining nano-architecture and mechanical properties. Scaffolds treated with PAA at 5000 ppm were rendered hydrophilic, with contact angles reduced to 0°. Therefore, PAA can provide economical, rapid, and effective sterilization of heat-sensitive polymeric electrospun scaffolds that are used in tissue engineering. PMID:24341350

  12. A simple and inexpensive enteric-coated capsule for delivery of acid-labile macromolecules to the small intestine*

    PubMed Central

    Miller, Darren S.; Parsons, Anne Michelle; Bresland, John; Herde, Paul; Pham, Duc Minh; Tan, Angel; Hsu, Hung-yao; Prestidge, Clive A.; Kuchel, Tim; Begg, Rezaul; Aziz, Syed Mahfuzul; Butler, Ross N.

    2015-01-01

    Understanding the ecology of the gastrointestinal tract and the impact of the contents on the host mucosa is emerging as an important area for defining both wellness and susceptibility to disease. Targeted delivery of drugs to treat specific small intestinal disorders such as small bowel bacterial overgrowth and targeting molecules to interrogate or to deliver vaccines to the remote regions of the small intestine has proven difficult. There is an unmet need for methodologies to release probes/drugs to remote regions of the gastrointestinal tract in furthering our understanding of gut health and pathogenesis. In order to address this concern, we need to know how the regional delivery of a surrogate labeled test compound is handled and in turn, if delivered locally as a liquid or powder, the dynamics of its subsequent handling and metabolism. In the studies we report on in this paper, we chose 13C sodium acetate (13C-acetate), which is a stable isotope probe that once absorbed in the small intestine can be readily measured non-invasively by collection and analysis of 13CO2 in the breath. This would provide information of gastric emptying rates and an indication of the site of release and absorptive capacity. In a series of in vitro and in vivo pig experiments, we assessed the enteric-protective properties of a commercially available polymer EUDRAGIT®L100-55 on gelatin capsules and also on DRcaps®. Test results demonstrated that DRcaps®coated with EUDRAGIT®L100-55 possessed enhanced enteric-protective properties, particularly in vivo. These studies add to the body of knowledge regarding gastric emptying in pigs and also begin the process of gathering specifications for the design of a simple and cost-effective enteric-coated capsule for delivery of acid-labile macromolecules to the small intestine. PMID:26160716

  13. Interaction between acid-labile subunit and insulin-like growth factor binding protein 3 expressed in Xenopus oocytes.

    PubMed

    Choi, Kyung-Yi; Lee, Dong-Hee

    2002-03-31

    The acid-labile subunit (ALS) associates with the insulinlike growth factor (IGF)-I or II, and the IGF binding protein-3 (IGFBP-3) in order to form a 150-kD complex in the circulation. This complex may regulate the serum IGFs by restricting them in the vascular system and promoting their endocrine actions. Little is known about how ALS binds to IGFBP3, which connects the IGFs to ALS. Xenopus oocyte was utilized to study the function of ALS in assembling IGFs into the ternary complexes. Xenopus oocyte was shown to correctly translate in vitro transcribed mRNAs of ALS and IGFBP3. IGFBP3 and ALS mRNAs were injected in a mixture, and their products were immunoprecipitated by antisera against ALS and IGFBP3. Contrary to traditional reports that ALS interacts only with IGF-bound IGFBP3, this study shows that ALS is capable of forming a binary complex with IGFBP3 in the absence of IGF. When cross-linked by disuccinimidyl suberate, the band that represents the ALSIGFBP3 complex was evident on the PAGE. IGFBP3 movement was monitored according to the distribution between the hemispheres. Following a localized translation in the vegetal hemisphere, IGFBP3 remained in the vegetal half in the presence of ALS. However, the mutant IGFBP3 freely diffused into the animal half, despite the presence of ALS, which is different from the wild type IGFBP3. This study, therefore, suggests that ALS may play an important role in sequestering IGFBP3 polypeptides via the intermolecular aggregation. Studies using this heterologous model will lead to a better understanding of the IGFBP3 and ALS that assemble into the ternary structure and circulate the IGF system. PMID:12297028

  14. Development of ultrasonic-assisted closed in-syringe extraction and derivatization for the determination of labile abietic acid and dehydroabietic acid in cosmetics.

    PubMed

    Liu, Jianjun; Liu, Mengge; Li, Xiu; Lu, Xiaomin; Chen, Guang; Sun, Zhiwei; Li, Guoliang; Zhao, Xianen; Zhang, Shijuan; Song, Cuihua; Wang, Hua; Suo, Yourui; You, Jinmao

    2014-12-01

    Two resin acids, abietic acid (AA) and dehydroabietic acid (DHAA), in cosmetics may cause allergy or toxicoderma, but remain inaccurately investigated due to their lability. In this work, an accurate, sensitive, efficient and convenient method, utilizing the ultrasonic-assisted closed in-syringe extraction and derivatization (UCSED) prior to high performance liquid chromatography (HPLC) coupled with fluorescence detection (FLD) and on-line tandem mass spectra (MS/MS), has been developed. Analytes are extracted by acetonitrile (10/1, v/m) in a sealed syringe under safe condition (60°C; 15 min; nitrogen atmosphere) and then in-syringe derivatized by 2-(2-(anthracen-10-yl)-1H-naphtho[2,3-d]imidazol-1-yl) ethyl-p-toluenesulfonate (ANITS) (8-fold, 93°C, 30 min, DMF as co-solvent, K2CO3 as catalyst). In UCSED, derivatization contributes to increase both analytical sensitivity and stability of analytes. Excellent linearity (r2≥0.9991) is achieved in wide range (75-3000 ng/mL (AA); 150-4500 ng/mL (DHAA)). Quite low detection limits (AA: 8.2-10.8 ng/mL; DHAA: 19.4-24.3 ng/mL) and limits of analyte concentration (LOAC) (AA: 30.0-44.5 ng/mL; DHAA: 70.9-86.7 ng/mL) ensure the trace analysis. This method is applied to the analysis of cosmetic samples, including depilatory wax strip, liquid foundation, mascara, eyeliner, eyebrow pencil and lip balm. No additional purification is required and no matrix effect is observed, demonstrating obvious advantages over conventional pretreatment such as solid phase extraction (SPE). Accuracy (RE: -3.2% to 2.51%), precision (RSD: 1.29-2.84%), recovery (95.20-103.63%; 95.51-104.22%) and repeatability (<0.23%; <2.87%) are significantly improved. Furthermore, this work plays a guiding role in developing a reasonable method for labile analytes. PMID:25456583

  15. Acid-labile pHPMA modification of four-arm oligoaminoamide pDNA polyplexes balances shielding and gene transfer activity in vitro and in vivo.

    PubMed

    Beckert, Linda; Kostka, Libor; Kessel, Eva; Krhac Levacic, Ana; Kostkova, Hana; Etrych, Tomas; Lächelt, Ulrich; Wagner, Ernst

    2016-08-01

    We report novel pH-reversibly surface-shielded polyplexes with enhanced gene transfer activity upon systemic administration. A four-arm-structured sequence-defined cationic oligomer KK[HK[(H-Sph-K)3HC]2]2 was designed and synthesized on solid-phase, containing additional lysine residues not only for improved pDNA polyplex stability, but also providing attachment points for subsequent polyplex functionalization with amine-reactive shielding polymers. Herein, the surface of polyplexes was shielded with hydrophilic polymers, monovalent PEG or monovalent and multivalent pHPMA, optionally attached to the polyplex via the acid-labile linker AzMMMan. Overall, surface modification with PEG or pHPMA resulted in a decrease in the zeta potential of polyplexes, consistent with the degree of surface shielding. At pH 6.0, only polyplexes modified via the acid-labile linkage showed an increase in zeta potential, consistent with a "deshielding" in acidic environment, expected as beneficial for endosomal escape. Shielding was more efficient for multivalent pHPMA (20kDa, 30kDa) as compared to monovalent pHPMA (10kDa, 20kDa, 30kDa) or PEG (5kDa). In vitro transfection studies revealed higher gene expression by the polyplexes with the acid-labile shield as compared to their irreversibly shielded counterparts. Intravenous administration of AzMMMan-pHPMA modified polyplexes in an in vivo tumor mouse model mediated enhanced gene expression in the subcutaneous tumor and reduced undesirable expression in the liver. PMID:27235729

  16. Effects of dissolved organic matter (DOM) sources and nature of solid extraction sorbent on recoverable DOM composition: Implication into potential lability of different compound groups.

    PubMed

    Chen, Meilian; Kim, Sunghwan; Park, Jae-Eun; Kim, Hyun Sik; Hur, Jin

    2016-07-01

    Noting the source-dependent properties of dissolved organic matter (DOM), this study explored the recoverable compounds by solid phase extraction (SPE) of two common sorbents (C18 and PPL) eluted with methanol solvent for contrasting DOM sources via fluorescence excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Fresh algae and leaf litter extracts DOM, one riverine DOM, and one upstream lacustrine DOM were selected for the comparison. C18 sorbent was generally found to extract more diverse molecular formula, relatively higher molecular weight, and more heteroatomic DOM compounds within the studied mass range than PPL sorbent except for the leaf litter extract. Even with the same sorbent, the main molecular features of the two end member DOM were distributed on different sides of the axes of a multivariate ordination, indicating the source-dependent characteristics of the recoverable compounds by the sorbents. In addition, further examination of the molecular formula uniquely present in the two end members and the upstream lake DOM suggested that proteinaceous, tannin-like, and heteroatomic DOM constituents might be potential compound groups which are labile and easily degraded during their mobilization into downstream watershed. This study provides new insights into the sorbent selectivity of DOM from diverse sources and potential lability of various compound groups. PMID:27117255

  17. Poly(ethylene oxide)-block-polyphosphoester-graft-paclitaxel Conjugates with Acid-labile Linkages as a pH-Sensitive and Functional Nanoscopic Platform for Paclitaxel Delivery

    PubMed Central

    Zou, Jiong; Zhang, Fuwu; Zhang, Shiyi; Pollack, Stephanie F.; Elsabahy, Mahmoud; Fan, Jingwei; Wooley, Karen L.

    2013-01-01

    There has been an increasing interest to develop new types of stimuli-responsive drug delivery vehicles with high drug loading and controlled release properties for chemotherapeutics. An acid-labile, polyphosphoester-based degradable, polymeric paclitaxel (PTX) conjugate containing ultra-high levels of PTX loading has been improved significantly, in this second generation development, which involves connection of each PTX molecule to the polymer backbone via a pH-sensitive β-thiopropionate linkage. The results for this system indicate that it has great potential as an effective anti-cancer agent. Poly(ethylene oxide)-block-polyphosphoester-graft-PTX drug conjugate (PEO-b-PPE-g-PTX G2) was synthesized by organocatalyst-promoted ring-opening polymerization of 2-(but-3-en-1-yloxy)-1,3,2-dioxaphospholane-2-oxide from a PEO macroinitiator, followed by thermo-promoted thiolene click conjugation of a thiol-functionalized PTX prodrug to the pendant alkene groups of the block copolymer. The PEO-b-PPE-g-PTX G2 formed well-defined nanoparticles in aqueous solution, by direct dissolution into water, with a number-averaged hydrodynamic diameter of 114 ± 31 nm. The conjugate had PTX loading capacity as high as 53 wt%, and a maximum PTX concentration of 0.68 mg/mL in water (vs. 1.7 μg/mL for free PTX). Although the PTX concentration is ca. 10× less than for our first generation material, its accelerated release allowed for similar free PTX concentrations vs. time. The PEO-b-PPE-g-PTX G2 exhibited accelerated drug release under acidic conditions (~50 wt% PTX released in 8 d) compared to neutral conditions (~20 wt% PTX released in 8 d) and compared to the first generation analog that contained ester linkages between PTX and the polymer backbone (<5 wt% PTX released in 4 d), due to their acid-sensitive hydrolytically-labile β-thiopropionate linkages between PTX molecules and the polymer backbone. The positive cell-killing activity of PEO-b-PPE-g-PTX G2 against two cancer cell

  18. Combination of acid labile detergent and C18 Empore™ disks for improved identification and sequence coverage of in-gel digested proteins.

    PubMed

    Koehn, Henning; Lau, Benjamin; Clerens, Stefan; Plowman, Jeffrey E; Dyer, Jolon M; Ramli, Umi Salamah; Deb-Choudhury, Santanu

    2011-04-01

    A protocol for improved extraction of peptides from in-gel protein digests, using a combination of the acid labile surfactant, sodium deoxycholate (SDC) and C18 Empore™ membranes, is presented. This approach results in better mass spectrum quality, higher numbers of identified peptide peaks and improved identification scores compared to standard tryptic digestion protocols, or protocols using only SDC or only C18 Empore™ disks. The advantages of the new protocol are demonstrated for two different types of samples: Merino wool intermediate filament proteins and Elaeis guineensis (oil palm) mesocarp proteins. PMID:21327873

  19. Protein covalent immobilization via its scarce thiol versus abundant amine groups: Effect on orientation, cell binding domain exposure and conformational lability.

    PubMed

    Ba, O M; Hindie, M; Marmey, P; Gallet, O; Anselme, K; Ponche, A; Duncan, A C

    2015-10-01

    Quantity, orientation, conformation and covalent linkage of naturally cell adhesive proteins adsorbed or covalently linked to a surface, are known to influence the preservation of their subsequent long term cell adhesion properties and bioactivity. In the present work, we explore two different strategies for the covalent linking of plasma fibronectin (pFN) - used as a cell adhesive model protein, onto a polystyrene (PS) surface. One is aimed at tethering the protein to the surface in a semi-oriented fashion (via one of the 4 free thiol reactive groups on the protein) with a heterofunctional coupling agent (SSMPB method). The other aims to immobilize the protein in a more random fashion by reaction between the abundant pendant primary amine bearing amino acids of the pFN and activated carboxylic surface functions obtained after glutaric anhydride surface treatment (GA method). The overall goal will be to verify the hypothesis of a correlation between covalent immobilization of a model cell adhesive protein to a PS surface in a semi-oriented configuration (versus randomly oriented) with promotion of enhanced exposure of the protein's cell binding domain. This in turn would lead to enhanced cell adhesion. Ideally the goal is to elaborate substrates exhibiting a long term stable protein monolayer with preserved cell adhesive properties and bioactivity for biomaterial and/or cell adhesion commercial plate applications. However, the initial restrictive objective of this paper is to first quantitatively and qualitatively investigate the reversibly (merely adsorbed) versus covalently irreversibly bound protein to the surface after the immobilization procedure. Although immobilized surface amounts were similar (close to the monolayer range) for all immobilization approaches, covalent grafting showed improved retention and stronger "tethering" of the pFN protein to the surface (roughly 40%) after SDS rinsing compared to that for mere adsorption (0%) suggesting an added value

  20. Labile (borderline) hypertension--new aspects of a common disorder.

    PubMed

    Kuchel, O; Cuche, J L; Hamet, P; Tolis, G; Messerli, F H; Barbeau, A; Boucher, R; Genest, J

    1975-09-01

    Labile hypertension in patients under 50 years of age (the non-atherosclerotic form) was found to be characterized by higher urinary excretion of catecholamines and particularly of homovanillic acid; when further analyzed it was shown to be a heterogeneous entity with two types of patients clinically and biochemically distinguishable from each other, from control subjects and from patients with stable hypertension. Reactivity to assuming an upright posture distinguishes one type of labile hypertension having a normal postural pulse rate response from another having an excessive postural increase in pulse rate. The first group also showed normal responses of plasma norepinephrine concentration and of urinary cyclic AMP to posture. The group with excessive pulse rate response, in contrast, showed a decrease in plasma norepinephrine and an excessive increase of urinary cyclic AMP excretion in response to upright posture. The results suggest that not only circulating catecholamines but also the reactivity of their target tissues (as probably reflected by cyclic AMP measurements) are important in bringing about signs of adrenergic excess. The hypothesis that cyclic AMP changes reflect beta-adrenergic receptor reactivity is strongly favoured by data indicating qualitative differences in cyclic AMP responses to beta-adrenergic stimulation or inhibition between control subjects and those labile hypertensive patients with clinical signs of excessive sympathetic reactivity. The study stresses the need for more precise definition of labile hypertension, for dynamic clinical and biochemical correlative studies, and for consideration not only of the circulating hormones but also of the "second messengers" (such as cyclic AMP and cyclic GMP) which reflect the cellular action of hormones. Blood pressure is a very labile parameter in health and disease. In one sense, therefore, hypertension can be considered "labile" in every hypertensive patient. Usually, however, labile (or

  1. Dialkylenecarbonate-Bridged Polysilsesquioxanes. Hybrid Organic-Inorganic Sol-Gels with a Thermally Labile Bridging Group

    SciTech Connect

    Assink, Roger A.; Baugher, Brigitta M.; Beach, James V.; Loy, Douglas A.; Shea, Kenneth J.; Small, James H.; Tran, Joseph

    1999-07-20

    In this paper, we introduce a new approach for altering the properties of bridged polysilsesquioxane xerogels using post-processing mobilization of the polymeric network. The bridging organic group contains latent functionalities that can be liberated thermally, photochemically, or by chemical means after the gel has been processed to a xerogel. These modifications can produce changes in density, volubility, porosity, and or chemical properties of the material. Since every monomer possesses two latent functional groups, the technique allows for the introduction of high levels of functionality in hybrid organic-inorganic materials. Dialkylenecarbonate-bridged polysilsesquioxane gels were prepared by the sol-gel polymerization of bis(triethoxysilylpropyl)carbonate (1) and bis(triethoxysilylisobutyl)-carbonate (2). Thermal treatment of the resulting non-porous xerogels and aerogels at 300-350 C resulted in quantitative decarboxylation of the dialkylenecarbonate bridging groups to give new hydroxyalkyl and olefinic substituted polysilsesquioxane monolithic xerogels and aerogels that can not be directly prepared through direct sol-gel polymerization of organotrialkoxysilanes.

  2. Acid-labile protein-adducted heterocyclic aromatic amines in human blood are not viable biomarkers of dietary exposure: A systematic study.

    PubMed

    Cooper, Kevin M; Brennan, Sarah F; Woodside, Jayne V; Cantwell, Marie; Guo, Xiaoxiao; Mooney, Mark; Elliott, Christopher T; Cuskelly, Geraldine J

    2016-05-01

    Heterocyclic aromatic amines (HCA) are carcinogenic mutagens formed during cooking of protein-rich foods. HCA residues adducted to blood proteins have been postulated as biomarkers of HCA exposure. However, the viability of quantifying HCAs following hydrolytic release from adducts in vivo and correlation with dietary intake are unproven. To definitively assess the potential of labile HCA-protein adducts as biomarkers, a highly sensitive UPLC-MS/MS method was validated for four major HCAs: 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), 2-amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx) and 2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline (7,8-DiMeIQx). Limits of detection were 1-5 pg/ml plasma and recoveries 91-115%. Efficacy of hydrolysis was demonstrated by HCA-protein adducts synthesised in vitro. Plasma and 7-day food diaries were collected from 122 fasting adults consuming their habitual diets. Estimated HCA intakes ranged from 0 to 2.5 mg/day. An extensive range of hydrolysis conditions was examined for release of adducted HCAs in plasma. HCA was detected in only one sample (PhIP, 9.7 pg/ml), demonstrating conclusively for the first time that acid-labile HCA adducts do not reflect dietary HCA intake and are present at such low concentrations that they are not feasible biomarkers of exposure. Identification of biomarkers remains important. The search should concentrate on stabilised HCA-peptide markers and use of untargeted proteomic and metabolomic approaches. PMID:26993956

  3. Synthesis and characterization of a PAMAM-OH derivative containing an acid-labile β-thiopropionate bond for gene delivery.

    PubMed

    Chen, Kang; Chen, Qing; Wang, Kuanglei; Zhu, Jia; Li, Weinan; Li, Wenpan; Qiu, Lipeng; Guan, Guannan; Qiao, Mingxi; Zhao, Xiuli; Hu, Haiyang; Chen, Dawei

    2016-07-25

    The present report describes the synthesis of a hydroxyl terminal PAMAM dendrimer (PAMAM-OH) derivative (PAMSPF). The hydroxyls of PAMAM-OH were attached to S-Methyl-l-cysteine (SMLC) via an acid-labile ester bond, named as β-thiopropionate bond, followed by modification with folic acid (FA) through a polyethylene glycol (PEG) linker. The degrees of attachment of SMLC and FA to the PAMAM-OH backbone were 83.9% and 12.8%, respectively. PAMSPF could condense DNA to form spherical nanoparticles with particle sizes of ∼200nm and remain stable in the presence of heparin and nuclease. The β-thiopropionate bond in PAMSPF was hydrolyzed completely and the DNA release rate was 95.8±3.3% after incubation under mildly acidic conditions at 37°C for 3h. PAMSPF/DNA was less cytotoxic to KB and HepG2 cells and exhibited a higher gene transfection efficiency than native PAMAM/DNA. The uptake assays showed that PAMSPF/DNA entered KB cells within 0.5h through folate receptor-mediated endocytosis and escaped from endosomes within 2h. In addition, PAMSPF/DNA displayed long circulation time along with excellent targeting of tumor sites in vivo. These findings demonstrate that PAMSPF is an excellent carrier for safe and effective gene delivery. PMID:27260132

  4. Block Copolymer Micelles with Acid-labile Ortho Ester Side-chains: Synthesis, Characterization, and Enhanced Drug Delivery to Human Glioma Cells

    PubMed Central

    Tang, Rupei; Ji, Weihang; Panus, David; Palumbo, R. Noelle; Wang, Chun

    2011-01-01

    A new type of block copolymer micelles for pH-triggered delivery of poorly water-soluble anticancer drugs has been synthesized and characterized. The micelles were formed by the self-assembly of an amphiphilic diblock copolymer consisting of a hydrophilic poly(ethylene glycol) (PEG) block and a hydrophobic polymethacrylate block (PEYM) bearing acid-labile ortho ester side-chains. The diblock copolymer was synthesized by atom transfer radical polymerization (ATRP) from a PEG macro-initiator to obtain well-defined polymer chain-length. The PEG-b-PEYM micelles assumed a stable core-shell structure in aqueous buffer at physiological pH with a low critical micelle concentration as determined by proton NMR and pyrene fluorescence spectroscopy. The hydrolysis of the ortho ester side-chain at physiological pH was minimal yet much accelerated at mildly acidic pHs. Doxorubicin (Dox) was successfully loaded into the micelles at pH 7.4 and was released at much higher rate in response to slight acidification to pH 5. Interestingly, the release of Dox at pH 5 followed apparently a biphasic profile, consisting of an initial fast phase of several hours followed by a sustained release period of several days. Dox loaded in the micelles was rapidly taken up by human glioma (T98G) cells in vitro, accumulating in the endolysosome and subsequently in the nucleus in a few hours, in contrast to the very low uptake of free drug at the same dose. The dose-dependent cytotoxicity of the Dox-loaded micelles was determined by the MTT assay and compared with that of the free Dox. While the empty micelles themselves were not toxic, the IC50 values of the Dox-loaded micelles were approximately ten-times (by 24 hours) and three-times (by 48 hours) lower than the free drug. The much enhanced potency in killing the multi-drug-resistant human glioma cells by Dox loaded in the micelles could be attributed to high intracellular drug concentration and the subsequent pH-triggered drug release. These

  5. Monoclonal anti-acid-labile subunit oligopeptide antibodies and their use in a two-site immunoassay for ALS measurement in humans.

    PubMed

    Stadler, S; Wu, Z; Dressendörfer, R A; Morrison, K M; Khare, A; Lee, P D; Strasburger, C J

    2001-06-01

    Quantification of the acid-labile subunit (ALS) has to date been restricted to immunoassays utilizing polyclonal antibodies. By immunization with N-terminal and C-terminal specific ALS oligopeptides, we generated monoclonal antibodies (mAbs) that target ALS-specific sequences outside the nonspecific leucine-rich repeats in the ALS molecule. For mAb selection, a special screening method was developed. Monoclonal antibody 5C9, which targets the N-terminus of ALS, is immobilized and the anti-ALS mAb 7H3, directed against the C-terminus, is biotinylated and used as tracer Ab. Due to the extreme pH-lability of ALS, changes in immunorecognition of ALS were investigated after acidification for protein unfolding in different pH ranges and in a time-dependent manner. It was determined that acidification of the serum samples to pH 2.7 for 30 min, followed by neutralization and dilution to 1:100 was the optimal acid-neutralization method. For standardization purposes, a serum pool derived from healthy volunteers was assigned the value 1 U/ml ALS. The sandwich assay has a working range with a linear dose-response curve in a log/log system between 0.005 and 10 U/ml. ALS levels in seven acromegalic patients ranged from 2.0 to 4.2 U/ml, and in 12 untreated growth hormone deficient patients from 0.036 to 0.986 U/ml (mean=0.45 U/ml). After 12 months of growth hormone therapy, ALS levels increased significantly to 1.18+/-0.45 U/ml (mean+/-SD; p<0.0006). The increase ranged from 0.48 to 1.4 U/ml. The change in ALS with growth hormone (GH) therapy correlated closer with the change in IGF-I (r=0.798, p=0.0057; Spearman rank correlation) than with the change in insulin-like growth factor binding protein (IGFBP3; r=0.549, p=0.057). This specific sandwich assay for the measurement of ALS provides a potentially valuable indicator of growth hormone secretory status. With this mAb-based immunofluorometric assay, the nonspecific detection of other proteins containing leucine-rich repeat

  6. Cytoplasmic Delivery of Liposomal Contents Mediated by an Acid-Labile Cholesterol-Vinyl Ether-PEG Conjugate

    PubMed Central

    Boomer, Jeremy A.; Qualls, Marquita M.; Inerowicz, H. Dorota; Haynes, Robert H.; Patri, G.V. Srilaksmi; Kim, Jong-Mok; Thompson, David H.

    2009-01-01

    An acid-cleavable PEG lipid, 1′-(4′-cholesteryloxy-3′-butenyl)-ω-methoxy-polyethylene[112] glycolate (CVEP), has been developed that produces stable liposomes when dispersed as a minor component (0.5–5 mol%) in 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE). Cleavage of CVEP at mildly acidic pH’s results in dePEGylation of the latently fusogenic DOPE liposomes, thereby triggering the onset of contents release. This paper describes the synthesis of CVEP via a six step sequence starting from the readily available precursors 1,4-butanediol, cholesterol, and mPEG acid. The hydrolysis rates and release kinetics from CVEP:DOPE liposome dispersions as a function of CVEP loading, as well as the cryogenic transmission electron microscopy and pH-dependent monolayer properties of 9:91 CVEP:DOPE mixtures, also are reported. When folate-receptor positive KB cells were exposed to calcein-loaded 5:95 CVEP:DOPE liposomes containing 0.1 mol% folate-modified 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-polyethylene[76] glycolamide (folate-PEG-DSPE), efficient delivery of the calcein cargo to the cytoplasm of the cells was observed as determined by fluorescence microscopy and flow cytometry. Fluorescence resonance energy transfer analysis of lipid mixing in these cells was consistent with membrane-membrane fusion between the liposome and endosomal membranes. PMID:19072698

  7. Labile aluminium chemistry downstream a limestone treated lake and an acid tributary: effects of warm winters and extreme rainstorms.

    PubMed

    Andersen, Dag O

    2006-08-01

    The outlet from the limestone treated Lake Terjevann consisted mainly of well-mixed lake water (mean pH 6.1) during the ice-free seasons including the unusually warm winters of 1992 and 1993. However, during the ice-covered period acidic water (mean pH 4.8, mean inorganic aluminium (Al(i)) about 160 microg/l) from the catchment draining under the lake ice dominated. A downstream tributary was generally acid and rich in aluminium (mean pH 4.6, Al(i) about 230 microg/l). After an extreme rainstorm loaded with sea-salts cation exchange in the soil resulted in more than a doubling of the Al(i) concentration (reaching about 500 microg/l). It took 3-4 months until the Al(i) concentration returned to pre-event levels. During the ice-covered period, the acidic outlet and tributary waters resulted in acidic conditions below the confluence (pH<4.8, Al(i) about 150 microg/l) while during the ice-free periods the more neutral outlet water resulted in higher pH and lower Al(i) concentrations (pH>5.2, Al(i) about 95 microg/l). However, during the latter climatic conditions the water was most probably more harmful to fish due to hydrolysing and polymerizing aluminium. After the sea-salt event, the increased Al(i) concentration in the tributary made the zone below the confluence potentially more toxic (pH approximately 5, Al(i) approximately 250 microg/l). Expected global warming resulting in winter mean temperatures above 0 degrees C may eliminate the seasonal acidification of the outlet from limestone-treated lakes creating permanent toxic mixing zones in the confluence below acidic aluminium-rich tributaries. Besides, more frequent rainstorms as a consequence of global warming may increase the frequency of sea-salt events and the Al(i) concentrations in the mixing zones. PMID:16269168

  8. Regulation of c-myc mRNA stability in vitro by a labile destabilizer with an essential nucleic acid component.

    PubMed Central

    Brewer, G; Ross, J

    1989-01-01

    The turnover rates of some mRNAs vary by an order of magnitude or more when cells change their growth pattern or differentiate. To identify regulatory factors that might be responsible for this variability, we investigated how cytosolic fractions affect mRNA decay in an in vitro system. A 130,000 X g supernatant (S130) from the cytosol of exponentially growing erythroleukemia cells contains a destabilizer that accelerates the decay of polysome-bound c-myc mRNA by eightfold or more compared with reactions lacking S130. The destabilizer is deficient in or absent from the S130 of cycloheximide-treated cells, indicating that it is labile or is repressed when translation is blocked. It is not a generic RNase, because it does not affect the turnover of delta-globin, gamma-globin, or histone mRNA and does not destabilize a major portion of polysomal polyadenylated mRNA. The destabilizer accelerates the turnover of the c-myc mRNA 3' region, as well as subsequent 3'-to-5' degradation of the mRNA body. It is inactivated in vitro by mild heating and by micrococcal nuclease, suggesting that it contains a nucleic acid component. c-myb mRNA is also destabilized in S130-supplemented in vitro reactions. These results imply that the stability of some mRNAs is regulated by cytosolic factors that are not associated with polysomes. Images PMID:2747642

  9. Application of nanoparticles for oral delivery of acid-labile lansoprazole in the treatment of gastric ulcer: in vitro and in vivo evaluations

    PubMed Central

    Alai, Milind; Lin, Wen Jen

    2015-01-01

    The aim of this study was to develop nanoparticles for oral delivery of an acid-labile drug, lansoprazole (LPZ), for gastric ulcer therapy. LPZ-loaded positively charged Eudragit® RS100 nanoparticles (ERSNPs-LPZ) and negatively charged poly(lactic-co-glycolic acid) nanoparticles (PLGANPs-LPZ) were prepared. The effect of charge on nanoparticle deposition in ulcerated and non-ulcerated regions of the stomach was investigated. The cellular uptake of nanoparticles in the intestine was evaluated in a Caco-2 cell model. The pharmacokinetic performance and ulcer healing response of LPZ-loaded nanoparticles following oral administration were evaluated in Wistar rats with induced ulcers. The prepared drug-loaded ERSNPs-LPZ and PLGANPs-LPZ possessed opposite surface charge (+38.5±0.3 mV versus −27.3±0.3 mV, respectively) and the particle size was around 200 nm with a narrow size distribution. The negatively charged PLGANPs adhered more readily to the ulcerated region (7.22%±1.21% per cm2), whereas the positively charged ERSNPs preferentially distributed in the non-ulcerated region (8.29%±0.35% per cm2). Both ERSNPs and PLGANPs were prominent uptake in Caco-2 cells, too. The nanoparticles sustained and prolonged LPZ concentrations up to 24 hours, and the half-life and mean residence time of LPZ were prolonged by 3.5-fold and 4.5-fold, respectively, as compared with LPZ solution. Oral administration of LPZ-loaded nanoparticles healed 92.6%–95.7% of gastric ulcers in Wistar rats within 7 days. PMID:26124659

  10. Export of pre-aged, labile DOM from a central California coastal upwelling system: Insights from D/L amino acids and Δ14C signatures

    NASA Astrophysics Data System (ADS)

    Walker, B. D.; Shen, Y.; Benner, R. H.; Druffel, E. R. M.

    2014-12-01

    Coastal upwelling zones are among the most productive regions in the world and play a major role in global carbon and nitrogen cycles. Recent research suggests that a substantial fraction of newly fixed organic matter is exported offshore in the form of dissolved organic matter (DOM). However, to date only a few studies have examined DOM composition in the context of production and export from upwelling systems. The ultimate fate and geochemical impact of coastal DOM exported to offshore and mesopelagic ecosystems also remains largely unknown. Between 2007-2009 we conducted a high-resolution biogeochemical time series at the Granite Canyon Marine Pollution Studies Lab in part to evaluate the seasonal production and export of DOM from the Central CA coast. Our previous work demonstrated substantial, albeit disparate, seasonal production of dissolved organic carbon and nitrogen (DOC, DON) - with high DON (and low C:N ratios) produced during upwelling and high DOC produced during summer/fall water column stratification (Walker and McCarthy, 2012). Here we present new total dissolved D/L amino acid (TDAA) and UV-oxidizable DOC radiocarbon (Δ14C) data with the goal of determining the relative sources (heterotrophic vs. autotrophic), bioavailability, microbial processing and 14C-ages of C-rich vs. N-rich DOM exported from this upwelling system. Our results suggest that C-rich DOM produced during water column stratification carries a large microbial signature (i.e. high D/L AA ratios and non-protein AA abundance), whereas N-rich DOM produced during upwelling appears to be fresh, autotrophic DOM (i.e. lowest D/L AA ratios and highest TDAA abundance). DOM Δ14C signatures also did not approximate in situ dissolved inorganic carbon (DIC), and instead were far more negative and highly correlated to water mass density. Together our results indicate a previously unrecognized source of highly labile yet pre-aged DOM potentially impacting offshore and mesopelagic ecosystems.

  11. Isolation of Labile Pseudohalogen NSO Species.

    PubMed

    Labbow, René; Michalik, Dirk; Reiß, Fabian; Schulz, Axel; Villinger, Alexander

    2016-06-27

    A new synthetic approach enabled the generation of highly labile thionylimide, H-NSO, which was trapped by adduct formation with the bulky Lewis acid B(C6 F5 )3 and fully characterized. For comparison, a series of different Me3 Si-NSO Lewis acid adducts were studied. Treatment of Me3 Si-NSO with the silylium ion [Me3 Si](+) led to the formation of the hitherto unknown iminosulfonium ion [Me3 Si-N=S-O-SiMe3 ](+) , which could be isolated and fully characterized as a salt in the presence of weakly coordinating carborate anions. PMID:27072533

  12. Dissolved organic carbon lability increases with water residence time in the alluvial aquifer of a river floodplain ecosystem

    NASA Astrophysics Data System (ADS)

    Helton, Ashley M.; Wright, Meredith S.; Bernhardt, Emily S.; Poole, Geoffrey C.; Cory, Rose M.; Stanford, Jack A.

    2015-04-01

    We assessed spatial and temporal patterns of dissolved organic carbon (DOC) lability and composition throughout the alluvial aquifer of the 16 km2 Nyack Floodplain in northwest Montana, USA. Water influx to the aquifer derives almost exclusively from the Middle Fork of the Flathead River, and water residence times within the aquifer range from days to months. Across seasons and channel discharge conditions, we measured DOC concentration, lability, and optical properties of aquifer water sampled from 12 wells, both near and ~3 m below the water table. Concentrations of DOC were typically low (542 ± 22.7 µg L-1; mean ± se), and the percentage of labile DOC averaged 18 ± 12% during 3 day laboratory assays. Parallel factor analysis of fluorescence excitation-emission matrices revealed two humic-like and two amino acid-like fluorescence groups. Total DOC, humic-like components, and specific UV absorbance decreased with water residence time, consistent with sorption to aquifer sediments. However, labile DOC (both concentration and fraction) increased with water residence time, suggesting a concurrent influx or production of labile DOC. Thus, although the carbon-poor, oxygen-rich aquifer is a net sink for DOC, recalcitrant DOC appears to be replaced with more labile DOC along aquifer flow paths. Our observation of DOC production in long flow paths contrasts with studies of hyporheic DOC consumption along short (centimeters to meters) flow paths and highlights the importance of understanding the role of labile organic matter production and/or influx in alluvial aquifer carbon cycling.

  13. Two groups challenge US acid rain efforts

    SciTech Connect

    Not Available

    1987-11-01

    In its report, Acid Rain Invades Our National Parks, the National Parks and Conservation Association (NPCA) says acid rain is being detected at all 27 national park monitoring sites. In 1980, 87 national parks expressed concern in a NPCA survey over acid rain. Repolled in 1986, more than half of the respondents reported that no research on acid rain was under way. The NPCA report concludes that the alarm that was sounded in 1980 fell largely on deaf ears, and calls for the structural and scientific reorganization of the National Park Service. The National Audubon Society shares NPCA's dissatisfaction with federal efforts to tackle the problem of acid rain and has taken testing into its own hands. Through its Citizens Acid Rain Monitoring Network, Audubon volunteers have collected readings of acidity at 64 monitoring stations in 31 states since July.

  14. 6-Bromo-7-hydroxy-3-methylcoumarin (mBhc) is an efficient multi-photon labile protecting group for thiol caging and three-dimensional chemical patterning.

    PubMed

    Mahmoodi, M Mohsen; Fisher, Stephanie A; Tam, Roger Y; Goff, Philip C; Anderson, Reid B; Wissinger, Jane E; Blank, David A; Shoichet, Molly S; Distefano, Mark D

    2016-09-21

    The photochemical release of chemical reagents and bioactive molecules provides a useful tool for spatio-temporal control of biological processes. However, achieving this goal requires the development of highly efficient one- and two-photon sensitive photo-cleavable protecting groups. Thiol-containing compounds play critical roles in biological systems and bioengineering applications. While potentially useful for sulfhydryl protection, the 6-bromo-7-hydroxy coumarin-4-ylmethyl (Bhc) group can undergo an undesired photoisomerization reaction upon irradiation that limits its uncaging efficiency. To address this issue, here we describe the development of 6-bromo-7-hydroxy-3-methylcoumarin-4-ylmethyl (mBhc) as an improved group for thiol-protection. One- and two-photon photolysis reactions demonstrate that a peptide containing a mBhc-caged thiol undergoes clean and efficient photo-cleavage upon irradiation without detectable photoisomer production. To test its utility for biological studies, a K-Ras-derived peptide containing an mBhc-protected thiol was prepared by solid phase peptide synthesis using Fmoc-Cys(mBhc)-OH for the introduction of the caged thiol. Irradiation of that peptide using either UV or near IR light in presence of protein farnesyltransferase (PFTase), resulted in generation of the free peptide which was then recognized by the enzyme and became farnesylated. To show the utility of this caging group in biomaterial applications, we covalently modified hydrogels with mBhc-protected cysteamine. Using multi-photon confocal microscopy, highly defined volumes of free thiols were generated inside the hydrogels and visualized via reaction with a sulfhydryl-reactive fluorophore. The simple synthesis of mBhc and its efficient removal by one- and two-photon processes make it an attractive protecting group for thiol caging in a variety of applications. PMID:27529405

  15. Combined use of UV-labile calcium chelators and calcium-sensitive dyes in a microscope with two light sources influencing different regions in a group of coordinated contracting cardiac myocytes

    NASA Astrophysics Data System (ADS)

    Pilarczyk, Goetz; Greulich, Karl-Otto

    1997-12-01

    The coordination of excitation in a biological system of cells such as cardiac myocytes in heart tissue has crucial influence on the function of the entire organ. This coordinated behavior can be visualized in a small group of embryonic cardiac myocytes derived from the hearts of unborn chicken. Loaded with a calcium sensitive dye the excitation can be imaged via the occurring transient rise in cytosolic calcium concentration. It can be shown that in regions with physiological or morphological restrictions the transient rise in cytosolic calcium occurs with a temporal delay compared to the ordinary array of coupled myocytes. The height of the transient rise of cytosolic calcium is related to the ability of the individual cell to participate in the coordinated contraction. The free cytosolic calcium concentration is decreased with the UV-labile calcium, chelator diazo-2. Our setup allows to decrease the free cytosolic calcium in a single cell of the contracting array of cells. This allows us to introduce mismatches in selected regions of the coordinated contraction and to visualize the effects simultaneously.

  16. Emotional lability and affective synchrony in borderline personality disorder.

    PubMed

    Schoenleber, Michelle; Berghoff, Christopher R; Tull, Matthew T; DiLillo, David; Messman-Moore, Terri; Gratz, Kim L

    2016-07-01

    Extant research on emotional lability in borderline personality disorder (BPD) has focused almost exclusively on lability of individual emotions or emotion types, with limited research considering how different types of emotions shift together over time. Thus, this study examined the temporal dynamics of emotion in BPD at the level of both individual emotions (i.e., self-conscious emotions [SCE], anger, and anxiety) and mixed emotions (i.e., synchrony between emotions). One hundred forty-four women from the community completed a diagnostic interview and laboratory study involving 5 emotion induction tasks (each of which was preceded and followed by a 5-min resting period or neutral task). State ratings of SCE, anger, and anxiety were provided at 14 time points (before and after each laboratory task and resting period). Hierarchical linear modeling results indicate that women with BPD reported greater mean levels of SCE and Anxiety (but not Anger), and greater lability of Anxiety. Women with BPD also exhibited greater variability in lability of all 3 emotions (suggestive of within-group differences in the relevance of lability to BPD). Results also revealed synchrony (i.e., positive relations) between each possible pair of emotions, regardless of BPD status. Follow-up regression analyses suggest the importance of accounting for lability when examining the role of synchrony in BPD, as the relation of SCE-Anger synchrony to BPD symptom severity was moderated by Anger and SCE lability. Specifically, synchronous changes in SCE and Anger were associated with greater BPD symptom severity when large shifts in SCE were paired with minor shifts in Anger. (PsycINFO Database Record PMID:27362623

  17. Acid-labile sulfides in shallow marine bottom sediments: A review of the impact on ecosystems in the Azov Sea, the NE Black Sea shelf and NW Adriatic lagoons

    NASA Astrophysics Data System (ADS)

    Sorokin, Yu. I.; Zakuskina, O. Yu

    2012-02-01

    Acid-labile sulfides (LS) increase in bottom sediments at sites in the Azov Sea, at the NE Black Sea shelf and in the coastal lagoons of NW Adriatic Sea experiencing direct impacts of anthropogenic pollution. Fresh anthropogenic organic matter stimulates the bacterial sulfate reduction and here the rate of the LS production overcomes their loss during the oxidation and pyritization. This results in the expansion of reduced sediment layer up to the bottom surface. The LS concentration in the reduced sediments varies between 300 and 2000 mg S l -1 of wet silt depending on the size of pollution loading and on the rate of sedimentation. In the oxidized sediments away from the direct pollution impact, the LS concentration did not exceed 100-150 mg S l -1. Being a strong cytochrome toxin, the LS adversely affect the coastal ecosystems. The concentrations over 600 mg S l -1 result in quasi total benthic mortality whereas >300-400 mg S l -1 depletes the benthic faunal abundance and taxonomic diversity. Accumulation of the LS in sediments also induces nocturnal hypoxia and stimulates domination of toxic cyanobacteria in the pelagic phytocenoses.

  18. pH-sensitive micelles based on acid-labile pluronic F68-curcumin conjugates for improved tumor intracellular drug delivery.

    PubMed

    Fang, Xiao-Bin; Zhang, Jin-Ming; Xie, Xi; Liu, Di; He, Cheng-Wei; Wan, Jian-Bo; Chen, Mei-Wan

    2016-04-11

    Curcumin (Cur) is a highly pleiotropic anticancer agent that inhibits cell proliferation and induces apoptosis in cancer cells. A variety of nano-systems constituted by polymer-drug conjugates have been designed to overcome its shortages on water solubility, chemical instability, and poor bioavailability. However, most of them suffer from ineffective release of Cur in cancer cells in vivo. This work developed a novel flexible acid-responsive micelle formulation by covalently conjugating Cur on the hydrophilic terminals of pluronic F68 chains via cis-aconitic anhydride linkers. The synthesized F68-Cis-Cur conjugates can readily precipitate to form homogeneous micelles with average size about 100nm in aqueous solution. In acid environments, F68-Cis-Cur conjugates would break down and subsequently release Cur rapidly, for the reason of pH-sensitive cleavage of cis-aconitic anhydride linkers. In vitro anticancer activity tests demonstrated that F68-Cis-Cur micelles induced higher cytotoxicity against both A2780 and SMMC 7721 cells than free Cur. It provided a larger decrease of mitochondrion membrane potential and induced cellular apoptosis. F68-Cis-Cur micelles remarkably increased cellular uptake of Cur than free Cur through caveolae-mediated endocytosis in an energy-dependent manner. This study demonstrates F68-Cis-Cur conjugation as a promising tool for improving intracellular drug delivery in cancer therapy. PMID:26784981

  19. Disruption of HLA class II antigen presentation in Burkitt lymphoma: implication of a 47 000 MW acid labile protein in CD4+ T-cell recognition

    PubMed Central

    God, Jason M; Zhao, Dan; Cameron, Christine A; Amria, Shereen; Bethard, Jennifer R; Haque, Azizul

    2014-01-01

    While Burkitt lymphoma (BL) has a well-known defect in HLA class I-mediated antigen presentation, the exact role of BL-associated HLA class II in generating a poor CD4+ T-cell response remains unresolved. Here, we found that BL cells are deficient in their ability to optimally stimulate CD4+ T cells via the HLA class II pathway. This defect in CD4+ T-cell recognition was not associated with low levels of co-stimulatory molecules on BL cells, as addition of external co-stimulation failed to elicit CD4+ T-cell activation by BL. Further, the defect was not caused by faulty antigen/class II interaction, because antigenic peptides bound with measurable affinity to BL-associated class II molecules. Interestingly, functional class II–peptide complexes were formed at acidic pH 5·5, which restored immune recognition. Acidic buffer (pH 5·5) eluate from BL cells contained molecules that impaired class II-mediated antigen presentation and CD4+ T-cell recognition. Biochemical analysis showed that these molecules were greater than 30 000 molecular weight in size, and proteinaceous in nature. In addition, BL was found to have decreased expression of a 47 000 molecular weight enolase-like molecule that enhances class II-mediated antigen presentation in B cells, macrophages and dendritic cells, but not in BL cells. These findings demonstrate that BL likely has multiple defects in HLA class II-mediated antigen presentation and immune recognition, which may be exploited for future immunotherapies. PMID:24628049

  20. Comparing Amino Acid Abundances and Distributions Across Carbonaceous Chondrite Groups

    NASA Technical Reports Server (NTRS)

    Burton, Aaron S.; Callahan, Michael P.; Glavin, Daniel P.; Elsila, Jamie E.; Dworkin, Jason P.

    2012-01-01

    Meteorites are grouped according to bulk properties such as chemical composition and mineralogy. These parameters can vary significantly among the different carbonaceous chondrite groups (CI, CM, CO, CR, CH, CB, CV and CK). We have determined the amino acid abundances of more than 30 primary amino acids in meteorites from each of the eight groups, revealing several interesting trends. There are noticeable differences in the structural diversity and overall abundances of amino acids between meteorites from the different chondrite groups. Because meteorites may have been an important source of amino acids to the prebiotic Earth and these organic compounds are essential for life as we know it, the observed variations of these molecules may have been important for the origins of life.

  1. Benzylidene Acetal Protecting Group as Carboxylic Acid Surrogate: Synthesis of Functionalized Uronic Acids and Sugar Amino Acids.

    PubMed

    Banerjee, Amit; Senthilkumar, Soundararasu; Baskaran, Sundarababu

    2016-01-18

    Direct oxidation of the 4,6-O-benzylidene acetal protecting group to C-6 carboxylic acid has been developed that provides an easy access to a wide range of biologically important and synthetically challenging uronic acid and sugar amino acid derivatives in good yields. The RuCl3 -NaIO4 -mediated oxidative cleavage method eliminates protection and deprotection steps and the reaction takes place under mild conditions. The dual role of the benzylidene acetal, as a protecting group and source of carboxylic acid, was exploited in the efficient synthesis of six-carbon sialic acid analogues and disaccharides bearing uronic acids, including glycosaminoglycan analogues. PMID:26572799

  2. Prevalence and predictors of affective lability after pediatric traumatic brain injury

    PubMed Central

    Vasa, Roma A.; Suskauer, Stacy J.; Thorn, Julia M.; Kalb, Luther; Grados, Marco A.; Slomine, Beth S.; Salorio, Cynthia F.; Gerring, Joan P.

    2016-01-01

    Objective Paediatric severe traumatic brain injury (TBI) is associated with significant postinjury affective and behavioral problems. Few studies have examined the prevalence and characteristics of affective lability after paediatric TBI. Methods 97 children with severe TBI were evaluated one year postinjury for the presence of affective lability using the Children’s Affective Lability Scale (CALS). Demographic, clinical, and brain lesion characteristics were also assessed. Results Affective lability significantly increased after injury. Eighty-six children had a preinjury CALS score of 1SD or less from the group preinjury mean (M = 8.11, SD = 9.31) of which 35 and 15 children had a 1SD and 2SD increase in their CALS score from pre- to postinjury, respectively. A variety of affective shifts manifested postinjury including anxiety, silliness, dysphoria, and irritability. The most severe symptoms were irritability and unpredictable temper outbursts. Risk factors for affective lability included elevated preinjury affective lability and psychosocial adversity as well as greater damage to the orbitofrontal cortex. Postinjury affective lability was most frequently associated with a postinjury diagnosis of attention-deficit hyperactivity disorder. Conclusions Affective lability is common after paediatric TBI and frequently manifests as irritability and unpredictable outbursts. Early intervention is needed to improve psychiatric outcomes. PMID:25950263

  3. Trimesic acid dimethyl sulfoxide solvate: space group revision

    PubMed Central

    Bernès, Sylvain; Hernández, Guadalupe; Portillo, Roberto; Gutiérrez, René

    2008-01-01

    The structure of the title solvate, C9H6O6·C2H6OS, was determined 30 years ago [Herbstein, Kapon & Wasserman (1978 ▶). Acta Cryst. B34, 1613–1617], with data collected at room temperature, and refined in the space group P21. The present redetermination, based on high-resolution diffraction data, shows that the actual space group is more likely to be P21/m. The crystal structure contains layers of trimesic acid molecules lying on mirror planes. A mirror plane also passes through the S and O atoms of the solvent molecule. The molecules in each layer are inter­connected through strong O—H⋯O hydrogen bonds, forming a two-dimensional supra­molecular network within each layer. The donor groups are the hydroxyls of the trimesic acid mol­ecules, while the acceptors are the carbonyl or the sulfoxide O atoms. PMID:21202984

  4. Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 1. Minor structures

    USGS Publications Warehouse

    Leenheer, J.A.; Wershaw, R. L.; Reddy, M.M.

    1995-01-01

    An investigation of the strong-acid characteristics (pKa 3.0 or less) of fulvic acid from the Suwannee River, Georgia, was conducted. Quantitative determinations were made for amino acid and sulfur-containing acid structures, oxalate half-ester structures, malonic acid structures, keto acid structures, and aromatic carboxyl-group structures. These determinations were made by using a variety of spectrometric (13C-nuclear magnetic resonance, infrared, and ultraviolet spectrometry) and titrimetric characterizations on fulvic acid or fulvic acid samples that were chemically derivatized to indicate certain functional groups. Only keto acid and aromatic carboxyl-group structures contributed significantly to the strong-acid characteristics of the fulvic acid; these structures accounted for 43% of the strong-acid acidity. The remaining 57% of the strong acids are aliphatic carboxyl groups in unusual and/or complex configurations for which limited model compound data are available.

  5. Comparison of Outcomes in Patients With Nonobstructive, Labile-Obstructive, and Chronically Obstructive Hypertrophic Cardiomyopathy.

    PubMed

    Pozios, Iraklis; Corona-Villalobos, Celia; Sorensen, Lars L; Bravo, Paco E; Canepa, Marco; Pisanello, Chiara; Pinheiro, Aurelio; Dimaano, Veronica L; Luo, Hongchang; Dardari, Zeina; Zhou, Xun; Kamel, Ihab; Zimmerman, Stefan L; Bluemke, David A; Abraham, M Roselle; Abraham, Theodore P

    2015-09-15

    Patients with nonobstructive hypertrophic cardiomyopathy (HC) are considered low risk, generally not requiring aggressive intervention. However, nonobstructive and labile-obstructive HC have been traditionally classified together, and it is unknown if these 2 subgroups have distinct risk profiles. We compared cardiovascular outcomes in 293 patients HC (96 nonobstructive, 114 labile-obstructive, and 83 obstructive) referred for exercise echocardiography and magnetic resonance imaging and followed for 3.3 ± 3.6 years. A subgroup (34 nonobstructive, 28 labile-obstructive, 21 obstructive) underwent positron emission tomography. The mean number of sudden cardiac death risk factors was similar among groups (nonobstructive: 1.4 vs labile-obstructive: 1.2 vs obstructive: 1.4 risk factors, p = 0.2). Prevalence of late gadolinium enhancement (LGE) was similar across groups but more non-obstructive patients had late gadolinium enhancement ≥20% of myocardial mass (23 [30%] vs 19 [18%] labile-obstructive and 8 [11%] obstructive, p = 0.01]. Fewer labile-obstructive patients had regional positron emission tomography perfusion abnormalities (12 [46%] vs nonobstructive 30 [81%] and obstructive 17 [85%], p = 0.003]. During follow-up, 60 events were recorded (36 ventricular tachycardia/ventricular fibrillation, including 30 defibrillator discharges, 12 heart failure worsening, and 2 deaths). Nonobstructive patients were at greater risk of VT/VF at follow-up, compared to labile obstructive (hazed ratio 0.18, 95% confidence interval 0.04 to 0.84, p = 0.03) and the risk persisted after adjusting for age, gender, syncope, family history of sudden cardiac death, abnormal blood pressure response, and septum ≥3 cm (p = 0.04). Appropriate defibrillator discharges were more frequent in nonobstructive (8 [18%]) compared to labile-obstructive (0 [0%], p = 0.02) patients. In conclusion, nonobstructive hemodynamics is associated with more pronounced fibrosis and ischemia than labile

  6. Cystic fibrosis, atopy, and airways lability.

    PubMed Central

    Silverman, M; Hobbs, F D; Gordon, I R; Carswell, F

    1978-01-01

    In a survey of cystic fibrosis (CF) in the Avon area, 48 children with CF from 40 families together with 71 of their parents were studied by spirometry, exercise tests, and pinch tests. A control group of 42 young adults was similarly tested; control data for children were taken from previously published work. The prevalence of atopy (any positive prick test) in children with CF was 48%. Sensitivity to grass pollens and house dust mite was no more common in these children (29%) than in a normal population (34%). Hypersensitivity to Aspergillus fumigatus was found in 35% of children with CF and was associated with severe lung disease. The parents had a normal pattern and prevalence of atopy. Exercise-induced airways obstruction was present in only 22% of children with CF; its association with severe lung disease rendered interpretation difficult. The parents had a normal response to exercise. Both hypersensitivity to A. fumigatus and exercise-induced airways lability had the features of acquired characteristics. There was nothing in the present study to support the hypothesis that the possession of a CF gene predisposed to atopy. PMID:365112

  7. Photo-lability of deep ocean dissolved black carbon

    NASA Astrophysics Data System (ADS)

    Stubbins, A.; Niggemann, J.; Dittmar, T.

    2012-01-01

    Dissolved black carbon (DBC), defined here as condensed aromatics isolated from seawater via PPL solid phase extraction and quantified as benzene polycarboxylic acid oxidation products, is a significant component of the oceanic dissolved organic carbon (DOC) pool. These condensed aromatics are widely distributed in the open ocean and appear to be tens of thousands of years old. As such DBC is regarded as highly refractory. In the current study, the photo-lability of DBC, DOC and coloured dissolved organic matter (CDOM; ultraviolet-visible absorbance) were determined over the course of a 28 d irradiation of North Atlantic Deep Water under a solar simulator. During the irradiation DBC fell from 1044 ± 164 nM C to 55 ± 15 nM C, a 20-fold decrease in concentration. Dissolved black carbon photo-degradation was more rapid and more extensive than for bulk CDOM and DOC. Further, the photo-lability of components of the DBC pool increased with their degree of aromatic condensation. These trends indicate that a continuum of compounds of varying photo-lability exists within the marine DOC pool. In this continuum, photo-lability scales with aromatic character, specifically the degree of condensation. Scaling the rapid photo-degradation of DBC to rates of DOC photo-mineralisation for the global ocean leads to an estimated photo-chemical half-life for oceanic DBC of less than 800 yr. This is more than an order of magnitude shorter than the apparent age of DBC in the ocean. Photo-degradation is therefore posited as the primary sink for oceanic DBC and the survival of DBC molecules in the oceans for millennia appears to be facilitated not by their inherent inertness but by the rate at which they are cycled through the surface ocean's photic zone.

  8. Gas phase acidity measurement of local acidic groups in multifunctional species: controlling the binding sites in hydroxycinnamic acids.

    PubMed

    Guerrero, Andres; Baer, Tomas; Chana, Antonio; González, Javier; Dávalos, Juan Z

    2013-07-01

    The applicability of the extended kinetic method (EKM) to determine the gas phase acidities (GA) of different deprotonable groups within the same molecule was tested by measuring the acidities of cinnamic, coumaric, and caffeic acids. These molecules differ not only in the number of acidic groups but in their nature, intramolecular distances, and calculated GAs. In order to determine independently the GA of groups within the same molecule using the EKM, it is necessary to selectively prepare pure forms of the hydrogen-bound heterodimer. In this work, the selectivity was achieved by the use of solvents of different vapor pressure (water and acetonitrile), as well as by variation of the drying temperature in the ESI source, which affected the production of heterodimers with different solvation energies and gas-phase dissociation energies. A particularly surprising finding is that the calculated solvation enthalpies of water and the aprotic acetonitrile are essentially identical, and that the different gas-phase products generated are apparently the result of their different vapor pressures, which affects the drying mechanism. This approach for the selective preparation of heterodimers, which is based on the energetics, appears to be quite general and should prove useful for other studies that require the selective production of heterodimers in ESI sources. The experimental results were supported by density functional theory (DFT) calculations of both gas-phase and solvated species. The experimental thermochemical parameters (deprotonation ΔG, ΔH, and ΔS) are in good agreement with the calculated values for the monofunctional cinnamic acid, as well as the multifunctional coumaric and caffeic acids. The measured GA for cinnamic acid is 334.5 ± 2.0 kcal/mol. The measured acidities for the COOH and OH groups of coumaric and caffeic acids are 332.7 ± 2.0, 318.7 ± 2.1, 332.2 ± 2.0, and 317.3 ± 2.2 kcal/mol, respectively. PMID:23799241

  9. ABO blood group glycans modulate sialic acid recognition on erythrocytes

    PubMed Central

    Cohen, Miriam; Hurtado-Ziola, Nancy

    2009-01-01

    ABH(O) blood group polymorphisms are based on well-known intraspecies variations in structures of neutral blood cell surface glycans in humans and other primates. Whereas natural antibodies against these glycans can act as barriers to blood transfusion and transplantation, the normal functions of this long-standing evolutionary polymorphism remain largely unknown. Although microbial interactions have been suggested as a selective force, direct binding of lethal pathogens to ABH antigens has not been reported. We show in this study that ABH antigens found on human erythrocytes modulate the specific interactions of 3 sialic acid-recognizing proteins (human Siglec-2, 1918SC influenza hemagglutinin, and Sambucus nigra agglutinin) with sialylated glycans on the same cell surface. Using specific glycosidases that convert A and B glycans to the underlying H(O) structure, we show ABH antigens stabilize sialylated glycan clusters on erythrocyte membranes uniquely for each blood type, generating differential interactions of the 3 sialic acid-binding proteins with erythrocytes from each blood type. We further show that by stabilizing such structures ABH antigens can also modulate sialic acid-mediated interaction of pathogens such as Plasmodium falciparum malarial parasite. Thus, ABH antigens can noncovalently alter the presentation of other cell surface glycans to cognate-binding proteins, without themselves being a direct ligand. PMID:19704115

  10. Maternal emotion socialization differentially predicts third-grade children's emotion regulation and lability.

    PubMed

    Rogers, Megan L; Halberstadt, Amy G; Castro, Vanessa L; MacCormack, Jennifer K; Garrett-Peters, Patricia

    2016-03-01

    Numerous parental emotion socialization factors have been implicated as direct and indirect contributors to the development of children's emotional competence. To date, however, no study has combined parents' emotion-related beliefs, behaviors, and regulation strategies in one model to assess their cumulative-as well as unique-contributions to children's emotion regulation. We considered the 2 components that have recently been distinguished: emotion regulation and emotional lability. We predicted that mothers' beliefs about the value of and contempt for children's emotions, mothers' supportive and nonsupportive reactions to their children's emotions, as well as mothers' use of cognitive reappraisal and suppression of their own emotions would each contribute unique variance to their children's emotion regulation and lability, as assessed by children's teachers. The study sample consisted of an ethnically and socioeconomically diverse group of 165 mothers and their third-grade children. Different patterns emerged for regulation and lability: Controlling for family income, child gender, and ethnicity, only mothers' lack of suppression as a regulatory strategy predicted greater emotion regulation in children, whereas mothers' valuing of children's emotions, mothers' lack of contempt for children's emotions, mothers' use of cognitive reappraisal to reinterpret events, and mothers' lack of emotional suppression predicted less lability in children. These findings support the divergence of emotion regulation and lability as constructs and indicate that, during middle childhood, children's lability may be substantially and uniquely affected by multiple forms of parental socialization. PMID:26641269

  11. Strong-acid, carboxyl-group structures in fulvic acid from the Suwannee River, Georgia. 2. Major structures

    USGS Publications Warehouse

    Leenheer, J.A.; Wershaw, R. L.; Reddy, M.M.

    1995-01-01

    Polycarboxylic acid structures that account for the strong-acid characteristics (pKa1 near 2.0) were examined for fulvic acid from the Suwannee River. Studies of model compounds demonstrated that pKa values near 2.0 occur only if the ??-ether or ??-ester groups were in cyclic structures with two to three additional electronegative functional groups (carboxyl, ester, ketone, aromatic groups) at adjacent positions on the ring. Ester linkage removal by alkaline hydrolysis and destruction of ether linkages through cleavage and reduction with hydriodic acid confirmed that the strong carboxyl acidity in fulvic acid was associated with polycarboxylic ??-ether and ??-ester structures. Studies of hypothetical structural models of fulvic acid indicated possible relation of these polycarboxylic structures with the amphiphilic and metal-binding properties of fulvic acid.

  12. Photo-lability of deep ocean dissolved black carbon

    NASA Astrophysics Data System (ADS)

    Stubbins, A.; Niggemann, J.; Dittmar, T.

    2012-05-01

    Dissolved black carbon (DBC), defined here as condensed aromatics isolated from seawater via PPL solid phase extraction and quantified as benzenepolycarboxylic acid (BPCA) oxidation products, is a significant component of the oceanic dissolved organic carbon (DOC) pool. These condensed aromatics are widely distributed in the open ocean and appear to be tens of thousands of years old. As such DBC is regarded as highly refractory. In the current study, the photo-lability of DBC, DOC and coloured dissolved organic matter (CDOM; ultraviolet-visible absorbance) were determined over the course of a 28 day irradiation of North Atlantic Deep Water under a solar simulator. During the irradiation DBC fell from 1044 ± 164 nM-C to 55 ± 15 nM-C, a 20-fold decrease in concentration. Dissolved black carbon photo-degradation was more rapid and more extensive than for bulk CDOM and DOC. The concentration of DBC correlated with CDOM absorbance and the quality of DBC indicated by the ratios of different BPCAs correlated with CDOM absorbance spectral slope, suggesting the optical properties of CDOM may provide a proxy for both DBC concentrations and quality in natural waters. Further, the photo-lability of components of the DBC pool increased with their degree of aromatic condensation. These trends indicate that a continuum of compounds of varying photo-lability exists within the marine DOC pool. In this continuum, photo-lability scales with aromatic character, specifically the degree of condensation. Scaling the rapid photo-degradation of DBC to rates of DOC photo-mineralisation for the global ocean leads to an estimated photo-chemical half-life for oceanic DBC of less than 800 years. This is more than an order of magnitude shorter than the apparent age of DBC in the ocean. Consequently, photo-degradation is posited as the primary sink for oceanic DBC and the apparent survival of DBC molecules in the oceans for millennia appears to be facilitated not by their inherent inertness but

  13. Atmospheric deposition of metallic pollutants over the Ligurian Sea: labile and residual inputs.

    PubMed

    Sandroni, Valérie; Migon, Christophe

    2002-05-01

    Atmospheric fluxes of six trace metals (Cd, Cr, Cu, Ni, Pb and Zn) with Al as a crustal reference were measured at Cap Ferrat (French Riviera) between February 1997 and July 1998. An original sampling protocol enabled the separation of labile (seawater at pH 2) and residual fractions in the total atmospheric input. Median acid-labile fractions were 91%, 69%, 83%, 84%, 97% and 98% of the total for Cd, Cr, Cu, Ni, Pb and Zn, respectively. Under the conditions used, lability of individual metals is related to the anthropogenic component of the samples. Enrichment factors and anthropogenic fraction are estimated for each metal. Some interannual changes are investigated (Pb, Zn). The observed increase of Zn inputs may be linked to local input from the Nice district waste plant (commissioned in 1988), 6.5 km away. PMID:12079071

  14. Harnessing Labile Bonds between Nanogels Particles to Create Self-Healing Materials

    NASA Astrophysics Data System (ADS)

    Kolmakov, German; Matyjaszewski, Krzysztof; Balazs, Anna

    2009-03-01

    Using computational modeling, we demonstrate the self-healing behavior of novel materials composed of nanoscopic gel particles that are interconnected into a macroscopic network by both stable and labile bonds. Under mechanical stress, the labile bonds between the nanogels can break and readily reform with reactive groups on neighboring units. This breaking and reforming allows the units in the network to undergo a structural rearrangement that preserves the mechanical integrity of the sample. The stable bonds between the nanogels play an essential role by forming a backbone that provides a mechanical strength to the material. The simulations show that just a relatively small fraction of such labile bonds (roughly 15%) are needed to prevent the catastrophic failure of the sample. The findings provide guidelines for creating high-strength, self-healing materials.

  15. Chemical leaching methods and measurements of marine labile particulate Fe

    NASA Astrophysics Data System (ADS)

    Revels, B. N.; John, S.

    2012-12-01

    Iron (Fe) is an essential nutrient for life. Yet its low solubility and concentration in the ocean limits marine phytoplankton productivity in many regions of the world. Dissolved phase Fe (<0.4μm) has traditionally been considered the most biologically accessible form, however, the particulate phase (>0.4μm) may contain an important, labile reservoir of Fe that may also be available to phytoplankton. However, concentration data alone cannot elucidate the sources of particulate Fe to the ocean and to what extent particulate iron may support phytoplankton growth. Isotopic analysis of natural particles may help to elucidate the biogeochemical cycling of Fe, though it is important to find a leaching method which accesses bioavailable Fe. Thirty-three different chemical leaches were performed on a marine sediment reference material, MESS-3. The combinations included four different acids (25% acetic acid, 0.01M HCl, 0.5M HCl, 0.1M H2SO4 at pH2), various redox conditions (0.02M hydroxylamine hydrochloride or 0.02M H2O2), three temperatures (25°C, 60°C, 90°C), and three time points (10 minutes, 2 hours, 24 hours). Leached Fe concentrations varied from 1mg/g to 35mg/g, with longer treatment times, stronger acids, and hotter temperatures generally associated with an increase in leached Fe. δ56Fe in these leaches varied from -1.0‰ to +0.2‰. Interestingly, regardless of leaching method used, there was a very similar relationship between the amount of Fe leached from the particles and the δ56Fe of this iron. Isotopically lighter δ56Fe values were associated with smaller amounts of leached Fe whereas isotopically heavier δ56Fe values were associated with larger amounts of leached Fe. Two alternate hypotheses could explain these data. Either, the particles may contain pools of isotopically light Fe that are easily accessed early in dissolution, or isotopically light Fe may be preferentially leached from the particle due to a kinetic isotope effect during dissolution

  16. Characterization and diagenesis of strong-acid carboxyl groups in humic substances

    USGS Publications Warehouse

    Leenheer, J.A.; Wershaw, R. L.; Brown, G.K.; Reddy, M.M.

    2003-01-01

    A small fraction of carboxylic acid functional groups in humic substances are exceptionally acidic with pKa values as low as 0.5. A review of acid-group theory eliminated most models and explanations for these exceptionally acidic carboxyl groups. These acidic carboxyl groups in Suwannee River fulvic acid were enriched by a 2-stage fractionation process and the fractions were characterized by elemental, molecular-weight, and titrimetric analyses, and by infrared and 13C- and 1H-nuclear magnetic resonance spectrometry. An average structural model of the most acidic fraction derived from the characterization data indicated a high density of carboxyl groups clustered on oxygen-heterocycle alicyclic rings. Intramolecular H-bonding between adjacent carboxyl groups in these ring structures enhanced stabilization of the carboxylate anion which results in low pKa1 values. The standard, tetrahydrofuran tetracarboxylic acid, was shown to have similar acidity characteristics to the highly acidic fulvic acid fraction. The end products of 3 known diagenetic pathways for the formation of humic substances were shown to result in carboxyl groups clustered on oxygen-heterocycle alicyclic rings.

  17. Labile carbon concentrations are strongly linked to plant production in Arctic tussock tundra soils

    NASA Astrophysics Data System (ADS)

    Darrouzet-Nardi, A.; Weintraub, M. N.; Euskirchen, E. S.; Steltzer, H.; Sullivan, P.

    2013-12-01

    The exchange of carbon and nutrients between plants and microbes is a key determinant of carbon balance in Arctic soils. Microbes rely on labile plant carbon for the energy they need to produce enzymes that can release nutrients and less energetically favorable carbon from soil organic matter. One of the main mechanisms of carbon transfer is rhizodeposition, the exudation of labile plant carbon such as sugars from roots into the rhizosphere. Despite the importance of this flow of energy and materials from plants to microbes, there have been few attempts to quantify labile carbon pools or fluxes in Arctic soils. To improve our knowledge of labile carbon dynamics in Arctic soils, we address two basic questions: (1) What are the seasonal patterns of labile carbon concentrations? and (2) How do seasonal patterns in labile carbon correlate with plant production, microbial biomass, and soil nutrients? We measured concentrations of total reducing sugars (TRS) in the soil solution of moist acidic tussock tundra on 28 dates during the 2012 growing season in 20 plots of an early snowmelt × warming experiment. We evaluated these total reducing sugar concentrations in the context of eddy flux carbon exchange data, plant NDVI, total dissolved carbon in soils, microbial biomass, and soil nutrients. Though we did not see treatment effects of the snowmelt × warming experiment, we did observe a clear seasonal pattern in TRS concentrations in which they started low at the time of thaw, then built to a maximum value around the time of peak plant physiology in July, followed by a decline as plants senesced. We observed a clear correlation between TRS and gross primary production (GPP). NDVI values also increased with TRS concentrations during the first half of the season and then leveled off as TRS began its decline. These relationships were in contrast to labile N concentrations, which remained at low concentrations all season. Our data suggest that rhizodeposition of labile carbon

  18. Labile iron in cells and body fluids: physiology, pathology, and pharmacology

    PubMed Central

    Cabantchik, Zvi Ioav

    2014-01-01

    In living systems iron appears predominantly associated with proteins, but can also be detected in forms referred as labile iron, which denotes the combined redox properties of iron and its amenability to exchange between ligands, including chelators. The labile cell iron (LCI) composition varies with metal concentration and substances with chelating groups but also with pH and the medium redox potential. Although physiologically in the lower μM range, LCI plays a key role in cell iron economy as cross-roads of metabolic pathways. LCI levels are continually regulated by an iron-responsive machinery that balances iron uptake versus deposition into ferritin. However, LCI rises aberrantly in some cell types due to faulty cell utilization pathways or infiltration by pathological iron forms that are found in hemosiderotic plasma. As LCI attains pathological levels, it can catalyze reactive O species (ROS) formation that, at particular threshold, can surpass cellular anti-oxidant capacities and seriously damage its constituents. While in normal plasma and interstitial fluids, virtually all iron is securely carried by circulating transferrin (Tf; that renders iron essentially non-labile), in systemic iron overload (IO), the total plasma iron binding capacity is often surpassed by a massive iron influx from hyperabsorptive gut or from erythrocyte overburdened spleen and/or liver. As plasma Tf approaches iron saturation, labile plasma iron (LPI) emerges in forms that can infiltrate cells by unregulated routes and raise LCI to toxic levels. Despite the limited knowledge available on LPI speciation in different types and degrees of IO, LPI measurements can be and are in fact used for identifying systemic IO and for initiating/adjusting chelation regimens to attain full-day LPI protection. A recent application of labile iron assay is the detection of labile components in intravenous iron formulations per se as well as in plasma (LPI) following parenteral iron administration

  19. CDC group IIc: phenotypic characteristics, fatty acid composition, and isoprenoid quinone content.

    PubMed Central

    Hollis, D G; Moss, C W; Daneshvar, M I; Wallace-Shewmaker, P L

    1996-01-01

    Twenty strains of glucose-utilizing, small gram-negative slightly pleomorphic rods that grew well aerobically and that were isolated from clinical specimens formed a phenotypically similar group that was designated CDC group IIc. The phenotypic characteristics of CDC group IIc were most similar to those of CDC groups IIe and IIh, the major differences being that CDC group IIc produced acid from sucrose, hydrolyzed esculin, and usually reduced nitrate. The CDC group IIc strains were analyzed by gas-liquid chromatography for their cellular fatty acid compositions, and all contained relatively large amounts of isobranched hydroxy and nonhydroxy acids. High-performance liquid chromatography and mass spectrometry analysis of the quinone extract showed menaquinone-6 as the major component. Both the cellular fatty acid and isoprenoid quinone compositions were consistent with the profiles of CDC groups IIe and IIh. Thirty percent of the isolates were from human blood. PMID:8862612

  20. Enhanced phagocytosis of group A streptococci M type 6 by oleic acid

    SciTech Connect

    Speert, D.P.; Quie, P.G.; Wannamaker, L.W.

    1981-04-01

    M protein, located on the surface fimbriae of group A streptococci, is antiphagocytic by unknown means. It is known that oleic acid kills group A streptococci and distorts the fimbriae. The effect of oleic acid on phagocytosis of group A streptococci was examined. Phagocytosis of a strain possessing M protein (M+) and its M- variant was assessed by uptake of radiolabeled bacteria and by chemiluminescence. The M- but not the M+ streptococci were well phagocytized and induced chemiluminescence. Oleic acid-killed and heat-killed streptococci (both M+ and M-) were readily phagocytized and induced sustained chemiluminescence. M+ streptococci killed by ultraviolet irradiation were inefficiently phagocytized and did not induce chemiluminescence. Oleic acid-killed M+ streptococci absorbed type-specific antibody. An extract of M protein reduced the bactericidal capacity of oleic acid. It is proposed that oleic acid may bind to and alter the M protein of group A streptococci and thereby enhance phagocytosis.

  1. Development of acid functional groups during the thermal degradation of wood and wood components

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study provides data on acid functional groups in charcoals and how the acid functional group content varies with the formation conditions. Chars were created from purified cellulose, purified lignin, pine wood, and pine bark. The charring temperatures and charring duration were controlled in a ...

  2. [Effects of straw application and earthworm inoculation on soil labile organic carbon].

    PubMed

    Yu, Jian-Guang; Li, Hui Xin; Chen, Xiao-Yun; Hu, Feng

    2007-04-01

    A six-year field plot experiment of rice-wheat rotation was conducted to study the effects of straw application and earthworm inoculation on cropland soil organic carbon and labile organic carbon. Five treatments were installed, i.e., CK, straw mulch (M), straw mulch plus earthworm inoculation (ME), incorporated straw with soil (I), and incorporated straw with soil plus earthworm inoculation (IE). The results showed that soil organic carbon content increased significantly after six years straw application, and treatment I was more efficient than treatment M. Earthworm inoculation under straw application had no significant effects on soil organic carbon content. Straw application, whether straw mulch or incorporated straw with soil, increased the content of soil labile organic carbon, and incorporated straw with soil was more beneficial to the increase of the contents of hot water-extractable carbon, potentially mineralizable carbon, acid-extractable carbon, readily oxidizable carbon, particulate organic carbon, and light fraction organic carbon. There was a little relationship between the quantitative variations of soil dissoluble organic carbon and microbial biomass carbon and the patterns of straw application. Among the treatments, the activity of soil organic carbon was decreased in the order of IF > I > M > ME > CK. Straw application pattern was the main factor affecting soil organic carbon and labile organic carbon, while earthworm inoculation was not universally significanfly effective to all kinds of soil labile organic carbon. PMID:17615878

  3. Fate and lability of silver in soils: Effect of ageing

    EPA Science Inventory

    The fate and lability of added soluble Ag in soils over time was examined by measurement of labile metal (E-value) by isotopic dilution using the 110mAg radioactive isotope and the solid-phase speciation of Ag by X-ray absorption near edge structure (XANES) spectrosco...

  4. Labile hypertension and jogging: new diagnostic tool or spurious discovery?

    PubMed Central

    Fitzgerald, W

    1981-01-01

    A labile hypertensive black man reviews his own personal history of hypertension, based on intensive self-study. The evidence suggests that aerobic isotonic exercise (jogging) depresses labile pressure values, forcing them down to near basal levels and preventing a rise to previous blood pressure levels for several hours. PMID:6780119

  5. Mayolenes: labile defensive lipids from the glandular hairs of a caterpillar (Pieris rapae).

    PubMed

    Smedley, Scott R; Schroeder, Frank C; Weibel, Douglas B; Meinwald, Jerrold; Lafleur, Katie A; Renwick, J Alan; Rutowski, Ronald; Eisner, Thomas

    2002-05-14

    Larvae of the European cabbage butterfly, Pieris rapae (Pieridae), are beset with glandular hairs, bearing droplets of a clear oily secretion at their tip. The fluid consists primarily of a series of chemically labile, unsaturated lipids, the mayolenes, which are derived from 11-hydroxylinolenic acid. In bioassays with the ant Crematogaster lineolata, the secretion was shown to be potently deterrent, indicating that the fluid plays a defensive role in nature. PMID:11997469

  6. Acid-labile mPEG-Vinyl Ether-1,2-Dioleylglycerol Lipids with Tunable pH Sensitivity: Synthesis and Structural Effects on Hydrolysis Rates, DOPE Liposome Release Performance and Pharmacokinetics

    PubMed Central

    Shin, Junhwa; Shum, Pochi; Grey, Jessica; Fujiwara, Shin-ichi; Malhotra, Guarov S.; González-Bonet, Andres; Hyun, Seok-Hee; Moase, Elaine; Allen, Theresa M.; Thompson, David H.

    2012-01-01

    A family of 3-methoxypoly(ethylene glycol)-vinyl ether-1,2-dioleylglycerol (mPEG-VE-DOG) lipopolymer conjugates, designed on the basis of DFT calculations to possess a wide range of proton affinities, was synthesized and tested for their hydrolysis kinetics in neutral and acidic buffers. Extruded ~100 nm liposomes containing these constructs in ≥90 mol% 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) produced dispersions that retained their calcein cargo for more than 2 days at pH 7.5, but released the encapsulated contents over a wide range of timescales as a function of the electronic properties of the vinyl ether linkage, the solution pH and the mPEG-VE-DOG composition in the membrane. The in vivo performance of two different 90:10 DOPE:mPEG-VE-DOG compositions was also evaluated for blood circulation time and biodistribution in mice, using 125I-tyraminylinulin as a label. The pharmacokinetic profiles gave a T1/2 of 7 h and 3 h for 90:10 DOPE:ST302 and 90:10 DOPE:ST502, respectively, with the liposomes being cleared predominantly by liver and spleen uptake. The behavior of these DOPE:mPEG-VE-DOG formulations is consistent with their relative rates of vinyl ether hydrolysis, i.e., the more acid-sensitive mPEG-VE-DOG derivatives produce faster leakage rates from DOPE:mPEG-VE-DOG liposomes, but decreased the blood circulation times in mice. These findings suggest that the vinyl ether-based PEG-lipid derivatives are promising agents for stabilizing acid-sensitive DOPE liposomes to produce formulations with a priori control over their pH-responsiveness in vitro. Our data also suggest, however, that the same factors that contribute to enhanced acid-sensitivity of the DOPE:mPEG-VE-DOG dispersions are also likely responsible for their reduced pharmacokinetic profiles. PMID:23030381

  7. Acid-labile mPEG-vinyl ether-1,2-dioleylglycerol lipids with tunable pH sensitivity: synthesis and structural effects on hydrolysis rates, DOPE liposome release performance, and pharmacokinetics.

    PubMed

    Shin, Junhwa; Shum, Pochi; Grey, Jessica; Fujiwara, Shin-ichi; Malhotra, Guarov S; González-Bonet, Andres; Hyun, Seok-Hee; Moase, Elaine; Allen, Theresa M; Thompson, David H

    2012-11-01

    A family of 3-methoxypoly(ethylene glycol)-vinyl ether-1,2-dioleylglycerol (mPEG-VE-DOG) lipopolymer conjugates, designed on the basis of DFT calculations to possess a wide range of proton affinities, was synthesized and tested for their hydrolysis kinetics in neutral and acidic buffers. Extruded ∼100 nm liposomes containing these constructs in ≥90 mol % 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) produced dispersions that retained their calcein cargo for more than 2 days at pH 7.5, but released the encapsulated contents over a wide range of time scales as a function of the electronic properties of the vinyl ether linkage, the solution pH, and the mPEG-VE-DOG composition in the membrane. The in vivo performance of two different 90:10 DOPE:mPEG-VE-DOG compositions was also evaluated for blood circulation time and biodistribution in mice, using (125)I-tyraminylinulin as a label. The pharmacokinetic profiles gave a t(1/2) of 7 and 3 h for 90:10 DOPE:ST302 and 90:10 DOPE:ST502, respectively, with the liposomes being cleared predominantly by liver and spleen uptake. The behavior of these DOPE:mPEG-VE-DOG formulations is consistent with their relative rates of vinyl ether hydrolysis, i.e., the more acid-sensitive mPEG-VE-DOG derivatives produced faster leakage rates from DOPE:mPEG-VE-DOG liposomes, but decreased the blood circulation times in mice. These findings suggest that the vinyl ether-based PEG-lipid derivatives are promising agents for stabilizing acid-sensitive DOPE liposomes to produce formulations with a priori control over their pH responsiveness in vitro. Our data also suggest, however, that the same factors that contribute to enhanced acid sensitivity of the DOPE:mPEG-VE-DOG dispersions are also likely responsible for their reduced pharmacokinetic profiles. PMID:23030381

  8. Capturing Labile Sulfenamide and Sulfinamide Serum Albumin Adducts of Carcinogenic Arylamines by Chemical Oxidation

    PubMed Central

    Peng, Lijuan; Turesky, Robert J.

    2013-01-01

    Aromatic amines and heterocyclic aromatic amines (HAAs) are a class of structurally related carcinogens that are formed during the combustion of tobacco or during the high temperature cooking of meats. These procarcinogens undergo metabolic activation by N-oxidation of the exocyclic amine group to produce N-hydroxylated metabolites, which are critical intermediates implicated in toxicity and DNA damage. The arylhydroxylamines and their oxidized arylnitroso derivatives can also react with cysteine (Cys) residues of glutathione or proteins to form, respectively, sulfenamide and sulfinamide adducts. However, sulfur-nitrogen linked adducted proteins are often difficult to detect because they are unstable and undergo hydrolysis during proteolytic digestion. Synthetic N-oxidized intermediates of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), a carcinogenic HAA produced in cooked meats, and 4-aminobiphenyl, a carcinogenic aromatic amine present in tobacco smoke were reacted with human serum albumin (SA) and formed labile sulfenamide or sulfinamide adducts at the Cys34 residue. Oxidation of the carcinogen-modified SA with m-chloroperoxybenzoic acid (m-CPBA) produced the arylsulfonamide adducts, which were stable to heat and the chemical reduction conditions employed to denature SA. The sulfonamide adducts of PhIP and 4-ABP were identified, by liquid chromatography/mass spectrometry, in proteolytic digests of denatured SA. Thus, selective oxidation of arylamine-modified SA produces stable arylsulfonamide-SA adducts, which may serve as biomarkers of these tobacco and dietary carcinogens. PMID:23240913

  9. Electroactive self-doped poly(amic acid) with oligoaniline and sulfonic acid groups: synthesis and electrochemical properties.

    PubMed

    Chi, Maoqiang; Wang, Shutao; Liang, Yuan; Chao, Danming; Wang, Ce

    2014-06-01

    A novel poly(amic acid) with pendant aniline tetramer and sulfonic acid groups (ESPAA) was synthesized by ternary polymerization and characterized by Fourier-transform infrared spectra, ((1))H NMR and gel permeation chromatography. The polymer showed good thermal stability and excellent solubility in the common organic solvents. The electrochemical properties were investigated carefully on a CHI 660A Electrochemical Workstation. The polymer displayed good electroactivity in acid, neutral and even in alkaline solutions (pH=1-10) due to the self-doping effect between aniline tetramer and sulfonic/carboxylic acid groups. It also exhibited satisfactory electrochromic performance with high contrast value, acceptable coloration efficiency and fast switching time in the range of pH=1-9. PMID:24703661

  10. Boronic acid as an efficient anchor group for surface modification of solid polyvinyl alcohol.

    PubMed

    Nishiyabu, Ryuhei; Shimizu, Ai

    2016-07-28

    We report the use of boronic acid as an anchor group for surface modification of solid polyvinyl alcohol (PVA); the surfaces of PVA microparticles, films, and nanofibers were chemically modified with boronic acid-appended fluorescent dyes through boronate esterification using a simple soaking technique in a short time under ambient conditions. PMID:27311634

  11. Effect of Amino Acids on Steady-State Growth of a Group A Hemolytic Streptococcus1

    PubMed Central

    Davies, Helen C.; Karush, Fred; Rudd, Joanne H.

    1965-01-01

    Davies, Helen C. (University of Pennsylvania, Philadelphia), Fred Karush, and Joanne H. Rudd. Effect of amino acids on steady-state growth of a group A hemolytic streptococcus. J. Bacteriol. 89:421–427. 1965.—A study has been made of amino acid utilization by a strain of type 4, group A streptococcus growing under steady-state conditions in a continuous-culture device and supplied with a completely synthetic medium. At a fixed growth rate, corresponding to a generation of time of 84 min, and with the pH maintained constant at 7.4, the bacterial turbidity was made dependent on the concentration of one of the amino acids of the defined medium. Under these conditions, the extracellular concentration of the limiting amino acid is fixed by the preset growth rate. The steady-state concentration of each of 14 essential l-amino acids was measured by means of C14-labeled amino acids in such limited cultures. At approximately equal turbidities, these concentrations ranged from 1.6 × 10−6m for methionine to 4.3 × 10−4m for glutamic acid. The rates of utilization of the amino acids ranged from 26 mμmoles per mg (dry weight) of bacteria per hr for histidine to 310 mμmoles per mg (dry weight) of bacteria per hr for glutamic acid. The percentage of the limiting amino acid used varied from 95% for threonine and methionine to 43% for gluamic acid. The rate of utilization of the limiting amino acid at unit concentration (tmoles per gram per hour per m) differed by a factor of 27 between extremes. These observations reflect the variation in the capacity of this streptococcal cell to take up and use different amino acids. PMID:14255710

  12. Cistrons encoding Escherichia coli heat-labile toxin.

    PubMed Central

    Dallas, W S; Gill, D M; Falkow, S

    1979-01-01

    The structure and products of the two cistrons encoding the Escherichia coli heat-labile toxin (LT) were studied. The LT deoxyribonucleic acid (DNA) region had been isolated as part of a DNA fragment from the plasmid P307, and this fragment was joined to the cloning vector pBR313. Deletion mutations of various lengths were introduced into the LT DNA region and into the adjacent DNA sequences. Analysis of the deletions indicated that the maximum size of the LT DNA region was 1.2 x 10(6) daltons. Two proteins of 11,500 daltons and 25,500 daltons had been shown to be encoded by the LT DNA region. The functions of these LT gene products were investigated. The 11,500-dalton protein had an adsorption activity for Y-1 adrenal cells, and this protein was shown to form aggregates of four or five monomers. The 25,500-dalton protein was shown to have an adenylate cyclase-activating activity. The two cistrons encoding for each of the LT proteins have been located on a genetic map of the LT DNA region. Both cistrons are probably transcribed from the same promoter. Images PMID:383697

  13. Bis(haloBODIPYs) with Labile Helicity: Valuable Simple Organic Molecules That Enable Circularly Polarized Luminescence.

    PubMed

    Ray, César; Sánchez-Carnerero, Esther M; Moreno, Florencio; Maroto, Beatriz L; Agarrabeitia, Antonia R; Ortiz, María J; López-Arbeloa, Íñigo; Bañuelos, Jorge; Cohovi, Komlan D; Lunkley, Jamie L; Muller, Gilles; de la Moya, Santiago

    2016-06-20

    Simple organic molecules (SOM) based on bis(haloBODIPY) are shown to enable circularly polarized luminescence (CPL), giving rise to a new structural design for technologically valuable CPL-SOMs. The established design comprises together synthetic accessibility, labile helicity, possibility of reversing the handedness of the circularly polarized emission, and reactive functional groups, making it unique and attractive as advantageous platform for the development of smart CPL-SOMs. PMID:27123965

  14. Synthesis, characterization and catalytic activity of acid-base bifunctional materials through protection of amino groups

    SciTech Connect

    Shao, Yanqiu; Liu, Heng; Yu, Xiaofang; Guan, Jingqi; Kan, Qiubin

    2012-03-15

    Graphical abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. Highlights: Black-Right-Pointing-Pointer The acid-base bifunctional material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized through protection of amino groups. Black-Right-Pointing-Pointer The obtained bifunctional material was tested for aldol condensation. Black-Right-Pointing-Pointer The SO{sub 3}H-SBA-15-NH{sub 2} catalyst containing amine and sulfonic acid groups exhibited excellent acid-basic properties. -- Abstract: Acid-base bifunctional mesoporous material SO{sub 3}H-SBA-15-NH{sub 2} was successfully synthesized under low acidic medium through protection of amino groups. X-ray diffraction (XRD), N{sub 2} adsorption-desorption, transmission electron micrographs (TEM), back titration, {sup 13}C magic-angle spinning (MAS) NMR and {sup 29}Si magic-angle spinning (MAS) NMR were employed to characterize the synthesized materials. The obtained bifunctional material was tested for aldol condensation reaction between acetone and 4-nitrobenzaldehyde. Compared with monofunctional catalysts of SO{sub 3}H-SBA-15 and SBA-15-NH{sub 2}, the bifunctional sample of SO{sub 3}H-SBA-15-NH{sub 2} containing amine and sulfonic acid groups exhibited excellent acid-basic properties, which make it possess high activity for the aldol condensation.

  15. Growth of group IV mycobacteria on medium containing various saturated and unsaturated fatty acids.

    PubMed Central

    Saito, H; Tomioka, H; Yoneyama, T

    1984-01-01

    Seventy-one strains of 15 species of rapidly growing mycobacteria were studied for their susceptibilities to fatty acids with 2 to 20 carbons by the agar dilution method at pH 7.0. Most mycobacteria other than potential pathogens (Mycobacterium fortuitum and Mycobacterium chelonei) were resistant to saturated fatty acids, except for lauric acid (C12:0) (MIC, 6.25 to 25 micrograms/ml) and capric acid (C10:0) (MIC, 50 to 100 micrograms#ml). M. fortuitum and M. chelonei were substantially insusceptible to these fatty acids. Unsaturated fatty acids with 16 to 20 carbons, except for C20:5, were highly toxic to group IV mycobacteria other than M. fortuitum, M. chelonei, Mycobacterium smegmatis, and Mycobacterium phlei, these being highly resistant to all the unsaturated acids, except for C16:1, C18:3, and C20:5. Introduction of double bonds to C16 to C20 fatty acids caused a marked increase in their activities that depended on the increase in the number of double bonds, at least up to three or four. M. fortuitum and M. chelonei were more resistant to the unsaturated fatty acids (particularly to C20:3 and C20:4) than the other group IV mycobacteria. PMID:6486760

  16. Adsorption of amino acids and glucose by sediments of Resurrection Bay, Alaska, USA: Functional group effects

    NASA Astrophysics Data System (ADS)

    Henrichs, Susan M.; Sugai, Susan F.

    1993-02-01

    The adsorption of amino acids and glucose was investigated in sediments from Resurrection Bay, Alaska. Adsorption of the basic amino acid lysine was greater than adsorption of glutamic acid, alanine, leucine, or glucose. Formaldehyde and heat treatments were used to separate adsorption from biological uptake, but can alter adsorption significantly; formaldehyde treatment, followed by a seawater rinse, was the most satisfactory. Much of the rapid amino acid adsorption by these sediments was due to the formation of ionic bonds, since adsorbed amino acids could be extracted using concentrated solutions of amino acid, cesium chloride, sodium citrate, ammonium chloride, or sodium acetate. However, most amino acid adsorption was not reversible by ion exchange solutions, indicating that additional processes or chemical reactions occur which result in irreversible binding to sediment. Consistent with literature reports of the negative surface charge of marine particulate matter, lysine (with a net positive charge) was adsorbed to the greatest extent and had the largest cation-exchangeable adsorption. However, negatively charged amino acid functional groups also influenced adsorption. Chemical modification of sediments with reagents reactive with aldehydes decreased lysine adsorption. This suggests that reactive functional groups of sediment organic matter contribute to adsorption, consistent with a melanoidintype reaction. An estimate of the rate of amino acid adsorption indicates that adsorption could produce a significant amount of the total refractory sediment organic nitrogen.

  17. Dihydrolipoic acid activates oligomycin-sensitive thiol groups and increases ATP synthesis in mitochondria.

    PubMed

    Zimmer, G; Mainka, L; Krüger, E

    1991-08-01

    Investigations with dihydrolipoic acid in rat heart mitochondria and mitoplasts reveal an activation of ATP-synthase up to 45%, whereas ATPase activities decrease by 36%. In parallel with an increase in ATP synthesis oligomycin-sensitive mitochondrial -SH groups are activated at 2-4 nmol dihydrolipoic acid/mg protein. ATPase activation by the uncouplers carbonylcyanide-p-trifluoromethoxyphenylhydrazone and oleate is diminished by dihydrolipoic acid, and ATP synthesis depressed by oleate is partially restored. No such efficiency of dihydrolipoic acid is seen with palmitate-induced ATPase activation or decrease of ATP synthesis. This indicates different interference of oleate and palmitate with mitochondria. In addition to its known coenzymatic properties dihydrolipoic acid may act as a substitute for coenzyme A, thereby diminishing the uncoupling efficiency of oleate. Furthermore, dihydrolipoic acid is a very potent antioxidant, shifting the -SH-S-S- equilibrium in mitochondria to the reduced state and improving the energetic state of cells. PMID:1832845

  18. Solving nucleic acid structures by molecular replacement: examples from group II intron studies

    SciTech Connect

    Marcia, Marco Humphris-Narayanan, Elisabeth; Keating, Kevin S.; Somarowthu, Srinivas; Rajashankar, Kanagalaghatta; Pyle, Anna Marie

    2013-11-01

    Strategies for phasing nucleic acid structures by molecular replacement, using both experimental and de novo designed models, are discussed. Structured RNA molecules are key players in ensuring cellular viability. It is now emerging that, like proteins, the functions of many nucleic acids are dictated by their tertiary folds. At the same time, the number of known crystal structures of nucleic acids is also increasing rapidly. In this context, molecular replacement will become an increasingly useful technique for phasing nucleic acid crystallographic data in the near future. Here, strategies to select, create and refine molecular-replacement search models for nucleic acids are discussed. Using examples taken primarily from research on group II introns, it is shown that nucleic acids are amenable to different and potentially more flexible and sophisticated molecular-replacement searches than proteins. These observations specifically aim to encourage future crystallographic studies on the newly discovered repertoire of noncoding transcripts.

  19. Hydrogen-bond acidic functionalized carbon nanotubes (CNTs) with covalently-bound hexafluoroisopropanol groups

    SciTech Connect

    Fifield, Leonard S.; Grate, Jay W.

    2010-06-01

    Fluorinated hydrogen-bond acidic groups are directly attached to the backbone of single walled carbon nanotubes (SWCNTs) without the introduction of intermediate electron donating surface groups. Hexafluoroalcohol functional groups are exceptionally strong hydrogen bond acids, and are added to the nanotube surface using the aryl diazonium approach to create hydrogen-bond acidic carbon nanotube (CNT) surfaces. These groups can promote strong hydrogen-bonding interactions with matrix materials in composites or with molecular species to be concentrated and sensed. In the latter case, this newly developed material is expected to find useful application in chemical sensors and in CNT-based preconcentrator devices for the detection of pesticides, chemical warfare agents and explosives.

  20. Evaluation of functional groups on amino acids in cyclic tetrapeptides in histone deacetylase inhibition.

    PubMed

    Islam, Md Shahidul; Bhuiyan, Mohammed P I; Islam, Md Nurul; Nsiama, Tienabe Kipassa; Oishi, Naoto; Kato, Tamaki; Nishino, Norikazu; Ito, Akihiro; Yoshida, Minoru

    2012-06-01

    The naturally occurring cyclic tetrapeptide, chlamydocin, originally isolated from fungus Diheterospora chlamydosphoria, consists of α-aminoisobutyric acid, L-phenylalanine, D-proline and an unusual amino acid (S)-2-amino-8-((S)-oxiran-2-yl)-8-oxooctanoic acid (Aoe) and inhibits the histone deacetylases (HDACs), a class of regulatory enzymes. The epoxyketone moiety of Aoe is the key functional group for inhibition. The cyclic tetrapeptide scaffold is supposed to play important role for effective binding to the surface of enzymes. In place of the epoxyketone group, hydroxamic acid and sulfhydryl group have been applied to design inhibitor ligands to zinc atom in catalytic site of HDACs. In the research for more potent HDAC inhibitors, we replaced the epoxyketone moiety of Aoe with different functional groups and synthesized a series of chlamydocin analogs as HDAC inhibitors. Among the functional groups, methoxymethylketone moiety showed as potent inhibition as the hydroxamic acid. On the contrary, we confirmed that borate, trifruoromethylketone, and 2-aminoanilide are almost inactive in HDAC inhibition. PMID:21638021

  1. Synthesis and Monolayer Behaviors of Novel Hybrid Corynomycolic Acids Containing Semifluoroalkyl Groups.

    PubMed

    Kawase, Tokuzo; Tamaki, Kazuki; Oida, Tatsuo

    2016-01-01

    In this work, novel hybrid-type corynomycolic acids [hybrid-OH and hybrid-COOH, with semifluoroalkyl groups (Rf-(CH2)n-: Rf = C4F9, n = 6 and Rf = C6F13, n = 3) located on the carbon atoms attached to the hydroxyl and carboxylic acid groups (C-OH and C-COOH), respectively] were successfully synthesized. The behaviors and formation of hybrid corynomycolic acid monolayers at the air-water interface were investigated by surface tension and surface pressure-area (π-A) measurements to clarify the effects of the Rf chain length, position of the semifluoroalkyl group, and surfactant molecule stereochemistry. Compared to dialkyl corynomycolic acid, both the critical micelle concentration (CMC) and the surface tension at the CMC (γCMC) of hybrid corynomycolic acids were reduced by the presence of the Rf group. With respect to the surface tension versus log concentration (γ vs. log C) isotherms, all syn-isomers of the hybrid-OH and hybrid-COOH acids showed two break points, while the anti-isomers showed only one break point. These different isotherms can be explained in terms of the steric repulsion between the two hydrophilic groups (OH and COO(-)), which depend on the stereochemistry of the surfactant. No effect of the location of the semifluoroalkyl group was observed. With respect to the formation of a monolayer film, four parameters-the lift-off area (AL), zero-pressure molecular area (A0), maximum of the Gibbs elastic modulus [EG (max)], and monolayer collapse pressure (πc)-were measured. Both AL and A0 of all hybrid corynomycolic acids were larger than the corresponding dialkyl acids due to the bulky and rigid Rf groups. Interestingly, syn- and anti-hybrids had almost identical isotherms on compression, although the values of πc of anti-hybrids were higher than those of syn-isomers. In addition, the values of EG (max) of hybrid-COOHs were slightly larger than those of the corresponding hybrid-OHs. Using the nascent soap method (agent-in-oil method), we found that

  2. Selective protection and relative importance of the carboxylic acid groups of zaragozic acid A for squalene synthase inhibition.

    PubMed

    Biftu, T; Acton, J J; Berger, G D; Bergstrom, J D; Dufresne, C; Kurtz, M M; Marquis, R W; Parsons, W H; Rew, D R; Wilson, K E

    1994-02-01

    Chemistry that allows selective modification of the carboxylic acid groups of the squalene synthase inhibitor zaragozic acid A (1) was developed and applied to the synthesis of compounds modified at the 3-,4-,5-,3,4-,3,5-, and 4,5-positions. A key step in this procedure is the selective debenzylation by transfer hydrogenolysis in the presence of other olefinic groups. These compounds were tested in the rat squalene synthase assay and in vivo mouse model. Modification at C3 retains significant enzyme potency and enhances oral activity, indicating that C3 is not essential for squalene synthase activity. Modification at C4 and C5 results in significant loss in enzyme activity. In contrast, substitution at C3 or C4 enhances in vivo activity. Furthermore, disubstitution at the C3 and C4 positions results in additive in vivo potency. PMID:8308869

  3. Potentiation of acid-sensing ion channel activity by peripheral group I metabotropic glutamate receptor signaling.

    PubMed

    Gan, Xiong; Wu, Jing; Ren, Cuixia; Qiu, Chun-Yu; Li, Yan-Kun; Hu, Wang-Ping

    2016-05-01

    Glutamate activates peripheral group I metabotropic glutamate receptors (mGluRs) and contributes to inflammatory pain. However, it is still not clear the mechanisms are involved in group I mGluR-mediated peripheral sensitization. Herein, we report that group I mGluRs signaling sensitizes acid-sensing ion channels (ASICs) in dorsal root ganglion (DRG) neurons and contributes to acidosis-evoked pain. DHPG, a selective group I mGluR agonist, can potentiate the functional activity of ASICs, which mediated the proton-induced events. DHPG concentration-dependently increased proton-gated currents in DRG neurons. It shifted the proton concentration-response curve upwards, with a 47.3±7.0% increase of the maximal current response to proton. Group I mGluRs, especially mGluR5, mediated the potentiation of DHPG via an intracellular cascade. DHPG potentiation of proton-gated currents disappeared after inhibition of intracellular Gq/11 proteins, PLCβ, PKC or PICK1 signaling. Moreover, DHPG enhanced proton-evoked membrane excitability of rat DRG neurons and increased the amplitude of the depolarization and the number of spikes induced by acid stimuli. Finally, peripherally administration of DHPG dose-dependently exacerbated nociceptive responses to intraplantar injection of acetic acid in rats. Potentiation of ASIC activity by group I mGluR signaling in rat DRG neurons revealed a novel peripheral mechanism underlying group I mGluRs involvement in hyperalgesia. PMID:26946972

  4. Proton transport pathways in an acid-base complex consisting of a phosphonic acid group and a 1,2,3-triazolyl group.

    PubMed

    Yue, Baohua; Yan, Liuming; Han, Shuaiyuan; Xie, Liqing

    2013-07-01

    The proton transport pathways in an acid-base complex consisting of a phosphonic acid group and a 1,2,3-triazolyl group were studied using density functional theory (DFT) calculations in terms of stable configurations and transition states of the molecular or ionic dimers and trimers and verified by proof-of-concept experiments including experimental measurements of overall conductivity and (1)H NMR and FTIR spectroscopy of the methylphosphonic acid (MPA) and 1,2,3-triazole (Tri) complex as well as overall proton conductivity of polymeric blend of poly(vinylphosphonic acid) (PVPA) and poly(4-vinyl-1H-1,2,3-triazole) (PVTri). From the DFT calculations of dimers and trimers composed of ethylphosphonic acid (EPA), Tri, and their deprotonated counterparts, it was concluded that the intermolecular hydrogen bonds of the transition states corresponding to proton transport are much shorter than those of stable configurations, but the O-H and N-H bonds are much longer than those of stable configurations. The tautomerization activation energy decreases from 0.927-1.176 eV in Tri-Tri dimers to 0.336-0.444 eV in the EPA-Tri dimers. From the proof-of-concept experiments, about a 50 fold increase in overall conductivity was observed in the MPA-Tri complex consisting of 10% (molar ratio) MPA compared to pure Tri, and the calculated activation energy is consistent with the experimental activation energy evaluated from temperature dependence of proton conductivity of pure Tri and the MPA-Tri complex. In addition, the fast proton exchange between MPA and Tri, consistent with the DFT calculations, was verified by (1)H NMR and FTIR spectroscopy. Finally, a polymeric blend of PVPA and PVTri was prepared, and its proton conductivity at about 2.1 mS·cm(-1) in anhydrous state at 100 °C was observed to be significantly higher than that of PVPA or of poly(VPA-co-1-vinyl-1,2,4-triazole). The proton conductivity of the polymeric PVPA and PVTri blend in humidity state is in the same range as

  5. Fatty acid composition of breast milk from three racial groups from Penang, Malaysia.

    PubMed

    Kneebone, G M; Kneebone, R; Gibson, R A

    1985-04-01

    The fatty acid composition of samples of breast milk obtained from 51 mothers (26 Malay, 15 Chinese, 10 Indian) residing in Penang, Malaysia was determined by gas chromatography. Despite living in close physical proximity the mothers from the three racial groups showed distinct cultural differences in dietary intake. These differences were reflected in differences in the fatty acid composition of breast milk samples. The milk of Chinese mothers was generally less saturated (41%) than that of Malay and Indian mothers (52 and 50% respectively). The milk of Chinese mothers was also richer in linoleic acid (17%) than that of Malay and Indian mothers (9% and 11% respectively). Overall the level of individual fatty acids fell within the range of values reported for Western mothers on well nourished diets and pointed to breast milk of high standard despite large variations in the diet of Malaysian mothers. PMID:3984928

  6. Quantifying Functional Group Interactions that Determine Urea Effects on Nucleic Acid Helix Formation

    PubMed Central

    Guinn, Emily J.; Schwinefus, Jeffrey J.; Cha, Hyo Keun; McDevitt, Joseph L.; Merker, Wolf E.; Ritzer, Ryan; Muth, Gregory W.; Engelsgjerd, Samuel W.; Mangold, Kathryn E.; Thompson, Perry J.; Kerins, Michael J.; Record, Thomas

    2013-01-01

    Urea destabilizes helical and folded conformations of nucleic acids and proteins, as well as protein-nucleic acid complexes. To understand these effects, extend previous characterizations of interactions of urea with protein functional groups, and thereby develop urea as a probe of conformational changes in protein and nucleic acid processes, we obtain chemical potential derivatives (μ23 = dμ2/dm3) quantifying interactions of urea (component 3) with nucleic acid bases, base analogs, nucleosides and nucleotide monophosphates (component 2) using osmometry and hexanol-water distribution assays. Dissection of these μ23 yields interaction potentials quantifying interactions of urea with unit surface areas of nucleic acid functional groups (heterocyclic aromatic ring, ring methyl, carbonyl and phosphate O, amino N, sugar (C,O)); urea interacts favorably with all these groups, relative to interactions with water. Interactions of urea with heterocyclic aromatic rings and attached methyl groups (as on thymine) are particularly favorable, as previously observed for urea-homocyclic aromatic ring interactions. Urea m-values determined for double helix formation by DNA dodecamers near 25°C are in the range 0.72 to 0.85 kcal mol−1 m−1 and exhibit little systematic dependence on nucleobase composition (17–42% GC). Interpretation of these results using the urea interaction potentials indicates that extensive (60–90%) stacking of nucleobases in the separated strands in the transition region is required to explain the m-value. Results for RNA and DNA dodecamers obtained at higher temperatures, and literature data, are consistent with this conclusion. This demonstrates the utility of urea as a quantitative probe of changes in surface area (ΔASA) in nucleic acid processes. PMID:23510511

  7. The geochemical model of neutral and acidic thermal water in the Tatun Volcano Group, Taiwan

    NASA Astrophysics Data System (ADS)

    Tsai, Y.; Kuo, C.; Liu, C.

    2013-12-01

    The geochemical model can provide a quantitative method for water-rock interaction and understand the processes of neutralization of initially acidic water. The Tatun Volcano Group (TVG) is one of the Quaternary volcanoes of northern Taiwan. In the Southern Sulfur River of the TVG, it has neutral and acidic thermal water that can provide good materials for modeling the flow path of acidic and neutral thermal water. This study collects 7 thermal springs and identifies into two types, which are neutral and acidic thermal water. The host rock of neutral thermal water has fresh andesitic rock and is weak fumaroles, and the field observations of acidic thermal waters have been alternated andesitic rock and strong degassing fumaroles. The Geochemist's Workbench software (GWB) can model the processes of neutralization of initially acidic water. Furthermore, this study will collect the meteoric water, thermal springs, and country rock along the Southern Sulfur River and use the GWB software to model the processes of neutralization of initially acidic water in the Southern Sulfur River in the future.

  8. p-Nitromandelic acid as a highly acid-stable safety-catch linker for solid-phase synthesis of peptide and depsipeptide acids.

    PubMed

    Isidro-Llobet, Albert; Alvarez, Mercedes; Burger, Klaus; Spengler, Jan; Albericio, Fernando

    2007-04-12

    [reaction: see text] p-Nitromandelic acid as a safety-catch linker for Boc/Bzl-SPPS of base-labile compounds like peptides and depsipeptides is described. This linker permits acidic removal of side-chain protection groups from the resin. For cleavage from the solid support, the p-nitro group was reduced with tin(II) chloride. After washing off the reducing agents, the (depsi)peptide acids with or without the side-chain protection schemes were obtained by microwave irradiation at 50 degrees C with 5% TFA in dioxane. PMID:17367151

  9. Development of Acid Functional Groups and Lactones During the Thermal Degradation of Wood and Wood Components

    USGS Publications Warehouse

    Rutherford, David W.; Wershaw, Robert L.; Reeves, James B., III

    2008-01-01

    Black carbon (pyrogenic materials including chars) in soils has been recognized as a substantial portion of soil organic matter, and has been shown to play a vital role in nutrient cycling; however, little is known concerning the properties of this material. Previous studies have largely been concerned with the creation of high-surface-area materials for use as sorbents. These materials have been manufactured at high temperature and have often been activated. Chars occurring in the environment can be formed over a wide range of temperature. Because it is extremely difficult to isolate black carbon once it has been incorporated in soils, chars produced in the laboratory under controlled conditions can be used to investigate the range of properties possible for natural chars. This report shows that charring conditions (temperature and time) have substantial impact on the acid functional group and lactone content of chars. Low temperatures (250?C) and long charring times (greater than 72 hours) produce chars with the highest acid functional group and lactone content. The charring of cellulose appears to be responsible for the creation of the acid functional group and lactones. The significance of this study is that low-temperature chars can have acid functional group contents comparable to humic materials (as high as 8.8 milliequivalents per gram). Acid functional group and lactone content decreases as charring temperature increases. The variation in formation conditions expected under natural fire conditions will result in a wide range of sorption properties for natural chars which are an important component of soil organic matter. By controlling the temperature and duration of charring, it is possible to tailor the sorption properties of chars, which may be used as soil amendments.

  10. Molecular insights into the microbial formation of marine dissolved organic matter: recalcitrant or labile?

    NASA Astrophysics Data System (ADS)

    Koch, B. P.; Kattner, G.; Witt, M.; Passow, U.

    2014-08-01

    The degradation of marine dissolved organic matter (DOM) is an important control variable in the global carbon cycle. For our understanding of the kinetics of organic matter cycling in the ocean, it is crucial to achieve a mechanistic and molecular understanding of its transformation processes. A long-term microbial experiment was performed to follow the production of non-labile DOM by marine bacteria. Two different glucose concentrations and dissolved algal exudates were used as substrates. We monitored the bacterial abundance, concentrations of dissolved and particulate organic carbon (DOC, POC), nutrients, amino acids and transparent exopolymer particles (TEP) for 2 years. The molecular characterization of extracted DOM was performed by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) after 70 days and after ∼2 years of incubation. Although glucose quickly degraded, a non-labile DOC background (5-9% of the initial DOC) was generated in the glucose incubations. Only 20% of the organic carbon from the algal exudate degraded within the 2 years of incubation. The degradation rates for the non-labile DOC background in the different treatments varied between 1 and 11 μmol DOC L-1 year-1. Transparent exopolymer particles, which are released by microorganisms, were produced during glucose degradation but decreased back to half of the maximum concentration within less than 3 weeks (degradation rate: 25 μg xanthan gum equivalents L-1 d-1) and were below detection in all treatments after 2 years. Additional glucose was added after 2 years to test whether labile substrate can promote the degradation of background DOC (co-metabolism; priming effect). A priming effect was not observed but the glucose addition led to a slight increase of background DOC. The molecular analysis demonstrated that DOM generated during glucose degradation differed appreciably from DOM transformed during the degradation of the algal exudates. Our

  11. Heterotrophic activity and biodegradation of labile and refractory compounds by groundwater and stream microbial populations.

    PubMed Central

    Ladd, T I; Ventullo, R M; Wallis, P M; Costerton, J W

    1982-01-01

    The bacteriology and heterotrophic activity of a stream and of nearby groundwater in Marmot Basin, Alberta, Canada, were studied. Acridine orange direct counts indicated that bacterial populations in the groundwater were greater than in the stream. Bacteria that were isolated from the groundwater were similar to species associated with soils. Utilization of labile dissolved organic material as measured by the heterotrophic potential technique with glutamic acid, phenylalanine, and glycolic acid as substrates was generally greater in the groundwater. In addition, specific activity indices for the populations suggested greater metabolic activity per bacterium in the groundwater. 14C-labeled lignocellulose, preferentially labeled in the lignin fraction by feeding Picea engelmannii [14C]phenylalanine, was mineralized by microorganisms in both the groundwater and the stream, but no more than 4% of the added radioactivity was lost as 14CO2 within 960 h. Up to 20% of [3'-14C]cinnamic acid was mineralized by microorganisms in both environments within 500 h. Both microbial populations appear to influence the levels of labile and recalcitrant dissolved organic material in mountain streams. PMID:7125651

  12. Using Stimulants to Treat ADHD-Related Emotional Lability

    PubMed Central

    Posner, Jonathan; Kass, Erica; Hulvershorn, Leslie

    2014-01-01

    Emotional lability, or sudden strong shifts in emotion, commonly occurs in youth with attention-deficit/hyperactivity disorder. Although these symptoms are impairing and disruptive, relatively little research has addressed their treatment, likely due to the difficulty of reliable and valid assessment. Promising signals for symptom improvement have come from recent studies using stimulants in adults, children and adolescents. Similarly, neuroimaging studies have begun to identify neurobiological mechanisms underlying stimulants’ impact on emotion regulation capacities. Here, we review these recent clinical and neuroimaging findings, as well as neurocognitive models for emotional lability in ADHD, issues of relevance to prescribers and the important role of psychiatric comorbidity with treatment choices. PMID:25135778

  13. Labile trace elements in carbonaceous chondrites - A survey

    NASA Technical Reports Server (NTRS)

    Xiao, Xiaoyue; Lipschutz, Michael E.

    1992-01-01

    Data are presented on 14 trace elements, including Co, Au, Ga, Rb, Sb, Ag, Se, Cs, Te, Zn, Cd, Bi, Tl, and In (nearly all of which are moderately or highly labile in meteorites), obtained by radiochemical neutron activation analyses of 42 C2-C6 chondrites, all but three from Antarctica. The data indicate that carbonaceous chondrites of petrographic types 2-6 define compositional continua. It is suggested that carbonaceous C2-C6 chondrites may reflect a mixture of material that formed at low temperatures and that contained cosmic levels of highly labile elements, with material that was devoid of them.

  14. Association of elevated levels of cellular lipoteichoic acids of group B streptococci with human neonatal disease.

    PubMed Central

    Nealon, T J; Mattingly, S J

    1983-01-01

    Cell-associated lipoteichoic acids (LTAs) from late-exponential-phase cultures (serotypes Ia, Ib, Ic, II, and III) of group B streptococci isolated from infected and asymptomatically colonized infants were quantitated and characterized by growing the organisms in a chemically defined medium containing [3H]glycerol and [14C]acetate. Cell pellets were extracted with 45% aqueous phenol and chloroform-methanol and subjected to DEAE-Sephacel anion-exchange chromatography. Elution profiles resolved three major peaks, I, II, and III, with glycerol and phosphate present in a 1:1 molar ratio in each peak, and results obtained by Ouchterlony immunodiffusion analysis confirmed the presence of poly(glycerol phosphate). Saponification indicated that [14C]acetate was incorporated into fatty acids of peaks I and II only, suggesting that these were cell-associated LTAs. Peak II was of small molecular weight (less than 10,000) and probably represented another species of LTA. Peaks I and II were further demonstrated to be LTA by their ability to sensitize human type O erythrocytes. Peak III lacked fatty acids and was shown to probably be deacylated LTA. Quantitation of cell-associated teichoic acid material produced by the group B streptococcal strains indicated that the clinical isolates from infants with early- or late-onset disease possessed significantly higher levels than did the asymptomatic (clinical isolates from infants without symptoms of disease) group B streptococcal strains. Images PMID:6341233

  15. Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes.

    PubMed

    Maity, Ayan; Teets, Thomas S

    2016-08-10

    This Review highlights stoichiometric reactions and elementary steps of catalytic reactions involving cooperative participation of transition-metal hydrides and main group Lewis acids. Included are reactions where the transition-metal hydride acts as a reactant as well as transformations that form the metal hydride as a product. This Review is divided by reaction type, illustrating the diverse roles that Lewis acids can play in mediating transformations involving transition-metal hydrides as either reactants or products. We begin with a discussion of reactions where metal hydrides form direct adducts with Lewis acids, elaborating the structure and dynamics of the products of these reactions. The bulk of this Review focuses on reactions where the transition metal and Lewis acid act in cooperation, and includes sections on carbonyl reduction, H2 activation, and hydride elimination reactions, all of which can be promoted by Lewis acids. Also included is a section on Lewis acid-base secondary coordination sphere interactions, which can influence the reactivity of hydrides. Work from the past 50 years is included, but the majority of this Review focuses on research from the past decade, with the intent of showcasing the rapid emergence of this field and the potential for further development into the future. PMID:27164024

  16. Boronic Acid Group: A Cumbersome False Negative Case in the Process of Drug Design.

    PubMed

    Katsamakas, Sotirios; Papadopoulos, Anastasios G; Hadjipavlou-Litina, Dimitra

    2016-01-01

    Herein we present, an exhaustive docking analysis considering the case of autotaxin (ATX). HA155, a small molecule inhibitor of ATX, is co-crystallized. In order to further extract conclusions on the nature of the bond formed between the ligands and the amino acid residues of the active site, density functional theory (DFT) calculations were undertaken. However, docking does not provide reproducible results when screening boronic acid derivatives and their binding orientations to protein drug targets. Based on natural bond orbital (NBO) calculations, the formed bond between Ser/Thr residues is characterized more accurately as a polar covalent bond instead of a simple nonpolar covalent one. The presented results are acceptable and could be used in screening as an active negative filter for boron compounds. The hydroxyl groups of amino acids are bonded with the inhibitor's boron atom, converting its hybridization to sp³. PMID:27617984

  17. Neuropsychological Correlates of Emotional Lability in Children with ADHD

    ERIC Educational Resources Information Center

    Banaschewski, Tobias; Jennen-Steinmetz, Christine; Brandeis, Daniel; Buitelaar, Jan K.; Kuntsi, Jonna; Poustka, Luise; Sergeant, Joseph A.; Sonuga-Barke, Edmund J.; Frazier-Wood, Alexis C.; Albrecht, Bjorn; Chen, Wai; Uebel, Henrik; Schlotz, Wolff; van der Meere, Jaap J.; Gill, Michael; Manor, Iris; Miranda, Ana; Mulas, Fernando; Oades, Robert D.; Roeyers, Herbert; Rothenberger, Aribert; Steinhausen, Hans-Christoph; Faraone, Stephen V.; Asherson, Philip

    2012-01-01

    Background: Emotional lability (EL) is commonly seen in patients with attention-deficit/hyperactivity disorder (ADHD). The reasons for this association remain currently unknown. To address this question, we examined the relationship between ADHD and EL symptoms, and performance on a range of neuropsychological tasks to clarify whether EL symptoms…

  18. Activation of the NLRP3 inflammasome by cellular labile iron.

    PubMed

    Nakamura, Kyohei; Kawakami, Toru; Yamamoto, Naoki; Tomizawa, Miyu; Fujiwara, Tohru; Ishii, Tomonori; Harigae, Hideo; Ogasawara, Kouetsu

    2016-02-01

    Cellular labile iron, which contains chelatable redox-active Fe(2+), has been implicated in iron-mediated cellular toxicity leading to multiple organ dysfunction. Iron homeostasis is controlled by monocytes/macrophages through their iron recycling and storage capacities. Furthermore, iron sequestration by monocytes/macrophages is regulated by pro-inflammatory cytokines including interleukin-1, highlighting the importance of these cells in the crosstalk between inflammation and iron homeostasis. However, a role for cellular labile iron in monocyte/macrophage-mediated inflammatory responses has not been defined. Here we describe how cellular labile iron activates the NLRP3 inflammasome in human monocytes. Stimulation of lipopolysaccharide-primed peripheral blood mononuclear cells with ferric ammonium citrate increases the level of cellular Fe(2+) levels in monocytes and induces production of interleukin-1β in a dose-dependent manner. This ferric ammonium citrate-induced interleukin-1β production is dependent on caspase-1 and is significantly inhibited by an Fe(2+)-specific chelator. Ferric ammonium citrate consistently induced interleukin-1β secretion in THP1 cells, but not in NLRP3-deficient THP1 cells, indicating a requirement for the NLRP3 inflammasome. Additionally, activation of the inflammasome is mediated by potassium efflux, reactive oxygen species-mediated mitochondrial dysfunction, and lysosomal membrane permeabilization. Thus, these results suggest that monocytes/macrophages not only sequestrate iron during inflammation, but also mediate inflammation in response to cellular labile iron, which provides novel insights into the role of iron in chronic inflammation. PMID:26577567

  19. How to Compute Labile Metal-Ligand Equilibria

    ERIC Educational Resources Information Center

    de Levie, Robert

    2007-01-01

    The different methods used for computing labile metal-ligand complexes, which are suitable for an iterative computer solution, are illustrated. The ligand function has allowed students to relegate otherwise tedious iterations to a computer, while retaining complete control over what is calculated.

  20. Memory expression is independent of memory labilization/reconsolidation.

    PubMed

    Barreiro, Karina A; Suárez, Luis D; Lynch, Victoria M; Molina, Víctor A; Delorenzi, Alejandro

    2013-11-01

    There is growing evidence that certain reactivation conditions restrict the onset of both the destabilization phase and the restabilization process or reconsolidation. However, it is not yet clear how changes in memory expression during the retrieval experience can influence the emergence of the labilization/reconsolidation process. To address this issue, we used the context-signal memory model of Chasmagnathus. In this paradigm a short reminder that does not include reinforcement allows us to evaluate memory labilization and reconsolidation, whereas a short but reinforced reminder restricts the onset of such a process. The current study investigated the effects of the glutamate antagonists, APV (0.6 or 1.5 μg/g) and CNQX (1 μg/g), prior to the reminder session on both behavioral expression and the reconsolidation process. Under conditions where the reminder does not initiate the labilization/reconsolidation process, APV prevented memory expression without affecting long-term memory retention. In contrast, APV induced amnesic effects in the long-term when administered before a reminder session that triggers reconsolidation. Under the present parametric conditions, the administration of CNQX prior to the reminder that allows memory to enter reconsolidation impairs this process without disrupting memory expression. Overall, the present findings suggest that memory reactivation--but not memory expression--is necessary for labilization and reconsolidation. Retrieval and memory expression therefore appear not to be interchangeable concepts. PMID:24149057

  1. Group A Streptococci Bind to Mucin and Human Pharyngeal Cells through Sialic Acid-Containing Receptors

    PubMed Central

    Ryan, Patricia A.; Pancholi, Vijaykumar; Fischetti, Vincent A.

    2001-01-01

    The first step in the colonization of group A streptococci (Streptococcus pyogenes) is adherence to pharyngeal epithelial cells. Prior to adherence to their target tissue, the first barrier that the streptococci encounter is the mucous layer of the respiratory tract. The present study was undertaken to characterize the interaction between mucin, the major glycoprotein component of mucus, and streptococci. We report here that S. pyogenes is able to bind to bovine submaxillary mucin in solid-phase microtiter plate assays. Western blots probed with 125I-labeled mucin and a panel of monoclonal antibodies revealed that the streptococcal M protein is one of two cell wall-associated proteins responsible for this binding. The binding was further localized to the N-terminal portion of the M molecule. Further analysis revealed that the M protein binds to the sialic acid moieties on mucin, and this interaction seems to be based on M-protein conformation rather than specific amino acid sequences. We found that sialic acid also plays a critical role in the adherence of an M6 streptococcal strain to the Detroit 562 human pharyngeal cell line and have identified α2-6-linked sialic acid as an important sialylated linkage for M-protein recognition. Western blot analysis of extracted pharyngeal cell membrane proteins identified three potential sialic acid-containing receptors for the M protein. The results are the first to show that sialic acid not only is involved in the binding of the streptococci to mucin but also plays an important role in adherence of group A streptococci to the pharyngeal cell surface. PMID:11705914

  2. H-binding groups in lignite vs. soil humic acids: NICA-Donnan and spectroscopic parameters

    SciTech Connect

    Drosos, M.; Jerzykiewicz, M.; Deligiannakis, Y.

    2009-04-15

    A comparative study has been carried out for two sets of humic acids isolated from lignites and soils. H-binding data were analyzed using the NICA-Donnan model, for three Greek lignite humic acids (HA) plus IHSS Leonardite reference HA, and five Greek soil HAs plus a commercial peat HA. {sup 13}C-CP-MAS NMR and H-binding data provide quantitative estimates for functional groups, showing that lignite HAs of diverse origin have strikingly homogeneous properties, while the H-binding structural units of soil HAs are characterized by a large degree of variability. Consistent differences between soil HA vs. lignite HA are revealed at the level of functional groups' concentrations. In the pH range 4 to 10, soil HA showed a charge variation < 3 (equiv kg{sup -1}) while lignite HAs showed a higher charge variation > 3.5 (equiv kg{sup -1}).

  3. Measuring the concentration of carboxylic acid groups in torrefied spruce wood.

    PubMed

    Khazraie Shoulaifar, Tooran; Demartini, Nikolai; Ivaska, Ari; Fardim, Pedro; Hupa, Mikko

    2012-11-01

    Torrefaction is moderate thermal treatment (∼200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction. PMID:22940339

  4. H-binding groups in lignite vs. soil humic acids: NICA-Donnan and spectroscopic parameters.

    PubMed

    Drosos, Marios; Jerzykiewicz, Maria; Deligiannakis, Yiannis

    2009-04-01

    A comparative study has been carried out for two sets of humic acids isolated from lignites and soils. H-binding data were analyzed using the NICA-Donnan model, for three Greek lignite humic acids (HA) plus IHSS Leonardite reference HA, and five Greek soil HAs plus a commercial peat HA. (13)C-CP-MAS NMR and H-binding data provide quantitative estimates for functional groups, showing that lignite HAs of diverse origin have strikingly homogeneous properties, while the H-binding structural units of soil HAs are characterized by a large degree of variability. Consistent differences between soil HA vs. lignite HA are revealed at the level of functional groups' concentrations. In the pH range 4 to 10, soil HA showed a charge variation <3 [equiv kg(-1)] while lignite HAs showed a higher charge variation >3.5 [equiv kg(-1)]. PMID:19144349

  5. Application of a chemical leach technique for estimating labile particulate aluminum, iron, and manganese in the Columbia River plume and coastal waters off Oregon and Washington

    NASA Astrophysics Data System (ADS)

    Berger, Carolyn J. M.; Lippiatt, Sherry M.; Lawrence, Michael G.; Bruland, Kenneth W.

    2008-02-01

    In order to determine the total concentration of bioavailable trace metals in seawater, measurement of both the dissolved and labile particulate fractions is necessary. Comparison of labile particulate metal concentrations from various researchers is limited because of differing definitions of the fraction that is potentially available to phytoplankton on a time frame of generations. A comparison experiment was conducted on coastal and riverine suspended particulate matter to determine the difference between several commonly used techniques that operationally define the labile particulate trace metal fraction. Furthermore, we compared two leach techniques for surface transect samples from within the Columbia River plume and water offshore of Oregon and Washington, United States. The particulate trace metal concentration in the leachate was determined by high-resolution inductively coupled plasma-mass spectrometry. From this comparison, one chemical leach was chosen to best define the labile particulate fraction of Al, Fe, and Mn: a weak acid leach (25% acetic acid at pH 2) with a mild reducing agent (0.02 M hydroxylamine hydrochloride) and a short heating step (10 min 90-95°C). This leach was applied to three surface transects within the Columbia River plume. These coastal waters were found to be rich in labile particulate trace metals that are directly delivered from the Columbia River and indirectly supplied via resuspension from upwelling over a broad continental shelf.

  6. Removal of transition metals from dilute aqueous solution by carboxylic acid group containing absorbent polymers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new carboxylic acid group containing resin with cation exchange capacity, 12.67 meq/g has been used to remove Cu2+, Co2+ and Ni2+ ions from dilute aqueous solution. The resin has Cu2+, Co2+ and Ni2+ removal capacity, 216 mg/g, 154 mg/g and 180 mg/g, respectively. The selectivity of the resin to ...

  7. Cooperative Effects in Aligned and Opposed Multicomponent Charge Gradients Containing Strongly Acidic, Weakly Acidic, and Basic Functional Groups.

    PubMed

    Ashraf, Kayesh M; Giri, Dipak; Wynne, Kenneth J; Higgins, Daniel A; Collinson, Maryanne M

    2016-04-26

    Bifunctionalized surface charge gradients in which the individual component gradients either align with or oppose each other have been prepared. The multicomponent gradients contain strongly acidic, weakly acidic, and basic functionalities that cooperatively interact to define surface wettability, nanoparticle binding, and surface charge. The two-step process for gradient formation begins by modifying a siloxane coated silicon wafer in a spatially dependent fashion first with an aminoalkoxysilane and then with a mercapto-functionalized alkoxysilane. Immersion in hydrogen peroxide leads to oxidation of the surface immobilized sulfhydryl groups and subsequent protonation of the surface immobilized amines. Very different surface chemistries were obtained from gradients that either align with or oppose each other. X-ray photoelectron spectroscopy (XPS) data show that the degree of amine group protonation depends on the local concentration of sulfonate groups, which form ion pairs with the resulting ammonium ions. Contact angle measurements show that these ion pairs greatly enhance the wettability of the gradient surface. Finally, studies of colloidal gold binding show that the presence of both amine and thiol moieties enhance colloid binding, which is also influenced by surface charge. Cooperativity is also revealed in the distribution of charges on uniform samples used as models of the gradient surfaces, as evaluated via zeta potential measurements. Most significantly, the net surface charge and how it changes with distance and solution pH strongly depend on whether the gradients in amine and thiol align or oppose each other. The aligned multicomponent gradients show the most interesting behavior in that there appears to be a point at pH ∼ 6.5 where surface charge remains constant with distance. Setting the pH above or below this transition point leads to changes in the direction of charge variation along the length of the substrate. PMID:27073019

  8. Lactic acid bacteria producing B-group vitamins: a great potential for functional cereals products.

    PubMed

    Capozzi, Vittorio; Russo, Pasquale; Dueñas, María Teresa; López, Paloma; Spano, Giuseppe

    2012-12-01

    Wheat contains various essential nutrients including the B group of vitamins. However, B group vitamins, normally present in cereals-derived products, are easily removed or destroyed during milling, food processing or cooking. Lactic acid bacteria (LAB) are widely used as starter cultures for the fermentation of a large variety of foods and can improve the safety, shelf life, nutritional value, flavor and overall quality of the fermented products. In this regard, the identification and application of strains delivering health-promoting compounds is a fascinating field. Besides their key role in food fermentations, several LAB found in the gastrointestinal tract of humans and animals are commercially used as probiotics and possess generally recognized as safe status. LAB are usually auxotrophic for several vitamins although certain strains of LAB have the capability to synthesize water-soluble vitamins such as those included in the B group. In recent years, a number of biotechnological processes have been explored to perform a more economical and sustainable vitamin production than that obtained via chemical synthesis. This review article will briefly report the current knowledge on lactic acid bacteria synthesis of vitamins B2, B11 and B12 and the potential strategies to increase B-group vitamin content in cereals-based products, where vitamins-producing LAB have been leading to the elaboration of novel fermented functional foods. In addition, the use of genetic strategies to increase vitamin production or to create novel vitamin-producing strains will be also discussed. PMID:23093174

  9. Quantification of Labile Soil Mercury by Stable Isotope Dilution Techniques

    NASA Astrophysics Data System (ADS)

    Shetaya, Waleed; Huang, Jen-How; Osterwalder, Stefan; Alewell, Christine

    2016-04-01

    Mercury (Hg) is a toxic element that can cause severe health problems to humans. Mercury is emitted to the atmosphere from both natural and anthropogenic sources and can be transported over long distances before it is deposited to aquatic and terrestrial environments. Aside from accumulation in soil solid phases, Hg deposited in soils may migrate to surface- and ground-water or enter the food chain, depending on its lability. There are many operationally-defined extraction methods proposed to quantify soil labile metals. However, these methods are by definition prone to inaccuracies such as non-selectivity, underestimation or overestimation of the labile metal pool. The isotopic dilution technique (ID) is currently the most promising method for discrimination between labile and non-labile metal fractions in soil with a minimum disturbance to soil-solid phases. ID assesses the reactive metal pool in soil by defining the fraction of metal both in solid and solution phases that is isotopically-exchangeable known as the 'E-value'. The 'E-value' represents the metal fraction in a dynamic equilibrium with the solution phase and is potentially accessible to plants. This is carried out by addition of an enriched metal isotope to soil suspensions and quantifying the fraction of metal that is able to freely exchange with the added isotope by measuring the equilibrium isotopic ratio by ICP-MS. E-value (mg kg‑1) is then calculated as follows: E-Value = (Msoil/ W) (CspikeVspike/ Mspike) (Iso1IAspike ‑Iso2IAspikeRss / Iso2IAsoil Rss - Iso1IAsoil) where M is the average atomic mass of the metal in the soil or the spike, W is the mass of soil (kg), Cspike is the concentration of the metal in the spike (mg L‑1), Vspike is the volume of spike (L), IA is isotopic abundance, and Rss is the equilibrium ratio of isotopic abundances (Iso1:Iso2). Isotopic dilution has been successfully applied to determine E-values for several elements. However, to our knowledge, this method has not

  10. Effect of land use and longitudinal gradient on carbon quality and lability in the Vesdre River catchment, Belgium

    NASA Astrophysics Data System (ADS)

    Gettel, G. M.; Bravo-Palacios, L.; Gupta, S.

    2011-12-01

    related to PARAFAC Component 5, C5) in the upstream portion of the catchment were associated with forested and peat lands, whereas low DOC concentration and high intensity of fluorophore T (tryptophan-like fraction, C8) characterized agriculture and urban areas in downstream portion of the catchment. The labile, semi-labile, and refractory pools were related to both land use and DOM quality. Peat was positively correlated with the size of the refractory pool, whereas agriculture and urban land use were positively correlated with the semi-labile pool. The labile pool was positively correlated with C1, while the refractory pool was correlated with C5 and C9 (the humic acid portion). Denitrification rate was correlated with C8. Interestingly, degradation constants (k) from 3- pool model were not correlated with land use or with fluorescence characteristics. In conclusion, this study shows that land-use is important in determining DOM quality, and that in turn, DOM quality affects lability. While not all aspects of the fluorescence properties were important to the functional properties of DOM, fluorescence may be useful in river-network models that aim to relate processing to land use and longitudinal gradient.

  11. Inhibition of nitrobenzene adsorption by water cluster formation at acidic oxygen functional groups on activated carbon.

    PubMed

    Kato, Yuichi; Machida, Motoi; Tatsumoto, Hideki

    2008-06-15

    The inhibition effect of nitrobenzene adsorption by water clusters formed at the acidic groups on activated carbon was examined in aqueous and n-hexane solution. The activated carbon was oxidized with nitric acid to introduce CO complexes and then outgassed in helium flow at 1273 K to remove them completely without changing the structural properties of the carbon as a reference adsorbent. The amounts of acidic functional groups were determined by applying Boehm titration. A relative humidity of 95% was used to adsorb water onto the carbon surface. Strong adsorption of water onto the oxidized carbon can be observed by thermogravimetric analysis. The adsorption kinetic rate was estimated to be controlled by diffusion from the kinetic analysis. Significant decline in both capacity and kinetic rate for nitrobenzene adsorption onto the oxidized carbon was also observed in n-hexane solution by preadsorption of water to the carbon surface, whereas it was not detected for the outgassed carbons. These results might reveal that water molecules forming clusters at the CO complexes inhibited the entrance of nitrobenzene into the interparticles of the carbon. PMID:18440013

  12. Labile Zn ions on octacalcium phosphate-derived Zn-containing hydroxyapatite surfaces

    NASA Astrophysics Data System (ADS)

    Honda, Yoshitomo; Anada, Takahisa; Morimoto, Shinji; Suzuki, Osamu

    2013-05-01

    We previously synthesized and characterized zinc-containing octacalcium phosphate (OCP) and its hydrolyzed Ca-deficient hydroxyapatite (HA). In the present report, we attempted to define the state of Zn in the OCP-derived Zn-calcium phosphates (CaPs) in relation to the presence of specific amino acids. Zn-containing OCPs were prepared in solutions that included Zn ions up to a concentration of 3.5 mM, and their hydrolyzates [hydrolyzed (hy)-Zn-CaP] were obtained in hot water. The materials were characterized by x-ray diffraction and scanning electron microscopy. The concentration of Ca and Zn ions at room temperature was determined by analyzing the supernatant after incubating the materials in α-minimal essential medium (α-MEM) and HEPES buffer including cysteine, histidine, lysine, aspartic acid, and glutamic acid. Zn ions were more dissolved in α-MEM than HEPES buffer in the absence of amino acids. The inclusion of the amino acids enhanced Zn dissolution by several hundred fold, even in HEPES buffer. Among the amino acids, both cysteine and histidine enhanced the release of Zn. The effect was particularly remarkable with cysteine even in the presence of the other amino acids tested. These results indicate that Zn ions are present as a surface labile pool, which tends to be preferentially desorbed by cysteine, a ubiquitous molecule present in serum.

  13. Investigation of the gas-phase hydrogen/deuterium exchange behavior of aromatic dicarboxylic acids in a quadrupole ion trap

    NASA Astrophysics Data System (ADS)

    Chipuk, Joseph E.; Brodbelt, Jennifer S.

    2007-11-01

    Gas-phase hydrogen/deuterium (H/D) exchange reactions of four deprotonated aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalic acid) with D2O were performed in a quadrupole ion trap mass spectrometer. Experimental results showed significant differences in the rate and extent of exchange when the relative position of the carboxylic acid groups varied. Spontaneous and near complete exchange of one aromatic hydrogen atom occurred when the carboxylic acid groups were in the meta-position, whereas no additional exchange was observed for either the ortho- or para-isomers or for the structurally similar naphthalic acid. Computational investigations support the participation of several possible exchange mechanisms with the contribution of each relying heavily on the relative orientation of the acid moieties. A relay mechanism that bridges the deprotonation site and the labile hydrogen site appears to be responsible for the H/D exchange of not only the labile hydrogen atom of isophthalic acid, but also for the formation of a stable carbanion and corresponding subsequent exchange of one aromatic hydrogen atom. The impact of hydrogen bonding on the relay mechanism is demonstrated by the reaction of phthalic acid as the extent and rate of reaction are greatly retarded by the favorable interaction of the two carboxylic acid groups. Finally, a flip-flop mechanism is likely responsible for the exchange of both terephthalic acid and 2,6-naphthalic acid where the reactive sites are too remote for exchange via relay.

  14. Palladium(II)-Catalyzed Tandem Synthesis of Acenes Using Carboxylic Acids as Traceless Directing Groups.

    PubMed

    Kim, Kiho; Vasu, Dhananjayan; Im, Honggu; Hong, Sungwoo

    2016-07-18

    A straightforward synthetic strategy for generating useful anthracene derivatives was developed involving palladium(II)-catalyzed tandem transformation with carboxylic acids as traceless directing groups. Carboxyl-directed C-H alkenylation, carboxyl-directed secondary C-H activation and rollover, intramolecular C-C bond formation, and decarboxylative aromatization are proposed as the key steps in the tandem reaction pathway. This novel synthetic route utilizes a broad range of substrates and provides a convenient synthetic tool that allows access to acenes. PMID:27244536

  15. Rhizosphere Environment and Labile Phosphorus Release from Organic Waste-Amended Soils.

    NASA Astrophysics Data System (ADS)

    Dao, Thanh H.

    2015-04-01

    Crop residues and biofertilizers are primary sources of nutrients for organic crop production. However, soils treated with large amounts of nutrient-enriched manure have elevated phosphorus (P) levels in regions of intensive animal agriculture. Surpluses occurred in these amended soils, resulting in large pools of exchangeable inorganic P (Pi) and enzyme-labile organic P (Po) that averaging 30.9 and 68.2 mg kg-1, respectively. Organic acids produced during crop residue decomposition can promote the complexation of counter-ions and decouple and release unbound Pi from metal and alkali metal phosphates. Animal manure and cover crop residues also contain large amounts of soluble organic matter, and likely generate similar ligands. However, a high degree of heterogeneity in P spatial distribution in such amended fields, arising from variances in substrate physical forms ranging from slurries to dried solids, composition, and diverse application methods and equipment. Distinct clusters of Pi and Po were observed, where accumulation of the latter forms was associated with high soil microbial biomass C and reduced phosphomonoesterases' activity. Accurate estimates of plant requirements and lability of soil P pools, and real-time plant and soil P sensing systems are critical considerations to optimally manage manure-derived nutrients in crop production systems. An in situ X-ray fluorescence-based approach to sensing canopy and soil XRFS-P was developed to improve the yield-soil P relationship for optimal nutrient recommendations in addition to allowing in-the-field verification of foliar P status.

  16. Chemical trapping of labile aldehyde intermediates in the metabolism of propranolol and oxprenolol.

    PubMed

    Goldszer, F; Tindell, G L; Walle, U K; Walle, T

    1981-11-01

    Propranolol is N-dealkylated to N-desisopropylpropranolol (DIP) by microsomal enzymes. DIP was shown in this study to be rapidly deaminated by monoamine oxidase (MAO). Thus, incubation of DIP (10(-4) M) with rat liver mitochondria for 90 min demonstrated 74.8 +/- 4.1% metabolism which was almost completely blocked by the MAO inhibitor pargyline (10(-5) M). The end products of this deamination were 3-(alpha-naphthoxy)-1,2-propylene glycol (Glycol) and 3-(alpha-naphthoxy)lactic acid (NLA). In the presence of excess NADH the Glycol was the major product whereas NLA was the major product in the presence of excess NAD+. The intermediate aldehyde in this deamination reaction, 3-(alpha-naphthoxy)-2-hydroxypropanal (Ald), was extremely labile and decomposed quantitatively to alpha-naphthol when removed from the incubates. However, the addition of methoxyamine hydrochloride directly to the incubates made it possible to chemically trap the intact Ald as an O-methyloxime and prove its structure by gas chromatography-mass spectrometry. The deamination of the primary amine of oxprenolol also gave rise to a labile aldehyde which could be trapped and identified as its O-methyloxime. PMID:7335950

  17. Synthesis and physicochemical properties of polysiloxane functionalized with aminoacetic acid groups

    NASA Astrophysics Data System (ADS)

    Lakiza, N. V.; Neudachina, L. K.

    2016-07-01

    Polysiloxane functionalized with aminoacetic acid groups was synthesized using sol-gel technology. Elemental analysis and FTIR spectroscopy were used to determine the composition of the polysiloxane show that it is a mesoporous material with a developed surface (109.4 m2/g). It was found that the selective properties of carboxymethylated polysiloxane towards transition metal ions simultaneously present in an ammonium acetate solution change in the order Zn < Cu > Ni > Co > Pb > Cd. It was shown that the sorption of copper(II) ions by carboxymethylated aminopropylpolysiloxane with particle sizes of 50-71 μm reaches its maximum level within 2 h; the rate-limiting step of the process is the chemical reaction between the ions and the polysiloxane functional groups; and the pseudo-second-order model is the best way of describing sorption.

  18. THz and mid-IR spectroscopy of interstellar ice analogs: methyl and carboxylic acid groups.

    PubMed

    Ioppolo, S; McGuire, B A; Allodi, M A; Blake, G A

    2014-01-01

    A fundamental problem in astrochemistry concerns the synthesis and survival of complex organic molecules (COMs) throughout the process of star and planet formation. While it is generally accepted that most complex molecules and prebiotic species form in the solid phase on icy grain particles, a complete understanding of the formation pathways is still largely lacking. To take full advantage of the enormous number of available THz observations (e.g., Herschel Space Observatory, SOFIA, and ALMA), laboratory analogs must be studied systematically. Here, we present the THz (0.3-7.5 THz; 10-250 cm(-1)) and mid-IR (400-4000 cm(-1)) spectra of astrophysically-relevant species that share the same functional groups, including formic acid (HCOOH) and acetic acid (CH3COOH), and acetaldehyde (CH3CHO) and acetone ((CH3)2CO), compared to more abundant interstellar molecules such as water (H2O), methanol (CH3OH), and carbon monoxide (CO). A suite of pure and mixed binary ices are discussed. The effects on the spectra due to the composition and the structure of the ice at different temperatures are shown. Our results demonstrate that THz spectra are sensitive to reversible and irreversible transformations within the ice caused by thermal processing, suggesting that THz spectra can be used to study the composition, structure, and thermal history of interstellar ices. Moreover, the THz spectrum of an individual species depends on the functional group(s) within that molecule. Thus, future THz studies of different functional groups will help in characterizing the chemistry and physics of the interstellar medium (ISM). PMID:25302394

  19. Ammonia capture in porous organic polymers densely functionalized with Brønsted acid groups.

    PubMed

    Van Humbeck, Jeffrey F; McDonald, Thomas M; Jing, Xiaofei; Wiers, Brian M; Zhu, Guangshan; Long, Jeffrey R

    2014-02-12

    The elimination of specific environmental and industrial contaminants, which are hazardous at only part per million to part per billion concentrations, poses a significant technological challenge. Adsorptive materials designed for such processes must be engendered with an exceptionally high enthalpy of adsorption for the analyte of interest. Rather than relying on a single strong interaction, the use of multiple chemical interactions is an emerging strategy for achieving this requisite physical parameter. Herein, we describe an efficient, catalytic synthesis of diamondoid porous organic polymers densely functionalized with carboxylic acids. Physical parameters such as pore size distribution, application of these materials to low-pressure ammonia adsorption, and comparison with analogous materials featuring functional groups of varying acidity are presented. In particular, BPP-5, which features a multiply interpenetrated structure dominated by <6 Å pores, is shown to exhibit an uptake of 17.7 mmol/g at 1 bar, the highest capacity yet demonstrated for a readily recyclable material. A complementary framework, BPP-7, features slightly larger pore sizes, and the resulting improvement in uptake kinetics allows for efficient adsorption at low pressure (3.15 mmol/g at 480 ppm). Overall, the data strongly suggest that the spatial arrangement of acidic sites allows for cooperative behavior, which leads to enhanced NH3 adsorption. PMID:24456083

  20. The difluoromethylene (CF2) group in aliphatic chains: Synthesis and conformational preference of palmitic acids and nonadecane containing CF2 groups.

    PubMed

    Wang, Yi; Callejo, Ricardo; Slawin, Alexandra M Z; O'Hagan, David

    2014-01-01

    The syntheses of palmitic acids and a nonadecane are reported with CF2 groups located 1,3 or 1,4 to each other along the aliphatic chain. Specifically 8,8,10,10- and 8,8,11,11-tetrafluorohexadecanoic acids (6b and 6c) are prepared as well as the singly modified analogue 8,8-difluorohexadecanoic acid (6a). Also 8,8,11,11-tetrafluorononadecane (27) is prepared as a pure hydrocarbon containing a 1,4-di-CF2 motif. The modified palmitic acids are characterized by differential scanning calorimetry (DSC) to determine melting points and phase behaviour relative to palmitic acid (62.5 °C). It emerges that 6c, with the CF2 groups placed 1,4- to each other, has a significantly higher melting point (89.9 °C) when compared to the other analogues and palmitic acid itself. It is a crystalline compound and the structure reveals an extended anti-zig-zag chain. Similarly 8,8,11,11-tetrafluorononadecane (27) adopts an extended anti-zig-zag structure. This is rationalized by dipolar relaxation between the two CF2 groups placed 1,4 to each other in the extended anti-zig-zag chain and suggests a design modification for long chain aliphatics which can introduce conformational stability. PMID:24454560

  1. The difluoromethylene (CF2) group in aliphatic chains: Synthesis and conformational preference of palmitic acids and nonadecane containing CF2 groups

    PubMed Central

    Wang, Yi; Callejo, Ricardo; Slawin, Alexandra M Z

    2014-01-01

    Summary The syntheses of palmitic acids and a nonadecane are reported with CF2 groups located 1,3 or 1,4 to each other along the aliphatic chain. Specifically 8,8,10,10- and 8,8,11,11-tetrafluorohexadecanoic acids (6b and 6c) are prepared as well as the singly modified analogue 8,8-difluorohexadecanoic acid (6a). Also 8,8,11,11-tetrafluorononadecane (27) is prepared as a pure hydrocarbon containing a 1,4-di-CF2 motif. The modified palmitic acids are characterized by differential scanning calorimetry (DSC) to determine melting points and phase behaviour relative to palmitic acid (62.5 °C). It emerges that 6c, with the CF2 groups placed 1,4- to each other, has a significantly higher melting point (89.9 °C) when compared to the other analogues and palmitic acid itself. It is a crystalline compound and the structure reveals an extended anti-zig-zag chain. Similarly 8,8,11,11-tetrafluorononadecane (27) adopts an extended anti-zig-zag structure. This is rationalized by dipolar relaxation between the two CF2 groups placed 1,4 to each other in the extended anti-zig-zag chain and suggests a design modification for long chain aliphatics which can introduce conformational stability. PMID:24454560

  2. Second international round robin for the quantification of serum non-transferrin-bound iron and labile plasma iron in patients with iron-overload disorders.

    PubMed

    de Swart, Louise; Hendriks, Jan C M; van der Vorm, Lisa N; Cabantchik, Z Ioav; Evans, Patricia J; Hod, Eldad A; Brittenham, Gary M; Furman, Yael; Wojczyk, Boguslaw; Janssen, Mirian C H; Porter, John B; Mattijssen, Vera E J M; Biemond, Bart J; MacKenzie, Marius A; Origa, Raffaella; Galanello, Renzo; Hider, Robert C; Swinkels, Dorine W

    2016-01-01

    Non-transferrin-bound iron and its labile (redox active) plasma iron component are thought to be potentially toxic forms of iron originally identified in the serum of patients with iron overload. We compared ten worldwide leading assays (6 for non-transferrin-bound iron and 4 for labile plasma iron) as part of an international inter-laboratory study. Serum samples from 60 patients with four different iron-overload disorders in various treatment phases were coded and sent in duplicate for analysis to five different laboratories worldwide. Some laboratories provided multiple assays. Overall, highest assay levels were observed for patients with untreated hereditary hemochromatosis and β-thalassemia intermedia, patients with transfusion-dependent myelodysplastic syndromes and patients with transfusion-dependent and chelated β-thalassemia major. Absolute levels differed considerably between assays and were lower for labile plasma iron than for non-transferrin-bound iron. Four assays also reported negative values. Assays were reproducible with high between-sample and low within-sample variation. Assays correlated and correlations were highest within the group of non-transferrin-bound iron assays and within that of labile plasma iron assays. Increased transferrin saturation, but not ferritin, was a good indicator of the presence of forms of circulating non-transferrin-bound iron. The possibility of using non-transferrin-bound iron and labile plasma iron measures as clinical indicators of overt iron overload and/or of treatment efficacy would largely depend on the rigorous validation and standardization of assays. PMID:26385212

  3. Second international round robin for the quantification of serum non-transferrin-bound iron and labile plasma iron in patients with iron-overload disorders

    PubMed Central

    de Swart, Louise; Hendriks, Jan C.M.; van der Vorm, Lisa N.; Cabantchik, Z. Ioav; Evans, Patricia J.; Hod, Eldad A.; Brittenham, Gary M.; Furman, Yael; Wojczyk, Boguslaw; Janssen, Mirian C.H.; Porter, John B.; Mattijssen, Vera E.J.M.; Biemond, Bart J.; MacKenzie, Marius A.; Origa, Raffaella; Galanello, Renzo; Hider, Robert C.; Swinkels, Dorine W.

    2016-01-01

    Non-transferrin-bound iron and its labile (redox active) plasma iron component are thought to be potentially toxic forms of iron originally identified in the serum of patients with iron overload. We compared ten worldwide leading assays (6 for non-transferrin-bound iron and 4 for labile plasma iron) as part of an international inter-laboratory study. Serum samples from 60 patients with four different iron-overload disorders in various treatment phases were coded and sent in duplicate for analysis to five different laboratories worldwide. Some laboratories provided multiple assays. Overall, highest assay levels were observed for patients with untreated hereditary hemochromatosis and β-thalassemia intermedia, patients with transfusion-dependent myelodysplastic syndromes and patients with transfusion-dependent and chelated β-thalassemia major. Absolute levels differed considerably between assays and were lower for labile plasma iron than for non-transferrin-bound iron. Four assays also reported negative values. Assays were reproducible with high between-sample and low within-sample variation. Assays correlated and correlations were highest within the group of non-transferrin-bound iron assays and within that of labile plasma iron assays. Increased transferrin saturation, but not ferritin, was a good indicator of the presence of forms of circulating non-transferrin-bound iron. The possibility of using non-transferrin-bound iron and labile plasma iron measures as clinical indicators of overt iron overload and/or of treatment efficacy would largely depend on the rigorous validation and standardization of assays. PMID:26385212

  4. Effect of site-directed mutagenic alterations on ADP-ribosyltransferase activity of the A subunit of Escherichia coli heat-labile enterotoxin.

    PubMed Central

    Lobet, Y; Cluff, C W; Cieplak, W

    1991-01-01

    Previous studies of the S1 subunit of pertussis toxin, an NAD(+)-dependent ADP-ribosyltransferase, suggested that a small amino-terminal region of amino acid sequence similarity to the active fragments of both cholera toxin and Escherichia coli heat-labile enterotoxin represents a region containing critical active-site residues that might be involved in the binding of the substrate NAD+. Other studies of two other bacterial toxins possessing ADP-ribosyltransferase activity, diphtheria toxin and Pseudomonas exotoxin A, have revealed the presence of essential glutamic acid residues vicinal to the active site. To help determine the relevance of these observations to activities of the enterotoxins, the A-subunit gene of the E. coli heat-labile enterotoxin was subjected to site-specific mutagenesis in the region encoding the amino-terminal region of similarity to the S1 subunit of pertussis toxin delineated by residues 6 through 17 and at two glutamic acid residues, 110 and 112, that are conserved in the active domains of all of the heat-labile enterotoxin variants and in cholera toxin. Mutant proteins in which arginine 7 was either deleted or replaced with lysine exhibited undetectable levels of ADP-ribosyltransferase activity. However, limited trypsinolysis of the arginine 7 mutants yielded fragmentation kinetics that were different from that yielded by the wild-type recombinant subunit or the authentic A subunit. In contrast, mutant proteins in which glutamic acid residues at either position 110 or 112 were replaced with aspartic acid responded like the wild-type subunit upon limited trypsinolysis, while exhibiting severely depressed, but detectable, ADP-ribosyltransferase activity. The latter results may indicate that either glutamic acid 110 or glutamic acid 112 of the A subunit of heat-labile enterotoxin is analogous to those active-site glutamic acids identified in several other ADP-ribosylating toxins. Images PMID:1908825

  5. Intrinsic acidity of aluminum, chromium (III) and iron (III) μ 3-hydroxo functional groups from ab initio electronic structure calculations

    NASA Astrophysics Data System (ADS)

    Rustad, James R.; Dixon, David A.; Felmy, Andrew R.

    2000-05-01

    Density functional calculations are performed on M 3(OH) 7(H 2O) 62+ and M 3O(OH) 6(H 2O) 6+ clusters for MAl, Cr(III), and Fe(III), allowing determination of the relative acidities of the μ 3-hydroxo and aquo functional groups. Contrary to previous predictions and rationalizations, Fe 3OH and Al 3OH groups have nearly the same intrinsic acidity, while Cr 3OH groups are significantly more acidic. The gas-phase acidity of the Fe 3OH site is in good agreement with the value predicted by the molecular mechanics model previously used to estimate the relative acidities of surface sites on iron oxides. [ J. R. Rustad et al. (1996)Geochim. Cosmochim. Acta 60, 1563]. Acidities of aquo functional groups were also computed for Al and Cr. The AlOH 2 site is more acidic than the Al 3OH site, whereas the Cr 3OH site is more acidic than the CrOH 2 site. These findings predict that the surface charging behavior of chromium oxides/oxyhydroxides should be distinguishable from their Fe, Al counterparts. The calculations also provide insight into why the lepidocrocite/boehmite polymorph is not observed for CrOOH.

  6. Functional groups of sialic acids involved in binding to siglecs (sialoadhesins) deduced from interactions with synthetic analogues.

    PubMed

    Kelm, S; Brossmer, R; Isecke, R; Gross, H J; Strenge, K; Schauer, R

    1998-08-01

    The siglecs, formerly called sialoadhesins, are a family of I-type lectins binding to sialic acids on the cell surface. Five members of this family have been identified: sialoadhesin, myelin-associated glycoprotein (MAG), Schwann cell myelin protein (SMP), CD22 and CD33. We have investigated the relevance of substituents at position C-9 and in the N-acetyl group of N-acetylneuraminic acid, using a series of synthetic sialic-acid analogues either on resialylated human erythrocytes or as free alpha-glycosides in hapten inhibition. All five siglecs require the hydroxy group at C-9 for binding, suggesting hydrogen bonding of this substituent with the binding site. Remarkable differences were found among the proteins in their specificity for modifications of the N-acetyl group. Whereas sialoadhesin, MAG and SMP do not tolerate a hydroxy group as in N-glycolylneuraminic acid, they bind to halogenated acetyl residues. In the case of MAG, N-fluoroacetylneuraminic acid is bound about 17-fold better than N-acetylneuraminic acid. In contrast, human and murine CD22 both show good affinity for N-glycolylneuraminic acid, but only human CD22 bound the halogenated compounds. In conclusion, our data indicate that interactions of the hydroxy group at position 9 and the N-acyl substituent contribute significantly to the binding strength. PMID:9738906

  7. Role of hydroxyl group in the inhibitive action of benzoic acid toward corrosion of aluminum in nitric acid

    SciTech Connect

    Yadav, P.N.S.; Singh, A.K.; Wadhwani, R.

    1999-10-01

    Corrosion inhibition action of benzoic acid, p-hydroxy benzoic acid, 2-4-dihydroxy benzoic acid, and 3-4-5-trihydroxy benzoic acid toward aluminum alloy 3003 (UNS A93003) in 20% (wt%) nitric acid (HNO{sub 3}) using different concentrations of these compounds at 30 C, 40 C, and 50 C has been studied thoroughly. 3-4-5-trihydroxy benzoic acid (inhibition efficiency (IE): 30% and 72%) was the most effective inhibitor followed by 2-4-dihydroxy benzoic acid (IE: 22% to 62%) p-hydroxy benzoic acid (IE: 11% to 52%), and benzoic acid (IE: 2.5% to 15%). IE increased with concentration and its maximum value was observed at 0.5% concentration of all inhibitors used. The percentage of IE of the inhibitors decreased with an increase in temperature from 30 C to 50 C. Values of heat adsorption and activation energy were calculated from weight loss data, which came out in the range for the reaction occurring at the surface. The behavior of inhibitors studied deviated from the Langmuir isotherm. The IE of higher hydroxy species was improved when more hydroxy centers were added. Anodic and cathodic polarization curves were shifted toward lower current density regions in the presence of inhibitors. This revealed that they were mixed inhibitors.

  8. A simple colorimetric chemosensor bearing a carboxylic acid group with high selectivity for CN-

    NASA Astrophysics Data System (ADS)

    Park, Gyeong Jin; Choi, Ye Won; Lee, Dongkuk; Kim, Cheal

    2014-11-01

    A new simple ‘naked eye' chemosensor 1 (sodium (E)-2-((2-(3-hydroxy-2-naphthoyl)hydrazono)methyl)benzoate) has been synthesized for detection of CN- in a mixture of DMF/H2O (9:1). The sensor 1 comprises of a naphthoic hydrazide as efficient hydrogen bonding donor group and a benzoic acid as the moiety with the water solubility. The receptor 1 showed high selectivity toward cyanide ions in a 1:1 stoichiometric manner, which induces a fast color change from colorless to yellow for CN- over other anions. Therefore, receptor 1 could be useful for cyanide detection in aqueous environment, displaying a high distinguishable selectivity from hydrogen bonded anions and being clearly visible to the naked eye.

  9. Nanoscale Distribution of Sulfonic Acid Groups Determines Structure and Binding of Water in Nafion Membranes.

    PubMed

    Ling, Xiao; Bonn, Mischa; Parekh, Sapun H; Domke, Katrin F

    2016-03-14

    The connection between the nanoscale structure of two chemically equivalent, yet morphologically distinct Nafion fuel-cell membranes and their macroscopic chemical properties is demonstrated. Quantification of the chemical interactions between water and Nafion reveals that extruded membranes have smaller water channels with a reduced sulfonic acid head group density compared to dispersion-cast membranes. As a result, a disproportionally large amount of non-bulk water molecules exists in extruded membranes, which also exhibit larger proton conductivity and larger water mobility compared to cast membranes. The differences in the physicochemical properties of the membranes, that is, the chemical constitution of the water channels and the local water structure, and the accompanying differences in macroscopic water and proton transport suggest that the chemistry of nanoscale channels is an important, yet largely overlooked parameter that influences the functionality of fuel-cell membranes. PMID:26895211

  10. Conjugal transfer and characterization of bacteriocin plasmids in group N (lactic acid) streptococci.

    PubMed Central

    Neve, H; Geis, A; Teuber, M

    1984-01-01

    Thirteen bacteriocin-producing strains of group N (lactic acid) streptococci were screened for their potential to transfer this property by conjugation to Streptococcus lactis subsp. diacetylactis Bu2-60. Bacteriocin production in three strains was plasmid encoded as shown by conjugal transfer and by analysis of cured, bacteriocin-negative derivatives of the donor strains and the transconjugants. With Streptococcus cremoris strains 9B4 and 4G6 and S. lactis subsp. diacetylactis 6F7 as donors, bacteriocin-producing transconjugants were isolated with frequencies ranging from ca. 2 X 10(-2) to 2 X 10(-1) per recipient cell. Bacteriocin-producing transconjugants had acquired a 39.6-megadalton plasmid from the donor strains 9B4 and 4G6, and a 75-megadalton plasmid from the donor strain 6F7. As shown by restriction endonuclease analysis, the plasmids from strains 9B4 and 4G6 were almost identical. The plasmid from strain 6F7 yielded some additional fragments not present in the two other plasmids. In hybridization experiments any of the three plasmids strongly hybridized with each other and with some other bacteriocin but nontransmissible plasmids from other S. cremoris strains. Homology was also detected to a variety of cryptic plasmids in lactic acid streptococci. Images PMID:6321437

  11. Leaching platinum-group metals in a sulfuric acid/chloride solution

    NASA Astrophysics Data System (ADS)

    Mahmoud, M. H. H.

    2003-04-01

    A leaching process was established based on the ability of platinum-group metals to form stable chloro-complexes in acidic chloride solutions. Industrial catalyst losses were examined for the recovery of platinum, palladium, and rhodium by leaching with a mixture of sulfuric acid and sodium chloride to avoid using aqua regia or autoclave conditions. Extraction of platinum and rhodium in 60% H2SO4 at 135°C steadily increased with increasing NaCl concentrations reaching 95% and 85%, respectively, at 0.1 M NaCl after two hours. By comparison, palladium was dissolved more quickly but also reached 85% under the same conditions. Extraction of each metal increased with temperatures up to 125°C but plateaued at higher temperatures. Similar behavior was observed with increasing H2SO4 concentrations up to 60%. More than 99% extraction of each metal was obtained after ten hours using 0.1 M NaCl and 60% H2SO4 at 125°C.

  12. Copoly(arlene ether)s containing pendant sulfonic acid groups as proton exchange membrane

    SciTech Connect

    Kim, Yu Seung; Kim, Dae Sik; Robertson, Gilles; Guiver, Michael

    2008-01-01

    A copoly(arylene ether) (PAE) with high fluorine content and a copoly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The P AE and PAEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2-phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. The sulfonic acid groups were introduced by mild post-sulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sP AE and sP AEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (DS) of 1.0 had high ion exchange capacities (IEC{sub v}(wet) (volume-based, wet state)) of 1.77 and 2.55 meq./cm{sup 3}, high proton conductivities of 135.4 and 140.1 mS/cm at 80 C, and acceptable volume-based water uptake of 44.5-51.9 vol% at 80 C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the area of outstanding properties in the trade-off plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based). Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion.

  13. Do Vermont's Floodplains Constitute an Important Source of Labile Carbon?

    NASA Astrophysics Data System (ADS)

    Perdrial, J. N.; Dolan, A.; Kemsley, M.

    2014-12-01

    Floodplains are extremely heterogeneous landscapes with respect to soil and sediment composition and can present an important source of carbon (C) during floods. For example, stream bank soils and sediments are zones of active erosion and deposition of sediment associated C. Due to the presence of plants, riparian soils contain high amounts of C that is exchanged between stream waters and banks. Abandoned channels and meander wetlands that remain hydrologically connected to the main channel contain high amounts of organic matter that can be flushed into the stream during high discharge. This heterogeneity, result of floodplain geomorphology, land cover and use, can profoundly impact the amount and type of dissolved organic matter (DOM) introduced into streams. In order to assess DOM characteristics leached from heterogeneous floodplain soils, aqueous soil extracts were performed on soil samples representative of different land covers (n=20) at four depths. Extracts were analyzed for dissolved organic C and total dissolved nitrogen with a Shimadzu C analyzer. Colored dissolved organic matter characteristics was measured with the Aqualog Fluorescence Spectrometer and quantified with parallel factor analysis (PARAFAC). Preliminary data from three floodplains in Vermont (Connecticut, Missisquoi and Mad River) show a 3D variability of longitudinal, lateral, and vertical extents on water-extractable, mobile C. Dissolved organic carbon concentrations in meander swamp samples were found up to 9 times higher than in those of soils from agricultural field indicative of an important C source. Although C concentrations in adjacent fields were low, high abundance of labile C (indicated by tryptophan-like fluorescence) in water extracts from fields indicates recent biological production of C. This labile C is easily processed by microbes and transformed to the greenhouse gas CO2. These results provide important information on the contribution and lability of different floodplain

  14. Metal contents of phytoplankton and labile particulate material in the North Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Twining, Benjamin S.; Rauschenberg, Sara; Morton, Peter L.; Vogt, Stefan

    2015-09-01

    Phytoplankton contribute significantly to global C cycling and serve as the base of ocean food webs. Phytoplankton require trace metals for growth and also mediate the vertical distributions of many metals in the ocean. We collected bulk particulate material and individual phytoplankton cells from the upper water column (<150 m) of the North Atlantic Ocean as part of the US GEOTRACES North Atlantic Zonal Transect cruise (GEOTRACES GA03). Particulate material was first leached to extract biogenic and potentially-bioavailable elements, and the remaining refractory material was digested in strong acids. The cruise track spanned several ocean biomes and geochemical regions. Particulate concentrations of metals associated primarily with lithogenic phases (Fe, Al, Ti) were elevated in surface waters nearest North America, Africa and Europe, and elements associated primarily with biogenic material (P, Cd, Zn, Ni) were also found at higher concentrations near the coasts. However metal/P ratios of labile particulate material were also elevated in the middle of the transect for Fe, Ni, Co, Cu, and V. P-normalized cellular metal quotas measured with synchrotron X-ray fluorescence (SXRF) were generally comparable to ratios in bulk labile particles but did not show mid-basin increases. Manganese and Fe ratios and cell quotas were higher in the western part of the section, nearest North America, and both elements were more enriched in bulk particles, relative to P, than in cells, suggesting the presence of labile oxyhydroxide particulate phases. Cellular Fe quotas thus did not increase in step with aeolian dust inputs, which are highest near Africa; these data suggest that the dust inputs have low bioavailability. Copper and Ni cell quotas were notably higher nearest the continental margins. Overall mean cellular metal quotas were similar to those measured in the Pacific and Southern Oceans except for Fe, which was approximately 3-fold higher in North Atlantic cells. Cellular Fe

  15. High Sensitivity Combined with Extended Structural Coverage of Labile Compounds via Nanoelectrospray Ionization at Subambient Pressures

    SciTech Connect

    Cox, Jonathan T.; Kronewitter, Scott R.; Shukla, Anil K.; Moore, Ronald J.; Smith, Richard D.; Tang, Keqi

    2014-10-07

    Subambient pressure ionization with nanoelectrospray (SPIN) has proven to be effective in producing ions with high efficiency and transmitting them to low pressures for high sensitivity mass spectrometry (MS) analysis. Here we present evidence that not only does the SPIN source improve MS sensitivity but also allows for gentler ionization conditions. The gentleness of a conventional heated capillary electrospray ionization (ESI) source and the SPIN source was compared by the liquid chromatography mass spectrometry (LC-MS) analysis of colominic acid. Colominic acid is a mixture of sialic acid polymers of different lengths containing labile glycosidic linkages between monomer units necessitating a gentle ion source. By coupling the SPIN source with high resolution mass spectrometry and using advanced data processing tools, we demonstrate much extended coverage of sialic acid polymer chains as compared to using the conventional ESI source. Additionally we show that SPIN-LC-MS is effective in elucidating polymer features with high efficiency and high sensitivity previously unattainable by the conventional ESI-LC-MS methods.

  16. An aldehyde group-based P-acid probe for selective fluorescence turn-on sensing of cysteine and homocysteine.

    PubMed

    Yang, Chunlei; Wang, Xiu; Shen, Lei; Deng, Wenping; Liu, Haiyun; Ge, Shenguang; Yan, Mei; Song, Xianrang

    2016-06-15

    A highly sensitive and selective turn on fluorescent probe P-acid-aldehyde (P-CHO) is developed for the determination of cysteine (Cys) and homocysteine (Hcy). The probe is designed and synthesized by incorporating the specific functional group aldehyde group for thiols into a stable π-conjugated material 4,4'-(2,5-dimethoxy-1,4-phenylene) bis(ethyne-2,1-diyl) dibenzoic acid (P-acid). The probe fluorescence is quenched through donor photoinduced electron transfer (d-PET) between the fluorophore (P-acid) and the recognition group (aldehyde group). In the presence of thiols, Cys and Hcy can selectively react with aldehyde group of the probe because the inhibition of d-PET between fluorophore and recognition group. Therefore, a turn-on fluorescent sensor was established for the fluorescence recovery. Under the optimized conditions, the fluorescence response of probe is directly proportional to the concentration of Cys in the range of 4-95 NM L(-1), with a detection limit 3.0 nM. In addition, the sensing system exhibits good selectively toward Cys and Hcy in the presence of other amino acids. It has been successfully applied for bioimaging of Cys and Hcy in living cells with low cell toxicity. PMID:26802748

  17. Pyrimidine-2-carboxylic Acid as an Electron-Accepting and Anchoring Group for Dye-Sensitized Solar Cells.

    PubMed

    Wu, Zhifang; Li, Xin; Ågren, Hans; Hua, Jianli; Tian, He

    2015-12-01

    We report a new dye (INPA) adopting pyrimidine-2-carboxylic acid as an electron-accepting and anchoring group to be used in dye-sensitized solar cells. IR spectral analysis indicates that the anchoring group may form two coordination bonds with TiO2 and so facilitate the interaction between the anchoring group and TiO2. The INPA-based cell exhibits an overall conversion efficiency of 5.45%, which is considerably higher than that obtained with cyanoacrylic acid commonly used as the electron acceptor. PMID:26581583

  18. A combination of omega-3 fatty acids, folic acid and B-group vitamins is superior at lowering homocysteine than omega-3 alone: A meta-analysis.

    PubMed

    Dawson, Samantha Loren; Bowe, Steven John; Crowe, Timothy Charles

    2016-06-01

    The aim of the study was to assess whether omega-3 polyunsaturated fatty acid supplementation alone or in combination with folic acid and B-group vitamins is effective in lowering homocysteine. The Medline Ovid, Embase and Cochrane databases were searched for randomized-controlled trial studies that intervened with omega-3 supplementation (with or without folic acid) and measured changes in homocysteine concentration. Studies were pooled using a random effects model for meta-analysis. Three different models were analyzed: all trials combined, omega-3 polyunsaturated fatty acid trials, and omega-3 polyunsaturated fatty acids with folic acid and B-group vitamin trials. Nineteen studies were included, consisting of 3267 participants completing 21 trials. Studies were heterogeneous; varying by dose, duration and participant health conditions. Across all trials, omega-3 supplementation was effective in lowering homocysteine by an average of 1.18μmol/L (95%CI: (-1.89, -0.48), P=.001). The average homocysteine-lowering effect was greater when omega-3 supplementation was combined with folic acid and B-group vitamins (-1.37μmol/L, 95%CI: (-2.38, -0.36), P<.01) compared to omega-3 supplementation alone (-1.09μmol/L 95%CI: (-2.04, -0.13), P=.03). Omega-3 polyunsaturated fatty acid supplementation was associated with a modest reduction in homocysteine. For the purposes of reducing homocysteine, a combination of omega-3s (0.2-6g/day), folic acid (150 - 2500μg/day) and vitamins B6 and B12 may be more effective than omega-3 supplementation alone. PMID:27188895

  19. An ultrahigh-resolution mass spectrometry index to estimate natural organic matter lability

    PubMed Central

    D'Andrilli, Juliana; Cooper, William T; Foreman, Christine M; Marshall, Alan G

    2015-01-01

    Rationale Determining the chemical constituents of natural organic matter (NOM) by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICRMS) remains the ultimate measure for probing its source material, evolution, and transport; however, lability and the fate of organic matter (OM) in the environment remain controversial. FTICRMS-derived elemental compositions are presented in this study to validate a new interpretative method to determine the extent of NOM lability from various environments. Methods FTICRMS data collected over the last decade from the same 9.4 tesla instrument using negative electrospray ionization at the National High Magnetic Field Laboratory in Tallahassee, Florida, was used to validate the application of a NOM lability index. Solid-phase extraction cartridges were used to isolate the NOM prior to FTICRMS; mass spectral peaks were calibrated internally by commonly identified NOM homologous series, and molecular formulae were determined for NOM composition and lability analysis. Results A molecular lability boundary (MLB) was developed from the FTICRMS molecular data, visualized from van Krevelen diagrams, dividing the data into more and less labile constituents. NOM constituents above the MLB at H/C ≥1.5 correspond to more labile material, whereas NOM constituents below the MLB, H/C <1.5, exhibit less labile, more recalcitrant character. Of all marine, freshwater, and glacial environments considered for this study, glacial ecosystems were calculated to contain the most labile OM. Conclusions The MLB extends our interpretation of FTICRMS NOM molecular data to include a metric of lability, and generally ranked the OM environments from most to least labile as glacial > marine > freshwater. Applying the MLB is useful not only for individual NOM FTICRMS studies, but also provides a lability threshold to compare and contrast molecular data with other FTICRMS instruments that survey NOM from around the world. Copyright © 2015

  20. [Universal implementation of pathogen inactivation in labile blood products is a major step towards transfusion safety].

    PubMed

    Cazenave, Jean-Pierre

    2010-12-01

    Transfusion of labile blood products (red cell concentrates, platelet concentrates and plasma) is vital in the absence of alternatives. Patients and doctors have always feared infections transmitted by blood, blood components and blood-derived drugs. It is potentially dangerous to delay implementation of pathogen inactivation in labile blood products pending a perfect process. Universal implementation of pathogen inactivation in labile blood products is a major step towards transfusion safety. PMID:22043595

  1. Visualization of Peroxynitrite-Induced Changes of Labile Zn2+ in the Endoplasmic Reticulum with Benzoresorufin-based Fluorescent Probes

    PubMed Central

    Lin, Wei; Buccella, Daniela; Lippard, Stephen J.

    2013-01-01

    Zn2+ plays essential roles in biology, and the homeostasis of Zn2+ is tightly regulated in all cells. Subcellular distribution and trafficking of labile Zn2+, and its interrelation with reactive nitrogen species, are poorly understood due to the scarcity of appropriate imaging tools. We report a new family of red-emitting fluorescent sensors for labile Zn2+, ZBR1-3, based on a benzoresorufin platform functionalized with dipicolylamine or picolylamine-derived metal binding groups. In combination, the pendant amines and fluorophore afford an [N3O] binding motif that resembles that of previously reported fluorescein-based sensors of the Zinpyr family, reproducing well their binding capabilities and yielding comparable Kd values in the subnanomolar and picomolar range. The ZBR sensors display up to 8.4-fold emission fluorescence enhancement upon Zn2+ binding in the cuvette, with similar responses obtained in live cells using standard wide-field fluorescence microscopy imaging. The new sensors localize spontaneously in the endoplasmic reticulum (ER) of various tested cell lines, allowing for organelle-specific monitoring of zinc levels in live cells. Study of ER zinc levels in neural stem cells (NSC) treated with a peroxynitrite generator, Sin-1, revealed an immediate decrease in labile Zn2+ thus providing evidence for a direct connection between ER stress and ER Zn2+ homeostasis. PMID:23902285

  2. Visualization of peroxynitrite-induced changes of labile Zn2+ in the endoplasmic reticulum with benzoresorufin-based fluorescent probes.

    PubMed

    Lin, Wei; Buccella, Daniela; Lippard, Stephen J

    2013-09-11

    Zn(2+) plays essential roles in biology, and the homeostasis of Zn(2+) is tightly regulated in all cells. Subcellular distribution and trafficking of labile Zn(2+), and its inter-relation with reactive nitrogen species, are poorly understood due to the scarcity of appropriate imaging tools. We report a new family of red-emitting fluorescent sensors for labile Zn(2+), ZBR1-3, based on a benzoresorufin platform functionalized with dipicolylamine or picolylamine-derived metal binding groups. In combination, the pendant amines and fluorophore afford an [N3O] binding motif that resembles that of previously reported fluorescein-based sensors of the Zinpyr family, reproducing well their binding capabilities and yielding comparable Kd values in the sub-nanomolar and picomolar ranges. The ZBR sensors display up to 8.4-fold emission fluorescence enhancement upon Zn(2+) binding in the cuvette, with similar responses obtained in live cells using standard wide-field fluorescence microscopy imaging. The new sensors localize spontaneously in the endoplasmic reticulum (ER) of various tested cell lines, allowing for organelle-specific monitoring of zinc levels in live cells. Study of ER zinc levels in neural stem cells treated with a peroxynitrite generator, Sin-1, revealed an immediate decrease in labile Zn(2+) thus providing evidence for a direct connection between ER stress and ER Zn(2+) homeostasis. PMID:23902285

  3. Aspirin's Active Metabolite Salicylic Acid Targets High Mobility Group Box 1 to Modulate Inflammatory Responses.

    PubMed

    Choi, Hyong Woo; Tian, Miaoying; Song, Fei; Venereau, Emilie; Preti, Alessandro; Park, Sang-Wook; Hamilton, Keith; Swapna, G V T; Manohar, Murli; Moreau, Magali; Agresti, Alessandra; Gorzanelli, Andrea; De Marchis, Francesco; Wang, Huang; Antonyak, Marc; Micikas, Robert J; Gentile, Daniel R; Cerione, Richard A; Schroeder, Frank C; Montelione, Gaetano T; Bianchi, Marco E; Klessig, Daniel F

    2015-01-01

    Salicylic acid (SA) and its derivatives have been used for millennia to reduce pain, fever and inflammation. In addition, prophylactic use of acetylsalicylic acid, commonly known as aspirin, reduces the risk of heart attack, stroke and certain cancers. Because aspirin is rapidly de-acetylated by esterases in human plasma, much of aspirin's bioactivity can be attributed to its primary metabolite, SA. Here we demonstrate that human high mobility group box 1 (HMGB1) is a novel SA-binding protein. SA-binding sites on HMGB1 were identified in the HMG-box domains by nuclear magnetic resonance (NMR) spectroscopic studies and confirmed by mutational analysis. Extracellular HMGB1 is a damage-associated molecular pattern molecule (DAMP), with multiple redox states. SA suppresses both the chemoattractant activity of fully reduced HMGB1 and the increased expression of proinflammatory cytokine genes and cyclooxygenase 2 (COX-2) induced by disulfide HMGB1. Natural and synthetic SA derivatives with greater potency for inhibition of HMGB1 were identified, providing proof-of-concept that new molecules with high efficacy against sterile inflammation are attainable. An HMGB1 protein mutated in one of the SA-binding sites identified by NMR chemical shift perturbation studies retained chemoattractant activity, but lost binding of and inhibition by SA and its derivatives, thereby firmly establishing that SA binding to HMGB1 directly suppresses its proinflammatory activities. Identification of HMGB1 as a pharmacological target of SA/aspirin provides new insights into the mechanisms of action of one of the world's longest and most used natural and synthetic drugs. It may also provide an explanation for the protective effects of low-dose aspirin usage. PMID:26101955

  4. Copoly(arylene ether)s containing pendant sulfonic acid groups as proton exchange membranes

    SciTech Connect

    Dae Sik, Kim; Yu Seung, Kim; Gilles, Robertson; Guiver, Michael D

    2009-01-01

    A copoly(arylene ether) (PAE) with high fluorine content and a copoly(arylene ether nitrile) (PAEN) with high nitrile content, each containing pendant phenyl sulfonic acids were synthesized. The PAE and P AEN were prepared from decafluorobiphenyl (DFBP) and difluorobenzonitrile (DFBN) respectively, by polycondensation with 2phenylhydroquinone (PHQ) by conventional aromatic nucleophilic substitution reactions. sulfonic acid groups were introduced by mild post-sulfonation exclusively on the para-position of the pendant phenyl ring in PHQ. The membrane properties of the resulting sulfonated copolymers sPAE and sPAEN were compared for fuel cell applications. The copolymers sPAE and sPAEN, each having a degree of sulfonation (OS) of 1.0 had high ion exchange capacities (IEC{sub v})(wet) (volume-based, wet state) of 1.77 and 2.55 meq./cm3, high proton conductivities of 135.4 and 140.1 mS/cm at 80 C, and acceptable volume-based water uptake of 44.5 -51.9 vol% at 80 C, respectively, compared to Nafion. The data points of these copolymer membranes are located in the upper left-hand corner in the trade-off plot of alternative hydrocarbon polyelectrolyte membranes (PEM) for the relationship between proton conductivity versus water uptake (weight based or volume based), i.e., high proton conductivity and low water uptake. Furthermore, the relative selectivity derived from proton conductivity and methanol permeability is higher than that of Nafion.

  5. Molecular Structures, Acid-Base Properties, and Formation of Group 6 Transition Metal Hydroxides

    SciTech Connect

    Li, Shenggang; Guenther, Courtney L.; Kelley, Matthew S.; Dixon, David A.

    2011-04-28

    Density functional theory (DFT) and coupled cluster theory (CCSD(T)) were used to study the group 6 metal (M = Cr, Mo, W) hydroxides: MO3-m(OH)2m (m = 1-3), M2O6-m(OH)2m (m = 1-5), M3O9-m(OH)2m (m = 1, 2), and M4O11(OH)2. The calculations were done up to the complete basis set (CBS) limit for the CCSD(T) method. Molecular structures of many low-energy conformers/isomers were located. Brønsted acidities in the gas phase and pKa values in aqueous solution were predicted for MO3-m(OH)2m (m = 1-3) and MnO3n-1(OH)2 (n = 2-4). In addition, Brønsted basicities and Lewis acidities (fluoride affinities) were predicted for MO3-m(OH)2m (m = 1-3) as well as the metal oxide clusters MnO3n (n = 1-3). The metal hydroxides were predicted to be strong Brønsted acids and weak to modest Brønsted bases and Lewis acids. The pKa values can have values as negative as -31. Potential energy surfaces for the hydrolysis of the MnO3n (n = 1-4) clusters were calculated. Heats of formation of the metal hydroxides were predicted from the calculated reaction energies, and the agreement with the limited available experimental data is good. The first hydrolysis step leading to the formation of MnO3n-1(OH)2 was predicted to be exothermic, with the exothermicity becoming less negative as n increases and essentially converged at n = 3. Reaction rate constants for the hydrogen transfer steps were calculated using transition state theory and RRKM theory. Further hydrolysis of MnO3n-1(OH)2 tends to be endothermic especially for M = Cr. Fifty-five DFT exchange-correlation functionals were benchmarked for the calculations of the reaction energies, complexation energies, and reaction barriers by comparing to our CCSD(T) results. Overall, the DFT results for the potential energy surfaces are semiquantitatively correct, but no single functional works for all processes and all three metals. Among the functionals benchmarked, the wB97, wB97X, B1B95, B97-1, mPW1LYP, and X3LYP functionals have the best

  6. Number of free hydroxyl groups on bile acid phospholipids determines the fluidity and hydration of model membranes.

    PubMed

    Sreekanth, Vedagopuram; Bajaj, Avinash

    2013-10-10

    Interactions of synthetic phospholipids with model membranes determines the drug release capabilities of phospholipid vesicles at diseased sites. We performed 1,6-diphenyl-1,3,5-hexatriene (DPH)-based fluorescence anisotropy, Laurdan-based membrane hydration, and differential scanning calorimetry (DSC) studies to cognize the interactions of three bile acid phospholipids, lithocholic acid-phosphocholine (LCA-PC), deoxycholic acid-phosphocholine (DCA-PC), and cholic acid-phosphocholine (CA-PC) with model membranes. These studies revealed that bile acid phospholipids increases membrane fluidity in DCA-PC > CA-PC > LCA-PC order, indicating that induction of membrane fluidity is contingent on the number and positioning of free hydroxyl groups on bile acids. Similarly, DCA-PC causes maximum membrane perturbations due to the presence of a free hydroxyl group, whereas LCA-PC induces gel phase in membranes due to hydrophobic bile acid acyl chain interactions. These DCA-PC-induced membrane perturbations induce a drastic decrease in phase transition temperature (Tm) as determined by calorimetric studies, whereas doping of LCA-PC causes phase transition broadening without change in Tm. Doping of CA-PC induces membrane perturbations and membrane hydration like DCA-PC but sharpening of phase transition at higher doping suggests self-association of CA-PC molecules. Therefore these differential mode of interactions between bile acid phospholipids and model membranes would help in the future for their use in drug delivery. PMID:24079709

  7. Functional group analysis in coal and on coal surfaces by NMR spectroscopy

    SciTech Connect

    Verkade, J.G.

    1990-01-01

    An accurate knowledge of the oxygen-bearing labile hydrogen functional groups (e.g., carboxylic acids, phenols and alcohols) in coal is required for today's increasingly sophisticated coal cleaning and beneficiation processes. Phospholanes (compounds having the general structure -POCH{sub 2}CH{sub 2}O (1)) are being investigated as reagents for the tagging of liable hydrogen functional groups in coal materials with the NMR-active {sup 31}P nucleus. Of twelve such reagents investigated so far, 2 (2-chloro-1,3-dioxaphospholane, ClPOCH{sub 2}CH{sub 2}O) and 8 (2-chloro-1,3-dithiaphospholane, ClPSCH{sub 2}CH{sub 2}S) have been found to be useful in identifying and quantitating, by {sup 31}P NMR spectroscopy, labile hydrogen functional groups in an Illinois No. 6 coal condensate. Reagent 2 has also been used to quantitate moisture in pyridine extracts of Argonne Premium Coal Samples. Preliminary {sup 119}Sn NMR spectroscopic results on model compounds with the new reagent CF{sub 3}C(O)NHSnMe{sub 3} (N-trimethylstannyltrifluoroacetamide, 14) suggest that labile hydrogen functional groups in coal materials may be more precisely identified with 14 than with phospholanes. 14 refs., 2 figs., 2 tabs.

  8. Following The Money: Characterizing the Dynamics of Microbial Ecosystems and Labile Organic Matter in Grassland Soils

    NASA Astrophysics Data System (ADS)

    Herbert, B. E.; McNeal, K. S.

    2006-12-01

    The dynamics of soil microbial ecosystems and labile fractions of soil organic matter in grasslands have important implications for the response of these critical ecosystems to perturbations. Organic, inorganic and genetic biomarkers in the solid (e.g. lipids, microbial DNA), liquid (e.g. porewater ions) or gaseous phases (e.g. carbon dioxide) have been used to characterize carbon cycling and soil microbial ecology. These proxies are generally limited in the amount of temporal information that they can provide (i.e., solid-phase proxies) or the amount of specific information they can provide about carbon sources or microbial community processes (e.g. inorganic gases). It is the aim of this research to validate the use of soil volatile organic carbon emissions (VOCs) as useful indicators of subsurface microbial community shifts and processes as a function of ecosystem perturbations. We present results of method validation using laboratory microcosm, where VOC metabolites as characterized by gas chromatography and mass spectrometry (GC-MS), were related to other proxies including carbon dioxide (CO2) via infra-red technology, and microbial community shifts as measured by Biolog© and fatty acid methyl ester (FAME) techniques. Experiments with soil collected from grasslands along the coastal margin region in southern Texas were preformed where environmental factors such as soil water content, soil type, and charcoal content are manipulated. Results indicate that over fifty identifiable VOC metabolites are produced from the soils, where many (~15) can be direct indicators of microbial ecology. Principle component analysis (PCA) evidences these trends through similar cluster patterns for the VOC results, the Biolog© results, and FAME. Regression analysis further shows that VOCs are significant (p < 0.05) indicators of microbial stress. Our results are encouraging that characterizing VOCs production in grassland soils are easy to measure, relatively inexpensive method

  9. Oxidative stress and labile plasmatic iron in anemic patients following blood therapy

    PubMed Central

    Fernandes, Marília Sabo; Rissi, Tatiana Tamborena; Zuravski, Luisa; Mezzomo, Juliana; Vargas, Carmen Regla; Folmer, Vanderlei; Soares, Félix Alexandre Antunes; Manfredini, Vanusa; Ahmed, Mushtaq; Puntel, Robson Luiz

    2014-01-01

    AIM: To determine the plasmatic iron content and evaluate the oxidative stress (OS) markers in subjects receiving blood therapy. METHODS: Thirty-nine individuals with unspecified anemia receiving blood transfusions and 15 healthy subjects were included in the study. Anemic subjects were divided into three subgrouP: (1) those that received up to five blood transfusions (n = 14); (2) those that received from five to ten transfusions (n = 11); and (3) those that received more than ten transfusions (n = 14). Blood samples were collected by venous arm puncture and stored in tubes containing heparin. The plasma and cells were separated by centrifugation and subsequently used for analyses. Statistical analyses were performed using Kruskal-Wallis analysis of variance followed by Dunn’s multiple comparison tests when appropriate. RESULTS: The eletrophoretic hemoglobin profiles of the subjects included in this study indicated that no patients presented with hemoglobinopathy. Labile plasmatic iron, ferritin, protein carbonyl, thiobarbituric acid-reactive substances (TBARS) and dichlorofluorescein diacetate oxidation were significantly higher (P < 0.05), whereas total thiol levels were significantly lower (P < 0.05) in transfused subjects compared to controls. Additionally, the activity of catalase, superoxide dismutase and glutathione peroxidase were significantly lower in the transfused subjects (P < 0.05). Antioxidant enzyme activities and total thiol levels were positively correlated (P < 0.05), and negatively correlated with the levels of protein carbonyl and TBARS (P < 0.05). In contrast, protein carbonyl and TBARS were positively correlated (P < 0.05). Altogether, these data confirm the involvement of OS in patients following therapy with repeated blood transfusions. CONCLUSION: Our data reveal that changes in OS markers are correlated with levels of labile plasmatic iron and ferritin and the number of transfusions. PMID:25254188

  10. Molecular insights into the microbial formation of marine dissolved organic matter: recalcitrant or labile?

    NASA Astrophysics Data System (ADS)

    Koch, B. P.; Kattner, G.; Witt, M.; Passow, U.

    2014-02-01

    The degradation of marine dissolved organic matter (DOM) is an important control variable in the global carbon cycle and dependent on the DOM composition. For our understanding of the kinetics of organic matter cycling in the ocean, it is therefore crucial to achieve a mechanistic and molecular understanding of its transformation processes. A long-term microbial experiment was performed to follow the production of non-labile DOM by marine bacteria. Two different glucose concentrations and dissolved algal exudates were used as substrates. We monitored the bacterial abundance, concentrations of dissolved and particulate organic carbon (DOC, POC), nutrients, amino acids, and transparent exopolymer particles (TEP) for two years. Ultrahigh resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) allowed the molecular characterization of extracted DOM after 70 days and after ∼2 years of incubation. Although glucose was quickly degraded, a DOC background was generated in glucose incubations. Only 20% of the organic carbon from algal exudate was degraded within the 2 years of incubation. TEP, which are released by micro-organisms, were produced during glucose degradation but decreased within less than three weeks back to half of the maximum concentration and were below detection in all treatments after 2 years. The molecular analysis demonstrated that DOM generated during glucose degradation differed appreciably from DOM produced during the degradation of the algal exudates. Our results led to several conclusions: (i) Higher substrate levels result in a higher level of non-labile DOC which is an important prerequisite for carbon sequestration in the ocean; (ii) TEP are generated by bacteria but are also degraded rapidly, thus limiting their potential contribution to carbon sequestration; (iii) The molecular signatures of DOM derived from algal exudates or glucose after 70 days of incubation differed strongly from refractory DOM. After 2 years

  11. High lability of sexual system over 250 million years of evolution in morphologically conservative tadpole shrimps

    PubMed Central

    2013-01-01

    Background Sexual system is a key factor affecting the genetic diversity, population structure, genome structure and the evolutionary potential of species. The sexual system androdioecy – where males and hermaphrodites coexist in populations – is extremely rare, yet is found in three crustacean groups, barnacles, a genus of clam shrimps Eulimnadia, and in the order Notostraca, the tadpole shrimps. In the ancient crustacean order Notostraca, high morphological conservatism contrasts with a wide diversity of sexual systems, including androdioecy. An understanding of the evolution of sexual systems in this group has been hampered by poor phylogenetic resolution and confounded by the widespread occurrence of cryptic species. Here we use a multigene supermatrix for 30 taxa to produce a comprehensive phylogenetic reconstruction of Notostraca. Based on this phylogenetic reconstruction we use character mapping techniques to investigate the evolution of sexual systems. We also tested the hypothesis that reproductive assurance has driven the evolution of androdioecy in Notostraca. Results Character mapping analysis showed that sexual system is an extremely flexible trait within Notostraca, with repeated shifts between gonochorism and androdioecy, the latter having evolved a minimum of five times. In agreement with the reproductive assurance hypothesis androdioecious notostracans are found at significantly higher latitudes than gonochoric ones indicating that post glacial re-colonisation may have selected for the higher colonisation ability conferred by androdioecy. Conclusions In contrast to their conserved morphology, sexual system in Notostraca is highly labile and the rare reproductive mode androdioecy has evolved repeatedly within the order. Furthermore, we conclude that this lability of sexual system has been maintained for at least 250 million years and may have contributed to the long term evolutionary persistence of Notostraca. Our results further our

  12. Light and heavy dansyl reporter groups in food chemistry: amino acid assay in beverages.

    PubMed

    Mazzotti, Fabio; Benabdelkamel, Hicham; Di Donna, Leonardo; Athanassopoulos, Constantinos M; Napoli, Anna; Sindona, Giovanni

    2012-07-01

    5-Dimethylamino-1-sulfonyl naphthalene (DNS, commonly referred as dansyl) is a functionality, bearing well-established properties in directing the fragmentation, by mass spectrometry (MS), of the corresponding ionized sulfonylated derivatives. This property is shared also by its labeled analogs. The use of d(0)/d(6) DNS derivatives is now exploited in the application of the well-established isotope dilution mass spectrometric approach in the assay of complex mixtures. A new method for the quantitation of amino acids (AAs) in beverages is therefore presented, which relies on liquid chromatographic separation of their N-dansylated derivatives followed by comparative electrospray tandem MS/MS of the d(0)/d(6) isobaric mixtures. Labeled and unlabeled DNS derivatives of the selected AAs are readily available by microwave-assisted synthetic protocols. The novelty of the method is represented by the use of heavy and light DNS-isotopologue providing suitable reporter groups. Multiple-reaction monitoring has been applied in the assay of AAs in wine, pineapple juice and bergamot juice with good-to-excellent results as proved by both relative standard deviation, lower than 15%, and by the accuracy values in the range 90-110%. PMID:22791261

  13. B-group vitamin production by lactic acid bacteria--current knowledge and potential applications.

    PubMed

    LeBlanc, J G; Laiño, J E; del Valle, M Juarez; Vannini, V; van Sinderen, D; Taranto, M P; de Valdez, G Font; de Giori, G Savoy; Sesma, F

    2011-12-01

    Although most vitamins are present in a variety of foods, human vitamin deficiencies still occur in many countries, mainly because of malnutrition not only as a result of insufficient food intake but also because of unbalanced diets. Even though most lactic acid bacteria (LAB) are auxotrophic for several vitamins, it is now known that certain strains have the capability to synthesize water-soluble vitamins such as those included in the B-group (folates, riboflavin and vitamin B(12) amongst others). This review article will show the current knowledge of vitamin biosynthesis by LAB and show how the proper selection of starter cultures and probiotic strains could be useful in preventing clinical and subclinical vitamin deficiencies. Here, several examples will be presented where vitamin-producing LAB led to the elaboration of novel fermented foods with increased and bioavailable vitamins. In addition, the use of genetic engineering strategies to increase vitamin production or to create novel vitamin-producing strains will also be discussed. This review will show that the use of vitamin-producing LAB could be a cost-effective alternative to current vitamin fortification programmes and be useful in the elaboration of novel vitamin-enriched products. PMID:21933312

  14. Removal of textile dyes and metallic ions using polyelectrolytes and macroelectrolytes containing sulfonic acid groups.

    PubMed

    Caldera Villalobos, M; Peláez Cid, A A; Herrera González, Ana M

    2016-07-15

    This work reports the removal of textile dyes and metallic ions by means of adsorption and coagulation-flocculation using two polyelectrolytes and two macroelectrolytes containing sulfonic acid groups. The adsorption of textile dyes was studied in aqueous solutions containing cationic dyes and in wastewater containing a vat dye. Also, removal of vat and naphthol dyes was studied using the process of coagulation-flocculation. The results show these materials possess elevated adsorption capacity, and they accomplished removal rates above 97% in aqueous solutions. The removal of the vat dye improved the quality of the wastewater notably, and an uncolored effluent was obtained at the end of the treatment. The treatment using adsorption decreased the values for coloration, conductivity, suspended solids, and pH. The removal of vat and naphthol dyes by means of coagulation-flocculation was studied as well, and removal rates of 90% were obtained. The polyelectrolytes and macroelectrolytes also proved effective in the adsorption of metallic ions in wastewater. The treatment using adsorption accomplished high removal rates of metallic ions, and it showed greater selectivity towards Cu(2+), Fe(3+) and Pb(2+). A decrease in the content of solids as well as the values for COD and conductivity was observed in the wastewater as well. The analyses of FT-IR indicated that cationic dyes and metallic ions were chemisorbed by means of ionic exchange. PMID:27082258

  15. Community Genomic and Proteomic Analyses of Chemoautotrophic Iron-Oxidizing "Leptospirillum rubarum" (Group II) and "Leptospirillum ferrodiazotrophum" (Group III) Bacteria in Acid Mine Drainage Biofilms

    SciTech Connect

    Goltsman, Daniela; Denef, Vincent; Singer, Steven; Verberkmoes, Nathan C; Lefsrud, Mark G; Mueller, Ryan; Dick, Gregory J.; Sun, Christine; Wheeler, Korin; Zelma, Adam; Baker, Brett J.; Hauser, Loren John; Land, Miriam L; Shah, Manesh B; Thelen, Michael P.; Hettich, Robert {Bob} L; Banfield, Jillian F.

    2009-01-01

    We analyzed near-complete population (composite) genomic sequences for coexisting acidophilic iron-oxidizing Leptospirillum group II and III bacteria (phylum Nitrospirae) and an extrachromosomal plasmid from a Richmond Mine, Iron Mountain, CA, acid mine drainage biofilm. Community proteomic analysis of the genomically characterized sample and two other biofilms identified 64.6% and 44.9% of the predicted proteins of Leptospirillum groups II and III, respectively, and 20% of the predicted plasmid proteins. The bacteria share 92% 16S rRNA gene sequence identity and >60% of their genes, including integrated plasmid-like regions. The extrachromosomal plasmid carries conjugation genes with detectable sequence similarity to genes in the integrated conjugative plasmid, but only those on the extrachromosomal element were identified by proteomics. Both bacterial groups have genes for community-essential functions, including carbon fixation and biosynthesis of vitamins, fatty acids, and biopolymers (including cellulose); proteomic analyses reveal these activities. Both Leptospirillum types have multiple pathways for osmotic protection. Although both are motile, signal transduction and methyl-accepting chemotaxis proteins are more abundant in Leptospirillum group III, consistent with its distribution in gradients within biofilms. Interestingly, Leptospirillum group II uses a methyl-dependent and Leptospirillum group III a methyl-independent response pathway. Although only Leptospirillum group III can fix nitrogen, these proteins were not identified by proteomics. The abundances of core proteins are similar in all communities, but the abundance levels of unique and shared proteins of unknown function vary. Some proteins unique to one organism were highly expressed and may be key to the functional and ecological differentiation of Leptospirillum groups II and III.

  16. Multi-Molar Absorption of CO2 by the Activation of Carboxylate Groups in Amino Acid Ionic Liquids.

    PubMed

    Chen, Feng-Feng; Huang, Kuan; Zhou, Yan; Tian, Zi-Qi; Zhu, Xiang; Tao, Duan-Jian; Jiang, De-En; Dai, Sheng

    2016-06-13

    A new strategy for multi-molar absorption of CO2 is reported based on activating a carboxylate group in amino acid ionic liquids. It was illustrated that introducing an electron-withdrawing site to amino acid anions could reduce the negative inductive effect of the amino group while simultaneously activating the carboxylate group to interact with CO2 very efficiently. An extremely high absorption capacity of CO2 (up to 1.69 mol mol(-1) ) in aminopolycarboxylate-based amino acid ionic liquids was thus achieved. The evidence of spectroscopic investigations and quantum-chemical calculations confirmed the interactions between two kinds of sites in the anion and CO2 that resulted in superior CO2 capacities. PMID:27136274

  17. Somatic antigens of Streptococcus group E. I. Comparison of extraction techniques.

    PubMed

    Payne, J B; Armstrong, C H

    1970-05-01

    Eleven Streptococcus group E strains, representing serotypes I, II, III, IV, V, and "untypable" isolates, were extracted by formamide, trichloroacetic acid, and hydrochloric acid under various conditions in an effort to determine the best method for recovering maximum amounts of group and type antigens. The group antigen was found to be relatively stable, and adequate amounts for identification purposes were recovered by a wide spectrum of conditions. Type-specific antigens were relatively labile, and were destroyed at low pH in acid hydrolysis or by prolonged heating in formamide hydrolysis. The best single procedure for recovering both type and group antigens from Streptococcus group E was formamide hydrolysis for 30 min at 180 C. PMID:5463578

  18. Studies of the prevalence and significance of radiolabeled bile acid malabsorption in a group of patients with idiopathic chronic diarrhea

    SciTech Connect

    Schiller, L.R.; Hogan, R.B.; Morawski, S.G.; Santa Ana, C.A.; Bern, M.J.; Norgaard, R.P.; Bo-Linn, G.W.; Fordtran, J.S.

    1987-01-01

    We studied radiolabeled fecal bile acid excretion in 11 normal subjects and 17 patients with idiopathic chronic diarrhea for three major purposes: to establish normal values for this test in the presence of increased stool volumes (induced in normal subjects by ingestion of poorly absorbable solutions); to test for bile acid malabsorption in the patients and to correlate this with an independent test of ileal function, the Schilling test; and to compare the results of the bile acid excretion test with the subsequent effect of a bile acid binding agent (cholestyramine) on stool weight. In normal subjects fecal excretion of the radiolabel was increased with increasing stool volumes. As a group, patients with idiopathic chronic diarrhea excreted radiolabeled bile acid more rapidly than normal subjects with induced diarrhea (t1/2 56 +/- 8 vs. 236 +/- 60 h, respectively, p less than 0.005). There was a statistically significant positive correlation between t1/2 of radiolabeled bile acid and Schilling test results in these patients. Although 14 of 17 patients absorbed labeled taurocholic acid less well than any of the normal subjects with comparable volumes of induced diarrhea, cholestyramine had no statistically significant effect on stool weight in the patient group, and in none of the patients was stool weight reduced to within the normal range. In summary, most patients with idiopathic chronic diarrhea have bile acid malabsorption (as measured by fecal excretion of labeled bile acid), but they do not respond to cholestyramine therapy with a significant reduction in stool weight. Although the significance of these findings was not clearly established, the most likely interpretation is that bile acid malabsorption is a manifestation of an underlying intestinal motility or absorptive defect rather than the primary cause of diarrhea.

  19. The role of labile sulfur compounds in thermochemical sulfate reduction

    NASA Astrophysics Data System (ADS)

    Amrani, Alon; Zhang, Tongwei; Ma, Qisheng; Ellis, Geoffrey S.; Tang, Yongchun

    2008-06-01

    The reduction of sulfate to sulfide coupled with the oxidation of hydrocarbons to carbon dioxide, commonly referred to as thermochemical sulfate reduction (TSR), is an important abiotic alteration process that most commonly occurs in hot carbonate petroleum reservoirs. In the present study we focus on the role that organic labile sulfur compounds play in increasing the rate of TSR. A series of gold-tube hydrous pyrolysis experiments were conducted with n-octane and CaSO4 in the presence of reduced sulfur (e.g. H2S, S°, organic S) at temperatures of 330 and 356 °C under a constant confining pressure. The in-situ pH was buffered to 3.5 (∼6.3 at room temperature) with talc and silica. For comparison, three types of oil with different total S and labile S contents were reacted under similar conditions. The results show that the initial presence of organic or inorganic sulfur compounds increases the rate of TSR. However, organic sulfur compounds, such as 1-pentanethiol or diethyldisulfide, were significantly more effective in increasing the rate of TSR than H2S or elemental sulfur (on a mole S basis). The increase in rate is achieved at relatively low concentrations of 1-pentanethiol, less than 1 wt% of the total n-octane, which is comparable to the concentration of organic S that is common in many oils (∼0.3 wt%). We examined several potential reaction mechanisms to explain the observed reactivity of organic LSC. First, the release of H2S from the thermal degradation of thiols was discounted as an important mechanism due to the significantly greater reactivity of thiol compared to an equivalent amount of H2S. Second, we considered the generation of olefines in association with the elimination of H2S during thermal degradation of thiols because olefines are much more reactive than n-alkanes during TSR. In our experiments, olefines increased the rate of TSR, but were less effective than 1-pentanethiol and other organic LSC. Third, the thermal decomposition of

  20. Grouping newly isolated docosahexaenoic acid-producing thraustochytrids based on their polyunsaturated fatty acid profiles and comparative analysis of 18S rRNA genes.

    PubMed

    Huang, Jianzhong; Aki, Tsunehiro; Yokochi, Toshihiro; Nakahara, Toro; Honda, Daiske; Kawamoto, Seiji; Shigeta, Seiko; Ono, Kazuhisa; Suzuki, Osamu

    2003-01-01

    Seven strains of marine microbes producing a significant amount of docosahexaenoic acid (DHA; C22:6, n-3) were screened from seawater collected in coastal areas of Japan and Fiji. They accumulate their respective intermediate fatty acids in addition to DHA. There are 5 kinds of polyunsaturated fatty acid (PUFA) profiles which can be described as (1) DHA/docosapentaenoic acid (DPA; C22:5, n-6), (2) DHA/DPA/eicosapentaenoic acid (EPA; C20:5, n-3), (3) DHA/EPA, (4) DHA/DPA/EPA/arachidonic acid (AA; C20:4, n-6), and (5) DHA/DPA/EPA/AA/docosatetraenoic acid (C22:4, n-6). These isolates are proved to be new thraustochytrids by their specific insertion sequences in the 18S rRNA genes. The phylogenetic tree constructed by molecular analysis of 18S rRNA genes from the isolates and typical thraustochytrids shows that strains with the same PUFA profile form each monophyletic cluster. These results suggest that the C20-22 PUFA profile may be applicable as an effective characteristic for grouping thraustochytrids. PMID:14730428

  1. Community genomic and proteomic analysis of chemoautotrophic, iron-oxidizing "Leptospirillum rubarum" (Group II) and Leptospirillum ferrodiazotrophum (Group III) in acid mine drainage biofilms

    SciTech Connect

    Goltsman, Daniela; Denef, Vincent; Singer, Steven; Verberkmoes, Nathan C; Lefsrud, Mark G; Mueller, Ryan; Dick, Gregory J.; Sun, Christine; Wheeler, Korin; Zelma, Adam; Baker, Brett J.; Hauser, Loren John; Land, Miriam L; Shah, Manesh B; Thelen, Michael P.; Hettich, Robert {Bob} L; Banfield, Jillian F.

    2009-01-01

    We analyzed near-complete population (composite) genomic sequences for coexisting acidophilic iron-oxidizing Leptospirillum Groups II and III bacteria (phylum Nitrospirae) and an extrachromosomal plasmid from a Richmond Mine, CA acid mine drainage (AMD) biofilm. Community proteomic analysis of the genomically characterized sample and two other biofilms identified 64.6% and 44.9% of the predicted proteins of Leptospirillum Groups II and III, respectively and 20% of the predicted plasmid proteins. The bacteria share 92% 16S rRNA gene sequence identity and > 60% of their genes, including integrated plasmid-like regions. The extrachromosomal plasmid encodes conjugation genes with detectable sequence similarity to genes in the integrated conjugative plasmid, but only those on the extrachromosomal element were identified by proteomics. Both bacteria have genes for community-essential functions, including carbon fixation, biosynthesis of vitamins, fatty acids and biopolymers (including cellulose); proteomic analyses reveal these activities. Both Leptospirillum types have multiple pathways for osmotic protection. Although both are motile, signal transduction and methyl-accepting chemotaxis proteins are more abundant in Leptospirillum Group III, consistent with its distribution in gradients within biofilms. Interestingly, Leptospirillum Group II uses a methyl-dependent and Leptospirillum Group III a methyl-independent response pathway. Although only Leptospirillum Group III can fix nitrogen, these proteins were not identified by proteomics. Abundances of core proteins are similar in all communities, but abundance levels of unique and shared proteins of unknown function vary. Some proteins unique to one organism were highly expressed and may be key to the functional and ecological differentiation of Leptospirillum Groups II and III.

  2. Characterization of acid functional groups of carbon dots by nonlinear regression data fitting of potentiometric titration curves

    NASA Astrophysics Data System (ADS)

    Alves, Larissa A.; de Castro, Arthur H.; de Mendonça, Fernanda G.; de Mesquita, João P.

    2016-05-01

    The oxygenated functional groups present on the surface of carbon dots with an average size of 2.7 ± 0.5 nm were characterized by a variety of techniques. In particular, we discussed the fit data of potentiometric titration curves using a nonlinear regression method based on the Levenberg-Marquardt algorithm. The results obtained by statistical treatment of the titration curve data showed that the best fit was obtained considering the presence of five Brønsted-Lowry acids on the surface of the carbon dots with constant ionization characteristics of carboxylic acids, cyclic ester, phenolic and pyrone-like groups. The total number of oxygenated acid groups obtained was 5 mmol g-1, with approximately 65% (∼2.9 mmol g-1) originating from groups with pKa < 6. The methodology showed good reproducibility and stability with standard deviations below 5%. The nature of the groups was independent of small variations in experimental conditions, i.e. the mass of carbon dots titrated and initial concentration of HCl solution. Finally, we believe that the methodology used here, together with other characterization techniques, is a simple, fast and powerful tool to characterize the complex acid-base properties of these so interesting and intriguing nanoparticles.

  3. Labile carbon and nitrogen from rhizoplane and surface soils of two perennial grasslands

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In semiarid perennial grasslands biogeochemical processes that drive nutrient dynamics may be more closely related to the quantity of labile SOM than to total SOM. A small ephemeral pool of labile soluble organic matter becomes active after pulse precipitation events. Rhizoplane soil associated with...

  4. Fully Synthetic Self-Adjuvanting α-2,9-Oligosialic Acid Based Conjugate Vaccines against Group C Meningitis

    PubMed Central

    2016-01-01

    α-2,9-Polysialic acid is an important capsular polysaccharide expressed by serotype C Neisseria meningitidis. Its protein conjugates are current vaccines against group C meningitis. To address some concerns about traditional protein conjugate vaccines, a new type of fully synthetic vaccines composed of oligosialic acids and glycolipids was explored. In this regard, α-2,9-linked di-, tri-, tetra-, and pentasialic acids were prepared and conjugated with monophosphoryl lipid A (MPLA). Immunological studies of the conjugates in C57BL/6J mouse revealed that they alone elicited robust immune responses comparable to that induced by corresponding protein conjugates plus adjuvant, suggesting the self-adjuvanting properties of MPLA conjugates. The elicited antibodies were mainly IgG2b and IgG2c, suggesting T cell dependent immunities. The antisera had strong and specific binding to α-2,9-oligosialic acids and to group C meningococcal polysaccharide and cell, indicating the ability of antibodies to selectively target the bacteria. The antisera also mediated strong bactericidal activities. Structure–activity relationship analysis of the MPLA conjugates also revealed that the immunogenicity of oligosialic acids decreased with elongated sugar chain, but all tested MPLA conjugates elicited robust immune responses. It is concluded that tri- and tetrasialic acid–MPLA conjugates are worthy of further investigation as the first fully synthetic and self-adjuvanting vaccines against group C meningitis. PMID:27163051

  5. Chemical Synthesis of a Hyaluronic Acid Decasaccharide

    PubMed Central

    Lu, Xiaowei; Kamat, Medha N.; Huang, Lijun; Huang, Xuefei

    2009-01-01

    The chemical synthesis of a hyaluronic acid decasaccharide using the pre-activation based chemoselective glycosylation strategy is described. Assembly of large oligosaccharides is generally challenging due to the increased difficulties in both glycosylation and deprotection. Indeed, the same building blocks previously employed for hyaluronic acid hexasaccharide syntheses failed to yield the desired decasaccharide. After extensive experimentation, the decasaccharide backbone was successfully constructed with an overall yield of 37% from disaccharide building blocks. The trichloroacetyl group was used as the nitrogen protective group for the glucosamine units and the addition of TMSOTf was found to be crucial to suppress the formation of trichloromethyl oxazoline side-product and enable high glycosylation yield. For deprotections, the combination of a mild basic condition and the monitoring methodology using 1H-NMR allowed the removal of all base-labile protective groups, which facilitated the generation of the fully deprotected HA decasaccharide. PMID:19764799

  6. In situ, high-resolution imaging of labile phosphorus in sediments of a large eutrophic lake.

    PubMed

    Ding, Shiming; Han, Chao; Wang, Yanping; Yao, Lei; Wang, Yan; Xu, Di; Sun, Qin; Williams, Paul N; Zhang, Chaosheng

    2015-05-01

    Understanding the labile status of phosphorus (P) in sediments is crucial for managing a eutrophic lake, but it is hindered by lacking in situ data particularly on a catchment scale. In this study, we for the first time characterized in situ labile P in sediments with the Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) technique at a two-dimensional (2D), submillimeter resolution in a large eutrophic lake (Lake Taihu, China, with an area of 2338 km(2)). The concentration of DGT-labile P in the sediment profiles showed strong variation mostly ranging from 0.01 to 0.35 mg L(-1) with a considerable number of hotspots. The horizontal heterogeneity index of labile P varied from 0.04 to 4.5. High values appeared at the depths of 0-30 mm, likely reflecting an active layer of labile P under the sediment-water interface (SWI). Concentration gradients of labile P were observed from the high-resolution 1D DGT profiles in both the sediment and overlying water layers close to the SWI. The apparent diffusion flux of P across the SWI was calculated between -21 and 65 ng cm(-2) d(-1), which showed that the sediments tended to be a source and sink of overlying water P in the algal- and macrophyte-dominated regions, respectively. The DGT-labile P in the 0-30 mm active layer showed a better correlation with overlying water P than the labile P measured by ex situ chemical extraction methods. It implies that in situ, high-resolution profiling of labile P with DGT is a more reliable approach and will significantly extend our ability in in situ monitoring of the labile status of P in sediments in the field. PMID:25720671

  7. Stabilized liquid membrane device (SLMD) for the passive, integrative sampling of labile metals in water

    USGS Publications Warehouse

    Brumbaugh, W.G.; Petty, J.D.; Huckins, J.N.; Manahan, S.E.

    2002-01-01

    A stabilized liquid membrane device (SLMD) is described for potential use as an in situ, passive, integrative sampler for cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) in natural waters. The SLMD (patent pending) consists of a 2.5-cm-wide by 15-cm-long strip of low-density polyethylene (LDPE) layflat tubing containing 1 mL of an equal mixture (v/v) of oleic acid (cis-9-octadecenoic acid) and EMO-8Q (7-[4-ethyl-1-methyloctyl]-8-quinolinol). The reagent mixture continuously diffuses to the exterior surface of the LDPE membrane, and provides for sequestration of several divalent metals for up to several weeks. Depending on sampler configuration, concentration factors of several thousand can be realized for these metal ions after just a few days. In addition to in situ deployment, the SLMD may be useful for laboratory determination of labile metal species in grab samples. Methods for minimizing the effects of water flow on the sampling rate are currently under investigation.

  8. Reversible lability by in situ reaction of self-assembled monolayers.

    PubMed

    Saavedra, Héctor M; Thompson, Christopher M; Hohman, J Nathan; Crespi, Vincent H; Weiss, Paul S

    2009-02-18

    We describe a new methodology for the fabrication of controllably displaceable monolayers using a carboxyl-functionalized self-assembled monolayer and in situ Fischer esterification, a simple and reversible chemical reaction. Using an 11-mercaptoundecanoic acid monolayer as a model system, we show that in situ esterification results in the creation of subtle chemical and structural defects. These defects promote molecular exchange reactions with n-dodecanethiol molecules, leading to the complete and rapid displacement of the exposed areas. Displacement results in well-ordered crystalline n-dodecanethiolate monolayer films. We also show that the complementary hydrolysis reaction can be employed to quench the reacted monolayer, significantly hindering further displacement. The generality of reversible lability was tested by applying the in situ esterification reaction to the structurally distinct carboxyl-functionalized molecule 3-mercapto-1-adamantanecarboxylic acid. Beyond its applicability to create mixed-composition monolayers, this methodology could be combined with chemical patterning techniques, such as microdisplacement printing, to fabricate complex functional surfaces. PMID:19170497

  9. Phase II study of zoledronic acid combined with docetaxel for non-small-cell lung cancer: West Japan Oncology Group

    PubMed Central

    Murakami, Haruyasu; Yamanaka, Takeharu; Seto, Takashi; Sugio, Kenji; Okamoto, Isamu; Sawa, Toshiyuki; Hirashima, Tomonori; Takeda, Koji; Atagi, Shinji; Fukuoka, Masahiro; Nakanishi, Yoichi; Nakagawa, Kazuhiko; Yamamoto, Nobuyuki

    2014-01-01

    The aim of this open-label, multicenter, randomized phase II trial was to evaluate the efficacy and safety of zoledronic acid in combination with docetaxel in previously treated patients with non-small-cell lung cancer (NSCLC) and bone metastases. In this study, patients randomly received docetaxel (60 mg/m2) with (group DZ) or without (group D) zoledronic acid every 21 days. There were 50 patients in each group, and the primary endpoint was progression-free survival. In an efficacy analysis of 94 patients (DZ, 48; D, 46), the median progression-free survival was 2.7 months (95% confidence interval [CI], 1.5–3.5 months) for the DZ group and 2.6 months (95% CI, 1.5–3.4 months) for the D group (stratified log-rank test, P = 0.89). The median overall survival was 10.4 months (95% CI, 7.0–15.8 months) for the DZ group and 9.7 months (95% CI, 6.1–12.5 months) for the D group (stratified log-rank test, P = 0.62). There were no clinically relevant differences in the frequencies of grade 3 or 4 adverse events between the two groups. No treatment-related deaths occurred in the DZ group. Zoledronic acid combined with docetaxel was well tolerated but did not meet the primary endpoint of demonstrating a longer progression-free survival in advanced NSCLC patients with bone metastases compared with docetaxel alone. This trial was registered with the University Hospital Medical Information Network (UMIN000001098). PMID:24837137

  10. Thiomers: Influence of molecular mass and thiol group content of poly(acrylic acid) on efflux pump inhibition.

    PubMed

    Grabovac, Vjera; Laffleur, Flavia; Bernkop-Schnürch, Andreas

    2015-09-30

    The aim of the present study was to investigate the influence of molecular mass and thiol group content of poly(acrylic acid)-cysteine conjugates on the permeation of sulforhodamine 101 and penicillin G. acting as substrates for multidrug resistance-associated protein 2 efflux pump. Poly(acrylic acids) of 2 kDa, 100 kDa, 250 kDa, 450 kDa and 3000 kDa were conjugated with cysteine. The thiol group content of all these polymers was in the range from 343.3 ± 48.4 μmol/g to 450.3 ± 76.1 μmol/g. Transport studies were performed on rat small intestine mounted in Ussing-type chambers. Since 250 kDa poly(acrylic acid) showed the highest permeation enhancing effect, additionally thiolated 250 kDa polyacrylates displaying 157.2 μmol/g, 223.0 ± 18.1 and 355.9 μmol/g thiol groups were synthesized in order to investigate the influence of thiol group content on the permeation enhancement. The permeation of sulforhodamine was 3.93- and 3.85-fold improved using 250 kDa poly(acrylic acid)-cysteine conjugate exhibiting 355.9 ± 39.5 μmol/g and 223.0 ± 18.1 μmol/g thiol groups. Using the same conjugates the permeation of penicillin G was 1.70- and 1.59-fold improved, respectively. The study demonstrates that thiolated poly(acrylic acid) inhibits Mrp2 mediated transport and that the extent of inhibition depends on the molecular mass and degree of thiolation of the polymer. PMID:26238816

  11. Influence of group composition of sulfonic acids on properties of sulfonate additives

    SciTech Connect

    Katrenko, T.I.; Bessonova, R.N.; Kuznetsova, M.G.; Potolovskii, L.A.

    1983-05-01

    Three types of sulfonic acids are formed in sulfonation of petroleum oils-- oil-soluble, oil-insoluble, and water-soluble. This study investigates the influence of the different acids on neutral calcium sulfonates. Samples are recovered from As-14 oil. Oil-insoluble synthesis failed. Water-soluble acid did synthesize with a mix of oil- and water-soluble sulfonates. Neutral calcium sulfonates synthesized from oil-soluble had good properties, from oil-insoluble, bad properties. Oil-insoluble sulfonate also has an inverse effect on cleanup, and it interferes with carbonation. These findings will help with improvements in the sulfonate additive manufacturing process.

  12. NMR contour maps as a new parameter of carboxyl's OH groups in amino acids recognition: A reason of tRNA-amino acid conjugation

    NASA Astrophysics Data System (ADS)

    Monajjemi, Majid; Wayne, Robert; Boggs, James E.

    2014-03-01

    In this work, we have applied a statistical method by computing statistical nucleus-independent chemical shifts (SNICS) in point of probes motions within a spatial shielding and de-shielding spaces around the OH groups of some amino acids. NMR contour maps as a new parameter have been created for amino-acyl-tRNA conjugation, by using a computational method to identify this model theoretically, it is critical to understand the reasons for tRNA-amino acid conjugation. DFT, NMR, 3D Gaussian distribution and Monte Carlo methods have been applied for Methionine, Serine, Histidine, Glycine and Glutamine to investigate the structural stability in the active parts of the amino acid-tRNA linkage by chemical shielding effects.

  13. Effect of warming on the degradation and production of low-molecular-weight labile organic carbon in an Arctic tundra soil

    DOE PAGESBeta

    Yang, Ziming; Wullschleger, Stan D.; Liang, Liyuan; Graham, David E.; Gu, Baohua

    2016-01-16

    The fate of soil organic carbon (SOC) stored in the Arctic permafrost is a key concern as temperatures continue to rise in the northern hemisphere. Studies and conceptual models suggest that SOC degradation is affected by the composition of SOC, but it is unclear exactly what portions of SOC are vulnerable to rapid breakdown and what mechanisms may be controlling SOC degradation upon permafrost thaw. Here, we examine the dynamic consumption and production of labile SOC in an anoxic incubation experiment using soil samples from the active layer at the Barrow Environmental Observatory, Barrow, Alaska, USA. Free-reducing sugars, alcohols, andmore » low-molecular-weight (LMW) organic acids were analyzed during incubation at either –2 or 8 °C for up to 240 days. Results show that simple sugar and alcohol SOC largely account for the initial rapid release of CO2 and CH4 through anaerobic fermentation, whereas the fermentation products, acetate and formate, are subsequently utilized as primary substrates for methanogenesis. Iron(III) reduction is correlated to acetate production and methanogenesis, suggesting its important role as an electron acceptor in tundra SOC respiration. These observations are further supported in a glucose addition experiment, in which rapid CO2 and CH4 production occurred concurrently with rapid production and consumption of labile organics such as acetate. However, addition of tannic acid, as a more complex organic substrate, showed little influence on the overall production of CO2 and CH4 and organic acids. Together our study shows that LMW labile organics in SOC control the initial rapid release of green-house gases upon warming. We thus present a conceptual framework for the labile SOC transformations and their relations to fermentation, iron reduction and methanogenesis, thereby providing the basis for improved model prediction of climate feedbacks in the Arctic.« less

  14. Pristine environments harbor a new group of oligotrophic 2,4-dichlorophenoxyacetic acid-degrading bacteria.

    PubMed Central

    Kamagata, Y; Fulthorpe, R R; Tamura, K; Takami, H; Forney, L J; Tiedje, J M

    1997-01-01

    2,4-Dichlorophenoxyacetic acid (2,4-D)-degrading bacteria were isolated from pristine environments which had no history of 2,4-D exposure. By using 2,4-D dye indicator medium or 14C-labeled 2,4-D medium, six strains were isolated from eight enrichment cultures capable of degrading 2,4-D. Phylogenetic analyses based on 16S ribosomal DNA (rDNA) sequencing and physiological properties revealed that one isolate from Hawaiian volcanic soil could be classified in the genus Variovorax (a member of the beta subdivision of the class Proteobacteria) and that the other five isolates from Hawaiian volcanic soils, Saskatchewan forest soil, and Chilean forest soil have 16S rDNAs with high degrees of similarity to those of the Bradyrhizobium group (a member of the alpha subdivision of the class Proteobacteria). All the isolates grow slowly on either nutrient media (0.1 x Bacto Peptone-tryptone-yeast extract-glucose [PTYG] or 0.1 x Luria broth [LB] medium) or 2,4-D medium, with mean generation times of 16 to 30 h, which are significantly slower than previously known 2,4-D degraders. Nutrient-rich media such as full-strength PTYG and LB medium did not allow their growth. PCR amplification using internal consensus sequences of tfdA (a gene encoding an enzyme for the first step of 2,4-D mineralization, found in pJP4 of Alcaligenes eutrophus JMP134 and some other 2,4-D-degrading bacteria) as primers and Southern hybridization with pJP4-tfdA as a probe revealed that the isolate belonging to the genus Variovorax carried the tfdA gene. This gene was transmissible to A. eutrophus JMP228 carrying a plasmid with a mutant tfdA gene. The other five isolates did not appear to carry tfdA, and 2,4-D-specific alpha-ketoglutarate-dependent dioxygenase activity could not be detected in cell lysates. These results indicate that 2,4-D-degrading bacteria in pristine environments are slow-growing bacteria and that most of their phylogenies and catabolic genes differ from those of 2,4-D degraders

  15. 5'to 3' nucleic acid synthesis using 3'-photoremovable protecting group

    DOEpatents

    Pirrung, Michael C.; Shuey, Steven W.; Bradley, Jean-Claude

    1999-01-01

    The present invention relates, in general, to a method of synthesizing a nucleic acid, and, in particular, to a method of effecting 5' to 3' nucleic acid synthesis. The method can be used to prepare arrays of oligomers bound to a support via their 5' end. The invention also relates to a method of effecting mutation analysis using such arrays. The invention further relates to compounds and compositions suitable for use in such methods.

  16. 5[prime] to 3[prime] nucleic acid synthesis using 3[prime]-photoremovable protecting group

    DOEpatents

    Pirrung, M.C.; Shuey, S.W.; Bradley, J.C.

    1999-06-01

    The present invention relates, in general, to a method of synthesizing a nucleic acid, and, in particular, to a method of effecting 5[prime] to 3[prime] nucleic acid synthesis. The method can be used to prepare arrays of oligomers bound to a support via their 5[prime] end. The invention also relates to a method of effecting mutation analysis using such arrays. The invention further relates to compounds and compositions suitable for use in such methods.

  17. Acetic acid bacteria: A group of bacteria with versatile biotechnological applications.

    PubMed

    Saichana, Natsaran; Matsushita, Kazunobu; Adachi, Osao; Frébort, Ivo; Frebortova, Jitka

    2015-11-01

    Acetic acid bacteria are gram-negative obligate aerobic bacteria assigned to the family Acetobacteraceae of Alphaproteobacteria. They are members of the genera Acetobacter, Gluconobacter, Gluconacetobacter, Acidomonas, Asaia, Kozakia, Swaminathania, Saccharibacter, Neoasaia, Granulibacter, Tanticharoenia, Ameyamaea, Neokomagataea, and Komagataeibacter. Many strains of Acetobacter and Komagataeibacter have been known to possess high acetic acid fermentation ability as well as the acetic acid and ethanol resistance, which are considered to be useful features for industrial production of acetic acid and vinegar, the commercial product. On the other hand, Gluconobacter strains have the ability to perform oxidative fermentation of various sugars, sugar alcohols, and sugar acids leading to the formation of several valuable products. Thermotolerant strains of acetic acid bacteria were isolated in order to serve as the new strains of choice for industrial fermentations, in which the cooling costs for maintaining optimum growth and production temperature in the fermentation vessels could be significantly reduced. Genetic modifications by adaptation and genetic engineering were also applied to improve their properties, such as productivity and heat resistance. PMID:25485864

  18. The Effect of Methyl, Hydroxyl, and Ketone Functional Groups on the Heterogeneous Oxidation of Succinic Acid Aerosol by OH Radicals

    NASA Astrophysics Data System (ADS)

    Chan, M.; Zhang, H.; Wilson, K. R.

    2013-12-01

    The heterogeneous oxidation of atmospheric organic aerosols can influence their effects on climate, human health, and visibility. During oxidation, functionalization occurs when an oxygenated functional group is added to a molecule, leaving the carbon skeleton intact. Fragmentation involves carbon-carbon bond cleavage and produces two products with smaller carbon numbers than the parent compound. To gain better insights into how the molecular structure of more oxygenated organic compounds affects heterogeneous reactivity, succinic acid aerosols are photo-oxidized in an aerosol flow tube reactor, and the reaction products are analyzed using Direct Analysis in Real Time Mass Spectrometry for online chemical analysis. The effect of various functional groups (CH3, OH, C=O) along the carbon backbone on the heterogeneous reaction mechanisms are also investigated using model compounds. For this series of compounds, the formation of more oxygenated products through functionalization can be explained by well-known condensation-phase reactions such as Russell and Bennett and Summers. The number of fragmentation products is found to increase with the presence of OH and CH3 groups. This can be attributed to the increased number of tertiary carbons, enhancing the fragmentation after multiple oxidation steps. Smaller dicaids (oxalic acid and malonic acid) can be formed through the fragmentation processes in the heterogeneous oxidation of succinic acid. The effect of molecular structure on reaction kinetics, volatilization, and the relative importance of functionalization and fragmentation pathways will be discussed.

  19. Membrane Transport Behavior and the Lability of Chloride on Polyphosphazenes Bearing Bulky Substituents

    SciTech Connect

    Frederick F. Stewart; John R. Klaehn; Christopher J. Orme

    2007-08-01

    Polyphosphazenes are an intriguing class of inorganic polymers where much of their functionality is derived from pendant groups attached to phosphorus. The backbone of the polymer consists of alternating phosphorus and nitrogen atoms where the bonding is conventionally drawn as alternating double and single bonds. Orbital nodes are located at each phosphorus atom resulting in electron delocalization between phosphorus atoms, but not through them. Thus, the polymer backbone has a high degree of flexibility where halogens or other leaving groups can be effectively displaced with nucleophiles. In this paper, the first known example of a polyphosphazene with large quantities of non-labile chloride substituents induced by neighboring group steric effects will be discussed. This example is the result of the substitution of poly[bis-chlorophosphazene] with the sodium salt of 3,5-di-tert-butylphenol where only 60% of the chlorines were displaced. This contrasts with the 100% substitution observed with other phenols (phenol, 4-tert-butylphenol, 3-methylphenol, etc.).

  20. Development and bioorthogonal activation of palladium-labile prodrugs of gemcitabine.

    PubMed

    Weiss, Jason T; Dawson, John C; Fraser, Craig; Rybski, Witold; Torres-Sánchez, Carmen; Bradley, Mark; Patton, E Elizabeth; Carragher, Neil O; Unciti-Broceta, Asier

    2014-06-26

    Bioorthogonal chemistry has become one of the main driving forces in current chemical biology, inspiring the search for novel biocompatible chemospecific reactions for the past decade. Alongside the well-established labeling strategies that originated the bioorthogonal paradigm, we have recently proposed the use of heterogeneous palladium chemistry and bioorthogonal Pd(0)-labile prodrugs to develop spatially targeted therapies. Herein, we report the generation of biologically inert precursors of cytotoxic gemcitabine by introducing Pd(0)-cleavable groups in positions that are mechanistically relevant for gemcitabine's pharmacological activity. Cell viability studies in pancreatic cancer cells showed that carbamate functionalization of the 4-amino group of gemcitabine significantly reduced (>23-fold) the prodrugs' cytotoxicity. The N-propargyloxycarbonyl (N-Poc) promoiety displayed the highest sensitivity to heterogeneous palladium catalysis under biocompatible conditions, with a reaction half-life of less than 6 h. Zebrafish studies with allyl, propargyl, and benzyl carbamate-protected rhodamines confirmed N-Poc as the most suitable masking group for implementing in vivo bioorthogonal organometallic chemistry. PMID:24867590

  1. Development and Bioorthogonal Activation of Palladium-Labile Prodrugs of Gemcitabine

    PubMed Central

    2014-01-01

    Bioorthogonal chemistry has become one of the main driving forces in current chemical biology, inspiring the search for novel biocompatible chemospecific reactions for the past decade. Alongside the well-established labeling strategies that originated the bioorthogonal paradigm, we have recently proposed the use of heterogeneous palladium chemistry and bioorthogonal Pd0-labile prodrugs to develop spatially targeted therapies. Herein, we report the generation of biologically inert precursors of cytotoxic gemcitabine by introducing Pd0-cleavable groups in positions that are mechanistically relevant for gemcitabine’s pharmacological activity. Cell viability studies in pancreatic cancer cells showed that carbamate functionalization of the 4-amino group of gemcitabine significantly reduced (>23-fold) the prodrugs’ cytotoxicity. The N-propargyloxycarbonyl (N-Poc) promoiety displayed the highest sensitivity to heterogeneous palladium catalysis under biocompatible conditions, with a reaction half-life of less than 6 h. Zebrafish studies with allyl, propargyl, and benzyl carbamate-protected rhodamines confirmed N-Poc as the most suitable masking group for implementing in vivo bioorthogonal organometallic chemistry. PMID:24867590

  2. Inactivation of viruses in labile blood derivatives. II. Physical methods

    SciTech Connect

    Horowitz, B.; Wiebe, M.E.; Lippin, A.; Vandersande, J.; Stryker, M.H.

    1985-11-01

    The thermal inactivation of viruses in labile blood derivatives was evaluated by addition of marker viruses (VSV, Sindbis, Sendai, EMC) to anti-hemophilic factor (AHF) concentrates. The rate of virus inactivation at 60 degrees C was decreased by at least 100- to 700-fold by inclusion of 2.75 M glycine and 50 percent sucrose, or 3.0 M potassium citrate, additives which contribute to retention of protein biologic activity. Nonetheless, at least 10(4) infectious units of each virus was inactivated within 10 hours. Increasing the temperature from 60 to 70 or 80 degrees C caused a 90 percent or greater loss in AHF activity. An even greater decline in the rate of virus inactivation was observed on heating AHF in the lyophilized state, although no loss in AHF activity was observed after 72 hours of heating at 60 degrees C. Several of the proteins present in lyophilized AHF concentrates displayed an altered electrophoretic mobility as a result of exposure to 60 degrees C for 24 hours. Exposure of lyophilized AHF to irradiation from a cobalt 60 source resulted in an acceptable yield of AHF at 1.0, but not at 2.0, megarads. At 1 megarad, greater than or equal to 6.0 logs of VSV and 3.3 logs of Sindbis virus were inactivated.

  3. Evolutionarily labile responses to a signal of aggressive intent.

    PubMed Central

    Moretz, Jason A; Morris, Molly R

    2003-01-01

    Males of many swordtail species possess vertical bar pigment patterns that are used both in courtship and agonistic interactions. Expression of the bars may function as a conventional threat signal during conflicts with rival males; bars intensify at the onset of aggression and fade in the subordinate male at contest's end. We used mirror image stimulation and bar manipulations to compare the aggressive responses of the males of four swordtail species to their barred and barless images. We found that having a response to the bars is tightly linked to having genes for bars, while the nature of the response the bars evoked varied across species. Specifically, we report the first known instance where closely related species exhibited differing and contradictory responses to a signal of aggressive motivation. Demonstrating that a signal conveys the same information across species (aggressive intent) while the response to that information has changed among species suggests that the nature of the responses are more evolutionarily labile than the signal. PMID:14613614

  4. Structural Lability of Barley Stripe Mosaic Virus Virions

    PubMed Central

    Semenyuk, Pavel I.; Abashkin, Dmitry A.; Kalinina, Natalya O.; Arutyunyan, Alexsandr M.; Solovyev, Andrey G.; Dobrov, Eugeny N.

    2013-01-01

    Virions of Barley stripe mosaic virus (BSMV) were neglected for more than thirty years after their basic properties were determined. In this paper, the physicochemical characteristics of BSMV virions and virion-derived viral capsid protein (CP) were analyzed, namely, the absorption and intrinsic fluorescence spectra, circular dichroism spectra, differential scanning calorimetry curves, and size distributions by dynamic laser light scattering. The structural properties of BSMV virions proved to be intermediate between those of Tobacco mosaic virus (TMV), a well-characterized virus with rigid rod-shaped virions, and flexuous filamentous plant viruses. The BSMV virions were found to be considerably more labile than expected from their rod-like morphology and a distant sequence relation of the BSMV and TMV CPs. The circular dichroism spectra of BSMV CP subunits incorporated into the virions, but not subunits of free CP, demonstrated a significant proportion of beta-structure elements, which were proposed to be localized mostly in the protein regions exposed on the virion outer surface. These beta-structure elements likely formed during virion assembly can comprise the N- and C-terminal protein regions unstructured in the non-virion CP and can mediate inter-subunit interactions. Based on computer-assisted structure modeling, a model for BSMV CP subunit structural fold compliant with the available experimental data was proposed. PMID:23613760

  5. Anticariogenic and phytochemical evaluation of Eucalyptus globules Labill.

    PubMed Central

    Ishnava, Kalpesh B.; Chauhan, Jenabhai B.; Barad, Mahesh B.

    2012-01-01

    In the present study, in vitro anticariogenic potential of ethyl acetate, hexane and methanol and aqueous extracts of plant leaves of Eucalyptus globules Labill. were evaluated by using four cariogenic bacteria, Lactobacillus acidophilus, Lactobacillus casei, Staphylococcus aureus and Streptococcus mutans. Agar well diffusion method and minimum inhibitory concentration (MIC) were used for this purpose. The ethyl acetate extracted fraction of plant leaves showed good inhibitory effects against all selected bacteria. In Eucalyptus globules, hexane and ethyl acetate extracts found highly effective against, Lactobacillus acidophilus with MIC value of 0.031 and 0.062 mg/mL, respectively. Qualitative phytochemical investigation of above extracts showed the presence of alkaloids, phenolic compounds, steroids, cardiac glycosides and terpenes. Based on the MIC value and bioautography, ethyl acetate of plant leaf was selected for further study. Further investigation on the structure elucidation of the bioactive compound using IR, GC-MS and NMR techniques revealed the presence of alpha-farnesene, a sesquiterpene. Eucalyptus globules plant leaf extracts have great potential as anticariogenic agents that may be useful in the treatment of oral disease. PMID:23961222

  6. Antiangiogenic nanotherapy with lipase-labile Sn-2 fumagillin prodrug

    PubMed Central

    Pan, Dipanjan; Sanyal, Nibedita; Schmieder, Anne H; Senpan, Angana; Kim, Benjamin; Yang, Xiaoxia; Hu, Grace; Allen, John S; Gross, Richard W; Wickline, Samuel A; Lanza, Gregory M

    2012-01-01

    Background The chemical instability of antiangiogenic fumagillin, combined with its poor retention during intravascular transit, requires an innovative solution for clinical translation. We hypothesized that an Sn-2 lipase-labile fumagillin prodrug in combination with a contact-facilitated drug delivery mechanism, could be used to address these problems. Methods αvβ3-targeted and nontargeted nanoparticles with and without fumagillin in the prodrug or native forms were evaluated in vitro and in vivo in the Matrigel™ (BD Biosciences, CA, USA) plug model of angiogenesis in mice. Results In vitro experiments demonstrated that the new fumagillin prodrug decreased viability at least as efficacious as the parent compound, on an equimolar basis. In the Matrigel mouse angiogenesis model, αvβ3-fumagillin prodrug decreased angiogenesis as measured by MRI (3T), while the neovasculature was unaffected with the control nanoparticles. Conclusion The present approach resolved the previously intractable problems of drug instability and premature release in transit to target sites. PMID:22709347

  7. Grouping of amino acids and recognition of protein structurally conserved regions by reduced alphabets of amino acids.

    PubMed

    Li, Jing; Wang, Wei

    2007-06-01

    Sequence alignment is a common method for finding protein structurally conserved/similar regions. However, sequence alignment is often not accurate if sequence identities between to-be-aligned sequences are less than 30%. This is because that for these sequences, different residues may play similar structural roles and they are incorrectly aligned during the sequence alignment using substitution matrix consisting of 20 types of residues. Based on the similarity of physicochemical features, residues can be clustered into a few groups. Using such simplified alphabets, the complexity of protein sequences is reduced and at the same time the key information encoded in the sequences remains. As a result, the accuracy of sequence alignment might be improved if the residues are properly clustered. Here, by using a database of aligned protein structures (DAPS), a new clustering method based on the substitution scores is proposed for the grouping of residues, and substitution matrices of residues at different levels of simplification are constructed. The validity of the reduced alphabets is confirmed by relative entropy analysis. The reduced alphabets are applied to recognition of protein structurally conserved/similar regions by sequence alignment. The results indicate that the accuracy or efficiency of sequence alignment can be improved with the optimal reduced alphabet with N around 9. PMID:17609897

  8. Leaving group activation by aromatic stacking: an alternative to general acid catalysis.

    PubMed

    Versées, Wim; Loverix, Stefan; Vandemeulebroucke, An; Geerlings, Paul; Steyaert, Jan

    2004-04-16

    General acid catalysis is a powerful and widely used strategy in enzymatic nucleophilic displacement reactions. For example, hydrolysis/phosphorolysis of the N-glycosidic bond in nucleosides and nucleotides commonly involves the protonation of the leaving nucleobase concomitant with nucleophilic attack. However, in the nucleoside hydrolase of the parasite Trypanosoma vivax, crystallographic and mutagenesis studies failed to identify a general acid. This enzyme binds the purine base of the substrate between the aromatic side-chains of Trp83 and Trp260. Here, we show via quantum chemical calculations that face-to-face stacking can raise the pKa of a heterocyclic aromatic compound by several units. Site-directed mutagenesis combined with substrate engineering demonstrates that Trp260 catalyzes the cleavage of the glycosidic bond by promoting the protonation of the purine base at N-7, hence functioning as an alternative to general acid catalysis. PMID:15050818

  9. Hydrogen-bond acidity of OH groups in various molecular environments (phenols, alcohols, steroid derivatives, and amino acids structures): experimental measurements and density functional theory calculations.

    PubMed

    Graton, Jérôme; Besseau, François; Brossard, Anne-Marie; Charpentier, Eloïse; Deroche, Arnaud; Le Questel, Jean-Yves

    2013-12-12

    The hydrogen-bond (H-bond) donating strengths of a series of 36 hydroxylic H-bond donors (HBDs) with N-methylpyrrolidinone have been measured in CCl4 solution by FTIR spectrometry. These data allow the definition of a H-bond acidity scale named pKAHY covering almost three pK units, corresponding to 16 kJ mol(-1). These results are supplemented by equilibrium constants determined in CH2Cl2 for one-third of the data set to study compounds showing a poor solubility in CCl4. A systematic comparison of these experimental results with theoretical data computed in the gas phase using DFT (density functional theory) calculations has also been carried out. Quantum electrostatic parameters appear to accurately describe the H-bond acidity of the hydroxyl group, whereas partial atomic charges according to the Merz-Singh-Kollman and CHelpG schemes are not suitable for this purpose. A substantial decrease of the H-bond acidity of the OH group is pointed out when the hydroxyl moiety is involved in intramolecular H-bond interactions. In such situations, the interactions are further characterized through AIM and NBO analyses, which respectively allow localizing the corresponding bond critical point and the quantification of a significant charge transfer from the available lone pair to the σ*OH antibonding orbital. Eventually, the H-bond ability of the hydroxyl groups of steroid derivatives and of lateral chains of amino acids are evaluated on the basis of experimental and/or theoretical data. PMID:24274054

  10. Effect of Strong Acid Functional Groups on Electrode Rise Potential in Capacitive Mixing by Double Layer Expansion

    SciTech Connect

    Hatzell, Marta C.; Raju, Muralikrishna; Watson, Valerie J.; Stack, Andrew G.; van Duin, Adri C. T.; Logan, Bruce E.

    2014-11-03

    We report that the amount of salinity-gradient energy that can be obtained through capacitive mixing based on double layer expansion depends on the extent the electric double layer (EDL) is altered in a low salt concentration (LC) electrolyte (e.g., river water). We show that the electrode-rise potential, which is a measure of the EDL perturbation process, was significantly (P = 10–5) correlated to the concentration of strong acid surface functional groups using five types of activated carbon. Electrodes with the lowest concentration of strong acids (0.05 mmol g–1) had a positive rise potential of 59 ± 4 mV in the LC solution, whereas the carbon with the highest concentration (0.36 mmol g–1) had a negative rise potential (₋31 ± 5 mV). Chemical oxidation of a carbon (YP50) using nitric acid decreased the electrode rise potential from 46 ± 2 mV (unaltered) to ₋6 ± 0.5 mV (oxidized), producing a whole cell potential (53 ± 1.7 mV) that was 4.4 times larger than that obtained with identical electrode materials (from 12 ± 1 mV). Changes in the EDL were linked to the behavior of specific ions in a LC solution using molecular dynamics and metadynamics simulations. The EDL expanded in the LC solution when a carbon surface (pristine graphene) lacked strong acid functional groups, producing a positive-rise potential at the electrode. In contrast, the EDL was compressed for an oxidized surface (graphene oxide), producing a negative-rise electrode potential. In conclusion, these results established the linkage between rise potentials and specific surface functional groups (strong acids) and demonstrated on a molecular scale changes in the EDL using oxidized or pristine carbons.

  11. Effect of Strong Acid Functional Groups on Electrode Rise Potential in Capacitive Mixing by Double Layer Expansion

    DOE PAGESBeta

    Hatzell, Marta C.; Raju, Muralikrishna; Watson, Valerie J.; Stack, Andrew G.; van Duin, Adri C. T.; Logan, Bruce E.

    2014-11-03

    We report that the amount of salinity-gradient energy that can be obtained through capacitive mixing based on double layer expansion depends on the extent the electric double layer (EDL) is altered in a low salt concentration (LC) electrolyte (e.g., river water). We show that the electrode-rise potential, which is a measure of the EDL perturbation process, was significantly (P = 10–5) correlated to the concentration of strong acid surface functional groups using five types of activated carbon. Electrodes with the lowest concentration of strong acids (0.05 mmol g–1) had a positive rise potential of 59 ± 4 mV in themore » LC solution, whereas the carbon with the highest concentration (0.36 mmol g–1) had a negative rise potential (₋31 ± 5 mV). Chemical oxidation of a carbon (YP50) using nitric acid decreased the electrode rise potential from 46 ± 2 mV (unaltered) to ₋6 ± 0.5 mV (oxidized), producing a whole cell potential (53 ± 1.7 mV) that was 4.4 times larger than that obtained with identical electrode materials (from 12 ± 1 mV). Changes in the EDL were linked to the behavior of specific ions in a LC solution using molecular dynamics and metadynamics simulations. The EDL expanded in the LC solution when a carbon surface (pristine graphene) lacked strong acid functional groups, producing a positive-rise potential at the electrode. In contrast, the EDL was compressed for an oxidized surface (graphene oxide), producing a negative-rise electrode potential. In conclusion, these results established the linkage between rise potentials and specific surface functional groups (strong acids) and demonstrated on a molecular scale changes in the EDL using oxidized or pristine carbons.« less

  12. Field method for rapid quantification of labile organic carbon in hyper-arid desert soils validated by two thermal methods

    NASA Astrophysics Data System (ADS)

    Fletcher, Lauren E.; Valdivia-Silva, Julio E.; Perez-Montaño, Saul; Condori-Apaza, Renee M.; Conley, Catharine A.; Navarro-Gonzalez, Rafael; McKay, Christopher P.

    2014-03-01

    The objective of this work was to develop a field method for the determination of labile organic carbon in hyper-arid desert soils. Industry standard methods rely on expensive analytical equipment that are not possible to take into the field, while scientific challenges require fast turn-around of large numbers of samples in order to characterize the soils throughout this region. Here we present a method utilizing acid-hydrolysis extraction of the labile fraction of organic carbon followed by potassium permanganate oxidation, which provides a quick and inexpensive approach to investigate samples in the field. Strict reagent standardization and calibration steps within this method allowed the determination of very low levels of organic carbon in hyper-arid soils, in particular, with results similar to those determined by the alternative methods of Calcination and Pyrolysis-Gas Chromatography-Mass Spectrometry. Field testing of this protocol increased the understanding of the role of organic materials in hyper-arid environments and allowed real-time, strategic decision making for planning for more detailed laboratory-based analysis.

  13. Synthesis, characterization, guest inclusion, and photophysical studies of gold nanoparticles stabilized with carboxylic acid groups of organic cavitands.

    PubMed

    Mondal, Barnali; Kamatham, Nareshbabu; Samanta, Shampa R; Jagadesan, Pradeepkumar; He, Jibao; Ramamurthy, V

    2013-10-15

    Water-soluble gold nanoparticles (AuNP) stabilized with cavitands having carboxylic acid groups have been synthesized and characterized by a variety of techniques. Apparently, the COOH groups similar to thiol are able to prevent aggregation of AuNP. These AuNP were stable either as solids or in aqueous solution. Most importantly, these cavitand functionalized AuNP were able to include organic guest molecules in their cavities in aqueous solution. Just like free cavitands (e.g., octa acid), cavitand functionalized AuNP includes guests such as 4,4'-dimethylbenzil and coumarin-1 through capsule formation. The exact structure of the capsular assembly is not known at this stage. Upon excitation there is communication between the excited guest present in the capsule and gold atoms and this results in quenching of phosphorescence from 4,4'-dimethylbenzil and fluorescence from coumarin-1. PMID:24059841

  14. Metal-organic coordination architectures of azole heterocycle ligands bearing acetic acid groups: Synthesis, structure and magnetic properties

    SciTech Connect

    Hu Bowen; Zhao Jiongpeng; Yang Qian; Hu Tongliang; Du Wenping; Bu Xianhe

    2009-10-15

    Four new coordination complexes with azole heterocycle ligands bearing acetic acid groups, [Co(L{sup 1}){sub 2}]{sub n} (1), [CuL{sup 1}N{sub 3}]{sub n} (2), [Cu(L{sup 2}){sub 2}.0.5C{sub 2}H{sub 5}OH.H{sub 2}O]{sub n} (3) and [Co(L{sup 2}){sub 2}]{sub n} (4) (here, HL{sup 1}=1H-imidazole-1-yl-acetic acid, HL{sup 2}=1H-benzimidazole-1-yl-acetic acid) have been synthesized and structurally characterized. Single-crystal structure analysis shows that 3 and 4 are 2D complexes with 4{sup 4}-sql topologies, while another 2D complex 1 has a (4{sup 3}){sub 2}(4{sup 6})-kgd topology. And 2 is a 3D complex composed dinuclear mu{sub 1,1}-bridging azido Cu{sup II} entities with distorted rutile topology. The magnetic properties of 1 and 2 have been studied. - Graphical Abstract: The synthesis, crystal structure, and magnetic properties of the new coordination complexes with azole heterocycle ligands bearing acetic acid groups are reported.

  15. Sulphydryl groups and iodo-(/sup 3/H)acetic acid labeling in proteolipids from Torpedo electroplax

    SciTech Connect

    Criado, M.; Aguilar, J.S.; De Robertis, E.

    1983-05-01

    Several fractions of proteolipids from Torpedo electroplax were separated by DEAE-cellulose chromatography in organic solvents, and the sulphydryl groups were determined by a spectrophotometric method. On the same fractions the covalent labeling with iodo-(/sup 3/H)acetic acid to sulphydryl groups was studied. In total proteolipids there were 30.3 nmol/mg protein of sulphydryl groups of which 20.6 nmoles were in the form of disulfide bonds and 10.9 nmol as free--SH groups. The highest content of sulphydryl groups (36.7 nmol/mg protein) was found in fraction II; while fraction I, that binds the cholinergic ligands, has a lower content (23.7 nmol/mg protein). The 42 Kdaltons polypeptide, which is the major band in Fraction II, has the strongest labeling with iodo-(/sup 3/H)acetic acid, while the 39 Kdaltons cholinergic polypeptide shows a lower labeling. The importance of proteolipids as channel-forming macromolecules is discussed in connection with the possible significance of the 42 Kdaltons polypeptide.

  16. Determination of labile copper, cobalt, and chromium in textile mill wastewater

    SciTech Connect

    Crain, J.S.; Essling, A.M.; Kiely, J.T.

    1997-01-01

    Copper, chromium, and cobalt species present in filtered wastewater effluent were separated by cation exchange and reverse phase chromatography. Three sample fractions were obtained: one containing metal cations (i.e., trivalent Cr, divalent Cu, and divalent Co), one containing organic species (including metallized dyes), and one containing other unretained species. The metal content of each fraction was determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The sum of the corrected data was compared to the metal content of a filtered effluent aliquot digested totally with fuming sulfuric acid. Other aliquots of the filtered effluent were spiked with the metals of interest and digested to confirm chemical yield and accuracy. Method detection limits were consistently below 20 {mu}g L{sup -1} for Cu, 30 {mu}g L{sup -1} for Co, and 10 {mu}g L{sup -1} for Cr. Spike recoveries for undifferentiated Cu and Cr were statistically indistinguishable from unity; although Co spike recoveries were slightly low ({approximately}95%), its chemical yield was 98%. Copper retention on the sodium sulfonate cation exchange resin was closely correlated with the [EDTA]/[Cu] ratio, suggesting that metals retained upon the cation exchange column were assignable to labile metal species; however, mass balances for all three elements, though reasonable ({approximately}90%), were significantly different from unity. Mechanical factors may have contributed to the material loss, but other data suggest that some metal species reacted irreversibly with the reverse phase column. 3 refs., 2 figs., 4 tabs.

  17. Apatite-forming ability of vinylphosphonic acid-based copolymer in simulated body fluid: effects of phosphate group content.

    PubMed

    Hamai, Ryo; Shirosaki, Yuki; Miyazaki, Toshiki

    2016-10-01

    Phosphate groups on materials surfaces are known to contribute to apatite formation upon exposure of the materials in simulated body fluid and improved affinity of the materials for osteoblast-like cells. Typically, polymers containing phosphate groups are organic matrices consisting of apatite-polymer composites prepared by biomimetic process using simulated body fluid. Ca(2+) incorporation into the polymer accelerates apatite formation in simulated body fluid owing because of increase in the supersaturation degree, with respect to apatite in simulated body fluid, owing to Ca(2+) release from the polymer. However, the effects of phosphate content on the Ca(2+) release and apatite-forming abilities of copolymers in simulated body fluid are rather elusive. In this study, a phosphate-containing copolymer prepared from vinylphosphonic acid, 2-hydroxyethyl methacrylate, and triethylene glycol dimethacrylate was examined. The release of Ca(2+) in Tris-NaCl buffer and simulated body fluid increased as the additive amount of vinylphosphonic acid increased. However, apatite formation was suppressed as the phosphate groups content increased despite the enhanced release of Ca(2+) from the polymer. This phenomenon was reflected by changes in the surface zeta potential. Thus, it was concluded that the apatite-forming ability of vinylphosphonic acid-2-hydroxyethyl methacrylate-triethylene glycol dimethacrylate copolymer treated with CaCl2 solution was governed by surface state rather than Ca(2+) release in simulated body fluid. PMID:27585911

  18. Trivalent chromium removal from aqueous solutions by a sol–gel synthesized silica adsorbent functionalized with sulphonic acid groups

    SciTech Connect

    Gomez-Gonzalez, Sergio Efrain; Carbajal-Arizaga, Gregorio Guadalupe; Manriquez-Gonzalez, Ricardo; De la Cruz-Hernandez, Wencel; Gomez-Salazar, Sergio

    2014-11-15

    Highlights: • Corpuscular sulphonic acid-functionalized silica holds improved uptake of chromium. • Mesopores on adsorbent facilitate (CH{sub 3}COO){sub 2}Cr{sup +} ion uptake on sulphonate sites. • Formation of chromium acetate sulphonate complex proposed from XPS results. • Fixed bed chromium uptake results suggest potential industrial use. - Abstract: A high capacity hybrid silica adsorbent was synthesized via sol–gel processing with sulphonic acid groups as trivalent chromium complex ions chelators from aqueous solutions. The synthesis included co-condensation of tetraethoxysilane (TEOS) with 3-(mercaptopropyl)trimethoxysilane (MPS), and oxidation of thiol to sulphonic acid groups. Chromium uptake kinetic, batch and fixed-bed experiments were performed to assess the removal of this metal from aqueous solutions. {sup 13}C, {sup 29}Si CPMAS NMR, FTIR, XPS were used to characterize the adsorbent structure and the nature of chromium complexes on the adsorbent surface. Chromium maximum uptake was obtained at pH 3 (72.8 mg/g). Elemental analysis results showed ligand density of 1.48 mmol sulphonic groups/g. About 407 mL of Cr(III) solution (311 mg/L) were treated to breakthrough point reaching ≤0.06 mg/L at the effluent. These results comply with USEPA regulation for chromium concentration in drinking water (≤0.1 mg/L). The adsorbent shows potential to be used in chromium separations to the industrial level.

  19. Multinomial logistic regression model to assess the levels in trans, trans-muconic acid and inferential-risk age group among benzene-exposed group.

    PubMed

    Mala, A; Ravichandran, B; Raghavan, S; Rajmohan, H R

    2010-08-01

    There are only a few studies performed on multinomial logistic regression on the benzene-exposed occupational group. A study was carried out to assess the relationship between the benzene concentration and trans-trans-muconic acid (t,t-MA), biomarkers in urine samples from petrol filling workers. A total of 117 workers involved in this occupation were selected for this current study. Generally, logistic regression analysis (LR) is a common statistical technique that could be used to predict the likelihood of categorical or binary or dichotomous outcome variables. The multinomial logistic regression equations were used to predict the relationship between benzene concentration and t,t-MA. The results showed a significant correlation between benzene and t,t-MA among the petrol fillers. Prediction equations were estimated by adopting the physical characteristic viz., age, experience in years and job categories of petrol filling station workers. Interestingly, there was no significant difference observed among experience in years. Petrol fillers and cashiers having a higher occupational risk were in the age group of ≤24 and between 25 and 34 years. Among the petrol fillers, the t,t-MA levels with exceeding ACGIH TWA-TLV level was showing to be more significant. This study demonstrated that multinomial logistic regression is an effective model for profiling the greatest risk of the benzene-exposed group caused by different explanatory variables. PMID:21120078

  20. Multinomial logistic regression model to assess the levels in trans, trans-muconic acid and inferential-risk age group among benzene-exposed group

    PubMed Central

    Mala, A.; Ravichandran, B.; Raghavan, S.; Rajmohan, H. R.

    2010-01-01

    There are only a few studies performed on multinomial logistic regression on the benzene-exposed occupational group. A study was carried out to assess the relationship between the benzene concentration and trans-trans-muconic acid (t,t-MA), biomarkers in urine samples from petrol filling workers. A total of 117 workers involved in this occupation were selected for this current study. Generally, logistic regression analysis (LR) is a common statistical technique that could be used to predict the likelihood of categorical or binary or dichotomous outcome variables. The multinomial logistic regression equations were used to predict the relationship between benzene concentration and t,t-MA. The results showed a significant correlation between benzene and t,t-MA among the petrol fillers. Prediction equations were estimated by adopting the physical characteristic viz., age, experience in years and job categories of petrol filling station workers. Interestingly, there was no significant difference observed among experience in years. Petrol fillers and cashiers having a higher occupational risk were in the age group of ≤24 and between 25 and 34 years. Among the petrol fillers, the t,t-MA levels with exceeding ACGIH TWA-TLV level was showing to be more significant. This study demonstrated that multinomial logistic regression is an effective model for profiling the greatest risk of the benzene-exposed group caused by different explanatory variables. PMID:21120078

  1. DETERMINATION OF APPARENT QUANTUM YIELD SPECTRA FOR THE FORMATION OF BIOLOGICALLY LABILE PHOTOPRODUCTS

    EPA Science Inventory

    Quantum yield spectra for the photochemical formation of biologically labile photoproducts from dissolved organic matter (DOM) have not been available previously, although they would greatly facilitate attempts to model photoproduct formation rates across latitudinal, seasonal, a...

  2. Neuropsychological correlates of emotional lability in children with ADHD

    PubMed Central

    Banaschewski, Tobias; Jennen-Steinmetz, Christine; Brandeis, Daniel; Buitelaar, Jan K.; Kuntsi, Jonna; Poustka, Luise; Sergeant, Joseph A.; Sonuga-Barke, Edmund J.; Frazier-Wood, Alexis C.; Albrecht, Björn; Chen, Wai; Uebel, Henrik; Schlotz, Wolff; van der Meere, Jaap J.; Gill, Michael; Manor, Iris; Miranda, Ana; Mulas, Fernando; Oades, Robert D.; Roeyers, Herbert; Rothenberger, Aribert; Steinhausen, Hans-Christoph; Faraone, Stephen V.; Asherson, Philip

    2012-01-01

    Background Emotional lability (EL) is commonly seen in patients with Attention Deficit/Hyperactivity Disorder (ADHD). The reasons for this association are currently unknown. To address this question we examined the relationship between ADHD and EL symptoms, and performance on a range of neuropsychological tasks to clarify whether EL symptoms are predicted by particular cognitive and/or motivational dysfunctions and whether these associations are mediated by the presence of ADHD symptoms. Methods A large multi-site sample of 424 carefully diagnosed ADHD cases and 564 unaffected siblings and controls aged 6 to 18 years performed a broad neuropsychological test battery, including a Go/No-Go Task, a warned 4-choice Reaction Time task, the Maudsley Index of Childhood Delay Aversion, and Digit span backwards. Neuropsychological variables were aggregated as indices of processing speed, response variability, executive functions, choice impulsivity and the influence of energetic and/or motivational factors. EL and ADHD symptoms were regressed on each neuropsychological variable in separate analyses controlling for age, gender and IQ, and, in subsequent regression analyses, for ADHD and EL symptoms respectively. Results Neuropsychological variables significantly predicted ADHD and EL symptoms with moderate to low regression coefficients. However, the association between neuropsychological parameters on EL disappeared entirely when the effect of ADHD symptoms was taken into account, revealing that the association between the neuropsychological performance measures and EL is completely mediated statistically by variations in ADHD symptoms. Conversely, neuropsychological effects on ADHD symptoms remained after EL symptom severity was taken into account. Conclusions The neuropsychological parameters examined here predict ADHD more strongly than EL. They cannot explain EL symptoms beyond what is already accounted for by ADHD symptom severity. The association between EL and ADHD

  3. ENSO Related Variations in the Flux and Labile Composition of Settling Particles in the Western Equatorial Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Gupta, L. P.; Kawahata, H.; Kawahata, H.

    2001-12-01

    Sediment trap moorings deployed in three distinct oceanographic zones along the equator in the western Pacific Ocean during 1991-93, 1994-95 and 1999 provided time series data on total mass and amino acid fluxes and composition of settling particulate organic matter (POM). The traps were deployed at shallow (970-1769 m) and deep (2060-4574 m) water depths, where seafloor depth ranged from 3181 to 4888 m, to collect settling particles over an interval of about 12-16 days. An intercomparison of annual averages of various parameters revealed discrete patterns in flux and composition of POM under the El Nino (1991-93, 1994-95) and La Nina (1999) conditions which prevailed over the equatorial Pacific during this experiment. In the hemipelagic zone of the far western equatorial Pacific, average total mass and amino acid fluxes were relatively higher during El Nino than during La Nina. However, in the oligotrophic warm pool and upwelling sites, total mass and amino acid fluxes were higher during La Nina. Influence of ENSO-related changes in the settling particle flux was much clearer in the hemipelagic zone compared to that in the warm pool. Average values of biogeochemical parameters such as mole ratios of Glucosamine/Galactosamine and amino acid/hexosamine, and bulk parameters like amino acid carbon and nitrogen contents relative to organic carbon and total nitrogen (THAA-C% and THAA-N%, respectively), and organic carbon normalized amino acid concentrations indicated that settling POM was more labile during La Nina at all the sites. The mole ratios Aspartic acid/beta-Alanine, Glutamic acid/gama-Aminobutyric acid, and relative mole concentration of non-protein amino acids (beta-Alanine + gama-Aminobutyric acid) suggested that POM degradation was enhanced during La Nina than during El Nino conditions at all sites.

  4. Synthesis and evaluation of novel dental monomer with branched carboxyl acid group

    PubMed Central

    Song, Linyong; Ye, Qiang; Ge, Xueping; Misra, Anil; Laurence, Jennifer S.; Berrie, Cynthia L.; Spencer, Paulette

    2014-01-01

    To enhance the water miscibility and increase the mechanical properties of dentin adhesives, a new glycerol-based monomer with vinyl and carboxylic acid, 4-((1,3-bis(-methacryloyloxy)propan-2-yl)oxy)-2-methylene-4-oxobutanoic acid (BMPMOB), was synthesized and characterized. Dentin adhesive formulations containing 2-hydroxyethyl methacrylate (HEMA), 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy) phenyl]propane (BisGMA), and BMPMOB were characterized with regard to real-time photopolymerization behavior, water sorption, dynamic mechanical analysis, and microscale three-dimensional internal morphologies and compared with HEMA/BisGMA controls. The experimental adhesive copolymers showed higher glass transition temperature and rubbery moduli, as well as improved water miscibility compared to the controls. The enhanced properties of the adhesive copolymers indicated that BMPMOB is a promising comonomer for dental restorative materials. PMID:24596134

  5. Hyaluronic acid nanogels with enzyme-sensitive cross-linking group for drug delivery.

    PubMed

    Yang, Chenchen; Wang, Xin; Yao, Xikuang; Zhang, Yajun; Wu, Wei; Jiang, Xiqun

    2015-05-10

    A methacrylation strategy was employed to functionalize hyaluronic acid and prepare hyaluronic acid (HA) nanogels. Dynamic light scattering, zeta potential analyzer and electron microscopy were utilized to characterize the nanogels and their enzyme-degradability in vitro. It was found that these nanogels had a spherical morphology with the diameter of about 70nm, and negative surface potential. When doxorubicin (DOX) was loaded into the nanogels, the diameter decreased to approximately 50nm with a drug loading content of 16% and encapsulation efficiency of 62%. Cellular uptake examinations showed that HA nanogels could be preferentially internalized by two-dimensional (2D) cells and three-dimensional (3D) multicellular spheroids (MCs) which both overexpress CD44 receptor. Near-infrared fluorescence imaging, biodistribution and penetration examinations in tumor tissue indicated that the HA nanogels could efficiently accumulate and penetrate the tumor matrix. In vivo antitumor evaluation found that DOX-loaded HA nanogels exhibited a significantly superior antitumor effect. PMID:25665867

  6. Chemical rescue, multiple ionizable groups, and general acid-base catalysis in the HDV genomic ribozyme.

    PubMed

    Perrotta, Anne T; Wadkins, Timothy S; Been, Michael D

    2006-07-01

    In the ribozyme from the hepatitis delta virus (HDV) genomic strand RNA, a cytosine side chain is proposed to facilitate proton transfer in the transition state of the reaction and, thus, act as a general acid-base catalyst. Mutation of this active-site cytosine (C75) reduced RNA cleavage rates by as much as one million-fold, but addition of exogenous cytosine and certain nucleobase or imidazole analogs can partially rescue activity in these mutants. However, pH-rate profiles for the rescued reactions were bell shaped, and only one leg of the pH-rate curve could be attributed to ionization of the exogenous nucleobase or buffer. When a second potential ionizable nucleobase (C41) was removed, one leg of the bell-shaped curve was eliminated in the chemical-rescue reaction. With this construct, the apparent pK(a) determined from the pH-rate profile correlated with the solution pK(a) of the buffer, and the contribution of the buffer to the rate enhancement could be directly evaluated in a free-energy or Brønsted plot. The free-energy relationship between the acid dissociation constant of the buffer and the rate constant for cleavage (Brønsted value, beta, = approximately 0.5) was consistent with a mechanism in which the buffer acted as a general acid-base catalyst. These data support the hypothesis that cytosine 75, in the intact ribozyme, acts as a general acid-base catalyst. PMID:16690998

  7. Nucleic acids encoding modified human immunodeficiency virus type 1 (HIV-1) group M consensus envelope glycoproteins

    DOEpatents

    Haynes, Barton F.; Gao, Feng; Korber, Bette T.; Hahn, Beatrice H.; Shaw, George M.; Kothe, Denise; Li, Ying Ying; Decker, Julie; Liao, Hua-Xin

    2011-12-06

    The present invention relates, in general, to an immunogen and, in particular, to an immunogen for inducing antibodies that neutralizes a wide spectrum of HIV primary isolates and/or to an immunogen that induces a T cell immune response. The invention also relates to a method of inducing anti-HIV antibodies, and/or to a method of inducing a T cell immune response, using such an immunogen. The invention further relates to nucleic acid sequences encoding the present immunogens.

  8. Saxitoxins and okadaic acid group: accumulation and distribution in invertebrate marine vectors from Southern Chile.

    PubMed

    García, Carlos; Pérez, Francisco; Contreras, Cristóbal; Figueroa, Diego; Barriga, Andrés; López-Rivera, Américo; Araneda, Oscar F; Contreras, Héctor R

    2015-01-01

    Harmful algae blooms (HABs) are the main source of marine toxins in the aquatic environment surrounding the austral fjords in Chile. Huichas Island (Aysén) has an history of HABs spanning more than 30 years, but there is limited investigation of the bioaccumulation of marine toxins in the bivalves and gastropods from the Region of Aysén. In this study, bivalves (Mytilus chilenses, Choromytilus chorus, Aulacomya ater, Gari solida, Tagelus dombeii and Venus antiqua) and carnivorous gastropods (Argobuccinum ranelliformes and Concholepas concholepas) were collected from 28 sites. Researchers analysed the accumulation of STX-group toxins using a LC with a derivatisation post column (LC-PCOX), while lipophilic toxins (OA-group, azapiracids, pectenotoxins and yessotoxins) were analysed using LC-MS/MS with electrospray ionisation (+/-) in visceral (hepatopancreas) and non-visceral tissues (mantle, adductor muscle, gills and foot). Levels of STX-group and OA-group toxins varied among individuals from the same site. Among all tissue samples, the highest concentrations of STX-group toxins were noted in the hepatopancreas in V. antiqua (95 ± 0.1 μg STX-eq 100 g(-1)), T. dombeii (148 ± 1.4 μg STX-eq 100 g(-1)) and G. solida (3232 ± 5.2 μg STX-eq 100 g(-1); p < 0.05); in the adductor muscle in M. chilensis (2495 ± 6.4 μg STX-eq 100 g(-1); p < 0.05) and in the foot in C. concholepas (81 ± 0.7 μg STX-eq 100 g(-1)) and T. dombeii (114 ± 1.2 μg STX-eq 100 g(-1)). The highest variability of toxins was detected in G. solida, where high levels of carbamate derivatives were identified (GTXs, neoSTX and STX). In addition to the detected hydrophilic toxins, OA-group toxins were detected (OA and DTX-1) with an average ratio of ≈1:1. The highest levels of OA-group toxins were in the foot of C. concholepas, with levels of 400.3 ± 3.6 μg OA eq kg(-1) (p < 0.05) and with a toxic profile composed of 90% OA. A wide range of OA-group toxins was detected in M. chilensis with a

  9. Effect of the Methylation and N-H Acidic Group on the Physicochemical Properties of Imidazolium-Based Ionic Liquids.

    PubMed

    Rodrigues, Ana S M C; Rocha, Marisa A A; Almeida, Hugo F D; Neves, Catarina M S S; Lopes-da-Silva, José A; Freire, Mara G; Coutinho, João A P; Santos, Luís M N B F

    2015-07-16

    This work presents and highlights the differentiation of the physicochemical properties of the [C1Him][NTf2], [C2Him][NTf2], [(1)C1(2)C1Him][NTf2], and [(1)C4(2)C1(3)C1im][NTf2] that is related with the strong bulk interaction potential, which highlights the differentiation on the physicochemical arising from the presence of the acidic group (N-H) as well as the methylation in position 2, C(2), of the imidazolium ring. Densities, viscosities, refractive indices, and surface tensions in a wide range of temperatures, as well as isobaric heat capacities at 298.15 K, for this IL series are presented and discussed. It was found that the volumetric properties are barely affected by the geometric and structural isomerization, following a quite regular trend. A linear correlation between the glass transition temperature, Tg, and the alkyl chain size was found; however, ILs with the acidic N-H group present a significant higher Tg than the [(1)CN-1(3)C1im][NTf2] and [(1)CN(3)CNim][NTf2] series. It was found that the most viscous ILs, ([(1)C1Him][NTf2], [(1)C2Him][NTf2], and [(1)C1(2)C1Him][NTf2]) have an acidic N-H group in the imidazolium ring in agreement with the observed increase of energy barrier of flow. The methylation in position 2, C(2), as well as the N-H acidic group in the imidazolium ring contribute to a significant variation in the cation-anion interactions and their dynamics, which is reflected in their charge distribution and polarizability leading to a significant differentiation of the refractive indices, surface tension, and heat capacities. The observed differentiation of the physicochemical properties of the [(1)C1Him][NTf2], [(1)C2Him][NTf2], [(1)C1(2)C1Him][NTf2], and [(1)C4(2)C1(3)C1im][NTf2] are an indication of the stronger bulk interaction potential, which highlights the effect that arises from the presence of the acidic group (N-H) as well as the methylation in position 2 of the imidazolium ring. PMID:26082427

  10. Multivariate Statistical Analysis of Labile Trace Elements in H Chondrites: Evidence for Meteoroid Streams

    NASA Astrophysics Data System (ADS)

    Wolf, S. F.; Lipschutz, M. E.

    1992-07-01

    Differences have been observed between meteorite populations with vastly different terrestrial ages, i.e. Antarctic and non-Antarctic meteorite populations (Koeberl and Cassidy, 1991 and references therein). Comparisons of labile trace element contents (Wolf and Lipschutz, 1992) and induced TL parameters (Benoit and Sears, 1992) in samples from Victoria Land and Queen Maud Land, populations which also differ in mean terrestrial age (Nishiizumi et al, 1989), show significant differences consistent with different average thermal histories. These differences are consistent with the proposition that the flux of meteoritic material to Earth varied temporally. Variations in the flux of meteoritic material over time scales of 10^5 10^6 y require the existence of undispersed streams of meteoroids of asteroidal origin which were initially disputed by Wetherill ( 1986) but have since been observed (Olsson-Steele, 1988; Oberst, 1989; Halliday et al. 1990). Orbital evidence for meteoroid and asteroid streams has been independently obtained by others, particularly Halliday et al.(1990) and Drummond (1991). A group of H chondrites of various petrographic types and diverse CRE ages that yielded 16 falls from 1855 until 1895 in the month of May has been proposed to be two co-orbital meteoroid streams with a common source (R. T. Dodd, personal communication). Compositional evidence of a preterrestrial association of the proposed stream members, if it exists, might be observed in the most sensitive indicators of genetic thermal history, the labile trace elements. We report RNAA data for the concentrations of 14 trace elements, mostly labile ones, (Ag, Au, Bi, Cd, Cs, Co, Ga, In, Rb, Sb, Se, Te, Tl, and Zn) in H4-6 ordinary chondrites. Variance of elemental concentrations within a subpopulation, the members of a proposed co-orbital meteorite stream for example, could be expected to be smaller than the variance for the entire population. We utilize multivariate linear regression and

  11. Characteristic constants of 2,2',4'-trihydroxyazobenzene-5-sulfonic acid, a reagent for spectrophotometric analysis

    USGS Publications Warehouse

    Fletcher, Mary H.

    1960-01-01

    The dye 2,2',4'-trihydroxyazobenzene-5-sulfonic acid, has shown promise as a reagent for the determination of zirconium. As the literature contains very little information about this dye, basic data pertinent to its use as a reagent were determined. The sulfonic acid group and all three of the hydroxy groups show acidic characteristics. Apparent dissociation constants were determined for the three more labile protons and the approximate order of magnitude for the fourth constant was estimated. Absorption spectra for the different ionization species are given. A curve is also included which shows the fraction of dye in the different ionization forms at acidities from 10.35M hydrochloric acid to pH 11.9. A sixth dye species was found in 1.0 to 8.4M potassium hydroxide solutions, but its nature is unknown.

  12. The conformational properties of α,β-dehydroamino acids with a C-terminal ester group.

    PubMed

    Siodłak, Dawid; Grondys, Justyna; Broda, Małgorzata A

    2011-10-01

    α,β-Dehydroamino acid esters occur in nature. To investigate their conformational properties, a systematic theoretical analysis was performed on the model molecules Ac-ΔXaa-OMe [ΔXaa = ΔAla, (E)-ΔAbu, (Z)-ΔAbu, ΔVal] at the B3LYP/6-311+ + G(d,p) level in the gas phase as well as in chloroform and water solutions with the self-consistent reaction field-polarisable continuum model method. The Fourier transform IR spectra in CCl(4) and CHCl(3) have been analysed as well as the analogous solid state conformations drawn from The Cambridge Structural Database. The ΔAla residue has a considerable tendency to adopt planar conformations C5 (ϕ, ψ ≈ - 180°, 180°) and β2 (ϕ, ψ ≈ - 180°, 0°), regardless of the environment. The ΔVal residue prefers the conformation β2 (ϕ, ψ ≈ - 120°, 0°) in a low polar environment, but the conformations α (ϕ, ψ ≈ - 55°, 35°) and β (ϕ, ψ ≈ - 55°, 145°) when the polarity increases. The ΔAbu residues reveal intermediate properties, but their conformational dispositions depend on configuration of the side chain of residue: (E)-ΔAbu is similar to ΔAla, whereas (Z)-ΔAbu to ΔVal. Results indicate that the low-energy conformation β2 is the characteristic feature of dehydroamino acid esters. The studied molecules constitute conformational patterns for dehydroamino acid esters with various side chain substituents in either or both Z and E positions. PMID:21805538

  13. Purified group X secretory phospholipase A(2) induced prominent release of arachidonic acid from human myeloid leukemia cells.

    PubMed

    Hanasaki, K; Ono, T; Saiga, A; Morioka, Y; Ikeda, M; Kawamoto, K; Higashino, K; Nakano, K; Yamada, K; Ishizaki, J; Arita, H

    1999-11-26

    Group X secretory phospholipase A(2) (sPLA(2)-X) possesses several structural features characteristic of both group IB and IIA sPLA(2)s (sPLA(2)-IB and -IIA) and is postulated to be involved in inflammatory responses owing to its restricted expression in the spleen and thymus. Here, we report the purification of human recombinant COOH-terminal His-tagged sPLA(2)-X, the preparation of its antibody, and the purification of native sPLA(2)-X. The affinity-purified sPLA(2)-X protein migrated as various molecular species of 13-18 kDa on SDS-polyacrylamide gels, and N-glycosidase F treatment caused shifts to the 13- and 14-kDa bands. NH(2)-terminal amino acid sequencing analysis revealed that the 13-kDa form is a putative mature sPLA(2)-X and the 14-kDa protein possesses a propeptide of 11 amino acid residues attached at the NH(2) termini of the mature protein. Separation with reverse-phase high performance liquid chromatography revealed that N-linked carbohydrates are not required for the enzymatic activity and pro-sPLA(2)-X has a relatively weak potency compared with the mature protein. The mature sPLA(2)-X induced the release of arachidonic acid from phosphatidylcholine more efficiently than other human sPLA(2) groups (IB, IIA, IID, and V) and elicited a prompt and marked release of arachidonic acid from human monocytic THP-1 cells compared with sPLA(2)-IB and -IIA with concomitant production of prostaglandin E(2). A prominent release of arachidonic acid was also observed in sPLA(2)-X-treated human U937 and HL60 cells. Immunohistochemical analysis of human lung preparations revealed its expression in alveolar epithelial cells. These results indicate that human sPLA(2)-X is a unique N-glycosylated sPLA(2) that releases arachidonic acid from human myeloid leukemia cells more efficiently than sPLA(2)-IB and -IIA. PMID:10567392

  14. Immobilization of DNA via oligonucleotides containing an aldehyde or carboxylic acid group at the 5' terminus.

    PubMed Central

    Kremsky, J N; Wooters, J L; Dougherty, J P; Meyers, R E; Collins, M; Brown, E L

    1987-01-01

    A general method for the immobilization of DNA through its 5'-end has been developed. A synthetic oligonucleotide, modified at its 5'-end with an aldehyde or carboxylic acid, was attached to latex microspheres containing hydrazide residues. Using T4 polynucleotide ligase and an oligonucleotide splint, a single stranded 98mer was efficiently joined to the immobilized synthetic fragment. After impregnation of the latex microspheres with the fluorescent dye, Nile Red and attachment of an aldehyde 16mer, 5 X 10(5) bead-DNA conjugates could be detected with a conventional fluorimeter. Images PMID:3562241

  15. NMR chemical shifts in amino acids: Effects of environments, electric field, and amine group rotation

    SciTech Connect

    Yoon, Young-Gui; Pfrommer, Bernd G.; Louie, Steven G.; Canning, Andrew

    2002-03-03

    The authors present calculations of NMR chemical shifts in crystalline phases of some representative amino acids such as glycine, alanine, and alanyl-alanine. To get an insight on how different environments affect the chemical shifts, they study the transition from the crystalline phase to completely isolated molecules of glycine. In the crystalline limit, the shifts are dominated by intermolecular hydrogen-bonds. In the molecular limit, however, dipole electric field effects dominate the behavior of the chemical shifts. They show that it is necessary to average the chemical shifts in glycine over geometries. Tensor components are analyzed to get the angle dependent proton chemical shifts, which is a more refined characterization method.

  16. Human platelets respond differentially to lysophosphatidic acids having a highly unsaturated fatty acyl group and alkyl ether-linked lysophosphatidic acids.

    PubMed Central

    Tokumura, Akira; Sinomiya, Junya; Kishimoto, Seishi; Tanaka, Tamotsu; Kogure, Kentaro; Sugiura, Takayuki; Satouchi, Kiyoshi; Waku, Keizo; Fukuzawa, Kenji

    2002-01-01

    Lysophosphatidic acid (LPA) is a physiological agonist that is produced by lysophospholipase D, phospholipase A(1) and phospholipase A(2) in the blood of animals. It exerts diverse biological actions on a broad range of animal cells. Specific receptors for this important agonist have been characterized. In this investigation, for the first time we prepared LPAs having a highly unsaturated fatty acyl group, such as the eicosapentaenoyl or docosahexaenoyl residue, and their acetylated derivatives. Human platelets aggregated more potently in response to the highly unsaturated acyl-LPAs than to LPAs with a C(18) fatty acyl group, such as an oleoyl group, while alkyl ether-linked LPAs (alkyl-LPA) had much stronger aggregating activity. Two positional isomers of LPAs with an arachidonoyl, eicosapentaenoyl or docosahexaenoyl group had equipotent aggregatory activity as well as the positional isomers of their acetylated analogues, indicating that putative LPA receptors could not distinguish the difference between the positional isomers. We found that platelet preparations from two individuals showed no aggregatory response to alkyl-LPAs, although they contained mRNAs for known LPA receptors in the following order of expression level: endothelial differentiation gene (Edg)-4>Edg-7>Edg-2. We also obtained evidence that 2-(p-amylcinnamoyl)amino-4-chlorobenzoic acid (ONO-RS-082), a phospholipase A(2) inhibitor, potentiated alkyl-LPA-induced platelet aggregation, but inhibited highly unsaturated acyl-LPA-induced platelet aggregation. These results indicated that human platelets express acyl-LPA-selective and alkyl-LPA-selective receptors on their plasma membrane. PMID:11982483

  17. Identification of csrR/csrS, a genetic locus that regulates hyaluronic acid capsule synthesis in group A Streptococcus.

    PubMed

    Levin, J C; Wessels, M R

    1998-10-01

    The hyaluronic acid capsule of group A Streptococcus (GAS) is an important virulence factor, but little is known about mechanisms that regulate capsule expression. Transposon Tn916 mutagenesis of the poorly encapsulated M-type 3 GAS strain DLS003 produced a transconjugant that exhibited a mucoid colony morphology, reflecting increased hyaluronic acid capsule production. Analysis of chromosomal DNA sequence immediately downstream of the transposon insertion identified two open reading frames, designated csrR and csrS, which exhibited sequence similarity to bacterial two-component regulatory systems. We constructed an in-frame deletion mutation within csrR, which encodes the putative response component. Replacement of the native csrR gene in the DLS003 chromosome with the mutant allele resulted in a sixfold increase in capsule production and a corresponding increase in transcription of the has operon, which contains the essential genes for hyaluronic acid synthesis. Increased capsule production by the csrR mutant strain was associated with enhanced resistance to complement-mediated opsonophagocytic killing in vitro and with a 500-fold increase in virulence in mice. These results establish CsrR as a negative regulator of hyaluronic acid capsule synthesis and suggest that it is part of a two-component regulatory system that influences capsule expression and virulence. PMID:9786197

  18. Group 11 complexes with amino acid derivatives: Synthesis and antitumoral studies.

    PubMed

    Ortego, Lourdes; Meireles, Margarida; Kasper, Cornelia; Laguna, Antonio; Villacampa, M Dolores; Gimeno, M Concepción

    2016-03-01

    Gold(I), gold(III), silver(I) and copper(I) complexes with modified amino acid esters and phosphine ligands have been prepared in order to test their cytotoxic activity. Two different phosphine fragments, PPh3 and PPh2py (py=pyridine), have been used. The amino acid esters have been modified by introducing an aromatic amine as pyridine that coordinates metal fragments through the nitrogen atom, giving complexes of the type [M(L)(PR3)](+) or [AuCl3(L)] (L=l-valine-N-(4-pyridylcarbonyl) methyl ester (L1), l-alanine-N-(4-pyridylcarbonyl) methyl ester (L2), l-phenylalanine-N-(4-pyridylcarbonyl) methyl-ester) (L3); M=Au(I), Ag(I), Cu(I), PR3=PPh3, PPh2py). The in vitro cytotoxic activity of metal complexes was tested against four tumor human cell lines and one tumor mouse cell line. A metabolic activity test (3-(4,5-dimethyl-thiazol-2-yl)-2,5-diphenyl tetrazolium bromide, MTT) was used and IC50 values were compared with those obtained for cisplatin. Several complexes displayed significant cytotoxic activities. In order to determine whether antiproliferation and cell death are associated with apoptosis, NIH-3T3 cells were exposed to five selected complexes (Annexin V+ FITC, PI) and analyzed by flow cytometry. These experiments showed that the mechanism by which the complexes inhibit cell proliferation inducing cell death in NIH-3T3 cells is mainly apoptotic. PMID:26780577

  19. Enhanced Sensitivity for Hydrogen Peroxide Detection: Polydiacetylene Vesicles with Phenylboronic Acid Head Group.

    PubMed

    Jia, Chen; Tang, Jie; Lu, Shengguo; Han, Yuwang; Huang, He

    2016-01-01

    It was recently reported that, besides UV irradiated polymerization, polymerization of diacetylene compounds could also been initiated by radicals generated from enzyme catalyzed hydrogen peroxide (H2O2) decomposition. A new optical sensing method for H2O2 was proposed based on this phenomenon. However, the sensitivity of this method is relatively lower than existed ones. In the present work, phenylboronic acid (PBA) functionalized 10, 12-pentacosadiynoic acid (PDA-PBA) was synthesized and its vesicles were formed successfully as colorimetric sensor for H2O2 detection. It was found that color change during the polymerization of vesicles composed of the PBA modified monomer is much stronger than that of the non-modified one. The response of PDA-PBA vesicles to H2O2 is 16 times more sensitive than that of the PDA. The absorption of PDA-PBA at 650 nm is linearly related to the concentration of H2O2 and a detection limit of ~5 μM could be achieved. PMID:26511954

  20. Energy evaluation of forest residues originated from Eucalyptus globulus Labill in Galicia.

    PubMed

    Núñez-Regueira, L; Proupín-Castiñeiras, J; Rodríguez-Añón, J A

    2002-03-01

    The possibility of retrieving the energy contained in forest residues originating from wood exploitation in Galicia (Spain) is evaluated. This study was made on Eucalyptus globulus Labill occupying a forest surface of 240000 ha. This species plays an important role in the economical development of Galicia, as it is the main forest species for production of pulp. Sampling was made over 1999 in seven different zones, three main stations plus four selected for comparison, situated in Galicia. The residues originating from cutting were sorted into three different groups and their calorific values were measured by static bomb calorimetry. These calorific values, close to 7200 kJ kg(-1), make possible the use of this residual biomass as an energy source. Calorific values were measured by static bomb calorimeter in an oxygen atmosphere. Flammability was determined using a standard epiradiator. Simultaneously, some other parameters, elementary chemical composition, heavy metal contents, moisture, density, ash percentage after combustion in the bomb, and main bioclimatic characteristics, were also determined. PMID:11848377

  1. Anatomical variation in Cactaceae and relatives: Trait lability and evolutionary innovation.

    PubMed

    Ogburn, R Matthew; Edwards, Erika J

    2009-02-01

    The cacti have undergone extensive specialization in their evolutionary history, providing an excellent system in which to address large-scale questions of morphological and physiological adaptation. Recent molecular phylogenetic studies suggest that (1) Pereskia, the leafy genus long interpreted as the sister group of all other cacti, is likely paraphyletic, and (2) Cactaceae are nested within a paraphyletic Portulacaceae as a member of the "ACPT" clade (Anacampseroteae, Cactaceae, Portulaca, and Talinum). We collected new data on the vegetative anatomy of the ACPT clade and relatives to evaluate whether patterns in the distributions of traits may provide insight into early events in the evolutionary transition to the cactus life form. Many traits had high levels of homoplasy and were mostly equivocal with regard to infraclade relationships of ACPT, although several characters do lend further support to a paraphyletic Pereskia. These include a thick stem cuticle, prominent stem mucilage cells, and hypodermal calcium oxalate druses, all of which are likely to be important traits for stem water storage and photosynthesis. We hypothesize that high lability of many putative "precursor" traits may have been critical in generating the organismal context necessary for the evolution of an efficient and integrated photosynthetic stem. PMID:21628195

  2. Synthesis, physical properties and cytotoxicity of stilbene-triazine derivatives containing amino acid groups as fluorescent whitening agents.

    PubMed

    Wan, Maosheng; Zhou, Shaoli; Jiao, Peifu; Cao, Chengbo; Guo, Jing

    2013-09-01

    A series of novel stilbene-triazine derivatives containing amino acid groups were synthesized and screened to evaluate their cytotoxicity. The UV absorptions of the derivatives were in the range of 240-450 nm. The absorption peaks of the cis-isomers and trans-isomers were in 281-291 nm and 353-361 nm, respectively. Their fluorescence emission peaks of the derivatives were located in the range of 400-650 nm. The whiteness data indicated that all the stilbene-triazine-amino acid derivatives showed excellent whitening effect on cotton fiber compared to untreated cotton. The preliminary cytotoxicity of these derivatives on a mouse fibroblast cell line (L-929 cells) was also investigated. The results showed that the compounds (7a-h) were nontoxic to L-929 cells as fluorescent whitening agents. PMID:23748838

  3. Effects of acidity and aluminim on the physiology and migratory behavior of Atlantic salmon smolts in Maina, USA

    USGS Publications Warehouse

    Magee, J.A.; Haines, T.A.; Kocik, J.F.; Beland, K.F.; McCormick, S.D.

    2001-01-01

    Atlantic salmon, Salmo salar, smolts of hatchery origin were held for 5 to 16 days in ambient (pH 6.35, labile Al = 60 ??g L-1), limed (pH 6.72, labile Al = 58.4 ??g L-1), or acidified (pH 5.47, labile Al=96 ??g L-1) water from the Narraguagus River in Maine, USA. Wild smolts were captured in the same river in rotary traps and held for up to two days in ambient river water. Osmoregulatory ability was assessed by measuring Na+/K+ ATPase activity, hematocrit, and blood Cl concentration in freshwater, and after 24-hr exposure to seawater. Hatchery smolts exposed to acidic water and wild smolts displayed sub-lethal ionoregulatory stress both in fresh and seawater, with mortalities of wild smolts in seawater. Using ultrasonic telemetry, hatchery-reared ambient and acid-exposed, and wild smolts were tracked as they migrated through freshwater and estuarine sections of the river. The proportion of wild smolts migrating during daylight hours was higher than for hatchery-reared smolts. Wild smolts remained in the freshwater portions of the river longer than either group of hatchery smolts, although survival during migration to seawater was similar for all three treatments. Acid-exposed hatchery-origin and wild Narraguagus River smolts were both under ionoregulatory stress that may have affected their migratory behavior, but not their survival for the time and area in which we tracked them.

  4. The Parmotrema acid test: a look at species delineation in the P. perforatum group 40 y later.

    PubMed

    Lendemer, James C; Allen, Jessica L; Noell, Nastassja

    2015-01-01

    Parmotrema perforatum and its relatives form a morphologically distinctive group of species, most of which are common and endemic to eastern North America. Species delimitation in this ecologically important group was the subject of extensive inquiry before the advent of molecular systematics and computationally intensive niche modeling. As part of a large-scale lichen biodiversity inventory of the Mid-Atlantic Coastal Plain, we used ITS sequence data to examine the utility of characters (morphological, chemical, reproductive, ecological) in circumscribing four species in this group (P. hypoleucinum, P. hypotropum, P. perforatum, P. subrigidum). We found that P. hypoleucinum and P. subrigidum as currently circumscribed are monophyletic and the latter comprises two chemotypes differing in the presence or absence of norstictic acid in addition to alectoronic acid. The sequences of P. hypotropum and P. perforatum, which are chemically identical species and differ only in reproductive mode, were intermixed in a single, well-supported clade. The two chemotypes of P. subrigidum are partially allopatric and their sequences are >99% identical. Nonetheless, niche modeling suggests they occupy significantly different ecological niches. These results provide a new perspective on much-debated questions on species circumscription in lichens and suggest new avenues for genetic, ecological and systematic research. PMID:26354803

  5. Key Role for the 12-Hydroxy Group in the Negative Ion Fragmentation of Unconjugated C24 Bile Acids.

    PubMed

    Lan, Ke; Su, Mingming; Xie, Guoxiang; Ferslew, Brian C; Brouwer, Kim L R; Rajani, Cynthia; Liu, Changxiao; Jia, Wei

    2016-07-19

    Host-gut microbial interactions contribute to human health and disease states and an important manifestation resulting from this cometabolism is a vast diversity of bile acids (BAs). There is increasing interest in using BAs as biomarkers to assess the health status of individuals and, therefore, an increased need for their accurate separation and identification. In this study, the negative ion fragmentation behaviors of C24 BAs were investigated by UPLC-ESI-QTOF-MS. The step-by-step fragmentation analysis revealed a distinct fragmentation mechanism for the unconjugated BAs containing a 12-hydroxyl group. The unconjugated BAs lacking 12-hydroxylation fragmented via dehydration and dehydrogenation. In contrast, the 12-hydroxylated ones, such as deoxycholic acid (DCA) and cholic acid (CA), employed dissociation routes including dehydration, loss of carbon monoxide or carbon dioxide, and dehydrogenation. All fragmentations of the 12-hydroxylated unconjugated BAs, characterized by means of stable isotope labeled standards, were associated with the rotation of the carboxylate side chain and the subsequent rearrangements accompanied by proton transfer between 12-hydroxyl and 24-carboxyl groups. Compared to DCA, CA underwent further cleavages of the steroid skeleton. Accordingly, the effects of stereochemistry on the fragmentation pattern of CA were investigated using its stereoisomers. Based on the knowledge gained from the fragmentation analysis, a novel BA, 3β,7β,12α-trihydroxy-5β-cholanic acid, was identified in the postprandial urine samples of patients with nonalcoholic steatohepatitis. The analyses used in this study may contribute to a better understanding of the chemical diversity of BAs and the molecular basis of human liver diseases that involve BA synthesis, transport, and metabolism. PMID:27322813

  6. Phylogenetic group- and species-specific oligonucleotide probes for single-cell detection of lactic acid bacteria in oral biofilms

    PubMed Central

    2011-01-01

    Background The purpose of this study was to design and evaluate fluorescent in situ hybridization (FISH) probes for the single-cell detection and enumeration of lactic acid bacteria, in particular organisms belonging to the major phylogenetic groups and species of oral lactobacilli and to Abiotrophia/Granulicatella. Results As lactobacilli are known for notorious resistance to probe penetration, probe-specific assay protocols were experimentally developed to provide maximum cell wall permeability, probe accessibility, hybridization stringency, and fluorescence intensity. The new assays were then applied in a pilot study to three biofilm samples harvested from variably demineralized bovine enamel discs that had been carried in situ for 10 days by different volunteers. Best probe penetration and fluorescent labeling of reference strains were obtained after combined lysozyme and achromopeptidase treatment followed by exposure to lipase. Hybridization stringency had to be established strictly for each probe. Thereafter all probes showed the expected specificity with reference strains and labeled the anticipated morphotypes in dental plaques. Applied to in situ grown biofilms the set of probes detected only Lactobacillus fermentum and bacteria of the Lactobacillus casei group. The most cariogenic biofilm contained two orders of magnitude higher L. fermentum cell numbers than the other biofilms. Abiotrophia/Granulicatella and streptococci from the mitis group were found in all samples at high levels, whereas Streptococcus mutans was detected in only one sample in very low numbers. Conclusions Application of these new group- and species-specific FISH probes to oral biofilm-forming lactic acid bacteria will allow a clearer understanding of the supragingival biome, its spatial architecture and of structure-function relationships implicated during plaque homeostasis and caries development. The probes should prove of value far beyond the field of oral microbiology, as many of

  7. Differential response of archaeal groups to land use change in an acidic red soil.

    PubMed

    Shen, Ju-Pei; Cao, Peng; Hu, Hang-Wei; He, Ji-Zheng

    2013-09-01

    Land use management, one of the most important aspects of anthropogenic disturbance to terrestrial ecosystems, has exerted overriding impacts on soil biogeochemical cycling and inhabitant microorganisms. However, the knowledge concerning response of different archaeal groups to long-term land use changes is still limited in terrestrial environments. Here we used quantitative polymerase chain reaction (qPCR) and denaturing gradient gel electrophoresis (DGGE) approaches to investigate the response of archaeal communities to four different land use practices, i.e. cropland, pine forest, restoration land and degradation land. qPCR analyses showed that expression of the archaeal amoA gene responds more sensitively to changes of land use. In particular, we observed, occurring at significantly lower numbers of archaeal amoA genes in degradation land samples, while the abundance of total archaea and Group 1.1c based on 16S rRNA gene copy numbers remained constant among the different treatments examined. Soil nitrate content is significantly correlated with archaeal amoA gene abundance, but not their bacterial counterparts. The percentage of archaea among total prokaryote communities increases with increasing depth, but has no significant relationship with total carbon, total nitrogen or pH. Soil pH was significantly correlated with total bacterial abundance. Based on results from PCR-DGGE, three land use practices (i.e. cropland, pine forest, restoration land) showed distinct dominant bands, which were mostly affiliated with Group 1.1a. Degradation land, however, was dominated by sequences belonging to Group 1.1c. Results from this study suggest that community structure of ammonia oxidizing archaea were significantly impacted by land use practices. PMID:23774250

  8. Methyl groups of thymine bases are important for nucleic acid recognition by DtxR.

    PubMed

    Chen, C S; White, A; Love, J; Murphy, J R; Ringe, D

    2000-08-29

    The expression of diphtheria toxin is controlled by the diphtheria toxin repressor (DtxR). Under conditions of high iron concentration, DtxR binds the tox operator to inhibit transcription. To study how DNA binding specificity is achieved by this repressor, we solved the crystal structure of the nickel(II) activated DtxR(C102D) mutant complexed with a 43mer DNA duplex containing the DtxR consensus binding sequence. Structural analysis of this complex and comparison with a previously determined DtxR(C102D)-Ni(II)-tox operator ternary complex revealed unusual van der Waals interactions between Ser37/Pro39 of the repressor helix-turn-helix (HTH) motif and the methyl groups of specific thymine bases in the consensus binding sequence. Gel mobility shift assays utilizing deoxyuridine modified duplex DNA probes proved the importance of these interactions: the four methyl groups shown to interact with Ser37/Pro39 in the crystal structure contribute a total of 3.4 kcal/mol to binding energy. Thus, in addition to making base-specific hydrogen-bonding interactions to the DNA through its Gln43 residue, DtxR also recognizes methyl groups at certain positions in the DNA sequence with its Ser37 and Pro39 side chains, to achieve binding specificity toward its cognate operator sequences. PMID:10956029

  9. Evolutionary stasis and lability in thermal physiology in a group of tropical lizards

    PubMed Central

    Muñoz, Martha M.; Stimola, Maureen A.; Algar, Adam C.; Conover, Asa; Rodriguez, Anthony J.; Landestoy, Miguel A.; Bakken, George S.; Losos, Jonathan B.

    2014-01-01

    Understanding how quickly physiological traits evolve is a topic of great interest, particularly in the context of how organisms can adapt in response to climate warming. Adjustment to novel thermal habitats may occur either through behavioural adjustments, physiological adaptation or both. Here, we test whether rates of evolution differ among physiological traits in the cybotoids, a clade of tropical Anolis lizards distributed in markedly different thermal environments on the Caribbean island of Hispaniola. We find that cold tolerance evolves considerably faster than heat tolerance, a difference that results because behavioural thermoregulation more effectively shields these organisms from selection on upper than lower temperature tolerances. Specifically, because lizards in very different environments behaviourally thermoregulate during the day to similar body temperatures, divergent selection on body temperature and heat tolerance is precluded, whereas night-time temperatures can only be partially buffered by behaviour, thereby exposing organisms to selection on cold tolerance. We discuss how exposure to selection on physiology influences divergence among tropical organisms and its implications for adaptive evolutionary response to climate warming. PMID:24430845

  10. Evolutionary stasis and lability in thermal physiology in a group of tropical lizards.

    PubMed

    Muñoz, Martha M; Stimola, Maureen A; Algar, Adam C; Conover, Asa; Rodriguez, Anthony J; Landestoy, Miguel A; Bakken, George S; Losos, Jonathan B

    2014-03-01

    Understanding how quickly physiological traits evolve is a topic of great interest, particularly in the context of how organisms can adapt in response to climate warming. Adjustment to novel thermal habitats may occur either through behavioural adjustments, physiological adaptation or both. Here, we test whether rates of evolution differ among physiological traits in the cybotoids, a clade of tropical Anolis lizards distributed in markedly different thermal environments on the Caribbean island of Hispaniola. We find that cold tolerance evolves considerably faster than heat tolerance, a difference that results because behavioural thermoregulation more effectively shields these organisms from selection on upper than lower temperature tolerances. Specifically, because lizards in very different environments behaviourally thermoregulate during the day to similar body temperatures, divergent selection on body temperature and heat tolerance is precluded, whereas night-time temperatures can only be partially buffered by behaviour, thereby exposing organisms to selection on cold tolerance. We discuss how exposure to selection on physiology influences divergence among tropical organisms and its implications for adaptive evolutionary response to climate warming. PMID:24430845

  11. Comparative electrochemical degradation of salicylic and aminosalicylic acids: Influence of functional groups on decay kinetics and mineralization.

    PubMed

    Florenza, Xavier; Garcia-Segura, Sergi; Centellas, Francesc; Brillas, Enric

    2016-07-01

    Solutions of 100 mL with 1.20 mM of salicylic acid (SA), 4-aminosalicylic acid (4-ASA) or 5-aminosalicylic acid (5-ASA) have been comparatively degraded by anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Trials were carried out with a stirred tank reactor with a BDD anode and an air-diffusion cathode for continuous H2O2 production. A marked influence of the functional groups of the drugs was observed in their decay kinetics, increasing in the order SA < 5-ASA < 4-ASA in AO-H2O2 and 5-ASA < SA < 4-ASA in EF and PEF, due to the different attack of OH generated at the BDD surface and in the bulk from Fenton's reaction, respectively. This effect was clearly observed when varying the current density between 16.7 and 100 mA cm(-2). The relative mineralization power of the processes always followed the sequence: AO-H2O2 < EF < PEF. The three drugs underwent analogous mineralization abatement up to 88% by AO-H2O2 at 100 mA cm(-2). The mineralization rate in EF and PEF grew in the order: 4-ASA < 5-ASA < SA. The most powerful process was PEF, attaining >98% mineralization for all the drugs at 100 mA cm(-2). Oxalic and oxamic acids were detected as final short-linear aliphatic carboxylic acids by ion-exclusion HPLC, allowing the fast photolysis of their Fe(III) complexes by UVA light to justify the high power of PEF. PMID:27045634

  12. In Situ, High-Resolution Profiles of Labile Metals in Sediments of Lake Taihu.

    PubMed

    Wang, Dan; Gong, Mengdan; Li, Yangyang; Xu, Lv; Wang, Yan; Jing, Rui; Ding, Shiming; Zhang, Chaosheng

    2016-01-01

    Characterizing labile metal distribution and biogeochemical behavior in sediments is crucial for understanding their contamination characteristics in lakes, for which in situ, high-resolution data is scare. The diffusive gradient in thin films (DGT) technique was used in-situ at five sites across Lake Taihu in the Yangtze River delta in China to characterize the distribution and mobility of eight labile metals (Fe, Mn, Zn, Ni, Cu, Pb, Co and Cd) in sediments at a 3 mm spatial resolution. The results showed a great spatial heterogeneity in the distributions of redox-sensitive labile Fe, Mn and Co in sediments, while other metals had much less marked structure, except for downward decreases of labile Pb, Ni, Zn and Cu in the surface sediment layers. Similar distributions were found between labile Mn and Co and among labile Ni, Cu and Zn, reflecting a close link between their geochemical behaviors. The relative mobility, defined as the ratio of metals accumulated by DGT to the total contents in a volume of sediments with a thickness of 10 mm close to the surface of DGT probe, was the greatest for Mn and Cd, followed by Zn, Ni, Cu and Co, while Pb and Fe had the lowest mobility; this order generally agreed with that defined by the modified BCR approach. Further analyses showed that the downward increases of pH values in surface sediment layer may decrease the lability of Pb, Ni, Zn and Cu as detected by DGT, while the remobilization of redox-insensitive metals in deep sediment layer may relate to Mn cycling through sulphide coprecipitation, reflected by several corresponding minima between these metals and Mn. These in situ data provided the possibility for a deep insight into the mechanisms involved in the remobilization of metals in freshwater sediments. PMID:27608033

  13. Whole-Ecosystem Labile Carbon Production in a North Temperate Deciduous Forest

    NASA Astrophysics Data System (ADS)

    Gough, C. M.; Flower, C. E.; Vogel, C. S.; Dragoni, D.; Curtis, P. S.

    2008-12-01

    Management for forest carbon (C) sequestration requires knowledge of the fate of photosynthetic C. Labile C is an essential intermediary between C assimilation and growth in deciduous forests, accumulating when photosynthetic C supply exceeds demand and later depleting when reallocated to growth during periods of depressed photosynthesis. We developed a new approach that combined meteorological and biometric C cycling data for a mixed deciduous forest in Michigan, USA, to provide novel estimates of whole-ecosystem labile C production (PLC) and reallocation to growth inferred from the temporal imbalance between carbon supply from canopy net C assimilation (Ac) and C demand for net primary production (NPP). We substantiated these estimates with measurements of Populus grandidentata and Quercus rubra wood non-structural carbohydrate (NSC) concentration and mass over two years. Our analysis showed that half of annual Ac was allocated to PLC rather than to immediate growth. Labile C produced during the latter half of summer later supported dormant-season growth and respiration, with 35% of NPP in a given year requiring labile C stored during previous years. Seasonal changes in wood NSC concentration and mass generally corroborated patterns of labile C production and reallocation to growth. We observed a negative relationship between current-year PLC and NPP, indicating that disparities between same-year meteorological and biometric net ecosystem production (NEP) estimates can arise when C assimilated via photosynthesis, a flux incorporated into meteorological NEP estimates, is diverted away from NPP, a flux included in biometric NEP estimates, and instead allocated to PLC. A large, annually recharging pool of labile C also may buffer growth from climate conditions that immediately affect Ac. We conclude that a broader understanding of labile C production and reallocation across ecosystems may be important to interpreting lagged canopy C cycling and growth processes.

  14. Protecting-Group-Free Total Synthesis of (-)-Lycopodine via Phosphoric Acid Promoted Alkyne Aza-Prins Cyclization.

    PubMed

    Ma, Donghui; Zhong, Zhuliang; Liu, Zaimin; Zhang, Mingjie; Xu, Shiyan; Xu, Dengyu; Song, Dengpeng; Xie, Xingang; She, Xuegong

    2016-09-01

    A protecting-group-free route for the total synthesis of (-)-lycopodine was demonstrated in only 8 steps from Wade's fawcettimine enone (12 steps from commercial availiable (R)-(+)-pulegone). The key core of this alkaloid was constructed through a phosphoric acid promoted and highly stereocontrolled alkyne aza-Prins cyclization reaction, synchronously establishing the bridged B-ring and the C13 quaternary stereocenter. Importantly, the synthesis further features a new efficient approach for the preparation of other lycopodine-type alkaloids. PMID:27529730

  15. Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study

    SciTech Connect

    Mehio, Nada; Lashely, Mark A.; Nugent, Joseph W.; Tucker, Lyndsay; Correia, Bruna; Do-Thanh, Chi-Linh; Dai, Sheng; Hancock, Robert D.; Bryantsev, Vyacheslav S.

    2015-01-26

    Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. It has been demonstrated repeatedly in the literature that the success of these materials is due to the amidoxime functional group. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pKa values that have been reported for the amidoxime functional group in the literature. To resolve this existing controversy we investigated the pKa values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopic titrations to measure the pKa values of representative amidoximes, acetamidoxime and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pKa values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance with a mean absolute error of 0.33 pKa units and 0.35 pKa units, respectively, and a root mean square deviation of 0.46 pKa units and 0.45 pKa units, respectively. Finally, we employ our two best methods to predict the pKa values of promising, uncharacterized amidoxime ligands. Hence, our study provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents used to mine uranium from seawater.

  16. Acidity of the amidoxime functional group in aqueous solution. A combined experimental and computational study

    DOE PAGESBeta

    Mehio, Nada; Lashely, Mark A.; Nugent, Joseph W.; Tucker, Lyndsay; Correia, Bruna; Do-Thanh, Chi-Linh; Dai, Sheng; Hancock, Robert D.; Bryantsev, Vyacheslav S.

    2015-01-26

    Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. It has been demonstrated repeatedly in the literature that the success of these materials is due to the amidoxime functional group. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pKa values that have been reported for the amidoxime functional group in the literature. To resolve this existing controversy we investigated the pKa values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopicmore » titrations to measure the pKa values of representative amidoximes, acetamidoxime and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pKa values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance with a mean absolute error of 0.33 pKa units and 0.35 pKa units, respectively, and a root mean square deviation of 0.46 pKa units and 0.45 pKa units, respectively. Finally, we employ our two best methods to predict the pKa values of promising, uncharacterized amidoxime ligands. Hence, our study provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents used to mine uranium from seawater.« less

  17. Analytical methods to determine phosphonic and amino acid group-containing pesticides.

    PubMed

    Stalikas, C D; Konidari, C N

    2001-01-12

    A comprehensive view on the possibilities of the most recently developed chromatographic methods and emerging techniques in the analysis of pesticides glyphosate, glufosinate, bialaphos and their metabolites is presented. The state-of-the-art of the individual pre-treatment steps (extraction, pre-concentration, clean-up, separation, quantification) of the employed analytical methods for this group of chemicals is reviewed. The advantages and drawbacks of the described analytical methods are discussed and the present status and future trends are outlined. PMID:11217016

  18. Highly Fluorescent Group 13 Metal Complexes with Cyclic, Aromatic Hydroxamic Acid Ligands

    SciTech Connect

    Seitz, Michael; Moore, Evan G.; Raymond, Kenneth N.

    2008-02-11

    The neutral complexes of two ligands based on the 1-oxo-2-hydroxy-isoquinoline (1,2-HOIQO) motif with group 13 metals (Al, Ga, In) show bright blue-violet luminescence in organic solvents. The corresponding transition can be attributed to ligand-centered singlet emission, characterized by a small Stokes shifts of only a few nm combined with lifetimes in the range between 1-3 ns. The fluorescence efficiency is high, with quantum yields of up to 37% in benzene solution. The crystal structure of one of the indium(III) complexes (trigonal space group R-3, a = b = 13.0384(15) {angstrom}, c = 32.870(8) {angstrom}, ? = {beta} = 90{sup o}, {gamma} = 120{sup o}, V = 4839.3(14) {angstrom}{sup 3}, Z = 6) shows a six-coordinate geometry around the indium center which is close to trigonal-prismatic, with a twist angle between the two trigonal faces of 20.7{sup o}. Time-dependent density functional theory (TD-DFT) calculations (Al and Ga: B3LYP/6-31G(d)); In: B3LYP/LANL2DZ of the fac and mer isomers with one of the two ligands indicate that there is no clear preference for either one of the isomeric forms of the metal complexes. In addition, the metal centers do not have a significant influence on the electronic structure, and as a consequence, on the predominant intraligand optical transitions.

  19. Acidity of the amidoxime functional group in aqueous solution: a combined experimental and computational study.

    PubMed

    Mehio, Nada; Lashely, Mark A; Nugent, Joseph W; Tucker, Lyndsay; Correia, Bruna; Do-Thanh, Chi-Linh; Dai, Sheng; Hancock, Robert D; Bryantsev, Vyacheslav S

    2015-02-26

    Poly(acrylamidoxime) adsorbents are often invoked in discussions of mining uranium from seawater. While the amidoxime-uranyl chelation mode has been established, a number of essential binding constants remain unclear. This is largely due to the wide range of conflicting pK(a) values that have been reported for the amidoxime functional group. To resolve this existing controversy we investigated the pK(a) values of the amidoxime functional group using a combination of experimental and computational methods. Experimentally, we used spectroscopic titrations to measure the pK(a) values of representative amidoximes, acetamidoxime, and benzamidoxime. Computationally, we report on the performance of several protocols for predicting the pK(a) values of aqueous oxoacids. Calculations carried out at the MP2 or M06-2X levels of theory combined with solvent effects calculated using the SMD model provide the best overall performance, with a root-mean-square deviation of 0.46 pK(a) units and 0.45 pK(a) units, respectively. Finally, we employ our two best methods to predict the pK(a) values of promising, uncharacterized amidoxime ligands, which provides a convenient means for screening suitable amidoxime monomers for future generations of poly(acrylamidoxime) adsorbents. PMID:25621618

  20. Effects of carbon substrate lability on carbon mineralization dynamics of tropical peat

    NASA Astrophysics Data System (ADS)

    Jauhiainen, Jyrki; Silvennoinen, Hanna; Könönen, Mari; Limin, Suwido; Vasander, Harri

    2016-04-01

    Extensive draining at tropical ombrotrophic peatlands in Southeast Asia has made them global 'hot spots' for greenhouse gas emissions. Management practises and fires have led to changed substrate status, which affects microbial processes. Here, we present the first data on how management practises affect carbon (C) mineralization processes at these soils. We compared the carbon mineralization potentials of pristine forest soils to those of drained fire affected soils at various depths, with and without additional labile substrates (glucose, glutamate and NO3-N) and in oxic and anoxic conditions by dedicated ex situ experiments. Carbon mineralization (CO2 and CH4 production) rates were higher in the pristine site peat, which contains more labile carbon due to higher input via vegetation. Production rates decreased with depth together with decreasing availability of labile carbon. Consequently, the increase in production rates after labile substrate addition was relatively modest from pristine site as compared to the managed site and from the top layers as compared to deeper layers. Methanogenesis had little importance in total carbon mineralization. Adding labile C and N enhanced heterotrophic CO2 production more than the sole addition of N. Surprisingly, oxygen availability was not an ultimate requirement for substantial CO2 production rates, but anoxic respiration yielded comparable rates, especially at the pristine soils. Flooding of these sites will therefore reduce, but not completely cease, peat carbon loss. Reintroduced substantial vegetation and fertilization in degraded peatlands can enrich recalcitrant peat with simple C and N compounds and thus increase microbiological activity.

  1. Synthesis and characterisation of a degradable poly(lactic acid)-poly(ethylene glycol) copolymer with biotinylated end groups.

    PubMed

    Salem, A K; Cannizzaro, S M; Davies, M C; Tendler, S J; Roberts, C J; Williams, P M; Shakesheff, K M

    2001-01-01

    Poly(lactic acid)-poly(ethylene glycol)-biotin (PLA-PEG-biotin) is a degradable polymer with protein resistant properties that can undergo rapid surface engineering in aqueous media to create biomimetic surfaces. Surface engineering of this polymer is dependent on biomolecular interactions between the biotin end group and the protein avidin. Given the vigorous conditions of synthesis, it is essential that the manufacture of the polymer does not alter the biotin structure or its molecular recognition. Equally, it is important that the incorporation of biotin does not adversely affect the physicochemical properties of the polymer. (1)H NMR provides evidence of biotin attachment and structural integrity. (1)H NMR, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC) analysis shows there is no significant effect on bulk properties induced by the biotin end group. Surface plasmon resonance (SPR) and fluorescent spectroscopy studies using the 2-(4'-hydroxyazobenzene) benzoic acid (HABA)/avidin complex show that the biotin moieties binding capabilities are not impaired by the synthesis. PMID:11749223

  2. Prediction of intramuscular fat content and major fatty acid groups of lamb M. longissimus lumborum using Raman spectroscopy.

    PubMed

    Fowler, Stephanie M; Ponnampalam, Eric N; Schmidt, Heinar; Wynn, Peter; Hopkins, David L

    2015-12-01

    A hand held Raman spectroscopic device was used to predict intramuscular fat (IMF) levels and the major fatty acid (FA) groups of fresh intact ovine M. longissimus lumborum (LL). IMF levels were determined using the Soxhlet method, while FA analysis was conducted using a rapid (KOH in water, methanol and sulphuric acid in water) extraction procedure. IMF levels and FA values were regressed against Raman spectra using partial least squares regression and against each other using linear regression. The results indicate that there is potential to predict PUFA (R(2)=0.93) and MUFA (R(2)=0.54) as well as SFA values that had been adjusted for IMF content (R(2)=0.54). However, this potential was significantly reduced when correlations between predicted and observed values were determined by cross validation (R(2)cv=0.21-0.00). Overall, the prediction of major FA groups using Raman spectra was more precise (relative reductions in error of 0.3-40.8%) compared to the null models. PMID:26188359

  3. Evaluation of a 7-Methoxycoumarin-3-carboxylic Acid Ester Derivative as a Fluorescent, Cell-Cleavable, Phosphonate Protecting Group.

    PubMed

    Wiemer, Andrew J; Shippy, Rebekah R; Kilcollins, Ashley M; Li, Jin; Hsiao, Chia-Hung Christine; Barney, Rocky J; Geng, M Lei; Wiemer, David F

    2016-01-01

    Cell-cleavable protecting groups often enhance cellular delivery of species that are charged at physiological pH. Although several phosphonate protecting groups have achieved clinical success, it remains difficult to use these prodrugs in live cells to clarify biological mechanisms. Here, we present a strategy that uses a 7-methoxycoumarin-3-carboxylic acid ester as a fluorescent protecting group. This strategy was applied to synthesis of an (E)-4-hydroxy-3-methyl-but-2-enyl diphosphate (HMBPP) analogue to assess cellular uptake and human Vγ9Vδ2 T cell activation. The fluorescent ester displayed low cellular toxicity (IC50 >100 μm) and strong T cell activation (EC50 =0.018 μm) relative to the unprotected anion (EC50 =23 μm). The coumarin-derived analogue allowed no-wash analysis of biological deprotection, which revealed rapid internalization of the prodrug. These results demonstrate that fluorescent groups can be applied both as functional drug delivery tools and useful biological probes of drug uptake. PMID:26503489

  4. A thermally responsive injectable hydrogel incorporating methacrylate-polylactide for hydrolytic lability

    PubMed Central

    Ma, Zuwei; Nelson, Devin M.; Hong, Yi; Wagner, William R.

    2011-01-01

    Injectable thermoresponsive hydrogels are of interest for a variety of biomedical applications, including regional tissue mechanical support as well as drug and cell delivery. Within this class of materials there is a need to provide options for gels with stronger mechanical properties as well as variable degradation profiles. To address this need, the hydrolytically labile monomer, methacrylate-polylactide (MAPLA), with an average 2.8 lactic acid units, was synthesized and copolymerized with N-isopropylacrylamide (NIPAAm) and 2-hydroxyethyl methacrylate (HEMA) to obtain bioabsorbable thermally responsive hydrogels. Poly(NIPAAm-co-HEMA-co-MAPLA) with three monomer feed ratios (84/10/6, 82/10/8 and 80/10/10) was synthesized and characterized with NMR, FTIR and GPC. The copolymers were soluble in saline at reduced temperature (<10°C), forming clear solutions that increased in viscosity with the MAPLA feed ratio. The copolymers underwent sol-gel transition at lower critical solution temperatures of 12.4, 14.0 and 16.2°C respectively and solidified immediately upon being placed in a 37°C water bath. The warmed hydrogels gradually excluded water to reach final water contents of ~45%. The hydrogels as formed were mechanically strong, with tensile strengths as high as 100 kPa and shear moduli of 60 kPa. All three hydrogels were completely degraded (solubilized) in PBS over a 6–8 month period at 37°C, with a higher MAPLA feed ratio resulting in a faster degradation period. Culture of primary vascular smooth muscle cells with degradation solutions demonstrated a lack of cytotoxicity. The synthesized hydrogels provide new options for biomaterial injection therapy where increased mechanical strength and relatively slow resorption rates would be attractive. PMID:20575552

  5. Members of a unique histidine acid phosphatase family are conserved amongst a group of primitive eukaryotic human pathogens.

    PubMed

    Shakarian, Alison M; Joshi, Manju B; Yamage, Mat; Ellis, Stephanie L; Debrabant, Alain; Dwyer, Dennis M

    2003-03-01

    Recently, we identified and characterized the genes encoding several distinct members of the histidine-acid phosphatase enzyme family from Leishmania donovani, a primitive protozoan pathogen of humans. These included genes encoding the heavily phosphorylated/glycosylated, tartrate-sensitive, secretory acid phosphatases (Ld SAcP-1 and Ld SAcP-2) and the unique, tartrate-resistant, externally-oriented, surface membrane-bound acid phosphatase (Ld MAcP) of this parasite. It had been previously suggested that these enzymes may play essential roles in the growth, development and survival of this organism. In this report, to further examine this hypothesis, we assessed whether members of the L. donovani histidine-acid phosphatase enzyme family were conserved amongst other pathogenic Leishmania and related trypanosomatid parasites. Such phylogenetic conservation would clearly indicate an evolutionary selection for this family of enzymes and strongly suggest and support an important functional role for acid phosphatases to the survival of these parasites. Results of pulsed field gel electrophoresis and Southern blotting showed that homologs of both the Ld SAcPs and Ld MAcP were present in each of the visceral and cutaneous Leishmania species examined (i.e. isolates of L. donovani, L. infantum, L. tropica, L. major and L. mexicana, respectively). Further, results of enzyme assays showed that all of these organisms expressed both tartrate-sensitive and tartrate-resistant acid phosphatase activities. In addition, homologs of both the Ld SAcPs and Ld MAcP genes and their corresponding enzyme activities were also identified in two Crithidia species (C. fasciculata and C. luciliae) and in Leptomonas seymouri. In contrast, Trypanosoma brucei, Trypanosoma cruzi and Phytomonas serpens had only very-low levels of such enzyme activities. Cumulatively, results of this study showed that homologs of the Ld SAcPs and Ld MAcP are conserved amongst all pathogenic Leishmania sps. suggesting

  6. Group X Secreted Phospholipase A2 Releases ω3 Polyunsaturated Fatty Acids, Suppresses Colitis, and Promotes Sperm Fertility.

    PubMed

    Murase, Remi; Sato, Hiroyasu; Yamamoto, Kei; Ushida, Ayako; Nishito, Yasumasa; Ikeda, Kazutaka; Kobayashi, Tetsuyuki; Yamamoto, Toshinori; Taketomi, Yoshitaka; Murakami, Makoto

    2016-03-25

    Within the secreted phospholipase A2(sPLA2) family, group X sPLA2(sPLA2-X) has the highest capacity to hydrolyze cellular membranes and has long been thought to promote inflammation by releasing arachidonic acid, a precursor of pro-inflammatory eicosanoids. Unexpectedly, we found that transgenic mice globally overexpressing human sPLA2-X (PLA2G10-Tg) displayed striking immunosuppressive and lean phenotypes with lymphopenia and increased M2-like macrophages, accompanied by marked elevation of free ω3 polyunsaturated fatty acids (PUFAs) and their metabolites. Studies usingPla2g10-deficient mice revealed that endogenous sPLA2-X, which is highly expressed in the colon epithelium and spermatozoa, mobilized ω3 PUFAs or their metabolites to protect against dextran sulfate-induced colitis and to promote fertilization, respectively. In colitis, sPLA2-X deficiency increased colorectal expression of Th17 cytokines, and ω3 PUFAs attenuated their production by lamina propria cells partly through the fatty acid receptor GPR120. In comparison, cytosolic phospholipase A2(cPLA2α) protects from colitis by mobilizing ω6 arachidonic acid metabolites, including prostaglandin E2 Thus, our results underscore a previously unrecognized role of sPLA2-X as an ω3 PUFA mobilizerin vivo, segregated mobilization of ω3 and ω6 PUFA metabolites by sPLA2-X and cPLA2α, respectively, in protection against colitis, and the novel role of a particular sPLA2-X-driven PUFA in fertilization. PMID:26828067

  7. The nature of peptide interactions with acid end-group PLGAs and facile aqueous-based microencapsulation of therapeutic peptides

    PubMed Central

    Sophocleous, Andreas M.; Desai, Kashappa-Goud H.; Mazzara, J. Maxwell; Tong, Ling; Cheng, Ji-Xin; Olsen, Karl F.; Schwendeman, Steven P.

    2013-01-01

    An important poorly understood phenomenon in controlled-release depots involves the strong interaction between common cationic peptides and low Mw free acid end-group poly(lactic-co-glycolic acids) (PLGAs) used to achieve continuous peptide release kinetics. The kinetics of peptide sorption to PLGA was examined by incubating peptide solutions of 0.2-4 mM octreotide or leuprolide acetate salts in 0.1 M HEPES buffer, pH 7.4, with polymer particles or films at 4-37 °C for 24 h. The extent of absorption/loading of peptides in PLGA particles/films was assayed by two-phase extraction and amino acid analysis. Confocal Raman microspectroscopy and stimulated Raman scattering (SRS) and laser scanning confocal imaging techniques were used to examine peptide penetration in the polymer phase. The release of sorbed peptide from leuprolide-PLGA particles was evaluated both in vitro (PBST + 0.02% sodium azide, 37 °C) and in vivo (male Sprague-Dawley rats). We found that when the PLGA-COOH chains are sufficiently mobilized, therapeutic peptides not only bind at the surface, a common belief to date, but can also internalized and distributed throughout the polymer phase at physiological temperature forming a salt with low-molecular weight PLGA-COOH. Importantly, absorption of leuprolide into low MW PLGA-COOH particles yielded ~17 wt% leuprolide loading in the polymer (i.e., ~70% of PLGA-COOH acids occupied), and the absorbed peptide was released from the polymer for > 2 weeks in a controlled fashion in vitro and as indicated by sustained testosterone suppression in male Sprague-Dawley rats. This new approach, which bypasses the traditional encapsulation method and associated production cost, opens up the potential for facile production of low-cost controlled-release injectable depots for leuprolide and related peptides. PMID:24021356

  8. Trace metal occurrences in acid-insoluble residues of the Ordovician Galena Group, southeastern Minnesota

    SciTech Connect

    Lively, R.S.; Mossler, J.H.; Morey, G.B. ); Hauck, S.A. . Natural Resources Research Inst.)

    1993-03-01

    Regional geochemical, studies on insoluble residues from Paleozoic carbonate rocks have become an integral part of the search for new Upper Mississippi Valley-type mineral deposits in the northern Midcontinent. The authors have extended these studies to southeastern Minnesota, an area well to the north of known lead-zinc deposits of commercial size and grade. In this region, a thin sequence of Upper Cambrian to Middle Ordovician strata unconformably overlies a complex Precambrian basement. More than 500 samples of limestone and dolomite from 40 drill holes and outcrops were analyzed for 29 related trace elements. Preliminary interpretations are based on the analysis of 380 samples of the Ordovician Galena Group from 37 localities. Results indicate that anomalous concentrations of Pb, Cu, zn, As, Cd, and Ni are confined to the southern half of the Galena subgroup area and extend less than 30 miles north of the Iowa border. The anomalous areas, as well as saddles between the, have a distinct northwest trend, coincident with structural features previously recognized in the Precambrian basement. The spatial relationships of the anomalies and the lack of direct correlation imply deposition from fluids moving north out of the main lead-zinc district along structural pathways. The lack of significant anomalies in the northern part of the subcrop area implies northwest weakening of the forces driving the metal-bearing fluids, as well as a decrease over distance in the absolute metal content of the migrating fluids.

  9. Enhanced photocatalytic hydrogen production by introducing the carboxylic acid group into cobaloxime catalysts.

    PubMed

    Wang, Junfei; Li, Chao; Zhou, Qianxiong; Wang, Weibo; Hou, Yuanjun; Zhang, Baowen; Wang, Xuesong

    2015-10-28

    A series of cobaloxime complexes, [Co(iii)(dmgH)2(py-m-X)Cl] (dmgH = dimethylglyoxime, py-m-X = meta-substituted pyridine, X = COOH (2), COOCH3 (3), CH2CH2COOH (6), and CH2CH2COOCH3 (7)), and [Co(iii)(dmgH)2(py-p-X)Cl], (py-p-X = para-substituted pyridine, X = COOH (4) and COOCH3 (5)), were synthesized and their photocatalytic H2 production activities were compared in an artificial photosynthesis system containing a xanthene dye Eosin Y as the photosensitizer (PS) and triethanolamine (TEOA) as the sacrificial reductant (SR) in CH3CN/H2O (1 : 1, pH = 7.5). Irrespective of substitution by an electron-donating or electron withdrawing group, the photocatalytic H2 production activities of 2-7 are all higher than that of [Co(iii)(dmgH)2(py)Cl] (1). Importantly, meta-substitution is more efficient than para-substitution, and COOH is more efficient than COOCH3, in enhancing the photocatalytic activities. 6 showed the highest activity among the examined complexes. The -CH2CH2- chain linking COOH and pyridine might play a role in the promising performance of 6, which makes the proton relay via interaction between COOH and dmgH possible. This work may open new avenues for developing more efficient cobaloxime-based H2 evolution catalysts (HERs). PMID:26394744

  10. The Isothiocyanato Moiety. An Ideal Protecting Group for Stereoselective Sialic Acid Glycoside Synthesis and Subsequent Diversification**

    PubMed Central

    Mandhapati, Appi Reddy; Rajender, Salla; Shaw, Jonathan

    2014-01-01

    The preparation of a crystalline, peracetyl adamantanyl thiosialoside donor protected by an isothiocyanate group is described. On activation at -78 C in the presence of typical carbohydrate acceptors this donor gives high yields of the corresponding sialosides with exquisite α-selectivity. The high selectivity extends to the 4-O-benzyl-protected 3-OH acceptors that are typically less reactive and selective than galactose 3,4-diols. Treatment of the α-sialosides with tris(trimethylsilyl)silane or allyltris(trimethylsilyl)silane sialosides replaces the C5-N5 bond by a C-H or a C-C bond. Reaction of the isothiocyanate-protected sialosides with thioacids achieves conversion into amides. Reaction of the isothiocyanate with an amine gives a thiourea, which can be converted to a guanidine. The very high α-selectivities observed with the new donor and the rich chemistry of the isothiocyante function considerably extend the scope for optimization at the sialoside 5-position. PMID:25446629

  11. A reactivity-based probe of the intracellular labile ferrous iron pool.

    PubMed

    Spangler, Benjamin; Morgan, Charles W; Fontaine, Shaun D; Vander Wal, Mark N; Chang, Christopher J; Wells, James A; Renslo, Adam R

    2016-09-01

    Improved methods for studying intracellular reactive Fe(II) are of significant interest for studies of iron metabolism and disease-relevant changes in iron homeostasis. Here we describe a highly selective reactivity-based probe in which a Fenton-type reaction with intracellular labile Fe(II) leads to unmasking of the aminonucleoside puromycin. Puromycin leaves a permanent and dose-dependent mark on treated cells that can be detected with high sensitivity and precision using a high-content, plate-based immunofluorescence assay. Using this new probe and screening approach, we detected alteration of cellular labile Fe(II) in response extracellular iron conditioning, overexpression of iron storage and/or export proteins, and post-translational regulation of iron export. We also used this new tool to demonstrate that labile Fe(II) pools are larger in cancer cells than in nontumorigenic cells. PMID:27376690

  12. Labile and Paroxysmal Hypertension: Common Clinical Dilemmas in Need of Treatment Studies.

    PubMed

    Mann, Samuel J

    2015-11-01

    Although "labile hypertension" is regularly encountered by clinicians, there is a paucity of information available to guide therapeutic decisions. This review discusses its clinical relevance, the limitations of current knowledge, and possible directions for future research and clinical management. Results of studies that assessed measures of blood pressure variability or reactivity are reviewed. The limited information about effects of antihypertensive drugs on blood pressure variability is discussed. Two different clinical presentations are differentiated: labile hypertension and paroxysmal hypertension. Labile hypertension remains a clinical impression without defined criteria or treatment guidance. Paroxysmal hypertension, also called pseudopheochromocytoma, presents as dramatic episodes of abrupt and severe blood pressure elevation. The disorder can be disabling. Although it regularly raises suspicion of a pheochromocytoma, such a tumor is found in <2 % of patients. The cause, which involves both emotional factors and the sympathetic nervous system, and treatment approaches, are presented. PMID:26370555

  13. The polychaete worm Nereis diversicolor increases mercury lability and methylation in intertidal mudflats.

    PubMed

    Sizmur, Tom; Canário, João; Edmonds, Samuel; Godfrey, Adam; O'Driscoll, Nelson J

    2013-08-01

    The polychaete worm Nereis diversicolor engineers its environment by creating oxygenated burrows in anoxic intertidal sediments. The authors carried out a laboratory microcosm experiment to test the impact of polychaete burrowing and feeding activity on the lability and methylation of mercury in sediments from the Bay of Fundy, Canada. The concentration of labile inorganic mercury and methylmercury in burrow walls was elevated compared to worm-free sediments. Mucus secretions and organic detritus in worm burrows increased labile mercury concentrations. Worms decreased sulfide concentrations, which increased Hg bioavailability to sulfate-reducing bacteria and increased methylmercury concentrations in burrow linings. Because the walls of polychaete burrows have a greater interaction with organisms, and the overlying water, the concentrations of mercury and methylmercury they contain is more toxicologically relevant to the base of a coastal food web than bulk samples. The authors recommend that researchers examining Hg in marine environments account for sediment dwelling invertebrate activity to more fully assess mercury bioavailability. PMID:23633443

  14. Radiation-induced heat-labile sites that convert into DNA double-strand breaks

    NASA Technical Reports Server (NTRS)

    Rydberg, B.; Chatterjee, A. (Principal Investigator)

    2000-01-01

    The yield of DNA double-strand breaks (DSBs) in SV40 DNA irradiated in aqueous solution was found to increase by more than a factor of two as a result of postirradiation incubation of the DNA at 50 degrees C and pH 8.0 for 24 h. This is in agreement with data from studies performed at 37 degrees C that were published previously. Importantly, similar results were also obtained from irradiation of mammalian DNA in agarose plugs. These results suggest that heat-labile sites within locally multiply damaged sites are produced by radiation and are subsequently transformed into DSBs. Since incubation at 50 degrees C is typically employed for lysis of cells in commonly used pulsed-field gel assays for detection of DSBs in mammalian cells, the possibility that heat-labile sites are present in irradiated cells was also studied. An increase in the apparent number of DSBs as a function of lysis time at 50 degrees C was found with kinetics that was similar to that for irradiated DNA, although the magnitude of the increase was smaller. This suggests that heat-labile sites are also formed in the cell. If this is the case, a proportion of DSBs measured by the pulsed-field gel assays may occur during the lysis step and may not be present in the cell as breaks but as heat-labile sites. It is suggested that such sites consist mainly of heat-labile sugar lesions within locally multiply damaged sites. Comparing rejoining of DSBs measured with short and long lysis procedure indicates that the heat-labile sites are repaired with fast kinetics in comparison with repair of the bulk of DSBs.

  15. Mood lability among offspring of parents with bipolar disorder and community controls

    PubMed Central

    Birmaher, Boris; Goldstein, Benjamin I; Axelson, David A; Monk, Kelly; Hickey, Mary Beth; Fan, Jieyu; Iyengar, Satish; Ha, Wonho; Diler, Rasim S; Goldstein, Tina; Brent, David; Ladouceur, Cecile D; Sakolsky, Dara; Kupfer, David J

    2013-01-01

    Objectives Early identification of bipolar disorder (BP) symptomatology is crucial for improving the prognosis of this illness. Increased mood lability has been reported in BP. However, mood lability is ubiquitous across psychiatric disorders and may be a marker of severe psychopathology and not specific to BP. To clarify this issue, this study examined the prevalence of mood lability and its components in offspring of BP parents and offspring of community control parents recruited through the Pittsburgh Bipolar Offspring Study. Methods Forty-one school-age BP offspring of 38 BP parents, 257 healthy or non-BP offspring of 174 BP parents, and 192 offspring of 117 control parents completed a scale that was developed to evaluate mood lability in youth, i.e., the Children’s Affective Lability Scale (CALS). Results A factor analysis of the parental CALS, and in part the child CALS, revealed Irritability, Mania, and Anxiety/Depression factors, with most of the variance explained by the Irritability factor. After adjusting for confounding factors (e.g., parental and offspring non-BP psychopathology), BP offspring of BP parents showed the highest parental and child total and factor scores, followed by the non-BP offspring of BP parents, and then the offspring of the controls. Conclusions Mood lability overall and mania-like, anxious/depressed, and particularly irritability symptoms may be a prodromal phenotype of BP among offspring of parents with BP. Prospective studies are warranted to clarify whether these symptoms will predict the development of BP and/or other psychopathology. If confirmed, these symptoms may become a target of treatment and biological studies before BP develops. PMID:23551755

  16. Atomically mixed Fe-group nanoalloys: catalyst design for the selective electrooxidation of ethylene glycol to oxalic acid.

    PubMed

    Matsumoto, Takeshi; Sadakiyo, Masaaki; Ooi, Mei Lee; Yamamoto, Tomokazu; Matsumura, Syo; Kato, Kenichi; Takeguchi, Tatsuya; Ozawa, Nobuki; Kubo, Momoji; Yamauchi, Miho

    2015-05-01

    We demonstrate electric power generation via the electrooxidation of ethylene glycol (EG) on a series of Fe-group nanoalloy (NA) catalysts in alkaline media. A series of Fe-group binary NA catalysts supported on carbon (FeCo/C, FeNi/C, and CoNi/C) and monometallic analogues (Fe/C, Co/C, and Ni/C) were synthesized. Catalytic activities and product distributions on the prepared Fe-group NA catalysts in the EG electrooxidation were investigated by cyclic voltammetry and chronoamperometry, and compared with those of the previously reported FeCoNi/C, which clarified the contributory factors of the metal components for the EG electrooxidation activity, C2 product selectivity, and catalyst durability. The Co-containing catalysts, such as Co/C, FeCo/C, and FeCoNi/C, exhibit relatively high catalytic activities for EG electrooxidation, whereas the catalytic performances of Ni-containing catalysts are relatively low. However, we found that the inclusion of Ni is a requisite for the prevention of rapid degradation due to surface modification of the catalyst. Notably, FeCoNi/C shows the highest selectivity for oxalic acid production without CO2 generation at 0.4 V vs. the reversible hydrogen electrode (RHE), resulting from the synergetic contribution of all of the component elements. Finally, we performed power generation using the direct EG alkaline fuel cell in the presence of the Fe-group catalysts. The power density obtained on each catalyst directly reflected the catalytic performances elucidated in the electrochemical experiments for the corresponding catalyst. The catalytic roles and alloying effects disclosed herein provide information on the design of highly efficient electrocatalysts containing Fe-group metals. PMID:25848911

  17. Intrinsic acidity of aluminum, chromium(III) and iron(III) {mu}{sub 3}-hydroxo functional groups from ab initio electronic structure calculations

    SciTech Connect

    Rustad, J.R.; Dixon, D.A.; Felmy, A.R.

    2000-05-01

    Density functional calculations are performed on M{sub 3}(OH){sub 7}(H{sub 2}O){sub 6}{sup 2+} and M{sub 3}O(OH){sub 6}(H{sub 2}O){sub 6}{sup +} clusters for M {double_bond} Al, Cr(III), and Fe(III), allowing determination of the relative acidities of the {mu}{sub 3}-hydroxo and aquo functional groups. Contrary to previous predictions and rationalizations, {double_bond}Fe{sub 3}OH and {double_bond}Al{sub 3}OH groups have nearly the same intrinsic acidity, while {double_bond}Cr{sub 3}OH groups are significantly more acidic. The gas-phase acidity of the Fe{sub 3}OH site is in good agreement with the value predicted by the molecular mechanics model previously used to estimate the relative acidities of surface sites on iron oxides. Acidities of aquo functional groups were also computed for Al and Cr. The {double_bond}AlOH{sub 2} site is more acidic than the {double_bond}Al{sub 3}OH site, whereas the {double_bond}Cr{sub 3}OH site is more acidic than the {double_bond}CrOH{sub 2} site. These findings predict that the surface charging behavior of chromium oxides/oxyhydroxides should be distinguishable from their Fe, Al counterparts. The calculations also provide insight into why the lepidocrocite/boehmite polymorph is not observed for CrOOH.

  18. The relation between gastric acid secretion and body habitus, blood groups, smoking, and the subsequent development of dyspepsia and duodenal ulcer

    PubMed Central

    Novis, B. H.; Marks, I. N.; Bank, S.; Sloan, A. W.

    1973-01-01

    One hundred and seventy-six students free of gastrointestinal disease were studied to establish normal acid secretion values for healthy male and female students by the augmented histamine test and to re-examine the relationship between gastric acid secretion and ABO blood groups, body weight, fat-free body mass, height, degree of ectomorphy and mesomorphy, the number of cigarettes smoked per day, and serum cholesterol. A prospective study was then carried out on gastric acid secretion and the subsequent development after 10 years of duodenal ulcers or dyspepsia. Young, healthy medical students have a fairly high mean basal and maximal acid output. There was very little difference in the mean acid outputs of the various ABO blood groups. A significant correlation was shown between acid output and body weight and fat-free body mass, but not with the other measurements of body build. Basal acid output was also related to the number of cigarettes smoked per day. Three students who subsequently developed duodenal ulcers all had a preexistent high level of acid secretion. The acid output was, however, similar in the groups who developed significant or minor dyspepsia or who remained asymptomatic. PMID:4696532

  19. Identification of the Presence of Variant Hemoglobin Using a Measurement of the Labile HbA1c (#C) Fraction.

    PubMed

    Koga, Masafumi; Inada, Shinya; Miyazaki, Ayako

    2016-07-01

    Labile HbA1c migrates in the #C fraction together with modified hemoglobin (such as carbamylated hemoglobin, acetaldehyde hemoglobin, and acetylated hemoglobin) when HbA1c is measured by Arkray's high-performance liquid chromatography (HPLC). It is assumed that most of the labile glycation products of variant hemoglobin do not migrate in #C fraction; in addition, a part of the stable glycation products of variant hemoglobin migrates in #C fraction. We hypothesized that subjects with variant hemoglobin are likely to show abnormally low or high values of #C fraction. In this study, we investigated this hypothesis. Twenty-one non-diabetic subjects with nine types of variant hemoglobin, and 103 non-diabetic subjects without variant hemoglobin were used. HbA1c and #C fraction were measured by Arkray's HPLC (HA-8180) using standard mode. The values of #C fraction in the control group were 1.75 ± 0.15% (range: 1.5-2.1%). The variant hemoglobin group reported #C fraction values of ≤1.3% in twelve subjects, ≥2.3% in five subjects, and within the reference range (1.4-2.2%) in three subjects. When the cutoff values of #C fraction were set at ≤1.3% and ≥2.3%, sensitivity and specificity were 86% and 100%, respectively. Most non-diabetic subjects with variant hemoglobin showed abnormal values of #C fraction. Measurement of #C fraction is a useful screening test for variant hemoglobin in non-diabetic subjects. PMID:27466298

  20. Breaking the dogma of the metal-coordinating carboxylate group in integrin ligands: introducing hydroxamic acids to the MIDAS to tune potency and selectivity.

    PubMed

    Heckmann, Dominik; Laufer, Burkhardt; Marinelli, Luciana; Limongelli, Vittorio; Novellino, Ettore; Zahn, Grit; Stragies, Roland; Kessler, Horst

    2009-01-01

    A suitable substitute: All integrin receptors bind their ligands, which contain an aspartate residue, in the metal-ion- dependent adhesion site (MIDAS). So far all attempts to replace the carboxyl group of aspartate with other, pharmacologically favorable isosteric groups have failed. Now it has been shown that a hydroxamic acid group can replace the carboxyl group; the resulting ligand retains its high binding activity. The picture shows one such ligand in the binding site of alphavbeta3. PMID:19343753

  1. The CovS/CovR acid response regulator is required for intracellular survival of group B Streptococcus in macrophages.

    PubMed

    Cumley, Nicola J; Smith, Leanne M; Anthony, Mark; May, Robin C

    2012-05-01

    Group B Streptococcus (GBS) is a leading cause of neonatal meningitis and septicemia. The ability of this organism to survive inside phagocytic cells is poorly understood but thought to be an important step for the establishment of disease in the host. Here, we demonstrate that GBS shows prolonged survival within J774 macrophages and that the capacity to survive is not significantly changed across a diverse range of strains representing different serotypes, multilocus sequence types (MLST), and sites of clinical isolation. Using staining for the lysosome-associated membrane protein (LAMP) and by pharmacological inhibition of phagosome acidification, we demonstrate that streptococci reside in a phagosome and that acidification of the phagosome is required for GBS to survive intracellularly. Moreover, we show that the GBS two-component system CovS/CovR, which is the major acid response regulator in this organism, is required for survival inside the phagosome. PMID:22331428

  2. The CovS/CovR Acid Response Regulator Is Required for Intracellular Survival of Group B Streptococcus in Macrophages

    PubMed Central

    Cumley, Nicola J.; Smith, Leanne M.; Anthony, Mark

    2012-01-01

    Group B Streptococcus (GBS) is a leading cause of neonatal meningitis and septicemia. The ability of this organism to survive inside phagocytic cells is poorly understood but thought to be an important step for the establishment of disease in the host. Here, we demonstrate that GBS shows prolonged survival within J774 macrophages and that the capacity to survive is not significantly changed across a diverse range of strains representing different serotypes, multilocus sequence types (MLST), and sites of clinical isolation. Using staining for the lysosome-associated membrane protein (LAMP) and by pharmacological inhibition of phagosome acidification, we demonstrate that streptococci reside in a phagosome and that acidification of the phagosome is required for GBS to survive intracellularly. Moreover, we show that the GBS two-component system CovS/CovR, which is the major acid response regulator in this organism, is required for survival inside the phagosome. PMID:22331428

  3. Infrared and Raman spectra of N-acetyl- L-amino acid methylamides with aromatic side groups

    NASA Astrophysics Data System (ADS)

    Matsuura, Hiroatsu; Hasegawa, Kodo; Miyazawa, Tatsuo

    Infrared and Raman spectra of N-acetyl- L-phenylalanine methylamide, N-acetyl- L-tyrosine methylamide and N-acetyl- L-tryptophan methylamide, as model compounds of aromatic amino acid residues in proteins, were measured in the solid state and in methanol solutions. Vibrational assignments of the spectra were made by utilizing the deuteration effect and by comparison with the spectra of related compounds which include toluene, p-cresol and 3-methylindole. The amide I, III and IV bands were strong in Raman scattering, but other characteristic amide bands were ill-defined. In the Raman spectra of methanol solutions, only the bands due to the aromatic side group vibrations were markedly observed, but those due to the peptide backbone vibrations were very weak, suggesting the coexistence of various molecular conformations in solution.

  4. Block and random copolymers bearing cholic acid and oligo(ethylene glycol) pendant groups: aggregation, thermosensitivity, and drug loading.

    PubMed

    Shao, Yu; Jia, Yong-Guang; Shi, Changying; Luo, Juntao; Zhu, X X

    2014-05-12

    A series of block and random copolymers consisting of oligo(ethylene glycol) and cholic acid pendant groups were synthesized via ring-opening metathesis polymerization of their norbornene derivatives. These block and random copolymers were designed to have similar molecular weights and comonomer ratios; both types of copolymers showed thermosensitivity in aqueous solutions with similar cloud points. The copolymers self-assembled into micelles in water as shown by dynamic light scattering and transmission electron microscopy. The hydrodynamic diameter of the micelles formed by the block copolymer is much larger and exhibited a broad and gradual shrinkage from 20 to 54 °C below its cloud point, while the micelles formed by the random copolymers are smaller in size but exhibited some swelling in the same temperature range. Based on in vitro drug release studies, 78% and 24% paclitaxel (PTX) were released in 24 h from micelles self-assembled by the block and random copolymers, respectively. PTX-loaded micelles formed by the block and random copolymers exhibited apparent antitumor efficacy toward the ovarian cancer cells with a particularly low half-maximal inhibitory concentration (IC50) of 27.4 and 40.2 ng/mL, respectively. Cholic acid-based micelles show promise as a versatile and potent platform for cancer chemotherapy. PMID:24725005

  5. Block and Random Copolymers Bearing Cholic Acid and Oligo(ethylene glycol) Pendant Groups: Aggregation, Thermosensitivity, and Drug Loading

    PubMed Central

    2015-01-01

    A series of block and random copolymers consisting of oligo(ethylene glycol) and cholic acid pendant groups were synthesized via ring-opening metathesis polymerization of their norbornene derivatives. These block and random copolymers were designed to have similar molecular weights and comonomer ratios; both types of copolymers showed thermosensitivity in aqueous solutions with similar cloud points. The copolymers self-assembled into micelles in water as shown by dynamic light scattering and transmission electron microscopy. The hydrodynamic diameter of the micelles formed by the block copolymer is much larger and exhibited a broad and gradual shrinkage from 20 to 54 °C below its cloud point, while the micelles formed by the random copolymers are smaller in size but exhibited some swelling in the same temperature range. Based on in vitro drug release studies, 78% and 24% paclitaxel (PTX) were released in 24 h from micelles self-assembled by the block and random copolymers, respectively. PTX-loaded micelles formed by the block and random copolymers exhibited apparent antitumor efficacy toward the ovarian cancer cells with a particularly low half-maximal inhibitory concentration (IC50) of 27.4 and 40.2 ng/mL, respectively. Cholic acid-based micelles show promise as a versatile and potent platform for cancer chemotherapy. PMID:24725005

  6. Functionalisation of mesoporous silica gel with 2-[(phosphonomethyl)-amino]acetic acid functional groups. Characterisation and application

    NASA Astrophysics Data System (ADS)

    Caldarola, Dario; Mitev, Dimitar P.; Marlin, Lucile; Nesterenko, Ekaterina P.; Paull, Brett; Onida, Barbara; Bruzzoniti, Maria Concetta; Carlo, Rosa Maria De; Sarzanini, Corrado; Nesterenko, Pavel N.

    2014-01-01

    A new complexing adsorbent was prepared by chemical modification of mesoporous silica Kieselgel 60 (dp = 37-63 μm, average pore size 6 nm, specific surface area 425 m2 g-1) with 3-glycidoxypropyltrimethoxysilane and 2-[(phosphonomethyl)amino]acetic acid (PMA), commonly known as glyphosate. The prepared adsorbent was fully characterised using elemental analysis, thermal gravimetric analysis (TGA), acid-base potentiometric titration, Fourier Transform Infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption isotherms at 77 K (BET), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). The concentration of bonded PMA groups calculated from the nitrogen content was 0.38 mmol per gram. The adsorption of transition metal ions on PMA functionalised silica (HEPMAS) was studied from aqueous solutions having different pH and the following selectivity was established, Zn(II) < Co(II) < Cd(II) < Mn(II) < Ni(II) < Cu(II). The calculated values of distribution coefficients D for the adsorption of ecotoxic metal ions on HEPMAS are 5.0 × 104, 4.9 × 105 and 2.6 × 104 for Zn(II), Pb(II) and Cd(II), respectively.

  7. Kinetics characterization of c-Src binding to lipid membranes: Switching from labile to persistent binding.

    PubMed

    Le Roux, Anabel-Lise; Busquets, Maria Antònia; Sagués, Francesc; Pons, Miquel

    2016-02-01

    Cell signaling by the c-Src proto-oncogen requires the attachment of the protein to the inner side of the plasma membrane through the myristoylated N-terminal region, known as the SH4 domain. Additional binding regions of lower affinity are located in the neighbor intrinsically disordered Unique domain and the structured SH3 domain. Here we present a surface plasmon resonance study of the binding of a myristoylated protein including the SH4, Unique and SH3 domains of c-Src to immobilized liposomes. Two distinct binding processes were observed: a fast and a slow one. The second process lead to a persistently bound form (PB) with a slower binding and a much slower dissociation rate than the first one. The association and dissociation of the PB form could be detected using an anti-SH4 antibody. The kinetic analysis revealed that binding of the PB form follows a second order rate law suggesting that it involves the formation of c-Src dimers on the membrane surface. A kinetically equivalent PB form is observed in a myristoylated peptide containing only the SH4 domain but not in a construct including the three domains but with a 12-carbon lauroyl substituent instead of the 14-carbon myristoyl group. The PB form is observed with neutral lipids but its population increases when the immobilized liposomes contain negatively charged lipids. We suggest that the PB form may represent the active signaling form of c-Src while the labile form provides the capacity for fast 2D search of the target signaling site on the membrane surface. PMID:26638178

  8. Linear and cyclic aliphatic carboxamides of the Murchison meteorite: Hydrolyzable derivatives of amino acids and other carboxylic acids

    NASA Astrophysics Data System (ADS)

    Cooper, G. W.; Cronin, J. R.

    1995-03-01

    Analyses of fractionated aqueous extracts of the Murchison meteorite by gas chromatographymass spectrometry after silylation with N-methyl-N ( tert-butyldimethylsilyl) trifluoroacetamide have revealed an extensive series of linear and cyclic aliphatic amides. These include monocarboxylic acid amides, dicarboxylic acid monoamides, hydroxy acid amides, lactams, carboxy lactams, lactims, N-acetyl amino acids, and substituted hydantoins. Numerous isomers and homologues through at least C 8 were observed in all cases, except for the N-acetyl amino acids and hydantoins. Carboxy lactams, lactams, hydantoins, and N-acetyl amino acids are converted to amino acids by acid hydrolysis, thus, these compounds qualitatively account for the earlier observation of acid-labile amino acid precursors in meteoritic extracts. Laboratory studies of the spontaneous decomposition of N-carbamyl-α-amino acids and their dehydration products, the 5-substituted hydantoins, have led to the recognition of a series of aqueous phase reactions by which amino acids and cyanic acid/cyanate ion in the primitive parent body might have given rise to several of the observed classes of amides, as well as to monocarboxylic acids, dicarboxylic acids, and hydroxy acids. A previously undescribed reaction of 5-substituted hydantoins with cyanic acid/cyanate ion to give carboxamides of the 5-substituent groups was observed in the course of these studies. The presence of an extensive suite of amides in a CM chondrite appears to be consistent with the interstellar-parent body formation hypothesis for the organic compounds of these meteorites. The presence of carboxy lactams and lactams along with free amino acids suggests the possibility of further chemical evolution of meteorite amino acids by thermal polymerization. The cyclic amides, given their potential for hydrogen-bonded pair formation, might be considered candidate bases for a primitive sequence coding system.

  9. Characterization and grouping of aquatic fulvic acids isolated from clear-water rivers and lakes in Japan.

    PubMed

    Tsuda, Kumiko; Mori, Hisayo; Asakawa, Daichi; Yanagi, Yukiko; Kodama, Hiroki; Nagao, Seiya; Yonebayashi, Koyo; Fujitake, Nobuhide

    2010-07-01

    Characteristics of aquatic fulvic acids (FAs) from 10 clear waters in Japan (around the temperate zone) were revealed by several analytical techniques-high performance size exclusion chromatography (HPSEC), elemental analysis, liquid-state (13)C NMR spectroscopy, isotopic analyses (delta(13)C and delta(15)N), and compared with those of International Humic Substances Society (IHSS) standard samples including FAs from brown waters (Suwannee, Pony, and Nordic FAs). Generally clear-water FAs were different from brown-water FAs in chemical properties. Weight-average molecular weights (Mw) of the clear-water FAs were similar to each other, whereas their elemental compositions and carbon species distribution were different. The clear-water FAs all exhibited a high proportion of alkyl carbons, which may be attributed to microbial activity. delta(13)C and delta(15)N values of the FAs indicated that there would be a huge gap between origin and chemical structure of clear-water FA. Results of the chemical structural analyses described above were not always linked to those of the isotopic analyses (delta(13)C and delta(15)N). Multivariate statistical analysis, i.e. cluster and principal component analysis was applied to reveal differences or similarities in a more objective manner. The FAs were always classified into two clear-water groups and one brown-water group. Aryl-C and O-Alkyl-C contents were important for the grouping. We speculate that the grouping might depend on the differences of aquatic microbial activity caused by the differences of residence time of water. PMID:20569962

  10. Metal-free protodeboronation of electron-rich arene boronic acids and its application to ortho-functionalization of electron-rich arenes using a boronic acid as a blocking group.

    PubMed

    Ahn, Su-Jin; Lee, Chun-Young; Kim, Nak-Kyoon; Cheon, Cheol-Hong

    2014-08-15

    The metal-free thermal protodeboronation of various electron-rich arene boronic acids was studied. Several reaction parameters controlling this protodeboronation, such as solvent, temperature, and a proton source, have been investigated. On the basis of these studies, suitable reaction conditions for protodeboronation of several types of electron-rich arene boronic acids were provided. On the basis of this protodeboronation, a new protocol for the synthesis of ortho-functionalized electron-rich arenes from these boronic acids was developed using the boronic acid moiety as a blocking group in the electrophilic aromatic substitution reaction, followed by the removal of the boronic acid moiety via thermal protodeboronation. Mechanistic studies suggested that this protodeboronation might proceed via the complex formation of a boronic acid with a proton source, followed by the carbon-boron bond fission through σ-bond metathesis, to afford the corresponding arene compound and boric acid. PMID:25052375

  11. A single amino acid substitution in the group 1 Trypanosoma brucei gambiense haptoglobin-hemoglobin receptor abolishes TLF-1 binding.

    PubMed

    DeJesus, E; Kieft, R; Albright, B; Stephens, N A; Hajduk, S L

    2013-01-01

    Critical to human innate immunity against African trypanosomes is a minor subclass of human high-density lipoproteins, termed Trypanosome Lytic Factor-1 (TLF-1). This primate-specific molecule binds to a haptoglobin-hemoglobin receptor (HpHbR) on the surface of susceptible trypanosomes, initiating a lytic pathway. Group 1 Trypanosoma brucei gambiense causes human African Trypanosomiasis (HAT), escaping TLF-1 killing due to reduced uptake. Previously, we found that group 1 T. b. gambiense HpHbR (TbgHpHbR) mRNA levels were greatly reduced and the gene contained substitutions within the open reading frame. Here we show that a single, highly conserved amino acid in the TbgHpHbR ablates high affinity TLF-1 binding and subsequent endocytosis, thus evading TLF-1 killing. In addition, we show that over-expression of TbgHpHbR failed to rescue TLF-1 susceptibility. These findings suggest that the single substitution present in the TbgHpHbR directly contributes to the reduced uptake and resistance to TLF-1 seen in these important human pathogens. PMID:23637606

  12. A Single Amino Acid Substitution in the Group 1 Trypanosoma brucei gambiense Haptoglobin-Hemoglobin Receptor Abolishes TLF-1 Binding

    PubMed Central

    DeJesus, E.; Kieft, R.; Albright, B.; Stephens, N. A.; Hajduk, S. L.

    2013-01-01

    Critical to human innate immunity against African trypanosomes is a minor subclass of human high-density lipoproteins, termed Trypanosome Lytic Factor-1 (TLF-1). This primate-specific molecule binds to a haptoglobin-hemoglobin receptor (HpHbR) on the surface of susceptible trypanosomes, initiating a lytic pathway. Group 1 Trypanosoma brucei gambiense causes human African Trypanosomiasis (HAT), escaping TLF-1 killing due to reduced uptake. Previously, we found that group 1 T. b. gambiense HpHbR (TbgHpHbR) mRNA levels were greatly reduced and the gene contained substitutions within the open reading frame. Here we show that a single, highly conserved amino acid in the TbgHpHbR ablates high affinity TLF-1 binding and subsequent endocytosis, thus evading TLF-1 killing. In addition, we show that over-expression of TbgHpHbR failed to rescue TLF-1 susceptibility. These findings suggest that the single substitution present in the TbgHpHbR directly contributes to the reduced uptake and resistance to TLF-1 seen in these important human pathogens. PMID:23637606

  13. The effects of anion exchange functional-group variations on the sorption of Pu(IV) from nitric acid

    SciTech Connect

    Marsh, S.F.

    1995-12-01

    A macroporous, polyvinylpyridine anion exchange resin has been used for more than five years at the Los Alamos Plutonium Facility to recover plutonium from nitrate media. This strong-base anion exchanger, Reillex{trademark} HPQ, offers higher capacity, faster kinetics, and significantly higher resistance to chemical and radiation damage than conventional polystyrene-based resins. In this study, we measured the sorption of Pu(IV) on Reillex{trademark} HPQ and on three macroporous, strong-base anion exchange resins that differ from Reillex{trademark} HPQ only in the alkyl group used to quaternize the pyridinium. nitrogen. These four resins, prepared by Reilly Industries, Inc., are copolymers of 1-alkyl-4-vinylpyridine, where the alkyl groups are methyl, butyl, hexyl, and octyl. We compare the trends in Pu(IV) sorption on these four resins to those obtained in our previous study of four polystyrene anion exchange resins having trimethyl, triethyl, tripropyl, and tributyl ammonium functionality. The Pu(IV) sorption was measured from 1 M to 9 M nitric acid in both studies.

  14. Probing the Influence of Protecting Groups on the Anomeric Equilibrium in Sialic Acid Glycosides with the Persistent Radical Effect

    PubMed Central

    2015-01-01

    A method for the investigation of the influence of protecting groups on the anomeric equilibrium in the sialic acid glycosides has been developed on the basis of the equilibration of O-sialyl hydroxylamines by reversible homolytic scission of the glycosidic bond following the dictates of the Fischer–Ingold persistent radical effect. It is found that a trans-fused 4O,5N-oxazolidinone group stabilizes the equatorial glycoside, i.e., reduces the anomeric effect, when compared to the 4O,5N-diacetyl protected systems. This effect is discussed in terms of the powerful electron-withdrawing nature of the oxazolidinone system, which in turn is a function of its strong dipole moment in the mean plane of the pyranose ring system. The new equilibration method displays a small solvent effect and is most pronounced in less polar media consistent with the anomeric effect in general. The unusual (for anomeric radicals) poor kinetic selectivity of anomeric sialyl radicals is discussed in terms of the planar π-type structure of these radicals and of competing 1,3-diaxial interactions in the diastereomeric transition states for trapping on the α- and β-faces of the radical. PMID:24606062

  15. A self-crosslinking thermosetting monomer with both epoxy and anhydride groups derived from Tung oil fatty acids: Synthesis and properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A self-crosslinking compound with epoxy groups and anhydride groups (GEMA) has been successfully synthesized from Tung oil fatty acid by reacting with maleic anhydride via the Diels-Alder reaction. GEMA has very good storage stability and can be cured with trace amounts of tertiary amine. This advan...

  16. Non-labile silver species in biosolids remain stable throughout 50 years of weathering and ageing.

    PubMed

    Donner, E; Scheckel, K; Sekine, R; Popelka-Filcoff, R S; Bennett, J W; Brunetti, G; Naidu, R; McGrath, S P; Lombi, E

    2015-10-01

    Increasing commercial use of nanosilver has focussed attention on the fate of silver (Ag) in the wastewater release pathway. This paper reports the speciation and lability of Ag in archived, stockpiled, and contemporary biosolids from the UK, USA and Australia, and indicates that biosolids Ag concentrations have decreased significantly over recent decades. XANES revealed the importance of reduced-sulfur binding environments for Ag speciation in materials ranging from freshly produced sludge to biosolids weathered under ambient environmental conditions for more than 50 years. Isotopic dilution with (110 m)Ag showed that Ag was predominantly non-labile in both fresh and aged biosolids (13.7% mean lability), with E-values ranging from 0.3 to 60 mg/kg and 5 mM CaNO3 extractable Ag from 1.2 to 609 μg/kg (0.002-3.4% of the total Ag). This study indicates that at the time of soil application, biosolids Ag will be predominantly Ag-sulfides and characterised by low isotopic lability. PMID:26021819

  17. Non-labile silver species in biosolids remain stable throughout 50 years of weathering and ageing.

    EPA Science Inventory

    Increasing commercial use of nanosilver has focussed attention on the fate of silver (Ag) in the wastewater release pathway. This paper reports the speciation and lability of Ag in archived, stockpiled, and contemporary biosolids from the UK, USA and Australia, and indicates that...

  18. Occurrence and abundance of carbohydrates and amino compounds in sequentially extracted labile soil organic matter fractions.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This study aimed to investigate the content of carbohydrates and amino compounds in three labile fraction of soil organic matter (SOM). Soil samples were collected from two agricultural fields in southern Italy and the light fraction (LF), the 500–53-µm particulate organic matter (POM) and the mobil...

  19. Labile compounds in plant litter reduce the sensitivity of decomposition to warming and altered precipitation.

    PubMed

    Suseela, Vidya; Tharayil, Nishanth; Xing, Baoshan; Dukes, Jeffrey S

    2013-10-01

    Together, climate and litter quality strongly regulate decomposition rates. Although these two factors and their interaction have been studied across species in continent-scale experiments, few researchers have studied how labile and recalcitrant compounds interact to influence decomposition, or the climate sensitivity of decomposition, within a litter type. Over a period of 3 yr, we studied the effects of warming and altered precipitation on mass loss and compound-specific decomposition using two litter types that possessed similar heteropolymer chemistry, but different proportions of labile and recalcitrant compounds. Climate treatments immediately affected the mass loss of the more recalcitrant litter, but affected the more labile litter only after 2 yr. After 3 yr, although both litter types had lost similar amounts of mass, warming (c. 4°C) and supplemental precipitation (150% of ambient) together accelerated the degradation of alkyl-carbon and lignin only in the more recalcitrant litter, highlighting the role of initial litter quality in determining whether the chemistry of litter residues converges or diverges under different climates. Our finding that labile compounds in litter reduce the climate sensitivity of mass loss and the decomposition of recalcitrant matrix is novel. Our results highlight the potential for litter quality to regulate the effect of climatic changes on the sequestration of litter-derived carbon. PMID:23822593

  20. Similarity of Monozygotic and Dizygotic Twins in Level and Lability of Subclinically Depressed Mood.

    ERIC Educational Resources Information Center

    Wierzbicki, Michael

    1986-01-01

    Ninety-two adult twin-pairs were recruited. Twin zygosity was determined by self-report inventory. Monozygotic twins resembled one another more than dizygotic twins in most measures of both level and lability of mood, which provides modest evidence for a genetic influence on subclinical levels of depression. (Author/ABB)

  1. Measurement of labile copper in wine by medium exchange stripping potentiometry utilising screen printed carbon electrodes.

    PubMed

    Clark, Andrew C; Kontoudakis, Nikolaos; Barril, Celia; Schmidtke, Leigh M; Scollary, Geoffrey R

    2016-07-01

    The presence of copper in wine is known to impact the reductive, oxidative and colloidal stability of wine, and techniques enabling measurement of different forms of copper in wine are of particular interest in understanding these spoilage processes. Electrochemical stripping techniques developed to date require significant pretreatment of wine, potentially disturbing the copper binding equilibria. A thin mercury film on a screen printed carbon electrode was utilised in a flow system for the direct analysis of labile copper in red and white wine by constant current stripping potentiometry with medium exchange. Under the optimised conditions, including an enrichment time of 500s and constant current of 1.0μA, the response range was linear from 0.015 to 0.200mg/L. The analysis of 52 red and white wines showed that this technique generally provided lower labile copper concentrations than reported for batch measurement by related techniques. Studies in a model system and in finished wines showed that the copper sulfide was not measured as labile copper, and that loss of hydrogen sulfide via volatilisation induced an increase in labile copper within the model wine system. PMID:27154696

  2. The role of hydroxyl group acidity on the activity of silica-supported secondary amines for the self-condensation of n-butanal.

    PubMed

    Shylesh, Sankaranarayanapillai; Hanna, David; Gomes, Joseph; Canlas, Christian G; Head-Gordon, Martin; Bell, Alexis T

    2015-02-01

    The catalytic activity of secondary amines supported on mesoporous silica for the self-condensation of n-butanal to 2-ethylhexenal can be altered significantly by controlling the Brønsted acidity of M--OH species present on the surface of the support. In this study, M--OH (M=Sn, Zr, Ti, and Al) groups were doped onto the surface of SBA-15, a mesoporous silica, prior to grafting secondary propyl amine groups on to the support surface. The catalytic activity was found to depend critically on the synthesis procedure, the nature and amount of metal species introduced and the spatial separation between the acidic sites and amine groups. DFT analysis of the reaction pathway indicates that, for weak Brønsted acid groups, such as Si--OH, the rate-limiting step is C--C bond formation, whereas for stronger Brønsted acid groups, such as Ti and Al, hydrolysis of iminium species produced upon C--C bond formation is the rate-limiting step. Theoretical analysis shows further that the apparent activation energy decreases with increasing Brønsted acidity of the M--OH groups, consistent with experimental observation. PMID:25314616

  3. A Longitudinal Study of Emotion Regulation, Emotion Lability/Negativity, and Internalizing Symptomatology in Maltreated and Nonmaltreated Children

    PubMed Central

    Kim-Spoon, Jungmeen; Cicchetti, Dante; Rogosch, Fred A.

    2013-01-01

    The longitudinal contributions of emotion regulation and emotion lability/negativity to internalizing symptomatology were examined in a low-income sample (171 maltreated and 151 nonmaltreated children, from age 7 to 10 years). Latent difference score models indicated that, for both maltreated and nonmaltreated children, emotion regulation was a mediator between emotion lability/negativity and internalizing symptomatology, whereas emotion lability/negativity was not a mediator between emotion regulation and internalizing symptomatology. Early maltreatment was associated with high emotion lability/negativity (age 7) that contributed to poor emotion regulation (age 8), which in turn was predictive of increases in internalizing symptomatology (from age 8 to 9). The results imply important roles of emotion regulation in the development of internalizing symptomatology, especially for children with high emotion lability/negativity. PMID:23034132

  4. Oxygen consumption and labile dissolved organic carbon uptake by benthic biofilms

    NASA Astrophysics Data System (ADS)

    de Falco, Natalie; Boano, Fulvio; Arnon, Shai

    2015-04-01

    Biogeochemical activity in streams is often magnified at interfaces, such as in the case of biofilm growth near the surface of the stream sediments. The objective of this study was to evaluate the relative importance of surficial biofilms versus the biofilm in the hyporheic zone to the processes of biodegradation of a labile dissolved organic carbon (DOC) and to oxygen consumption. Experiments were conducted in a recirculating flume, equipped with a drainage system that enables the control on losing and gaining fluxes. A surficial biofilm was developed over a sandy streambed with dune-shaped bed forms, by providing labile DOC (sodium benzoate) and nitrate. Homogeneously distributed biofilm was obtained by the same feeding strategy but with mixing the sediments manually on a daily basis. After the biofilm growth period, transformation of the labile DOC under different overlying velocities and losing or gaining fluxes was studied after spiking with sodium benzoate and by monitoring the decrease in DOC concentration in the bulk water over time using an online UV/Vis spectrophotometer. In addition, oxygen profiles across the water-streambed interface were measured at different locations along the bed form using oxygen microelectrodes. Preliminary results showed that the rate of labile DOC degradation increased exponentially with increasing overlying water velocity, regardless of the type of biofilm. Gaining and losing conditions did not play a critical role in the DOC degradation regardless of the type of biofilm, because the labile DOC was quickly utilized close to the surface. Under losing conditions, complete depletion of oxygen was observed within the top 5 millimeters, regardless of the biofilm type. In contrast, oxygen profiles under gaining condition showed an incomplete consumption of oxygen followed by an increase in the concentration of oxygen deeper in the sediments due to the upward flow of oxygenated groundwater. The results suggest that the transformation

  5. Theoretical study of chlordecone and surface groups interaction in an activated carbon model under acidic and neutral conditions.

    PubMed

    Gamboa-Carballo, Juan José; Melchor-Rodríguez, Kenia; Hernández-Valdés, Daniel; Enriquez-Victorero, Carlos; Montero-Alejo, Ana Lilian; Gaspard, Sarra; Jáuregui-Haza, Ulises Javier

    2016-04-01

    Activated carbons (ACs) are widely used in the purification of drinking water without almost any knowledge about the adsorption mechanisms of the persistent organic pollutants. Chlordecone (CLD, Kepone) is an organochlorinated synthetic compound that has been used mainly as agricultural insecticide. CLD has been identified and listed as a persistent organic pollutant by the Stockholm Convention. The selection of the best suited AC for this type of contaminants is mainly an empirical and costly process. A theoretical study of the influence of AC surface groups (SGs) on CLD adsorption is done in order to help understanding the process. This may provide a first selection criteria for the preparation of AC with suitable surface properties. A model of AC consisting of a seven membered ring graphene sheet (coronene) with a functional group on the edge was used to evaluate the influence of the SGs over the adsorption. Multiple Minima Hypersurface methodology (MMH) coupled with PM7 semiempirical Hamiltonian was employed in order to study the interactions of the chlordecone with SGs (hydroxyl and carboxyl) at acidic and neutral pH and different hydration conditions. Selected structures were re-optimized using CAM-B3LYP to achieve a well-defined electron density to characterize the interactions by the Quantum Theory of Atoms in Molecules approach. The deprotonated form of surface carboxyl and hydroxyl groups of AC models show the strongest interactions, suggesting a chemical adsorption. An increase in carboxylic SGs content is proposed to enhance CLD adsorption onto AC at neutral pH conditions. PMID:26945637

  6. Further studies on the glycerol teichoic acid of walls of Staphylococcus lactis I3. Location of the phosphodiester groups and their susceptibility to hydrolysis with alkali

    PubMed Central

    Archibald, A. R.; Baddiley, J.; Heckels, J. E.; Heptinstall, S.

    1971-01-01

    1. The teichoic acid from walls of Staphylococcus lactis I3 is readily degraded in dilute alkali. 2. Degradation proceeds by selective hydrolysis of that phosphodiester group attached to an alcoholic hydroxyl group of the N-acetylglucosamine and gives a repeating unit in high yield. 3. Further studies on a different repeating unit isolated by partial acid hydrolysis have shown that the glycerol diphosphate is attached to the 4-hydroxyl group of the N-acetylglucosamine and not to the 3-hydroxyl group as was proposed earlier. 4. The susceptibility towards hydrolysis by alkali of other structural types of teichoic acid has been examined and found to vary markedly according to their structure. PMID:5158917

  7. Using isotopic dilution to assess chemical extraction of labile Ni, Cu, Zn, Cd and Pb in soils.

    PubMed

    Garforth, J M; Bailey, E H; Tye, A M; Young, S D; Lofts, S

    2016-07-01

    Chemical extractants used to measure labile soil metal must ideally select for and solubilise the labile fraction, with minimal solubilisation of non-labile metal. We assessed four extractants (0.43 M HNO3, 0.43 M CH3COOH, 0.05 M Na2H2EDTA and 1 M CaCl2) against these requirements. For soils contaminated by contrasting sources, we compared isotopically exchangeable Ni, Cu, Zn, Cd and Pb (EValue, mg kg(-1)), with the concentrations of metal solubilised by the chemical extractants (MExt, mg kg(-1)). Crucially, we also determined isotopically exchangeable metal in the soil-extractant systems (EExt, mg kg(-1)). Thus 'EExt - EValue' quantifies the concentration of mobilised non-labile metal, while 'EExt - MExt' represents adsorbed labile metal in the presence of the extractant. Extraction with CaCl2 consistently underestimated EValue for Ni, Cu, Zn and Pb, while providing a reasonable estimate of EValue for Cd. In contrast, extraction with HNO3 both consistently mobilised non-labile metal and overestimated the EValue. Extraction with CH3COOH appeared to provide a good estimate of EValue for Cd; however, this was the net outcome of incomplete solubilisation of labile metal, and concurrent mobilisation of non-labile metal by the extractant (MExtEValue). The Na2H2EDTA extractant mobilised some non-labile metal in three of the four soils, but consistently solubilised the entire labile fraction for all soil-metal combinations (MExt ≈ EExt). Comparison of EValue, MExt and EExt provides a rigorous means of assessing the underlying action of soil chemical extraction methods and could be used to refine long-standing soil extraction methodologies. PMID:27153236

  8. Glaciers as a source of ancient and labile organic matter to the marine environment.

    PubMed

    Hood, Eran; Fellman, Jason; Spencer, Robert G M; Hernes, Peter J; Edwards, Rick; D'Amore, David; Scott, Durelle

    2009-12-24

    Riverine organic matter supports of the order of one-fifth of estuarine metabolism. Coastal ecosystems are therefore sensitive to alteration of both the quantity and lability of terrigenous dissolved organic matter (DOM) delivered by rivers. The lability of DOM is thought to vary with age, with younger, relatively unaltered organic matter being more easily metabolized by aquatic heterotrophs than older, heavily modified material. This view is developed exclusively from work in watersheds where terrestrial plant and soil sources dominate streamwater DOM. Here we characterize streamwater DOM from 11 coastal watersheds on the Gulf of Alaska that vary widely in glacier coverage (0-64 per cent). In contrast to non-glacial rivers, we find that the bioavailability of DOM to marine microorganisms is significantly correlated with increasing (14)C age. Moreover, the most heavily glaciated watersheds are the source of the oldest ( approximately 4 kyr (14)C age) and most labile (66 per cent bioavailable) DOM. These glacial watersheds have extreme runoff rates, in part because they are subject to some of the highest rates of glacier volume loss on Earth. We estimate the cumulative flux of dissolved organic carbon derived from glaciers contributing runoff to the Gulf of Alaska at 0.13 +/- 0.01 Tg yr(-1) (1 Tg = 10(12) g), of which approximately 0.10 Tg is highly labile. This indicates that glacial runoff is a quantitatively important source of labile reduced carbon to marine ecosystems. Moreover, because glaciers and ice sheets represent the second largest reservoir of water in the global hydrologic system, our findings indicate that climatically driven changes in glacier volume could alter the age, quantity and reactivity of DOM entering coastal oceans. PMID:20033045

  9. Low Bacterial Diversity and High Labile Organic Matter Concentrations in the Sediments of the Medee Deep-Sea Hypersaline Anoxic Basin

    PubMed Central

    Akoumianaki, Ioanna; Nomaki, Hidetaka; Pachiadaki, Maria; Kormas, Konstantinos Ar.; Kitazato, Hiroshi; Tokuyama, Hidekazu

    2012-01-01

    Studies in the center and margin of the Medee Basin, a Mediterranean deep-sea hypersaline anoxic basin, and at a reference site during Penelope cruise (2007), revealed the existence of a 7 m-thick halocline, with high salinity (328 psu), and high sedimentary organic carbon and biopolymer concentrations. The 194 16S rRNA sequences retrieved were grouped into 118 unique phylotypes. Pseudomonas gessardii, dominated in the center, while 33 phylotypes were detected at the margin and 73 at the reference site. The study suggested conditions hostile to bacteria in the sediments of the Medee Basin and preservation of sedimentary labile organic matter. PMID:22504432

  10. Aspirin’s Active Metabolite Salicylic Acid Targets High Mobility Group Box 1 to Modulate Inflammatory Responses

    PubMed Central

    Choi, Hyong Woo; Tian, Miaoying; Song, Fei; Venereau, Emilie; Preti, Alessandro; Park, Sang-Wook; Hamilton, Keith; Swapna, G V T; Manohar, Murli; Moreau, Magali; Agresti, Alessandra; Gorzanelli, Andrea; De Marchis, Francesco; Wang, Huang; Antonyak, Marc; Micikas, Robert J; Gentile, Daniel R; Cerione, Richard A; Schroeder, Frank C; Montelione, Gaetano T; Bianchi, Marco E; Klessig, Daniel F

    2015-01-01

    Salicylic acid (SA) and its derivatives have been used for millennia to reduce pain, fever and inflammation. In addition, prophylactic use of acetylsalicylic acid, commonly known as aspirin, reduces the risk of heart attack, stroke and certain cancers. Because aspirin is rapidly de-acetylated by esterases in human plasma, much of aspirin’s bioactivity can be attributed to its primary metabolite, SA. Here we demonstrate that human high mobility group box 1 (HMGB1) is a novel SA-binding protein. SA-binding sites on HMGB1 were identified in the HMG-box domains by nuclear magnetic resonance (NMR) spectroscopic studies and confirmed by mutational analysis. Extracellular HMGB1 is a damage-associated molecular pattern molecule (DAMP), with multiple redox states. SA suppresses both the chemoattractant activity of fully reduced HMGB1 and the increased expression of proinflammatory cytokine genes and cyclooxygenase 2 (COX-2) induced by disulfide HMGB1. Natural and synthetic SA derivatives with greater potency for inhibition of HMGB1 were identified, providing proof-of-concept that new molecules with high efficacy against sterile inflammation are attainable. An HMGB1 protein mutated in one of the SA-binding sites identified by NMR chemical shift perturbation studies retained chemoattractant activity, but lost binding of and inhibition by SA and its derivatives, thereby firmly establishing that SA binding to HMGB1 directly suppresses its proinflammatory activities. Identification of HMGB1 as a pharmacological target of SA/aspirin provides new insights into the mechanisms of action of one of the world’s longest and most used natural and synthetic drugs. It may also provide an explanation for the protective effects of low-dose aspirin usage. PMID:26101955

  11. The effect of functional groups on the SO2 adsorption on carbon surface I: A new insight into noncovalent interaction between SO2 molecule and acidic oxygen-containing groups

    NASA Astrophysics Data System (ADS)

    Liu, Xin; Sun, Fei; Qu, Zhibin; Gao, Jihui; Wu, Shaohua

    2016-04-01

    For the aim to give a new insight into the interactions between SO2 molecule and carbon surface and the effect of acidic oxygen-containing groups, density functional theory and noncovalent interaction analysis in terms of reduced density gradient were employed to investigate both the intensity and type of the interactions. The results indicate that the physisorption of SO2 molecule mainly occurs on the basal plane of pure carbon surface due to van der Waals interactions, however, when acidic oxygen-containing groups were decorated on the carbon surface, they would facilitate SO2 adsorption as a result of hydrogen bonding and dipole-dipole interactions. What's more, these groups could not affect the chemisorption of SO2 remarkably, no matter they are near the adsorption sites or not. In addition, calculation results show that the interactions between SO2 and acidic oxygen-containing groups are in physisorption nature, which challenges a long-held the viewpoint of irreversible chemisorption. Acidic oxygen-containing groups could boost the effective surface area of carbon by enhancing the physisorption on edge positions.

  12. Stabilization of labile organic C along a chronosequence of soil development: mineralogical vs. biological controls

    NASA Astrophysics Data System (ADS)

    McFarland, J. W.; Waldrop, M. P.; Strawn, D.; Harden, J. W.

    2010-12-01

    Soil organic matter (SOM) represents an important reservoir for carbon (C), nitrogen (N), and other essential nutrients. Consequently, variation in SOM turnover rates regulates resource availability for soil microbial activity and plant growth. Long-term SOM stabilization generally involves restricted microbial access to SOM through a variety of processes including complexation with soil minerals. These organo-mineral interactions are influenced by mineral composition and texture, often related to soil age. Soil microorganisms also influence the stabilization of C inputs to the pedosphere through the production of refractory residues controlled in part by C allocation patterns during metabolism. In this study we examined, simultaneously, the contribution of these two C stabilizing mechanisms by ‘tracing’ the fate of two 13C-labeled substrates (glucose and p-hydroxybenzoic acid) along a 1600Kya chronosequence of soil development along the Cowlitz River in southwest Washington. Our objective was to evaluate the relationship between mineralogical and biological controls over C sequestration in soils. Mineralogical analyses were done using the selective dissolutions ammonium oxalate (AOD), and dithionite-citrate extraction (CBD). In this cool, humid environment, intermediate aged soils derived from the late Wisconsin Evans Creek drift (24ka) had the highest AOD extractable Al, Fe, and Si, indicating a higher concentration of poorly crystalline minerals relative to other terraces. Correspondingly, CBD extractable Fe increases with soil age, further supporting the idea that crystalline iron oxides are also more prevalent with weathering. Turnover of both 13C-labeled substrates was rapid (< 12.5 hrs) However, the proportion of substrate mineralized to CO2 varied among terraces. Mineralization to CO2 was significantly lower at 24ka than that for the other three age classes (0.25k, 220k, and 1,600k years bp), corresponding to higher recovery of 13C in bulk soil for this

  13. Teichuronic acid reducing terminal N-acetylglucosamine residue linked by phosphodiester to peptidoglycan of Micrococcus luteus

    SciTech Connect

    Gassner, G.T.; Dickie, J.P.; Hamerski, D.A.; Magnuson, J.K.; Anderson, J.S. )

    1990-05-01

    Teichuronic acid-peptidoglycan complex isolated from Micrococcus luteus cells by lysozyme digestion in osmotically stabilized medium was treated with mild acid to cleave the linkage joining teichuronic acid to peptidoglycan. This labile linkage was shown to be the phosphodiester which joins N-acetylglucosamine, the residue located at the reducing end of the teichuronic acid, through its anomeric hydroxyl group to a 6-phosphomuramic acid, a residue of the glycan strand of peptidoglycan. {sup 31}P nuclear magnetic resonance spectroscopy of the lysozyme digest of cell walls demonstrated the presence of a phosphodiester which was converted to a phosphomonoester by the conditions which released teichuronic acid from cell walls. Reduction of acid-liberated reducing end groups by NaB{sup 3}H{sub 4} followed by complete acid hydrolysis yielded ({sup 3}H) glucosaminitol from the true reducing end residue of teichuronic acid and ({sup 3}H)glucitol from the sites of fragmentation of teichuronic acid. The amount of N-acetylglucosamine detected was approximately stoichiometric with the amount of phosphate in the complex. Partial fragmentation of teichuronic acid provides an explanation of the previous erroneous identification of the reducing end residue.

  14. The contents of labile sulfides in the bottom sediments of the central part of the Sea of Azov: Impact on benthic communities

    NASA Astrophysics Data System (ADS)

    Sorokin, Yu. I.; Burkatskii, O. N.

    2007-10-01

    At 17 stations in the central part of the Sea of Azov, the contents of labile (acid-soluble) sulfides were determined in the upper layer (0-3 cm) of the bottom sediments. At 14 of these stations, the contents of sulfides in the oozy silts were over 300 mg S/dm3 of wet sediment; at seven of the stations, the contents of sulfide were as high as 420-720 mg S/dm3 of wet ooze, or 0.1-0.2% of dry weight. At the other three stations, where neutral matter such as shells and sand prevailed in the samples, the contents of sulfides varied from 80 to 110 mg S/dm3. At these stations, a high density and species diversity of the benthic fauna was retained. At other stations with labile sulfide contents over 200-300 mg S/dm3, the benthos biomass decreased by one or two orders of magnitude. At most of them, it was below 3 g/m2 and the small gastropod Hydrobia tolerant to sulfides dominated. The data obtained show that, in the central part of the Sea of Azov, reduced sediments with high contents of labile sulfides migrate towards the bottom surface, which conforms to the high intensity of the hydrogen sulfide formation process caused by the bacterial sulfate reduction. The study considers the environmental effects of the sulfide contamination of the upper layer of the bottom sediments in the Sea of Azov as a key factor causing the recurrent hypoxy in the near-bottom layers of the water, the suffocation occurrence, and the progressive depletion of the benthic and pelagic fauna.

  15. Allele variants of enterotoxigenic Escherichia coli heat-labile toxin are globally transmitted and associated with colonization factors.

    PubMed

    Joffré, Enrique; von Mentzer, Astrid; Abd El Ghany, Moataz; Oezguen, Numan; Savidge, Tor; Dougan, Gordon; Svennerholm, Ann-Mari; Sjöling, Åsa

    2015-01-01

    Enterotoxigenic Escherichia coli (ETEC) is a significant cause of morbidity and mortality in the developing world. ETEC-mediated diarrhea is orchestrated by heat-labile toxin (LT) and heat-stable toxins (STp and STh), acting in concert with a repertoire of more than 25 colonization factors (CFs). LT, the major virulence factor, induces fluid secretion after delivery of a monomeric ADP-ribosylase (LTA) and its pentameric carrier B subunit (LTB). A study of ETEC isolates from humans in Brazil reported the existence of natural LT variants. In the present study, analysis of predicted amino acid sequences showed that the LT amino acid polymorphisms are associated with a geographically and temporally diverse set of 192 clinical ETEC strains and identified 12 novel LT variants. Twenty distinct LT amino acid variants were observed in the globally distributed strains, and phylogenetic analysis showed these to be associated with different CF profiles. Notably, the most prevalent LT1 allele variants were correlated with major ETEC lineages expressing CS1 + CS3 or CS2 + CS3, and the most prevalent LT2 allele variants were correlated with major ETEC lineages expressing CS5 + CS6 or CFA/I. LTB allele variants generally exhibited more-stringent amino acid sequence conservation (2 substitutions identified) than LTA allele variants (22 substitutions identified). The functional impact of LT1 and LT2 polymorphisms on virulence was investigated by measuring total-toxin production, secretion, and stability using GM1-enzyme-linked immunosorbent assays (GM1-ELISA) and in silico protein modeling. Our data show that LT2 strains produce 5-fold more toxin than LT1 strains (P < 0.001), which may suggest greater virulence potential for this genetic variant. Our data suggest that functionally distinct LT-CF variants with increased fitness have persisted during the evolution of ETEC and have spread globally. PMID:25404692

  16. Comparative Analysis of the Cytotoxic Effects of Okadaic Acid-Group Toxins on Human Intestinal Cell Lines

    PubMed Central

    Ferron, Pierre-Jean; Hogeveen, Kevin; Fessard, Valérie; Le Hégarat, Ludovic

    2014-01-01

    The phycotoxin, okadaic acid (OA) and dinophysistoxin 1 and 2 (DTX-1 and -2) are protein phosphatase PP2A and PP1 inhibitors involved in diarrhetic shellfish poisoning (DSP). Data on the toxicity of the OA-group toxins show some differences with respect to the in vivo acute toxicity between the toxin members. In order to investigate whether OA and congeners DTX-1 and -2 may induce different mechanisms of action during acute toxicity on the human intestine, we compared their toxicological effects in two in vitro intestinal cell models: the colorectal adenocarcinoma cell line, Caco-2, and the intestinal muco-secreting cell line, HT29-MTX. Using a high content analysis approach, we evaluated various cytotoxicity parameters, including apoptosis (caspase-3 activation), DNA damage (phosphorylation of histone H2AX), inflammation (translocation of NF-κB) and cell proliferation (Ki-67 production). Investigation of the kinetics of the cellular responses demonstrated that the three toxins induced a pro-inflammatory response followed by cell cycle disruption in both cell lines, leading to apoptosis. Our results demonstrate that the three toxins induce similar effects, as no major differences in the cytotoxic responses could be detected. However DTX-1 induced cytotoxic effects at five-fold lower concentrations than for OA and DTX-2. PMID:25196936

  17. Activation of Plant Innate Immunity by Extracellular High Mobility Group Box 3 and Its Inhibition by Salicylic Acid

    PubMed Central

    Choi, Hyong Woo; Manohar, Murli; Manosalva, Patricia; Tian, Miaoying; Moreau, Magali; Klessig, Daniel F.

    2016-01-01

    Damage-associated molecular pattern molecules (DAMPs) signal the presence of tissue damage to induce immune responses in plants and animals. Here, we report that High Mobility Group Box 3 (HMGB3) is a novel plant DAMP. Extracellular HMGB3, through receptor-like kinases BAK1 and BKK1, induced hallmark innate immune responses, including i) MAPK activation, ii) defense-related gene expression, iii) callose deposition, and iv) enhanced resistance to Botrytis cinerea. Infection by necrotrophic B. cinerea released HMGB3 into the extracellular space (apoplast). Silencing HMGBs enhanced susceptibility to B. cinerea, while HMGB3 injection into apoplast restored resistance. Like its human counterpart, HMGB3 binds salicylic acid (SA), which results in inhibition of its DAMP activity. An SA-binding site mutant of HMGB3 retained its DAMP activity, which was no longer inhibited by SA, consistent with its reduced SA-binding activity. These results provide cross-kingdom evidence that HMGB proteins function as DAMPs and that SA is their conserved inhibitor. PMID:27007252

  18. Group B Streptococcus Engages an Inhibitory Siglec through Sialic Acid Mimicry to Blunt Innate Immune and Inflammatory Responses In Vivo

    PubMed Central

    Chang, Yung-Chi; Olson, Joshua; Beasley, Federico C.; Tung, Christine; Zhang, Jiquan; Crocker, Paul R.; Varki, Ajit; Nizet, Victor

    2014-01-01

    Group B Streptococcus (GBS) is a common agent of bacterial sepsis and meningitis in newborns. The GBS surface capsule contains sialic acids (Sia) that engage Sia-binding immunoglobulin-like lectins (Siglecs) on leukocytes. Here we use mice lacking Siglec-E, an inhibitory Siglec of myelomonocytic cells, to study the significance of GBS Siglec engagement during in vivo infection. We found GBS bound to Siglec-E in a Sia-specific fashion to blunt NF-κB and MAPK activation. As a consequence, Siglec-E-deficient macrophages had enhanced pro-inflammatory cytokine secretion, phagocytosis and bactericidal activity against the pathogen. Following pulmonary or low-dose intravenous GBS challenge, Siglec-E KO mice produced more pro-inflammatory cytokines and exhibited reduced GBS invasion of the central nervous system. In contrast, upon high dose lethal challenges, cytokine storm in Siglec-E KO mice was associated with accelerated mortality. We conclude that GBS Sia mimicry influences host innate immune and inflammatory responses in vivo through engagement of an inhibitory Siglec, with the ultimate outcome of the host response varying depending upon the site, stage and magnitude of infection. PMID:24391502

  19. Specific excitonic interactions in the aggregates of hyaluronic acid and cyanine dyes with different lengths of methine group.

    PubMed

    Tobata, H; Sagawa, T

    2016-03-01

    The absorption and circular dichroism (CD) spectra of three types of cyanine dyes with different lengths of methine group (3,3'-diethylthiadicarbocyanine iodide, DTDC; 3,3'-diethylthiacarbocyanine iodide, DTC; and 3,3'-diethylthiacyanine iodide, DTTHC) in an aqueous solution were compared with and without hyaluronic acid (HA), which has a helical structure. DTDC forms chiral H- and J-aggregates, whereas DTC and DTTHC are unable to form any aggregates. DTDC also forms H- and J-aggregates in the presence of sodium polyacrylate (PA) with a random-coil structure; however, the PA-DTDC aggregates exhibit no chirality. These results suggest that the chirality of HA-DTDC aggregates is induced by the helical structure of HA. In 2.4 vol% and 10 vol% methanol, HA-DTDC aggregates displayed different patterns of temperature dependence, whereas no aggregation was observed in 30 vol% methanol. The solubility of DTDC in a mixed solvent of water and methanol is generally improved by the addition of methanol, which prevents the aggregation of DTDC. PMID:26815728

  20. Preparation of water-soluble hyperbranched polyester nanoparticles with sulfonic acid functional groups and their micelles behavior, anticoagulant effect and cytotoxicity.

    PubMed

    Han, Qiaorong; Chen, Xiaohan; Niu, Yanlian; Zhao, Bo; Wang, Bingxiang; Mao, Chun; Chen, Libin; Shen, Jian

    2013-07-01

    Biocompatibility of nanoparticles has been attracting great interest in the development of nanoscience and nanotechnology. Herein, the aliphatic water-soluble hyperbranched polyester nanoparticles with sulfonic acid functional groups (HBPE-SO3 NPs) were synthesized and characterized. They are amphiphilic polymeric nanoparticles with hydrophobic hyperbranched polyester (HBPE) core and hydrophilic sulfonic acid terminal groups. Based on our observations, we believe there are two forms of HBPE-SO3 NPs in water under different conditions: unimolecular micelles and large multimolecular micelles. The biocompatibility and anticoagulant effect of the HBPE-SO3 NPs were investigated using coagulation tests, hemolysis assay, morphological changes of red blood cells (RBCs), complement and platelet activation detection, and cytotoxicity (MTT). The results confirmed that the sulfonic acid terminal groups can substantially enhance the anticoagulant property of HBPE, and the HBPE-SO3 NPs have the potential to be used in nanomedicine due to their good bioproperties. PMID:23718279

  1. Dicarboxylic acid anhydride condensation with compounds containing active methylene groups. 4: Some 4-nitrophthalic anhydride condensation reactions

    NASA Technical Reports Server (NTRS)

    Oskaja, V.; Rotberg, J.

    1985-01-01

    By 4-nitrophthalic anhydride condensation with acetoacetate in acetic anhydride and triethylamine solution with subsequent breakdown of the intermediate condensation product, 5-nitroindanedione-1,3 was obtained. A 4-nitrophthalic anhydride with acetic anhydride, according to reaction conditions, may yield two products: in the presence of potassium acetate and at high temperatures 4-(or 5-)-nitro-2-acetylbenzoic acid is formed: in the presence of triethylamine and at room temperature 5-( or 6-)-nitrophthalic acetic acid is isolated. A 4-nitrophthalic anhydride and malonic acid in pyridine solution according to temperature yield either 5-( or 6-)-nitrophthalic acetic acid or 4-(or 5-)-nitro-2-acetylbenzoic acid.

  2. Comparative Study on Single-Molecule Junctions of Alkane- and Benzene-Based Molecules with Carboxylic Acid/Aldehyde as the Anchoring Groups.

    PubMed

    Chen, Fang; Peng, Lin-Lu; Hong, Ze-Wen; Mao, Jin-Chuan; Zheng, Ju-Fang; Shao, Yong; Niu, Zhen-Jiang; Zhou, Xiao-Shun

    2016-12-01

    We have measured the alkane and benzene-based molecules with aldehyde and carboxylic acid as anchoring groups by using the electrochemical jump-to-contact scanning tunneling microscopy break junction (ECSTM-BJ) approach. The results show that molecule with benzene backbone has better peak shape and intensity than those with alkane backbone. Typically, high junction formation probability for same anchoring group (aldehyde and carboxylic acid) with benzene backbone is found, which contributes to the stronger attractive interaction between Cu and molecules with benzene backbone. The present work shows the import role of backbone in junction, which can guide the design molecule to form effective junction for studying molecular electronics. PMID:27566686

  3. Flocculated meltwater particles control Arctic land-sea fluxes of labile iron

    NASA Astrophysics Data System (ADS)

    Markussen, Thor Nygaard; Elberling, Bo; Winter, Christian; Andersen, Thorbjørn Joest

    2016-04-01

    Glacial meltwater systems supply the Arctic coastal ocean with large volumes of sediment and potentially bioavailable forms of iron, nitrogen and carbon. The particulate fraction of this supply is significant but estuarine losses have been thought to limit the iron supply from land. Here, our results reveal how flocculation (particle aggregation) involving labile iron may increase horizontal transport rather than enhance deposition close to the source. This is shown by combining field observations in Disko Fjord, West Greenland, and laboratory experiments. Our data show how labile iron affects floc sizes, shapes and densities and consequently yields low settling velocities and extended sediment plumes. We highlight the importance of understanding the flocculation mechanisms when examining fluxes of meltwater transported iron in polar regions today and in the future, and we underline the influence of terrestrial hotspots on the nutrient and solute cycles in Arctic coastal waters.

  4. The Effect of Multiple Parallel Bonds on the Self-healing of Labile Crosslinked Nanogel Networks

    NASA Astrophysics Data System (ADS)

    Salib, Isaac G.; Kolmakov, German V.; Gnegy, Chet N.; Matyjaszewski, Krzysztof; Balazs, Anna C.

    2011-03-01

    We develop a hybrid computational approach to examine the mechanical properties and self-healing behavior of nanogel particles that are crosslinked primarily by highly reactive bonds that can break and readily remake (labile bonds). The individual nanogels are modeled via the lattice spring model (LSM). The crosslinks between the nanogels are simulated via a modified Hierarchical Bell Model (HBM), which allows us to capture both the rupturing and reforming of multiple, parallel bonds due to an applied force. Using our hybrid HBM/LSM, we simulate the behavior of the crosslinked nanogels under a tensile deformation. In these simulations, each labile linkage between the nanogels contains at most N parallel bonds. We reveal that while numerous parallel bonds within a linkage enhance the strength of the material, these bonds diminish the ductility and the ability of the material to undergo the structural rearrangements that are necessary for self-repair.

  5. Flocculated meltwater particles control Arctic land-sea fluxes of labile iron.

    PubMed

    Markussen, Thor Nygaard; Elberling, Bo; Winter, Christian; Andersen, Thorbjørn Joest

    2016-01-01

    Glacial meltwater systems supply the Arctic coastal ocean with large volumes of sediment and potentially bioavailable forms of iron, nitrogen and carbon. The particulate fraction of this supply is significant but estuarine losses have been thought to limit the iron supply from land. Here, our results reveal how flocculation (particle aggregation) involving labile iron may increase horizontal transport rather than enhance deposition close to the source. This is shown by combining field observations in Disko Fjord, West Greenland, and laboratory experiments. Our data show how labile iron affects floc sizes, shapes and densities and consequently yields low settling velocities and extended sediment plumes. We highlight the importance of understanding the flocculation mechanisms when examining fluxes of meltwater transported iron in polar regions today and in the future, and we underline the influence of terrestrial hotspots on the nutrient and solute cycles in Arctic coastal waters. PMID:27050673

  6. Flocculated meltwater particles control Arctic land-sea fluxes of labile iron

    PubMed Central

    Markussen, Thor Nygaard; Elberling, Bo; Winter, Christian; Andersen, Thorbjørn Joest

    2016-01-01

    Glacial meltwater systems supply the Arctic coastal ocean with large volumes of sediment and potentially bioavailable forms of iron, nitrogen and carbon. The particulate fraction of this supply is significant but estuarine losses have been thought to limit the iron supply from land. Here, our results reveal how flocculation (particle aggregation) involving labile iron may increase horizontal transport rather than enhance deposition close to the source. This is shown by combining field observations in Disko Fjord, West Greenland, and laboratory experiments. Our data show how labile iron affects floc sizes, shapes and densities and consequently yields low settling velocities and extended sediment plumes. We highlight the importance of understanding the flocculation mechanisms when examining fluxes of meltwater transported iron in polar regions today and in the future, and we underline the influence of terrestrial hotspots on the nutrient and solute cycles in Arctic coastal waters. PMID:27050673

  7. Adhesin degradation accelerates delivery of heat-labile toxin by enterotoxigenic Escherichia coli.

    PubMed

    Roy, Koushik; Kansal, Rita; Bartels, Scott R; Hamilton, David J; Shaaban, Salwa; Fleckenstein, James M

    2011-08-26

    Many enteric pathogens, including enterotoxigenic Escherichia coli (ETEC), produce one or more serine proteases that are secreted via the autotransporter (or type V) bacterial secretion pathway. These molecules have collectively been referred to as SPATE proteins (serine protease autotransporter of the Enterobacteriaceae). EatA, an autotransporter previously identified in ETEC, possesses a functional serine protease motif within its secreted amino-terminal passenger domain. Although this protein is expressed by many ETEC strains and is highly immunogenic, its precise function is unknown. Here, we demonstrate that EatA degrades a recently characterized adhesin, EtpA, resulting in modulation of bacterial adhesion and accelerated delivery of the heat-labile toxin, a principal ETEC virulence determinant. Antibodies raised against the passenger domain of EatA impair ETEC delivery of labile toxin to epithelial cells suggesting that EatA may be an effective target for vaccine development. PMID:21757737

  8. Clinical Usefulness of Oral Supplementation with Alpha-Lipoic Acid, Curcumin Phytosome, and B-Group Vitamins in Patients with Carpal Tunnel Syndrome Undergoing Surgical Treatment

    PubMed Central

    Pajardi, Giorgio; Bortot, Paola; Ponti, Veronica; Novelli, Chiara

    2014-01-01

    We investigated the clinical usefulness of oral supplementation with a combination product containing alpha-lipoic acid, curcumin phytosome, and B-group vitamins in 180 patients with carpal tunnel syndrome (CTS), scheduled to undergo surgical decompression of the median nerve. Patients in Group A (n = 60) served as controls and did not receive any treatment either before or after surgery. Patients in Group B (n = 60) received oral supplementation twice a day for 3 months both before and after surgery (totaling 6 months of supplementation). Patients in Group C (n = 60) received oral supplementation twice a day for 3 months before surgery only. Patients in Group B showed significantly lower nocturnal symptoms scores compared with Group A subjects at both 40 days and 3 months after surgery (both P values <0.05). Moreover, patients in Group B had a significantly lower number of positive Phalen's tests at 3 months compared with the other study groups (P < 0.05). We conclude that oral supplementation with alpha-lipoic acid, curcumin phytosome, and B-group vitamins twice a day both before and after surgery is safe and effective in CTS patients scheduled to undergo surgical decompression of the median nerve. PMID:24563654

  9. Clinical usefulness of oral supplementation with alpha-lipoic Acid, curcumin phytosome, and B-group vitamins in patients with carpal tunnel syndrome undergoing surgical treatment.

    PubMed

    Pajardi, Giorgio; Bortot, Paola; Ponti, Veronica; Novelli, Chiara

    2014-01-01

    We investigated the clinical usefulness of oral supplementation with a combination product containing alpha-lipoic acid, curcumin phytosome, and B-group vitamins in 180 patients with carpal tunnel syndrome (CTS), scheduled to undergo surgical decompression of the median nerve. Patients in Group A (n = 60) served as controls and did not receive any treatment either before or after surgery. Patients in Group B (n = 60) received oral supplementation twice a day for 3 months both before and after surgery (totaling 6 months of supplementation). Patients in Group C (n = 60) received oral supplementation twice a day for 3 months before surgery only. Patients in Group B showed significantly lower nocturnal symptoms scores compared with Group A subjects at both 40 days and 3 months after surgery (both P values <0.05). Moreover, patients in Group B had a significantly lower number of positive Phalen's tests at 3 months compared with the other study groups (P < 0.05). We conclude that oral supplementation with alpha-lipoic acid, curcumin phytosome, and B-group vitamins twice a day both before and after surgery is safe and effective in CTS patients scheduled to undergo surgical decompression of the median nerve. PMID:24563654

  10. A Solvent-Free Thermosponge Nanoparticle Platform for Efficient Delivery of Labile Proteins

    PubMed Central

    2015-01-01

    Protein therapeutics have gained attention recently for treatment of a myriad of human diseases due to their high potency and unique mechanisms of action. We present the development of a novel polymeric thermosponge nanoparticle for efficient delivery of labile proteins using a solvent-free polymer thermo-expansion mechanism with clinical potential, capable of effectively delivering a range of therapeutic proteins in a sustained manner with no loss of bioactivity, with improved biological half-lives and efficacy in vivo. PMID:25333768

  11. Protein degradation by ubiquitin–proteasome system in formation and labilization of contextual conditioning memory

    PubMed Central

    Sol Fustiñana, María; de la Fuente, Verónica; Federman, Noel; Freudenthal, Ramiro

    2014-01-01

    The ubiquitin–proteasome system (UPS) of protein degradation has been evaluated in different forms of neural plasticity and memory. The role of UPS in such processes is controversial. Several results support the idea that the activation of this system in memory consolidation is necessary to overcome negative constrains for plasticity. In this case, the inhibition of the UPS during consolidation impairs memory. Similar results were reported for memory reconsolidation. However, in other cases, the inhibition of UPS had no effect on memory consolidation and reconsolidation but impedes the amnesic action of protein synthesis inhibition after retrieval. The last finding suggests a specific action of the UPS inhibitor on memory labilization. However, another interpretation is possible in terms of the synthesis/degradation balance of positive and negative elements in neural plasticity, as was found in the case of long-term potentiation. To evaluate these alternative interpretations, other reconsolidation-interfering drugs than translation inhibitors should be tested. Here we analyzed initially the UPS inhibitor effect in contextual conditioning in crabs. We found that UPS inhibition during consolidation impaired long-term memory. In contrast, UPS inhibition did not affect memory reconsolidation after contextual retrieval but, in fact, impeded memory labilization, blocking the action of drugs that does not affect directly the protein synthesis. To extend these finding to vertebrates, we performed similar experiments in contextual fear memory in mice. We found that the UPS inhibitor in hippocampus affected memory consolidation and blocked memory labilization after retrieval. These findings exclude alternative interpretations to the requirement of UPS in memory labilization and give evidence of this mechanism in both vertebrates and invertebrates. PMID:25135196

  12. Protein degradation by ubiquitin-proteasome system in formation and labilization of contextual conditioning memory.

    PubMed

    Sol Fustiñana, María; de la Fuente, Verónica; Federman, Noel; Freudenthal, Ramiro; Romano, Arturo

    2014-09-01

    The ubiquitin-proteasome system (UPS) of protein degradation has been evaluated in different forms of neural plasticity and memory. The role of UPS in such processes is controversial. Several results support the idea that the activation of this system in memory consolidation is necessary to overcome negative constrains for plasticity. In this case, the inhibition of the UPS during consolidation impairs memory. Similar results were reported for memory reconsolidation. However, in other cases, the inhibition of UPS had no effect on memory consolidation and reconsolidation but impedes the amnesic action of protein synthesis inhibition after retrieval. The last finding suggests a specific action of the UPS inhibitor on memory labilization. However, another interpretation is possible in terms of the synthesis/degradation balance of positive and negative elements in neural plasticity, as was found in the case of long-term potentiation. To evaluate these alternative interpretations, other reconsolidation-interfering drugs than translation inhibitors should be tested. Here we analyzed initially the UPS inhibitor effect in contextual conditioning in crabs. We found that UPS inhibition during consolidation impaired long-term memory. In contrast, UPS inhibition did not affect memory reconsolidation after contextual retrieval but, in fact, impeded memory labilization, blocking the action of drugs that does not affect directly the protein synthesis. To extend these finding to vertebrates, we performed similar experiments in contextual fear memory in mice. We found that the UPS inhibitor in hippocampus affected memory consolidation and blocked memory labilization after retrieval. These findings exclude alternative interpretations to the requirement of UPS in memory labilization and give evidence of this mechanism in both vertebrates and invertebrates. PMID:25135196

  13. Labile and stabilised fractions of soil organic carbon in some intensively cultivated alluvial soils.

    PubMed

    Verma, B C; Datta, S P; Rattan, R K; Singh, A K

    2013-11-01

    The present investigation was undertaken in view of the limited information on the relative proportion of labile and stabilized fractions of soil organic carbon (SOC) in intensively cultivated lands, particularly under tropics. The specific objectives were i) to study the comparative recovery of SOC by different methods of labile carbon estimation under intensively cultivated lands and ii) to evaluate the impact of agricultural practices on carbon management index. For this purpose, in all, 105 surface soil samples were collected from intensively cultivated tube well and sewage irrigated agricultural lands. These samples were analysed for total as well as labile pools of SOC. Results indicated that Walkley and Black, KMnO4-oxidizable and microbial biomass carbon constituted the total SOC to the extent of 10.2 to 47.4, 1.66 to 23.2 and 0.30 to 5.49%, respectively with the corresponding mean values of 26.2, 9.16 and 2.15%. Lability of SOC was considerably higher in sewage irrigated soils than tube well irrigated soils under intensive cropping. Under soybean-wheat, the higher values of carbon management index (CMI) (279 and 286) were associated with the treatments where entire amount of nitrogen was supplied through FYM. Similar results were obtained under rice-wheat, whereas in case of maize-wheat the highest value of CMI was recorded under treatment receiving NPK through chemical fertilizer along with green manure. There was also a significant improvement in CMI under integrated (chemical fertilizer + organics) and chemical fertilizer-treated plots. The values of CMI ranged from 220 to 272 under cultivated lands receiving irrigation through sewage and industrial effluents. PMID:24555339

  14. Calcium oscillations and T-wave lability precede ventricular arrhythmias in acquired long QT type 2

    PubMed Central

    Němec, Jan; Kim, Jong J.; Gabris, Beth; Salama, Guy

    2010-01-01

    Background Alternans of intracellular Ca2+ (Cai) underlies T-wave alternans, a predictor of cardiac arrhythmias. A related phenomenon, T-Wave Lability (TWL), precedes Torsade de Pointes (TdP) in patients and animal models with impaired repolarization. However, the role of Cai in TWL remains unexplored. Methods Action potentials (APs) and Cai transients, (CaTs) were mapped optically from paced Langendorff female rabbit hearts (n=8) at 1.2s cycle length, after AV node ablation. Hearts were perfused with normal Tyrode's solution then with dofetilide (0.5 μM) and reduced [K+] (2 mM) and [Mg2+] (0.5 mM) to elicit long QT type 2 (LQT2). Lability of EKG, voltage and Cai signals were evaluated during regular paced rhythm, before and after dofetilide perfusion. Results In LQT2, lability of Cai, voltage and EKG signals increased during paced rhythm, before the appearance of early afterdepolarizations (EADs). LQT2 resulted in AP prolongation and multiple (1-3) additional Cai upstrokes, while APs remained monophasic. When EADs appeared, Cai rose before voltage upstrokes at the origins of propagating EADs. Interventions (i.e. ryanodine and thapsigargin, n=3 or low [Ca]o and nifedipine, n=4) that suppressed Cai oscillations also abolished EADs. Conclusions In LQT2, Cai oscillations (CaiO) precede EADs by minutes, indicating that they result from spontaneous sarcoplasmic reticulum Ca2+ release rather than spontaneous ICaL reactivation. CaiO likely produce oscillations of Na/Ca exchange current, INCX. Depolarizing INCX during the AP plateau contributes to the generation of EADs by re-activating Ca2+-channels that have recovered from inactivation. TWL reflects CaTs and APs lability that occur before EADs and TdP. PMID:20599524

  15. Bacillithiol is a major buffer of the labile zinc pool in Bacillus subtilis

    PubMed Central

    Ma, Zhen; Chandrangsu, Pete; Helmann, Tyler C.; Romsang, Adisak; Gaballa, Ahmed; Helmann, John D.

    2014-01-01

    Intracellular zinc levels are tightly regulated since zinc is an essential cofactor for numerous enzymes, yet can be toxic when present in excess. The majority of intracellular zinc is tightly associated with proteins and is incorporated during synthesis from a poorly defined pool of kinetically labile zinc. In Bacillus subtilis, this labile pool is sensed by equilibration with the metalloregulator Zur, as an indication of zinc sufficiency, and by CzrA, as an indication of zinc excess. Here, we demonstrate that the low molecular weight thiol bacillithiol (BSH) serves as a major buffer of the labile zinc pool. Upon shift to conditions of zinc excess, cells transiently accumulate zinc in a low molecular weight pool, and this accumulation is largely dependent on BSH. Cells lacking BSH are more sensitive to zinc stress, and they induce zinc efflux at lower external zinc concentrations. Thiol reactive agents such as diamide and cadmium induce zinc efflux by interfering with the Zn-buffering function of BSH. Our data provide new insights into intracellular zinc buffering and may have broad relevance given the presence of BSH in pathogens and the proposed role of zinc sequestration in innate immunity. PMID:25213752

  16. Comparison of metal lability in air-dried and fresh dewatered drinking water treatment residuals.

    PubMed

    Wang, Changhui; Pei, Yuansheng; Zhao, Yaqian

    2015-01-01

    In this work, the labilities of Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sr, V and Zn in air-dried (for 60 days) and fresh dewatered WTRs were compared using the Toxicity Characteristic Leaching Procedure (TCLP), fractionation, in vitro digestion and a plant enrichment test. The results showed that the air-dried and fresh dewatered WTRs had different properties, e.g., organic matter composition and available nutrients. The air-dried and fresh dewatered WTRs were non-haf zardous according to the TCLP assessment method used in the United States; however, the metals in the two types of WTRs had different lability. Compared with the metals in the fresh dewatered WTRs, those in the air-dried WTRs tended to be in more stable fractions and also exhibited lower bioaccessibility and bioavailability. Therefore, air-drying can decrease the metal lability and thereby reduce the potential metal pollution risk of WTRs. PMID:25560259

  17. Substrate lability and plant activity controls greenhouse gas release from Neotropical peatland

    NASA Astrophysics Data System (ADS)

    Sjogersten, Sofie; Hoyos, Jorge; Lomax, Barry; Turner, Ben; Wright, Emma

    2014-05-01

    Almost one third of global CO2 emissions resulting from land use change and substantial CH4 emissions originate from tropical peatlands. However, our understanding of the controls of CO2 and CH4 release from tropical peatlands are limited. The aim of this study was to investigate the role of peat lability and the activity of the vegetation on gas release using a combination of field and laboratory experiments. We demonstrated that peat lability constrained CH4 production to the surface peat under anaerobic conditions. The presence of plants shifted the C balance from a C source to a C sink with respect to CO2 while the activity of the root system strongly influenced CH4 emissions through its impact on soil O2 inputs. Both field and laboratory data suggest a coupling between the photosynthetic activity of the vegetation and the release of both CO2 and CH4 following the circadian rhythm of the dominant plant functional types. Forest clearance for agriculture resulted in elevated CH4 release, which we attribute in part to the cessation of root O2 inputs to the peat. We conclude that high emissions of CO2 and CH4 from forested tropical peatlands are likely driven by labile C inputs from the vegetation but that root O2 release may limit CH4 emissions.

  18. Evolution of phenotypic plasticity and environmental tolerance of a labile quantitative character in a fluctuating environment.

    PubMed

    Lande, R

    2014-05-01

    Quantitative genetic models of evolution of phenotypic plasticity are used to derive environmental tolerance curves for a population in a changing environment, providing a theoretical foundation for integrating physiological and community ecology with evolutionary genetics of plasticity and norms of reaction. Plasticity is modelled for a labile quantitative character undergoing continuous reversible development and selection in a fluctuating environment. If there is no cost of plasticity, a labile character evolves expected plasticity equalling the slope of the optimal phenotype as a function of the environment. This contrasts with previous theory for plasticity influenced by the environment at a critical stage of early development determining a constant adult phenotype on which selection acts, for which the expected plasticity is reduced by the environmental predictability over the discrete time lag between development and selection. With a cost of plasticity in a labile character, the expected plasticity depends on the cost and on the environmental variance and predictability averaged over the continuous developmental time lag. Environmental tolerance curves derived from this model confirm traditional assumptions in physiological ecology and provide new insights. Tolerance curve width increases with larger environmental variance, but can only evolve within a limited range. The strength of the trade-off between tolerance curve height and width depends on the cost of plasticity. Asymmetric tolerance curves caused by male sterility at high temperature are illustrated. A simple condition is given for a large transient increase in plasticity and tolerance curve width following a sudden change in average environment. PMID:24724972

  19. Labile synthetic cadmium complexes are not bioavailable to Pseudokirchneriella subcapitata in resin buffered solutions.

    PubMed

    Verheyen, L; Merckx, R; Smolders, E

    2012-11-15

    The Free Ion Activity Model (FIAM) predicts that cadmium (Cd) uptake by organisms is identical for solutions with the same free Cd(2+) concentration and inorganic composition. Clear exceptions to the FIAM have been shown for Cd uptake by plant roots, periphyton and human cells where labile Cd complexes increase bioavailability and which has been attributed to their role in enhancing Cd diffusion towards the uptake cells. Here, we assessed the role of labile Cd complexes on Cd uptake by algae, for which diffusion limitations should be less pronounced due to their smaller size. Long-term (3 days) Cd uptake by the green algae Pseudokirchneriella subcapitata was measured in resin buffered solutions with or without synthetic ligands and at three Cd(2+) ion activities (pCd 8.2-5.7). The free Cd(2+) activity was maintained during the test using a metal-selective resin located in the algal bottles. Total dissolved Cd increased up to 35-fold by adding the synthetic ligands at constant Cd(2+) activity. In contrast, Cd uptake by algae increased maximally 2.8 fold with increasing concentration of the synthetic ligands and the availability of the complexes were maximally 5.2% relative to Cd(2+) for NTA and CDTA complexes. It is concluded that labile Cd complexes do not greatly enhance Cd bioavailability to the unicellular algae and calculations suggest that Cd transport from solution to these small cells is not rate limiting. PMID:22903064

  20. Are more diverse parts of the mammalian skull more labile?

    PubMed

    Linde-Medina, Marta; Boughner, Julia C; Santana, Sharlene E; Diogo, Rui

    2016-04-01

    Morphological variation is unevenly distributed within the mammalian skull; some of its parts have diversified more than others. It is commonly thought that this pattern of variation is mainly the result of the structural organization of the skull, as defined by the pattern and magnitude of trait covariation. Patterns of trait covariation can facilitate morphological diversification if they are aligned in the direction of selection, or these patterns can constrain diversification if oriented in a different direction. Within this theoretical framework, it is thought that more variable parts possess patterns of trait covariation that made them more capable of evolutionary change, that is, are more labile. However, differences in the degree of morphological variation among skull traits could arise despite variation in trait lability if, for example, some traits have evolved at a different rate and/or undergone stabilizing selection. Here, we test these hypotheses in the mammalian skull using 2D geometric morphometrics to quantify skull shape and estimating constraint, rates of evolution, and lability. Contrary to the expectations, more variable parts of the skull across mammalian species are less capable of evolutionary change than are less variable skull parts. Our results suggest that patterns of morphological variation in the skull could result from differences in rate of evolution and stabilizing selection. PMID:27069580

  1. Involvement of vasodilator mechanisms in arterial pressure lability after sino-aortic baroreceptor denervation in rat.

    PubMed Central

    Zhang, Z Q; Barrès, C; Julien, C

    1995-01-01

    1. To examine the regional haemodynamic basis of arterial pressure lability seen after sino-aortic baroreceptor denervation (SAD), simultaneous beat-to-beat recordings of arterial pressure and indices of regional blood flows (Doppler probes around the subdiaphragmatic and lower abdominal aortae and the superior mesenteric artery) were performed in the same conscious rats (n = 7) before, 1 and 14 days after SAD. 2. Acute SAD increased arterial pressure, decreased regional blood flows and vascular conductances, and potentiated the depressor and vasodilator effects of ganglionic blockade with trimethaphan, suggesting sympathetic overactivity. All parameters chronically returned to or near normal. 3. Both acute and chronic SAD increased the variability of arterial pressure and of regional conductances. Arterial pressure lability was characterized by a mixture of depressor and pressor events which were associated with regional vasodilatations and vasoconstrictions, respectively. This haemodynamic pattern was not affected by acute beta-adrenoceptor blockade with propranolol. 4. In conscious rats, the baroreceptor reflex acts to buffer the spontaneous variability of regional vascular conductances and thereby stabilizes arterial pressure. Sino-aortic baroreceptor denervation-induced arterial pressure lability does not depend on the level of sympathetic activation, and is determined by the relative contribution of depressor and pressor events accompanied by extensive vasodilatations and vasoconstrictions, respectively. Vasodilatations are not caused by the stimulation of vascular beta 2-adrenoceptors. PMID:7714834

  2. Labile soil carbon inputs mediate the soil microbial community composition and plant residue decomposition rates

    SciTech Connect

    De Graaff, Marie-Anne; Classen, Aimee T; Castro Gonzalez, Hector F; Schadt, Christopher Warren

    2010-01-01

    Root carbon (C) inputs may regulate decomposition rates in soil, and in this study we ask: how do labile C inputs regulate decomposition of plant residues, and soil microbial communities? In a 14 d laboratory incubation, we added C compounds often found in root exudates in seven different concentrations (0, 0.7, 1.4, 3.6, 7.2, 14.4 and 21.7 mg C g{sup -1} soil) to soils amended with and without {sup 13}C-labeled plant residue. We measured CO{sub 2} respiration and shifts in relative fungal and bacterial rRNA gene copy numbers using quantitative polymerase chain reaction (qPCR). Increased labile C input enhanced total C respiration, but only addition of C at low concentrations (0.7 mg C g{sup -1}) stimulated plant residue decomposition (+2%). Intermediate concentrations (1.4, 3.6 mg C g{sup -1}) had no impact on plant residue decomposition, while greater concentrations of C (> 7.2 mg C g{sup -1}) reduced decomposition (-50%). Concurrently, high exudate concentrations (> 3.6 mg C g{sup -1}) increased fungal and bacterial gene copy numbers, whereas low exudate concentrations (< 3.6 mg C g{sup -1}) increased metabolic activity rather than gene copy numbers. These results underscore that labile soil C inputs can regulate decomposition of more recalcitrant soil C by controlling the activity and relative abundance of fungi and bacteria.

  3. Investigation of acyl migration in mono- and dicaffeoylquinic acids under aqueous basic, aqueous acidic, and dry roasting conditions.

    PubMed

    Deshpande, Sagar; Jaiswal, Rakesh; Matei, Marius Febi; Kuhnert, Nikolai

    2014-09-17

    Acyl migration in chlorogenic acids describes the process of migration of cinnamoyl moieties from one quinic acid alcohol group to another, thus interconverting chlorogenic acid regioisomers. It therefore constitutes a special case of transesterification reaction. Acyl migration constitutes an important reaction pathway in both coffee roasting and brewing, altering the structure of chlorogenic acid initially present in the green coffee bean. In this contribution we describe detailed and comprehensive mechanistic studies comparing inter- and intramolecular acyl migration involving the seven most common chlorogenic acids in coffee. We employe aqueous acidic and basic conditions mimicking the brewing of coffee along with dry roasting conditions. We show that under aqueous basic conditions intramolecular acyl migration is fully reversible with basic hydrolysis competing with acyl migration. 3-Caffeoylquinic acid was shown to be most labile to basic hydrolysis. We additionally show that the acyl migration process is strongly pH dependent with increased transesterification taking place at basic pH. Under dry roasting conditions acyl migration competes with dehydration to form lactones. We argue that acyl migration precedes lactonization, with 3-caffeoylquinic acid lactone being the predominant product. PMID:25116442

  4. Photodissociation/gas diffusion/ion chromatography system for determination of total and labile cyanide in waters

    SciTech Connect

    Liu, Yan; Rocklin, R.D.; Joyce, R.J.; Doyle, M.J. )

    1990-04-01

    An automated system for determination of total and labile cyanide in water samples has been developed. The stable metal-cyanide complexes such as Fe(CN){sub 6}{sup 3{minus}} are photodissociated in an acidic medium with an on-line pyrex glass reaction coil irradiated by an intense Hg lamp. The released cyanide (HCN) is separated from most interferences in the sample matrix and is collected in a dilute NaOH solution by gas diffusion using a hydrophobic porous membrane separator. The cyanide ion is then separated from remaining interferences such as sulfide by ion exchange chromatography and is detected by an amperometric detector. The characteristics of the automated system were studied with solutions of free cyanide and metal-cyanide complexes. The results of cyanide determination for a number of wastewater samples obtained with the new method were compared with those obtained with the standard method. The sample throughput of the system is eight samples per hour and the detection limit for total cyanide is 0.1 {mu}g/L.

  5. Modulation of dendritic cell endocytosis and antigen processing pathways by Escherichia coli heat-labile enterotoxin and mutant derivatives.

    PubMed

    Petrovska, Liljana; Lopes, Luciene; Simmons, Cameron P; Pizza, Mariagrazia; Dougan, Gordon; Chain, Benjamin M

    2003-03-28

    Escherichia coli heat-labile enterotoxin (LT) is known to be a potent adjuvant of both the mucosal and systemic immune systems but the mechanism of action leading to adjuvant activity remains incompletely understood. This study investigates the action of LT and LT mutants with impaired enzymatic activity, on the function of dendritic cells. Wild-type LT and LTR72, which retains some ADP ribosyltransferase activity, induced a selective increase in cell surface expression of B7.1, and a selective decrease of CD40 expression on mouse bone marrow derived dendritic cells. LTK63 and LT-B had no obvious effect on the expression of these antigens on similar dendritic cells. LT-treated dendritic cells also showed a profoundly impaired ability to present protein antigen (ovalbumin) to cognate T cells, although this effect was not observed with non-toxic LT mutants. LT and LTR72-treated cells showed a slower rate of receptor-mediated endocytosis as measured by flow cytometric analysis of uptake of fluorescently labelled dextran. Furthermore, confocal microscopy showed changes in the intracellular distribution of endocytosed molecules, and of the class II containing acidic antigen processing compartments. This response of dendritic cells to toxin is likely to play an important role in determining the adjuvant activity of these molecules. PMID:12615441

  6. Self-assembly and cytotoxicity study of waterwheel-like dinuclear metal complexes: the first metal complexes appended with multiple free hydroxamic acid groups.

    PubMed

    Wang, Wen-Hua; Liu, Wei-Sheng; Wang, Ya-Wen; Li, Yang; Zheng, Li-Fang; Wang, Da-Qi

    2007-02-01

    Two waterwheel-like dinuclear complexes [M(2)(PHA)(4)(H(2)O)(2)] (M = Cu(II) (1), Zn(II) (2); HPHA = phthal-hydroxamic acid) appended with four free hydroxamic acid groups, namely, free hydroxamic acid metal complexes (FHAMCs) have been synthesized and characterized. The crystal structure of complex 1 was determined by single crystal X-ray diffraction, which adopts the paddlewheel motif with four bidentate carboxylate ligands joining two Cu(II) ions. The relative cytotoxicities of compounds 1 and 2 against SMMC-7721 and HO-8910 cell lines are similar and more predominant than HPHA (IC(50): Cu(II)>Zn(II)>HPHA). The synergic effect of the bound water molecules, multiple free hydroxamic acid groups and dimetal active sites with bridging carboxylate may have significant impacts on their pharmacological activity. As the prototype for a new class of hydroxamic acid derivatives, the self-assembly of FHAMCs presents a promising new strategy in designing multiple hydroxamic acids with remarkable bioactivities. PMID:17125839

  7. Hmb(off/on) as a switchable thiol protecting group for native chemical ligation.

    PubMed

    Qi, Yun-Kun; Tang, Shan; Huang, Yi-Chao; Pan, Man; Zheng, Ji-Shen; Liu, Lei

    2016-05-01

    A new thiol protecting group Hmb(off/on) is described, which has a switchable activity that may be useful in the chemical synthesis of proteins. When placed on the side chain of Cys, Cys(Hmb(off)) is stable to trifluoroacetic acid (TFA) in the process of solid-phase peptide synthesis. When Cys(Hmb(off)) is treated with neutral aqueous buffers, it is cleanly converted to acid-labile Cys(Hmb(on)), which can later be fully deprotected by TFA to generate free Cys. The utility of Cys(Hmb(off/on)) is demonstrated by the chemical synthesis of an erythropoietin segment, EPO[Cys(98)-Arg(166)]-OH through native chemical ligation. PMID:27102373

  8. Metal and metalloid indicator electrodes for the non-aqueous potentiometric titration of weak acids: comparative evaluation of group III, IV and V main-group elements.

    PubMed

    Greenhow, E J; Al-Mudarris, B F

    Indicator electrodes constructed from aluminium, gallium, indium, thallium, carbon, silicon, germanium, tin, lead, arsenic, antimony and bismuth have been evaluated for the potentiometric titration of solutions of benzoic acid in dimethylformamide and 4-methyl-2-pentanone. The aluminium, gallium, silicon and arsenic electrodes have also been evaluated for the determination of 3,5-xylenol in the same two solvents. Aluminium, gallium, indium, silicon, germanium, antimony and bismuth electrodes are superior to, or compare favourably with, a glass electrode for the determination of benzoic acid, when the criterion of efficiency is the sharpness of the end-point inflexion. In non-aqueous titrations of 3,5-xylenol, aluminium and gallium electrodes are similar in efficiency to the glass electrode for determinations in dimethylformamide solution, while the gallium electrode is superior to the glass electrode when 4-methyl-2-pentanone is the solvent. Possible relationships between the properties of the electrode element and the end-point sharpness when it is used as an indicator electrode are briefly considered. PMID:18961658

  9. The Synthesis of a Dipeptide from its Component Amino Acids: Protecting Groups in the Elementary Organic Laboratory.

    ERIC Educational Resources Information Center

    Young, Paul E.; Campbell, Andrew

    1982-01-01

    A simple, three-step procedure for synthesizing a dipeptide from its component amino acids is described. The dipeptide synthesized uses inexpensive amino acids having hydrocarbon side-chains and can be observed in E/Z forms by nuclear magnetic resonance spectroscopy. Each step in the synthesis produces white crystalline products using standard…

  10. Copolymeric hexyl acrylate-methacrylic acid microspheres - surface vs. bulk reactive carboxyl groups. Coulometric and colorimetric determination and analytical applications for heterogeneous microtitration.

    PubMed

    Stelmach, Emilia; Maksymiuk, Krzysztof; Michalska, Agata

    2016-10-01

    Copolymeric acrylate microspheres were prepared from hexyl acrylate using different amounts of methacrylic acid, resulting in a series of microspheres of gradually changing properties. The distribution of carboxyl groups - between surface and bulk of microspheres was evaluated. Bulk reactive carboxyl groups were determined using reverse coulometric titration with H(+) ions, following hydroxide ions have been generated and allowed to react with microspheres in the first step. It was found that the number of reactive carboxyl groups available in copolymeric microspheres is lower compared to number of methacrylic acid units used for polymerization process. Moreover, there is correlation between the number of groups introduced and found to be reactive in microspheres. On the other hand, the number of surface reactive groups was proportional to the number of groups introduced in course of polymerization. Thus, the surface reactive groups can be used as reagent, in novel heterogeneous microtitration procedure, in which a constant number of microspheres of different carboxyl groups contents is introduced to the sample to react with the analyte. The applicability of novel proposed method was tested on the example of Ni(2+) determination. PMID:27474305

  11. Assessing the Selectivity of Extractant Solutions for Recovering Labile Arsenic Associated with Iron (Hydr)oxides and Sulfides in Sediments

    EPA Science Inventory

    Sequential extractions can provide analytical constraints on the identification of mineral phases that control arsenic speciation in sediments. Model solids were used in this study to evaluate different solutions designed to extract arsenic from relatively labile solid phases. ...

  12. The evolution of labile traits in sex- and age-structured populations.

    PubMed

    Childs, Dylan Z; Sheldon, Ben C; Rees, Mark

    2016-03-01

    Many quantitative traits are labile (e.g. somatic growth rate, reproductive timing and investment), varying over the life cycle as a result of behavioural adaptation, developmental processes and plastic responses to the environment. At the population level, selection can alter the distribution of such traits across age classes and among generations. Despite a growing body of theoretical research exploring the evolutionary dynamics of labile traits, a data-driven framework for incorporating such traits into demographic models has not yet been developed. Integral projection models (IPMs) are increasingly being used to understand the interplay between changes in labile characters, life histories and population dynamics. One limitation of the IPM approach is that it relies on phenotypic associations between parents and offspring traits to capture inheritance. However, it is well-established that many different processes may drive these associations, and currently, no clear consensus has emerged on how to model micro-evolutionary dynamics in an IPM framework. We show how to embed quantitative genetic models of inheritance of labile traits into age-structured, two-sex models that resemble standard IPMs. Commonly used statistical tools such as GLMs and their mixed model counterparts can then be used for model parameterization. We illustrate the methodology through development of a simple model of egg-laying date evolution, parameterized using data from a population of Great tits (Parus major). We demonstrate how our framework can be used to project the joint dynamics of species' traits and population density. We then develop a simple extension of the age-structured Price equation (ASPE) for two-sex populations, and apply this to examine the age-specific contributions of different processes to change in the mean phenotype and breeding value. The data-driven framework we outline here has the potential to facilitate greater insight into the nature of selection and its

  13. Reduced contribution of thermally-labile sugar lesions to DNA double-strand break formation after exposure to neutrons.

    PubMed

    Singh, Satyendra K; Wu, Wenqi; Stuschke, Martin; Bockisch, Andreas; Iliakis, George

    2012-12-01

    In cells exposed to ionizing radiation, double-strand breaks (DSBs) form within clustered damage sites from lesions disrupting the DNA sugar-phosphate backbone. It is commonly assumed that DSBs form promptly and are immediately detected and processed by the cellular DNA damage response apparatus. However, DSBs also form by delayed chemical conversion of thermally-labile sugar lesions (TLSL) to breaks. We recently reported that conversion of thermally-labile sugar lesions to breaks occurs in cells maintained at physiological temperatures. Here, we investigate the influence of radiation quality on the formation of thermally-labile sugar lesions dependent DSBs. We show that, although the yields of total DSBs are very similar after exposure to neutrons and X rays, the yields of thermally-labile sugar lesions dependent DSBs from neutrons are decreased in comparison to that from X rays. Thus, the yields of prompt DSBs for neutrons are greater than for X rays. Notably, after neutron irradiation the decreased yield of thermally-labile sugar lesion dependent DSBs is strongly cell line dependent, likely reflecting subtle differences in DNA organization. We propose that the higher ionization density of neutrons generates with higher probability prompt DSBs within ionization clusters and renders the ensuing chemical evolution of thermally-labile sugar lesions inconsequential to DNA integrity. Modification of thermally-labile sugar lesion evolution may define novel radiation protection strategies aiming at decreasing DSB formation by chemically preserving thermally-labile sugar lesions until other DSB contributing lesions within the clustered damage site are removed by non-DSB repair pathways. PMID:23088767

  14. The tool of microbial genomics research for interpreting the lability of permafrost carbon and potential greenhouse gas feedbacks at different scales of resolution.

    NASA Astrophysics Data System (ADS)

    Waldrop, M. P.; Machelprang, R.; Hultman, J.; Wickland, K. P.

    2012-12-01

    One quarter of the earth's terrestrial surface is underlain by permafrost, or perennially frozen soils. Permafrost soils contain approximately 25% to 50% of the total global soil carbon pool nearly double the atmospheric carbon (C) reservoir. Decomposition of this C by microorganisms may produce globally significant quantities of both carbon dioxide and methane. These processes provide a positive feedback between climate change and the altered biogeochemistry of northern ecosystems. The fate of carbon residing in thawing permafrost soils depends on a number of physical factors including the thermal properties of soils (which affect heat flow rates), its disturbance regime (controlling changes in physical properties), and hydrologic regime (where soil-water interactions can rapidly thaw permafrost). Yet the mechanism of soil organic matter decomposition and greenhouse gas production operates primarily through the microbial loop: growth, carbon and nutrient mineralization, electron transfer, and enzyme production. We tested whether molecular analysis of microbial communities can be utilized as an indicator of permafrost C lability and potential greenhouse gas production from permafrost soils across multiple temporal and spatial scales. For short term studies of lability we compared rates of C turnover in soil incubations to chemical indices of soil lability, soil enzymes, and the abundance of soil microbial populations. Permafrost soils for the incubation ranged from frozen peatlands to dry uplands and Pleistocene Yedoma. For analysis at the annual to decadal scale, we utilized a permafrost thaw gradient at the Bonanza Creek LTER near Fairbanks Alaska. At this gradient, a Black Spruce forest underlain by permafrost thawed to form a thermokarst bog <50 years ago. Over the short term (months), the lability of permafrost C is reflected in the chemistry of dissolved constituents of permafrost, and it is also reflected in the change in abundance of total soil bacteria

  15. Complexes of adamantane-based group 13 Lewis acids and superacids: Bonding analysis and thermodynamics of hydrogen splitting.

    PubMed

    El-Hamdi, Majid; Solà, Miquel; Poater, Jordi; Timoshkin, Alexey Y

    2016-06-01

    The electronic structure and chemical bonding in donor-acceptor complexes formed by group 13 element adamantane and perfluorinated adamantane derivatives EC9 R'15 (E = B, Al; R' = H, F) with Lewis bases XR3 and XC9 H15 (X = N, P; R= H, CH3 ) have been studied using energy decomposition analysis at the BP86/TZ2P level of theory. Larger stability of complexes with perfluorinated adamantane derivatives is mainly due to better electrostatic and orbital interactions. Deformation energies of the fragments and Pauli repulsion are of less importance, with exception for the boron-phosphorus complexes. The MO analysis reveals that LUMO energies of EC9 R'15 significantly decrease upon fluorination (by 4.7 and 3.6 eV for E = B and Al, respectively) which results in an increase of orbital interaction energies by 27-38 (B) and 15-26 (Al) kcal mol(-1) . HOMO energies of XR3 increase in order PH3  < NH3  < PMe3  < PC9 H15  < NMe3  < NC9 H15 . For the studied complexes, there is a linear correlation between the dissociation energy of the complex and the energy difference between HOMO of the donor and LUMO of the acceptor. The fluorination of the Lewis acid significantly reduces standard enthalpies of the heterolytic hydrogen splitting H2  + D + A = [HD](+)  + [HA](-) . Analysis of several types of the [HD](+) ···[HA](-) ion pair formation in the gas phase reveals that structures with additional H···F interactions are energetically favorable. Taking into account the ion pair formation, hydrogen splitting is predicted to be highly exothermic in case of the perfluorinated derivatives both in the gas phase and in solution. Thus, fluorinated adamantane-based Lewis superacids are attractive synthetic targets for the construction of the donor-acceptor cryptands. © 2016 Wiley Periodicals, Inc. PMID:26931238

  16. Effect of excess dietary iron as ferrous sulfate and excess dietary ascorbic acid on liver zinc, copper and sulfhydryl groups and the ovary

    SciTech Connect

    Edwards, C.H.; Adkins, J.S.; Harrison, B.

    1986-03-05

    Female guinea pigs of the NIH 13/N strain, weighing between 475 and 512 g, were fed diets supplemented with 50 to 2500 mg of iron per kg of diet as ferrous sulfate and 0.2 to 8.0 g of ascorbic acid per kg of diet. A significant effect was observed on tissue copper and zinc, ovary weight and liver protein sulfhydryl groups. The mean ovary weight for guinea pigs fed 2500 mg of iron was significantly less than that of animals fed 50 mg of iron, 0.045 +/- 0.012 g and 0.061 +/- 0.009 g, respectively. Liver zinc content of animals fed 2500 mg of iron and 200 mg of ascorbic acid per kg of diet was significantly less than that of animals fed 50 mg of iron and 200 mg of ascorbic acid, 16.3 +/- 3.3 ..mu..g and 19.6 +/- 1.6 ..mu..g, respectively. There was no difference in liver copper due to dietary iron, but when dietary ascorbic acid was increased to 8 g per kg of diet, there was a significant decrease (from 22.8 +/- 8.1 ..mu..g to 10.5 +/- 4.8 ..mu..g) in liver copper. Excess dietary ascorbic acid decreased ovarian zinc significantly when increased to 8 g per kg of diet, 2929 +/- 919 ..mu..g vs 1661 +/- 471 ..mu..g, respectively, when compared to the control group.

  17. Main-group compounds selectively oxidize mixtures of methane, ethane, and propane to alcohol esters.

    PubMed

    Hashiguchi, Brian G; Konnick, Michael M; Bischof, Steven M; Gustafson, Samantha J; Devarajan, Deepa; Gunsalus, Niles; Ess, Daniel H; Periana, Roy A

    2014-03-14

    Much of the recent research on homogeneous alkane oxidation has focused on the use of transition metal catalysts. Here, we report that the electrophilic main-group cations thallium(III) and lead(IV) stoichiometrically oxidize methane, ethane, and propane, separately or as a one-pot mixture, to corresponding alcohol esters in trifluoroacetic acid solvent. Esters of methanol, ethanol, ethylene glycol, isopropanol, and propylene glycol are obtained with greater than 95% selectivity in concentrations up to 1.48 molar within 3 hours at 180°C. Experiment and theory support a mechanism involving electrophilic carbon-hydrogen bond activation to generate metal alkyl intermediates. We posit that the comparatively high reactivity of these d(10) main-group cations relative to transition metals stems from facile alkane coordination at vacant sites, enabled by the overall lability of the ligand sphere and the absence of ligand field stabilization energies in systems with filled d-orbitals. PMID:24626925

  18. Contribution of cytochrome P450 and UDT-glucuronosyltransferase to the metabolism of drugs containing carboxylic acid groups: risk assessment of acylglucuronides using human hepatocytes.

    PubMed

    Jinno, Norimasa; Tagashira, Mizuka; Tsurui, Kazuyuki; Yamada, Shizuo

    2014-08-01

    1. In order to evaluate the inhibition activity of 1-aminobenzotriazole (ABT) and (-)-borneol (borneol) against cytochrome P450 (CYP) and UDP-glucuronosyltransferase (UGT), the substrates of these metabolic enzymes were incubated with ABT and borneol in human hepatocytes. We found that 3 mM ABT and 300 μM borneol were the most suitable experimental levels to specifically inhibit CYP and UGT. 2. Montelukast, mefenamic acid, flufenamic acid, diclofenac, tienilic acid, gemfibrozil, ibufenac and repaglinide were markedly metabolized in human hepatocytes, and the metabolism of gemfibrozil, mefenamic acid and flufenamic acid was inhibited by borneol. With regard to repaglinide, montelukast, diclofenac and tienilic acid, metabolism was inhibited by ABT. Ibufenac was partly inhibited by both inhibitors. Zomepirac, tolmetin, ibuprofen, indomethacin and levofloxacin were moderately metabolized by human hepatocytes, and the metabolism of zomepirac, ibuprofen and indomethacin was equally inhibited by both ABT and borneol. The metabolism of tolmetin was strongly inhibited by ABT, and was also inhibited weakly by borneol. Residual drugs, telmisartan, valsartan, furosemide, naproxen and probenecid were scarcely metabolized. 3. Although we attempted to predict the toxicological risks of drugs containing carboxylic groups from the combination chemical stability and CLint via UGT, the results indicated that this combination was not sufficient and that clinical daily dose is important. PMID:24575896

  19. Participation of ABH glycoconjugates in the secretory response to Escherichia coli heat-labile toxin in rabbit intestine.

    PubMed

    Galván, E M; Roth, G A; Monferran, C G

    1999-08-01

    The ability of membrane ABH blood group-active glycoconjugates to act as receptors of the heat-labile enterotoxin of Escherichia coli (LTh) was studied in vitro and in vivo when GM1 was blocked by the cholera toxin B subunit. Rabbits were classified as AB or H based on intestinal ABH-antigenic activities. Brush border membranes from AB rabbits contained 4 times more LTh binding sites than the H ones. LTh interaction could be inhibited by lectins that recognize ABH determinants. LTh induced a similar dose-dependent secretory response in ligated ileal loops of both types of animals. Anti-AB antibodies and Ulex europaeus I lectin could significantly reduce the fluid accumulation in AB and H rabbits, respectively. LTh caused adenylate cyclase activation even when GM1 was blocked, and this effect was abolished by the addition of specific ABH ligands. These results suggest that ABH glycoconjugates are involved in the host secretory response to LTh in rabbit intestine. PMID:10395858

  20. The Benzyl Ester Group of Amino Acid Monomers Enhances Substrate Affinity and Broadens the Substrate Specificity of the Enzyme Catalyst in Chemoenzymatic Copolymerization.

    PubMed

    Ageitos, Jose Manuel; Yazawa, Kenjiro; Tateishi, Ayaka; Tsuchiya, Kousuke; Numata, Keiji

    2016-01-11

    The chemoenzymatic polymerization of amino acid monomers by proteases involves a two-step reaction: the formation of a covalent acyl-intermediate complex between the protease and the carboxyl ester group of the monomer and the subsequent deacylation of the complex by aminolysis to form a peptide bond. Although the initiation with the ester group of the monomer is an important step, the influence of the ester group on the polymerization has not been studied in detail. Herein, we studied the effect of the ester groups (methyl, ethyl, benzyl, and tert-butyl esters) of alanine and glycine on the synthesis of peptides using papain as the catalyst. Alanine and glycine were selected as monomers because of their substantially different affinities toward papain. The efficiency of the polymerization of alanine and glycine benzyl esters was much greater than that of the other esters. The benzyl ester group therefore allowed papain to equally polymerize alanine and glycine, even though the affinity of alanine toward papain is substantially higher. The characterization of the copolymers of alanine and glycine in terms of the secondary structure and thermal properties revealed that the thermal stability of the peptides depends on the amino acid composition and resultant secondary structure. The current results indicate that the nature of the ester group drastically affects the polymerization efficiency and broadens the substrate specificity of the protease. PMID:26620763

  1. Synthesis, structural characterization and antimicrobial activities of diorganotin(IV) complexes with azo-imino carboxylic acid ligand: Crystal structure and topological study of a doubly phenoxide-bridged dimeric dimethyltin(IV) complex appended with free carboxylic acid groups

    NASA Astrophysics Data System (ADS)

    Roy, Manojit; Roy, Subhadip; Devi, N. Manglembi; Singh, Ch. Brajakishor; Singh, Keisham Surjit

    2016-09-01

    Diorganotin(IV) complexes appended with free carboxylic acids were synthesized by reacting diorganotin(IV) dichlorides [R2SnCl2; R = Me (1), Bu (2) and Ph (3)] with an azo-imino carboxylic acid ligand i.e. 2-{4-hydroxy-3-[(2-hydroxyphenylimino)methyl]phenylazo}benzoic acid in presence of triethylamine. The complexes were characterized by elemental analysis, IR and multinuclear NMR (1H, 13C and 119Sn) spectroscopy. The structure of 1 in solid state has been determined by X-ray crystallography. Crystal structure of 1 reveals that the compound crystallizes in monoclinic space group P21/c and is a dimeric dimethyltin(IV) complex appended with free carboxylic acid groups. In the structure of 1, the Sn(IV) atoms are hexacoordinated and have a distorted octahedral coordination geometry in which two phenoxy oxygen atoms and the azomethine nitrogen atom of the ligand coordinate to each tin atom. One of the phenoxy oxygen atom bridges the two tin centers resulting in a planar Sn2O2 core. Topological analysis is used for the description of molecular packing in 1. Tin NMR spectroscopy study indicates that the complexes have five coordinate geometry around tin atom in solution state. Since the complexes have free carboxylic acids, these compounds could be further used as potential metallo-ligands for the synthesis of other complexes. The synthesized diorganotin(IV) complexes were also screened for their antimicrobial activities and compound 2 showed effective antimicrobial activities.

  2. Interactions between recalcitrant and labile organic carbon in streams - Can stream biofilms mediate a priming effect?

    NASA Astrophysics Data System (ADS)

    Bengtsson, M. M.; Wagner, K.; Herberg, E. R.; Burns, N. R.; Wanek, W.; Battin, T. J.

    2012-04-01

    Inland waters - such as streams, rivers and lakes - are increasingly recognized as important components in the global carbon cycle. Dissolved organic carbon (DOC) in these systems is diverse in structure, origin and reactivity, and a fraction of it is regarded as recalcitrant to microbial degradation. In soils, degradation of recalcitrant carbon is often controlled by the availability of labile carbon sources. This is linked to the priming effect (PE). Mounting evidence suggests that PE is also important in aquatic ecosystems but there are so far very few studies addressing this topic. Biofilms are vital components of aquatic ecosystems. In stream biofilms, heterotrophic bacteria and algae coexist in close proximity, exposing the bacteria to both recalcitrant DOC of terrestrial origin and labile organic carbon from the algae. We hypothesize that this makes stream biofilms hotspots for PE. We used plug-flow bioreactors inoculated with natural stream biofilm bacterial communities to test the potential of a priming effect in aquatic ecosystems. The bioreactors were amended with an isotope-labeled plant extract serving as a model of recalcitrant DOC in streams. Labile carbon sources, in the form of glucose and an algal extract were added to induce PE. Nitrate and phosphate were also added to assess the role of these inorganic nutrients on carbon uptake. Microbial uptake of the different carbon sources was monitored by measuring the concentrations and isotopic ratios of respired CO2, biomass and DOC. Our results suggest that the priming effect plays a role in stream carbon cycling and that it is potentially an important process in other aquatic ecosystems.

  3. Total and Labile Phosphorus Concentrations as Influenced by Riparian Buffer Soil Properties.

    PubMed

    Young, Eric O; Ross, Donald S

    2016-01-01

    Riparian buffers can act as a phosphorus (P) source under active stream bank erosion. Using soil and landscape variables (soil series, drainage class, organic matter, and pH) to index P concentrations could improve P loss risk tools for buffers. The objectives of this study were (i) to determine if soil properties could predict total and labile P concentrations within a 10-ha riparian buffer and (ii) to quantify the degree of spatial dependence of P and related properties. Soil samples were taken in 15-cm increments to a depth of 60 cm using a grid ( = 71) from an established riparian buffer along the Rock River in Vermont. Total soil P (TP), plant-available P determined by Modified Morgan extraction (MM-P), pH, soil organic matter (SOM), soil texture, and select cations were measured. We found that TP (152-1536 mg P kg) and MM-P (0.4-14.6 mg kg) ranged widely, with distinct differences between soil series. Mean TP and MM-P were greater in alluvial and glaciolacustrine soils compared with glacial till. Across all samples, MM-P was weakly related to soil properties; however, total labile P (orthophosphate + organic P measured by ICP) and unreactive labile P (ICP-P - colorimetric-P) could both be predicted by SOM ( = 0.59 and 0.73, respectively). Strong spatial dependence was found for P and related properties as revealed by geospatial analyses. Results show that P availability in the buffer was strongly related to soil genesis and support site-specific approaches for P loss risk evaluation in buffers. PMID:26828185

  4. Labile Low-Molecular-Mass Metal Complexes in Mitochondria: Trials and Tribulations of a Burgeoning Field.

    PubMed

    Lindahl, Paul A; Moore, Michael J

    2016-08-01

    Iron, copper, zinc, manganese, cobalt, and molybdenum play important roles in mitochondrial biochemistry, serving to help catalyze reactions in numerous metalloenzymes. These metals are also found in labile "pools" within mitochondria. Although the composition and cellular function of these pools are largely unknown, they are thought to be comprised of nonproteinaceous low-molecular-mass (LMM) metal complexes. Many problems must be solved before these pools can be fully defined, especially problems stemming from the lability of such complexes. This lability arises from inherently weak coordinate bonds between ligands and metals. This is an advantage for catalysis and trafficking, but it makes characterization difficult. The most popular strategy for investigating such pools is to detect them using chelator probes with fluorescent properties that change upon metal coordination. Characterization is limited because of the inevitable destruction of the complexes during their detection. Moreover, probes likely react with more than one type of metal complex, confusing analyses. An alternative approach is to use liquid chromatography (LC) coupled with inductively coupled plasma mass spectrometry (ICP-MS). With help from a previous lab member, the authors recently developed an LC-ICP-MS approach to analyze LMM extracts from yeast and mammalian mitochondria. They detected several metal complexes, including Fe580, Fe1100, Fe1500, Cu5000, Zn1200, Zn1500, Mn1100, Mn2000, Co1200, Co1500, and Mo780 (numbers refer to approximate masses in daltons). Many of these may be used to metalate apo-metalloproteins as they fold inside the organelle. The LC-based approach also has challenges, e.g., in distinguishing artifactual metal complexes from endogenous ones, due to the fact that cells must be disrupted to form extracts before they are passed through chromatography columns prior to analysis. Ultimately, both approaches will be needed to characterize these intriguing complexes and to

  5. Labile Compounds in Plant Litter Reduce the Sensitivity of Decomposition to Warming and Altered Precipitation

    NASA Astrophysics Data System (ADS)

    Suseela, V.; Tharayil, N.; Xing, B.; Dukes, J. S.

    2013-12-01

    Together, climate and litter quality strongly regulate decomposition rates. While these two factors and their interaction have been studied across species in continent-scale experiments, few researchers have studied how labile and recalcitrant compounds interact to influence decomposition, or the climate sensitivity of decomposition, within a litter type. Over a period of three years, we studied the effects climate change on mass loss and compound-specific decomposition using two litter types that differed in the relative proportions of labile and recalcitrant compounds, but that had heteropolymers with similar molecular structure. We examined how warming and altered precipitation affected the decomposition of two types of Polygonum cuspidatum (Japanese knotweed) litter (stem litter that was either newly senesced or one year old), at the Boston-Area Climate Experiment (BACE), in Massachusetts, USA. We placed litter bags in an old-field ecosystem exposed to four levels of warming (up to 4oC) and three levels of precipitation (ambient, drought (-50%) and wet (+50%) treatments. The compound-specific degradation of litter was assessed using Diffuse Reflectance Infrared Fourier Transform Spectroscopy and 13C Nuclear Magnetic Resonance Spectroscopy. Climate treatments immediately affected mass loss of the more recalcitrant litter, but affected the more labile litter only after two years. After three years, although both litter types had lost similar amounts of mass, warming (~4oC) and supplemental precipitation (150% of ambient) together accelerated degradation of alkyl-carbon and lignin only in the more recalcitrant litter, highlighting the role of initial litter quality in determining whether the chemistry of litter residues converges or diverges under different climates. The results from this study indicate that the effect of climate on litter decomposition depends on the quality of litter; litter with a greater initial proportion of labile compounds was less

  6. Inhibition of heat-labile cholera and Escherichia coli enterotoxins by brefeldin A.

    PubMed

    Donta, S T; Beristain, S; Tomicic, T K

    1993-08-01

    Cholera enterotoxin and the related heat-labile enterotoxins of Escherichia coli enter their target cells through noncoated vesicles, but how the toxins are processed intracellularly and how they get to their targeted enzyme, adenylate cyclase, remain to be defined. Brefeldin A, an inhibitor of the trans-Golgi network, is shown herein to transiently block the morphologic and enzymatic effects of the toxin at a step distal to the initial binding process but prior to activation of adenylate cyclase by the toxin. It is likely, therefore, that these toxins are processed by the Golgi apparatus before trafficking to the membrane adenylate cyclase. PMID:8392970

  7. Inhibition of heat-labile cholera and Escherichia coli enterotoxins by brefeldin A.

    PubMed Central

    Donta, S T; Beristain, S; Tomicic, T K

    1993-01-01

    Cholera enterotoxin and the related heat-labile enterotoxins of Escherichia coli enter their target cells through noncoated vesicles, but how the toxins are processed intracellularly and how they get to their targeted enzyme, adenylate cyclase, remain to be defined. Brefeldin A, an inhibitor of the trans-Golgi network, is shown herein to transiently block the morphologic and enzymatic effects of the toxin at a step distal to the initial binding process but prior to activation of adenylate cyclase by the toxin. It is likely, therefore, that these toxins are processed by the Golgi apparatus before trafficking to the membrane adenylate cyclase. Images PMID:8392970

  8. Epithelial to mesenchymal transition-the roles of cell morphology, labile adhesion and junctional coupling.

    PubMed

    Abdulla, Tariq; Luna-Zurita, Luis; de la Pompa, José Luis; Schleich, Jean-Marc; Summers, Ron

    2013-08-01

    Epithelial to mesenchymal transition (EMT) is a fundamental process during development and disease, including development of the heart valves and tumour metastases. An extended cellular Potts model was implemented to represent the behaviour emerging from autonomous cell morphology, labile adhesion, junctional coupling and cell motility. Computer simulations normally focus on these functional changes independently whereas this model facilitates exploration of the interplay between cell shape changes, adhesion and migration. The simulation model is fitted to an in vitro model of endocardial EMT, and agrees with the finding that Notch signalling increases cell-matrix adhesion in addition to modulating cell-cell adhesion. PMID:23787029

  9. Analysis of carbon functional groups in mobile humic acid and recalcitrant calcium humate extracted from eight US soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Solid state 13C nuclear magnetic resonance (NMR) spectroscopy is a common tool to study the structure of soil humic fractions; however, knowledge regarding carbon structural relationships in humic fractions is limited. In this study, mobile humic acid (MHA) and recalcitrant calcium humate (CaHA) fr...

  10. Comparison of the influence of polyaspartic acid and polylysine functional groups on the adsorption at the Cr2O3-Aqueous polymer solution interface

    NASA Astrophysics Data System (ADS)

    Ostolska, Iwona; Wiśniewska, Małgorzata

    2014-08-01

    Polyamino acids are a group of synthesized polymers obtained by polymerization of a given kind of amino acid monomer. Because of high biodegradability of this class of polymers, they can be used as flocculation or stabilization agents in the environmental aspects. Therefore determination of their influence on the stability of the aqueous suspension of metal oxides is important. An influence of different functional groups of polyamino acids, their molecular weight and concentration on the adsorption at the chromium (III) oxide (Cr2O3)-aqueous solution interface was determined. Experiments were carried out for four values of solution pH varying from 3 to 10 (3, 4, 7.6 and 10, respectively). Two polymers were used: anionic polyaspartic acid (ASP) of 6800 and 27,000 as well as polylysine (LYS) of 4900 and 33,000 molecular weights. Changes of surface charge density of colloidal Cr2O3 in the presence and in the absence of macromolecular substances were determined using potentiometric titration. In these studies the influence of the concentration and molecular weight of the ionic polymers on the pHpzc value was determined. Additionally, due to the lack of appropriate literature data, potentiometric titration of the selected polymers was performed to determine pKa values.

  11. Phosphorylation of Lipin 1 and Charge on the Phosphatidic Acid Head Group Control Its Phosphatidic Acid Phosphatase Activity and Membrane Association*

    PubMed Central

    Eaton, James M.; Mullins, Garrett R.; Brindley, David N.; Harris, Thurl E.

    2013-01-01

    The lipin gene family encodes a class of Mg2+-dependent phosphatidic acid phosphatases involved in the de novo synthesis of phospholipids and triglycerides. Unlike other enzymes in the Kennedy pathway, lipins are not integral membrane proteins, and they need to translocate from the cytosol to intracellular membranes to participate in glycerolipid synthesis. The movement of lipin 1 within the cell is closely associated with its phosphorylation status. Although cellular analyses have demonstrated that highly phosphorylated lipin 1 is enriched in the cytosol and dephosphorylated lipin 1 is found on membranes, the effects of phosphorylation on lipin 1 activity and binding to membranes has not been recapitulated in vitro. Herein we describe a new biochemical assay for lipin 1 using mixtures of phosphatidic acid (PA) and phosphatidylethanolamine that reflects its physiological activity and membrane interaction. This depends on our observation that lipin 1 binding to PA in membranes is highly responsive to the electrostatic charge of PA. The studies presented here demonstrate that phosphorylation regulates the ability of the polybasic domain of lipin 1 to recognize di-anionic PA and identify mTOR as a crucial upstream signaling component regulating lipin 1 phosphorylation. These results demonstrate how phosphorylation of lipin 1 together with pH and membrane phospholipid composition play important roles in the membrane association of lipin 1 and thus the regulation of its enzymatic activity. PMID:23426360

  12. The wall teichoic acids of Lactobacillus plantarum N.I.R.D. C106. Location of the phosphodiester groups and separation of the chains

    PubMed Central

    Archibald, A. R.; Coapes, Hilary E.

    1971-01-01

    1. The identities of the component glycerol glucosides of the wall teichoic acids of Lactobacillus plantarum N.I.R.D. C106 have been confirmed by methylation analysis. These glucosides are α-d-glucopyranosyl-(1→1)-l-glycerol, α-d-glucopyranosyl-(1→2)-α-d-glucopyranosyl-(1→1)-l-glycerol and α-d-glucopyranosyl-(1→3)-α-d-glucopyranosyl-(1→1)-l-glycerol. 2. These units are connected by phosphodiester groups attached to the 3(l)-hydroxyl group of glycerol and the 6-hydroxyl group of the non-reducing terminal glucose residues in the adjacent unit. 3. Concanavalin A forms a precipitate with the teichoic acid and the material so precipitated contains only the α-d-glucopyranosyl-(1→2)-α-d-glucopyranosyl -(1→1)-l-glycerol component. This unit is therefore present in a homogeneous polymer so that the teichoic acid is a mixture of this and of other possibly homogeneous chains containing the other two components. PMID:4332541

  13. Impact of primary amine group from aminophospholipids and amino acids on marine phospholipids stability: non-enzymatic browning and lipid oxidation.

    PubMed

    Lu, F S H; Nielsen, N S; Baron, C P; Diehl, B W K; Jacobsen, C

    2013-11-15

    The main objective of this study was to investigate the oxidative stability and non-enzymatic browning reactions of marine PL in the presence or in the absence of primary amine group from aminophospholipids and amino acids. Marine phospholipids liposomal dispersions were prepared from two authentic standards (phosphatidylcholine and phosphatidylethanolamine) and two purified PL from marine sources with and without addition of amino acids (leucine, methionine and lysine). Samples were incubated at 60°C for 0, 2, 4 and 6days. Non-enzymatic browning reactions were investigated through measurement of (i) Strecker derived volatiles, (ii) yellowness index (YI), (iii) hydrophobic and (iv) hydrophilic pyrroles content. The oxidative stability of the samples was assessed through measurement of secondary lipid derived volatile oxidation products. The result showed that the presence of PE and amino acids caused the formation of pyrroles, generated Strecker derived volatiles, decreased the YI development and lowered lipid oxidation. The lower degree of lipid oxidation in liposomal dispersions containing amino acids might be attributed to antioxidative properties of pyrroles or amino acids. PMID:23790862

  14. Bioanalytical applications of isothermal nucleic acid amplification techniques.

    PubMed

    Deng, Huimin; Gao, Zhiqiang

    2015-01-01

    The most popular in vitro nucleic acid amplification techniques like polymerase chain reaction (PCR) including real-time PCR are costly and require thermocycling, rendering them unsuitable for uses at point-of-care. Highly efficient in vitro nucleic acid amplification techniques using simple, portable and low-cost instruments are crucial in disease diagnosis, mutation detection and biodefense. Toward this goal, isothermal amplification techniques that represent a group of attractive in vitro nucleic acid amplification techniques for bioanalysis have been developed. Unlike PCR where polymerases are easily deactivated by thermally labile constituents in a sample, some of the isothermal nucleic acid amplification techniques, such as helicase-dependent amplification and nucleic acid sequence-based amplification, enable the detection of bioanalytes with much simplified protocols and with minimal sample preparations since the entire amplification processes are performed isothermally. This review focuses on the isothermal nucleic acid amplification techniques and their applications in bioanalytical chemistry. Starting off from their amplification mechanisms and significant properties, the adoption of isothermal amplification techniques in bioanalytical chemistry and their future perspectives are discussed. Representative examples illustrating the performance and advantages of each isothermal amplification technique are discussed along with some discussion on the advantages and disadvantages of each technique. PMID:25467448

  15. Relationship between the lability of sediment-bound metals (Cd, Cu, Zn) and their bioaccumulation in benthic invertebrates

    NASA Astrophysics Data System (ADS)

    Amiard, J.-C.; Geffard, A.; Amiard-Triquet, C.; Crouzet, C.

    2007-04-01

    The present study has investigated metal contamination at nine sites (10 sampling stations) from the English Channel to the Mediterranean Sea, including low level and highly contaminated sediments. Both total and labile concentrations of metals were determined in superficial sediments. The influence of different pHs was tested and metal lability at pHs encountered in the gut of invertebrates (the ragworm Nereis diversicolor, the blue mussel Mytilus edulis, the Japanese oyster Crassostrea gigas) was compared with the distribution of metals in various operationally defined geochemical fractions. Cd showed the highest lability and Cu the lowest, whereas Zn lability was intermediate. Metal concentrations were determined in bivalves at six sites and in worms at three sites. Cd in living organisms and labile Cd in sediments increased in proportion over the gradient of contamination. This relationship did not always hold for Cu and Zn and these exceptions are discussed. Even if sediments are not the only source of metal contamination in marine invertebrates, the procedure proposed here to assess metal bioavailability by remobilising sediment-bound metals at physiological pHs, seems a significant improvement of the existing methodologies of risk assessment.

  16. Fatty acids binding to human serum albumin: Changes of reactivity and glycation level of Cysteine-34 free thiol group with methylglyoxal.

    PubMed

    Pavićević, Ivan D; Jovanović, Vesna B; Takić, Marija M; Penezić, Ana Z; Aćimović, Jelena M; Mandić, Ljuba M

    2014-10-17

    Fatty acids (FAs) binding to human serum albumin (HSA) could lead to the changes of Cys-34 thiol group accessibility and reactivity, i.e. its scavenger capacity and antioxidant property. The influence of saturated, mono and poly unsaturated, and fish oil FAs binding to HSA on the carbonylation level and the reactivity of HSA-SH and HSA modified with methylglyoxal (MG-HSA-SH) was investigated. Changes of thiol group reactivity were followed by determination of pseudo first order rate constant (k') for thiols reaction with 5,5'-dithiobis(2-nitrobenzoic acid). HSA changes were monitored using native PAG electrophoresis and fluorescence spectroscopy. For FA/HSA molar ratios screening, qTLC and GC were used. FAs increase thiol group carbonylation levels from 8% to 20%. The k' values obtained for FAs-free HSA-SH and FAs-free MG-HSA-SH are almost equal (7.5×10(-3) and 7.7×10(-3)s(-1), resp.). Binding of all FAs amplify the reactivity (k' values from 14.6×10(-3) to 26.0×10(-3)s(-1)) of HSA-SH group for 2-3.5times in the order: palmitic, docosahexaenoic, fish oil extract, stearic, oleic, myristic and eicosapentaenoic acid, due to HSA conformational changes. FAs-bound MG-HSA-SH samples follow that pattern, but their k' values (from 9.8×10(-3) to 14.3×10(-3)s(-1)) were lower compared to unmodified HSA due to additional conformation changes of HSA molecules during carbonylation. Carbonylation level and reactivity of Cys34 thiol group of unmodified and carbonylated HSA depend on type of FAs bound to HSA, which implies the possibility for modulation of -SH reactivity (scavenger capacity and antioxidant property) by FAs as a supplement. PMID:25451573

  17. Inactivation of the cysteine protease SpeB affects hyaluronic acid capsule expression in group A streptococci.

    PubMed

    Woischnik, M; Buttaro, B A; Podbielski, A

    2000-04-01

    The human pathogen Streptococcus pyogenes expresses several virulence factors that are required for the pathogens survival within the host and the concomitant development of disease. To examine the influence of one virulence factor, the extracellular cysteine protease SpeB, on the expression of other virulence factors, the speB structural gene of a serotype M3 and M49 strain was inactivated. Morphologic examination, quantification of extracellular hyaluronic acid capsule, and Northern blot analysis of the isogenic speB -mutants revealed a strain-dependent decrease of hyaluronic acid capsule production and an increase in superoxide dismutase transcription. The transcription of streptolysin O (slo), di- and oligo-peptide permease (dpp, opp), hyaluronidase (hyl), streptokinase (ska) and streptococcal pyrogenic exotoxin A (speA) was unaffected. PMID:10764613

  18. A natural protecting group strategy to carry an amino acid starter unit in the biosynthesis of macrolactam polyketide antibiotics.

    PubMed

    Shinohara, Yuji; Kudo, Fumitaka; Eguchi, Tadashi

    2011-11-16

    Macrolactam antibiotics are an important class of macrocyclic polyketides that contain a unique nitrogen-containing starter unit. In the present study, a set of starter biosynthetic enzymes in the macrolactam antibiotic vicenistatin was characterized. We found that the protection-deprotection strategy of the aminoacyl-ACP intermediate was critical in this system. On the basis of bioinformatics, the described pathway is also proposed as a common method for carrying amino acids in the biosynthesis of other macrolactam antibiotics. PMID:22010945

  19. Heat-Labile Enterotoxin IIa, a Platform To Deliver Heterologous Proteins into Neurons

    PubMed Central

    Chen, Chen; Przedpelski, Amanda; Tepp, William H.; Pellett, Sabine; Johnson, Eric A.

    2015-01-01

    ABSTRACT Cholera toxin (CT) and the related heat-labile enterotoxins (LT) of Escherichia coli have been implicated as adjuvants in human therapies, but reactivity upon intranasal delivery dampened efforts to develop other clinical applications. However, each CT family member variant has unique biological properties that may warrant development as therapeutic platforms. In the current study, a nontoxic variant of the heat-labile enterotoxin IIa (LTIIa) was engineered to deliver heterologous, functional proteins into the cytosol of neurons. As proof of principle, the LTIIa variant delivered two cargos into neurons. LTIIa delivered β-lactamase efficiently into cells containing complex gangliosides, such as GD1b, as host receptors. LTIIa delivery of β-lactamase was sensitive to brefeldin A, an inhibitor that collapses the Golgi compartment into the endoplasmic reticulum, but not sensitive to treatment with botulinum neurotoxin D (BoNT/D), an inhibitor of synaptic vesicle cycling. LTIIa delivered a single-chain, anti-BoNT/A camelid antibody that inhibited SNAP25 cleavage during post-BoNT/A exposure of neurons. Delivery of functional, heterologous protein cargos into neurons demonstrates the potential of LTII variants as platforms to deliver therapies to inactivate toxins and microbial infections and to reverse the pathology of human neurodegenerative diseases. PMID:26265718

  20. Evaluation of commercial antisera for serotyping heat-labile antigens of Campylobacter jejuni and Campylobacter coli.

    PubMed Central

    Nicholson, M A; Patton, C M

    1993-01-01

    Commercial antisera for serotyping 22 heat-labile antigens of Campylobacter jejuni and Campylobacter coli were evaluated by using 66 isolates from human and nonhuman sources. Test results were compared with results of tests using antisera produced at the Centers for Disease Control (CDC), Atlanta, Ga. All strains (three isolates of each of the 22 serotypes) were typeable with the CDC antisera. Of 66 test strains, 39 (59%) were typed as the same serotype with both sets of antisera. Twenty-four strains (36%), including two heat-labile serotype reference strains, were nonreactive with the commercial antisera, and three strains (4.5%) were typed as serotypes different from those obtained with CDC antisera. Five of the 22 commercial antisera correctly serotyped all homologous strains. Our study indicated that two polyvalent antiserum pools, 7 unabsorbed antisera, and 16 absorbed monovalent antisera are weak and need modification to enhance their antibody titers. Further studies are necessary to explain the antigenic change to a different serotype in three strains. PMID:8463402

  1. Novel diffusive gradients in thin films technique to assess labile sulfate in soil.

    PubMed

    Hanousek, Ondrej; Mason, Sean; Santner, Jakob; Chowdhury, Md Mobaroqul Ahsan; Berger, Torsten W; Prohaska, Thomas

    2016-09-01

    A novel diffusive gradients in thin films (DGT) technique for sampling labile soil sulfate was developed, based on a strong basic anion exchange resin (Amberlite IRA-400) for sulfate immobilization on the binding gel. For reducing the sulfate background on the resin gels, photopolymerization was applied instead of ammonium persulfate-induced polymerization. Agarose cross-linked polyacrylamide (APA) hydrogels were used as diffusive layer. The sulfate diffusion coefficient in APA gel was determined as 9.83 × 10(-6) ± 0.35 × 10(-6) cm(2) s(-1) at 25 °C. The accumulated sulfate was eluted in 1 mol L(-1) HNO3 with a recovery of 90.9 ± 1.6 %. The developed method was tested against two standard extraction methods for soil sulfate measurement. The obtained low correlation coefficients indicate that DGT and conventional soil test methods assess differential soil sulfate pools, rendering DGT a potentially important tool for measuring labile soil sulfate. PMID:27491301

  2. Constraints on Transport and Emplacement Mechanisms of Labile Fractions in Lunar Cold Traps

    NASA Technical Reports Server (NTRS)

    Rickman, D.; Gertsch, L.

    2014-01-01

    Sustaining the scientific exploration of the Solar System will require a significant proportion of the necessary fuels and propellants, as well as other bulk commodities, to be produced from local raw materials [1]. The viability of mineral production depends on the ability to locate and characterize mineable deposits of the necessary feedstocks. This requires, among other things, a workable understanding of the mechanisms by which such deposits form, which is the subject of Economic Geology. Multiple deposition scenarios are possible for labile materials on the Moon. This paper suggests labile fractions moved diffusely through space; deposits may grow richer with depth until low porosity rock; lateral transport is likely to have occurred with the regolith, at least for short distances; crystalline ice may not exist; the constituent phases could be extremely complex. At present we can constrain the sources only mildly; once on the Moon, the transport mechanisms inherently mix and therefore obscure the origins. However, the importance of expanding our understanding of ore-forming processes on the Moon behooves us to make the attempt. Thus begins a time of new inquiry for Economic Geology.

  3. Structure and function of cholera toxin and the related Escherichia coli heat-labile enterotoxin.

    PubMed Central

    Spangler, B D

    1992-01-01

    Cholera and the related Escherichia coli-associated diarrheal disease are important problems confronting Third World nations and any area where water supplies can become contaminated. The disease is extremely debilitating and may be fatal in the absence of treatment. Symptoms are caused by the action of cholera toxin, secreted by the bacterium Vibrio cholerae, or by a closely related heat-labile enterotoxin, produced by Escherichia coli, that causes a milder, more common traveler's diarrhea. Both toxins bind receptors in intestinal epithelial cells and insert an enzymatic subunit that modifies a G protein associated with the adenylate cyclase complex. The consequent stimulated production of cyclic AMP, or other factors such as increased synthesis of prostaglandins by intoxicated cells, initiates a metabolic cascade that results in the excessive secretion of fluid and electrolytes characteristic of the disease. The toxins have a very high degree of structural and functional homology and may be evolutionarily related. Several effective new vaccine formulations have been developed and tested, and a growing family of endogenous cofactors is being discovered in eukaryotic cells. The recent elucidation of the three-dimensional structure of the heat-labile enterotoxin has provided an opportunity to examine and compare the correlations between structure and function of the two toxins. This information may improve our understanding of the disease process itself, as well as illuminate the role of the toxin in studies of signal transduction and G-protein function. Images PMID:1480112

  4. [Effects of land use change on soil labile organic carbon in Central Jiangxi of China].

    PubMed

    Du, Man-Yi; Fan, Shao-Hui; Liu, Guang-Lu; Qi, Liang-Hua; Guo, Bao-Hu; Tang, Xiao-Lu; Xiao, Fu-Ming

    2013-10-01

    Selecting the 15-year abandoned land (AL) and three forest lands [Phyllostachys edulis plantation (PE), Schima superba secondary forest (SS), and Cunninghamia Lanceolata plantation (CL)] in Anfu County of Jiangxi Province as test objects, this paper studied the effects of land use change on the soil organic carbon (SOC) pool and soil labile organic carbon (SLOC) contents. The soil organic carbon (SOC), microbial biomass carbon (MBC), hot- water extractable carbon (HWC), and readily oxidizable carbon (ROC) contents in the test lands were all in the order of PE>CL>SS>AL. As compared with those in AL, the SOC content, soil carbon stock, and soil labile organic carbon (SLOC) contents in the three forest lands all decreased with increasing soil depth, and had an obvious accumulation in surface soil. The proportions of different kinds of SLOC to soil total organic carbon differed markedly, among which, ROC had the highest proportion, while MBC had the smallest one. There existed significant relationships between SOC, MBC, HWC, and ROC. The MBC, HWC, and ROC contained higher content of active carbon, and were more sensitive to the land use change, being able to be used as the indicators for evaluating the soil quality and fertility in central Jiangxi Province. PMID:24483085

  5. Novel diffusive gradients in thin films technique to assess labile sulfate in soil

    PubMed Central

    Ahsan Chowdhury, Md Mobaroqul; Berger, Torsten W.; Prohaska, Thomas

    2016-01-01

    A novel diffusive gradients in thin films (DGT) technique for sampling labile soil sulfate was developed, based on a strong basic anion exchange resin (Amberlite IRA-400) for sulfate immobilization on the binding gel. For reducing the sulfate background on the resin gels, photopolymerization was applied instead of ammonium persulfate-induced polymerization. Agarose cross-linked polyacrylamide (APA) hydrogels were used as diffusive layer. The sulfate diffusion coefficient in APA gel was determined as 9.83 × 10−6 ± 0.35 × 10-6 cm2 s−1 at 25 °C. The accumulated sulfate was eluted in 1 mol L−1 HNO3 with a recovery of 90.9 ± 1.6 %. The developed method was tested against two standard extraction methods for soil sulfate measurement. The obtained low correlation coefficients indicate that DGT and conventional soil test methods assess differential soil sulfate pools, rendering DGT a potentially important tool for measuring labile soil sulfate. PMID:27491301

  6. Interaction of macrophage migration inhibitory factor with ceruloplasmin: role of labile copper ions.

    PubMed

    Kostevich, Valeria A; Sokolov, Alexey V; Grudinina, Natalia A; Zakharova, Elena T; Samygina, Valeria R; Vasilyev, Vadim B

    2015-10-01

    Macrophage migration inhibitory factor (MIF), a pro-inflammatory cytokine, is a target for pharmacological treatment of sepsis and malignant tumors. Inhibition of tautomerase activity of MIF in reaction with p-hydroxyphenylpyruvate (HPP) was observed in the presence of ceruloplasmin (CP), a copper-containing plasma protein. Binding labile copper ions to CP (CP+Cu(II)) is a prerequisite for MIF inhibiting. CP+Cu(II) is shown to be an uncompetitive inhibitor of MIF (Ki ~ 37 nM), which suggests formation of a complex 'MIF-HPP-CP-Cu(II)'. Filtration of CP+Cu(II) on a column with Chelex-100, otherwise the presence of high concentrations of histidine, cysteine or methionine abrogated the inhibitory effect of CP. Adding salts of Co(II) and Ni(II) that replace copper ions in the labile sites prevented the inhibitory effect of CP+Cu(II). Limited proteolysis of CP by thrombin diminished its oxidase activity in reaction with p-phenylenediamine, but endowed it with the capacity of inhibiting MIF. Covalent modification of MIF by phenylmethylsulfonyl fluoride (PMSF) resulted in binding of MIF-PMSF to CP immobilized on CM5 chip, the dissociation constant being 4.2 μM. In D-galactosamine-sensitized mice CP+Cu(II) increased the LPS-induced lethality from 54 to 100%, while administration of antibodies against MIF prevented the lethal effect. The enhancement by CP+Cu(II) of the pro-inflammatory signal of MIF is discussed. PMID:26091949

  7. Regeneration of spent three-way catalysts with nano-structured platinum group metals by gas and acid treatments.

    PubMed

    Kim, Sang Chai; Nahm, Seung Won; Wang, Geun Shim; Seo, Seong Gyu; Lee, Jae Wook

    2008-10-01

    The influence of physicochemical treatments on the catalytic activity of the spent nano-structured three way catalysts (TWCs) was examined to evaluate the possibility of using spent TWCs for removing VOCs. Thermal gases and acid aqueous solutions were used to regenerate the spent nano-structured TWCs. The characterization of the spent catalyst and its modified forms was carried out by using XRD, TEM, ICP, and N2 adsorption-desorption isotherms. The catalytic activity tests revealed that the spent nano-structured TWCs have a great potential for removing toxic compounds. The activities of catalysts were also found to be highly dependent on the treatment conditions. The acid aqueous treatments were very useful for improving the catalytic activity because they removed various contaminants such as fuel additives, lubricant oil additives, and metallic compounds. However, the thermal gas treated TWCs were less active than the parent TWCs. Furthermore, the activities of the catalysts treated with acids were closely connected with the remaining Pt/Al ratios. PMID:19198464

  8. Characterization of Group V Dubnium Homologs on DGA Extraction Chromatography Resin from Nitric and Hydrofluoric Acid Matrices

    SciTech Connect

    Despotopulos, J D; Sudowe, R

    2012-02-21

    somewhere between Nb and Pa. Much more recent studies have examined the properties of Db from HNO{sub 3}/HF matrices, and suggest Db forms complexes similar to those of Pa. Very little experimental work into the behavior of element 114 has been performed. Thermochromatography experiments of three atoms of element 114 indicate that the element 114 is at least as volatile as Hg, At, and element 112. Lead was shown to deposit on gold at temperatures about 1000 C higher than the atoms of element 114. Results indicate a substantially increased stability of element 114. No liquid phase studies of element 114 or its homologs (Pb, Sn, Ge) or pseudo-homologs (Hg, Cd) have been performed. Theoretical predictions indicate that element 114 is should have a much more stable +2 oxidation state and neutral state than Pb, which would result in element 114 being less reactive and less metallic than Pb. The relativistic effects on the 7p{sub 1/2} electrons are predicted to cause a diagonal relationship to be introduced into the periodic table. Therefore, 114{sup 2+} is expected to behave as if it were somewhere between Hg{sup 2+}, Cd{sup 2+}, and Pb{sup 2+}. In this work two commercially available extraction chromatography resins are evaluated, one for the separation of Db homologs and pseudo?homologs from each other as well as from potential interfering elements such as Group IV Rf homologs and actinides, and the other for separation of element 114 homologs. One resin, Eichrom's DGA resin, contains a N,N,N',N'-tetra-n-octyldiglycolamide extractant, which separates analytes based on both size and charge characteristics of the solvated metal species, coated on an inert support. The DGA resin was examined for Db chemical systems, and shows a high degree of selectivity for tri-, tetra-, and hexavalent metal ions in multiple acid matrices with fast kinetics. The other resin, Eichrom's Pb resin, contains a di-t-butylcyclohexano 18-crown-6 extractant with isodecanol solvent, which separates

  9. Cu lability and bioavailability in an urban stream during baseflow versus stormflow

    NASA Astrophysics Data System (ADS)

    Vadas, T.; Luan, H.

    2012-12-01

    Urban streams are dynamic systems with many anthropogenic inputs and stressors. Existing contaminant inputs are regulated through total maximum daily loads. Techniques for assessing that load are based on a combination of acute and chronic water quality criteria, biotic ligand models, and physical, chemical and biological assessments. In addition, the apportionment of reduction in load to different sources is based on total mass and not, for example, on bioavailable fraction. Our understanding of the impact of different metal inputs to stream impairment is limited. Free metal ions are understood to play a role in direct cellular uptake, but metal speciation (e.g. free metal, labile metals, or size fractionated) is relevant to more complex stream food webs. As part of an ongoing study, this work examines dissolved and particulate Cu concentrations in the Hockanum River, Vernon, CT situated in a developed watershed. Stream samples were taken during baseflow as well as stormflow upstream and downstream of wastewater treatment plant and stormwater runoff inputs. In addition, diffusive gradient in thin-film (DGT) devices which measure labile metal concentrations and cultured periphyton were used to examine bioavailable fractions. Total and filtered Cu concentrations ranged from about 1.3 to 10.7 μg/L, and 0.9 to 5.1 μg/L, respectively. Cu concentrations always increased downstream of the wastewater treatment plant by about 1.1-2 times, and effluent accounted for about 30% of baseflow. Generally, small increases (<10%) in concentration were observed in metals directly downstream of stormwater inlets, likely due to low volumes of runoff contributed from stormwater outfalls during these sampling periods. However, Cu concentrations were elevated (about 2-5 times higher) at all sites downstream from the wastewater treatment plant downstream sampling point, suggesting contributions from sediment resuspension. DGT measured concentrations represented 30 to 70% of dissolved Cu

  10. Effect of electron-donating substituent groups on aromatic ring on photoluminescence properties of complexes of benzoic acid-functionalized polysulfone with Eu(III) ions.

    PubMed

    Gao, Baojiao; Chen, Lulu; Chen, Tao

    2015-10-14

    By molecular design and via polymer reactions, methoxybenzoic acid (MOBA) and hydroxybenzoic acid (HBA) were bonded onto the side chains of polysulfone (PSF) for preparing two benzoic acid-functionalized PSFs, PSF-MOBA and PSF-HBA, respectively. Based on full characterization of their structures, the two macromolecule ligands were made to coordinate to Eu(3+) ions, and two binary polymer-rare earth complexes, PSF-(MOBA)3-Eu(III) and PSF-(HBA)3-Eu(III), were obtained. At the same time, using phenanthroline (Phen) as a second small-molecule ligand, the corresponding two ternary complexes, PSF-(MOBA)3-Eu(III)-Phen1 and PSF-(HBA)3-Eu(III)-Phen1, were also prepared. The photo physical behaviors of these complexes were examined in depth, and the luminescent properties of these prepared polymer-rare earth complexes were mainly investigated. The experimental results show that the two electron-donating substituent groups on the aromatic ring of the bonded benzoic acid significantly affect the luminescence properties of these complexes of benzoic acid-functionalized PSF and Eu(III) ions, and they can effectively strengthen the fluorescence emission intensities of the complexes. The possible reason is that through the p-π conjugative effect, the two electron-donating substituent groups can remarkably decline the triplet state energy levels of the bonded ligand MOBA and HBA, and strengthen the matching degree of energy between the triplet state energy level of the ligand and the resonant energy level of Eu(III) ions, resulting in the enhancement of fluorescence emission intensities of the complexes. Besides, the fluorescence emissions of the binary complexes are stronger than those of the corresponding ternary complexes because of the synergistic coordination effect of Phen with the macromolecular ligand. PMID:26355714

  11. A Facile Method for Oxidation of Primary Alcohols to Carboxylic Acids and Its Application in Glycosaminoglycan Syntheses

    PubMed Central

    Huang, Lijun; Teumelsan, Nardos; Huang, Xuefei

    2006-01-01

    A convenient two-step, one-pot procedure was developed for the conversion of primary alcohols to carboxylic acids. The alcohol was first treated with NaOCl and TEMPO under phase-transfer conditions, followed by NaClO2 oxidation in one pot. This reaction is applicable to a wide range of alcohols and the mild reaction conditions are compatible with many sensitive functional groups, including electron-rich aromatic rings, acid-labile isopropylidene ketal and glycosidic linkages, and oxidation-prone thioacetal, p-methoxybenzyl, and allyl moieties. Several glycosaminoglycans such as heparin, chondroitin, and hyaluronic acid oligosaccharides have been synthesized in high yields by using this new oxidation protocol. PMID:16637084

  12. Acidity and lipolysis by group V secreted phospholipase A(2) strongly increase the binding of apoB-100-containing lipoproteins to human aortic proteoglycans.

    PubMed

    Lähdesmäki, Katariina; Öörni, Katariina; Alanne-Kinnunen, Mervi; Jauhiainen, Matti; Hurt-Camejo, Eva; Kovanen, Petri T

    2012-02-01

    Local acidic areas characterize diffuse intimal thickening (DIT) and advanced atherosclerotic lesions. The role of acidity in the modification and extra- and intracellular accumulation of triglyceride-rich VLDL and IDL particles has not been studied before. Here, we examined the effects of acidic pH on the activity of recombinant human group V secreted phospholipase A(2) (sPLA(2)-V) toward small VLDL (sVLDL), IDL, and LDL, on the binding of these apoB-100-containing lipoproteins to human aortic proteoglycans, and on their uptake by human monocyte-derived macrophages. At acidic pH, the ability of sPLA(2)-V to lipolyze the apoB-100-containing lipoproteins was moderately, but significantly, increased while binding of the lipoproteins to proteoglycans increased >60-fold and sPLA(2)-V-modification further doubled the binding. Moreover, acidic pH more than doubled macrophage uptake of soluble complexes of sPLA(2)-V-LDL with aortic proteoglycans. Proteoglycan-affinity chromatography at pH 7.5 and 5.5 revealed that sVLDL, IDL, and LDL consisted of populations with different proteoglycan-binding affinities, and, surprisingly, the sVLDL fractions with the highest proteoglycan-affinity contained only low amounts of apolipoproteins E and C-III. Our results suggest that in atherosclerotic lesions with acidic extracellular pH, sPLA(2)-V is able to lipolyze sVLDL, IDL, and LDL, and increase their binding to proteoglycans. This is likely to provoke extracellular accumulation of lipids derived from these atherogenic lipoprotein particles and to increase the progression of the atherosclerotic lesions. PMID:22041135

  13. The carbon distribution among the functional groups of humic acids isolated by sequential alkaline extraction from gray forest soil

    NASA Astrophysics Data System (ADS)

    Kholodov, V. A.; Konstantinov, A. I.; Perminova, I. V.

    2009-11-01

    Preparations of humic acids (HAs) were isolated from a gray forest soil by sequential alkaline extraction. From a sample of 500 g, HA preparations of 2.24, 0.23, and 0.20 g were obtained from the first, second, and third alkaline extracts, respectively. The structure of the preparations was determined by 13C NMR spectroscopy. At each next extraction step, the portion of aliphatic fragments in the HA preparations increased and the content of aromatic structures decreased. The conclusion was drawn that a single extraction is sufficient for obtaining a representative HA sample.

  14. Design, synthesis, structure, and dehydrogenation reactivity of a water-soluble o-iodoxybenzoic acid derivative bearing a trimethylammonium group.

    PubMed

    Cui, Li-Qian; Dong, Zhi-Lei; Liu, Kai; Zhang, Chi

    2011-12-16

    5-Trimethylammonio-1,3-dioxo-1,3-dihydro-1λ(5)-benzo[d][1,2]iodoxol-1-ol anion (AIBX 1a), an o-iodoxybenzoic acid (IBX) derivative having the trimethylammonium moiety on its phenyl ring, possesses very good solubility in water and distinct oxidative properties from IBX, which is demonstrated in the oxidation of various β-keto esters to the corresponding dehydrogenated products using water as cosolvent. The regeneration of AIBX 1a can be easily realized from the reaction mixture due to its good water solubility. PMID:22082110

  15. pH-Responsive Non-Ionic Diblock Copolymers: Ionization of Carboxylic Acid End-Groups Induces an Order–Order Morphological Transition**

    PubMed Central

    Lovett, Joseph R; Warren, Nicholas J; Ratcliffe, Liam P D; Kocik, Marzena K; Armes, Steven P

    2015-01-01

    A carboxylic acid based reversible additionfragmentation transfer (RAFT) agent is used to prepare gels composed of worm-like diblock copolymers using two non-ionic monomers, glycerol monomethacrylate (GMA) and 2-hydroxypropyl methacrylate (HPMA). Ionization of the carboxylic acid end-group on the PGMA stabilizer block induces a worm-to-sphere transition, which in turn causes immediate degelation. This morphological transition is fully reversible as determined by TEM and rheology studies and occurs because of a subtle change in the packing parameter for the copolymer chains. A control experiment where the methyl ester derivative of the RAFT agent is used to prepare the same diblock copolymer confirms that no pH-responsive behavior occurs in this case. This end-group ionization approach is important for the design of new pH-responsive copolymer nano-objects as, unlike polyacids or polybases, only a minimal amount of added base (or acid) is required to drive the morphological transition. PMID:25418214

  16. pH-responsive non-ionic diblock copolymers: ionization of carboxylic acid end-groups induces an order-order morphological transition.

    PubMed

    Lovett, Joseph R; Warren, Nicholas J; Ratcliffe, Liam P D; Kocik, Marzena K; Armes, Steven P

    2015-01-19

    A carboxylic acid based reversible additionfragmentation transfer (RAFT) agent is used to prepare gels composed of worm-like diblock copolymers using two non-ionic monomers, glycerol monomethacrylate (GMA) and 2-hydroxypropyl methacrylate (HPMA). Ionization of the carboxylic acid end-group on the PGMA stabilizer block induces a worm-to-sphere transition, which in turn causes immediate degelation. This morphological transition is fully reversible as determined by TEM and rheology studies and occurs because of a subtle change in the packing parameter for the copolymer chains. A control experiment where the methyl ester derivative of the RAFT agent is used to prepare the same diblock copolymer confirms that no pH-responsive behavior occurs in this case. This end-group ionization approach is important for the design of new pH-responsive copolymer nano-objects as, unlike polyacids or polybases, only a minimal amount of added base (or acid) is required to drive the morphological transition. PMID:25418214

  17. In situ high-resolution evaluation of labile arsenic and mercury in sediment of a large shallow lake.

    PubMed

    Wang, Chao; Yao, Yu; Wang, Peifang; Hou, Jun; Qian, Jin; Yuan, Ye; Fan, Xiulei

    2016-01-15

    The precise evaluation of arsenic (As) and mercury (Hg) bioavailability in sediment is crucial to controlling As and Hg contamination, but traditional ex situ measurements hamper comprehensive analysis of labile As and Hg in sediment. In this study, we characterized in situ labile As and Hg in sediment of Lake Hongze using the zirconium (Zr) oxide diffusive gradients in thin films (DGT) technique and 3-mercaptopropyl functionalized silica gel DGT, respectively. The concentrations of DGT-labile As and Hg in the sediment profiles were found to exhibit considerable variation, ranging from 0.15 to 4.15 μg L(-1) for As and from 0.04 to 1.35 μg L(-1) for Hg. As and Hg flux values, calculated based on the concentration gradients measured from the DGT profiles for both the overlying water and sediment close to the sediment-water interface, were used to determine the contamination status of As and Hg. Flux values of As and Hg were between -0.066 and 0.067 ng cm(-2)d(-1) and between -0.0187 and 0.0181 ng cm(-2)d(-1), respectively. The GNU's Not Unix R (GNU R) programming language was used to identify outliers of As and Hg at various depths at the sampling sites. The results indicate that the sites with the most outliers were all located in the regions that were seriously affected by contaminants from the Huai River. The DGT-labile As and Hg concentrations in the 0-30 mm layer were found to be significantly correlated with concentrations of labile As and Hg, total dissolved As and Hg, and total As and Hg in the overlying water, as indicated by ex situ measurements. Results show that DGT is a reliable and high-resolution technique that can be used for in situ monitoring of the labile fractions of As and Hg in sediment in fresh water bodies. PMID:26398454

  18. Distinguishing two groups of flavin reductases by analyzing the protonation state of an active site carboxylic acid.

    PubMed

    Dumit, Verónica I; Cortez, Néstor; Matthias Ullmann, G

    2011-07-01

    Flavin-containing reductases are involved in a wide variety of physiological reactions such as photosynthesis, nitric oxide synthesis, and detoxification of foreign compounds, including therapeutic drugs. Ferredoxin-NADP(H)-reductase (FNR) is the prototypical enzyme of this family. The fold of this protein is highly conserved and occurs as one domain of several multidomain enzymes such as the members of the diflavin reductase family. The enzymes of this family have emerged as fusion of a FNR and a flavodoxin. Although the active sites of these enzymes are very similar, different enzymes function in opposite directions, that is, some reduce oxidized nicotinamide adenine dinucleotide phosphate (NADP(+)) and some oxidize reduced nicotinamide adenine dinucleotide phosphate (NADPH). In this work, we analyze the protonation behavior of titratable residues of these enzymes through electrostatic calculations. We find that a highly conserved carboxylic acid in the active site shows a different titration behavior in different flavin reductases. This residue is deprotonated in flavin reductases present in plastids, but protonated in bacterial counterparts and in diflavin reductases. The protonation state of the carboxylic acid may also influence substrate binding. The physiological substrate for plastidic enzymes is NADP(+), but it is NADPH for the other mentioned reductases. In this article, we discuss the relevance of the environment of this residue for its protonation and its importance in catalysis. Our results allow to reinterpret and explain experimental data. PMID:21538544

  19. A Naturally Occurring Single Amino Acid Replacement in Multiple Gene Regulator of Group A Streptococcus Significantly Increases Virulence

    PubMed Central

    Sanson, Misu; O'Neill, Brian E.; Kachroo, Priyanka; Anderson, Jeff R.; Flores, Anthony R.; Valson, Chandni; Cantu, Concepcion C.; Makthal, Nishanth; Karmonik, Christof; Fittipaldi, Nahuel; Kumaraswami, Muthiah; Musser, James M.; Olsen, Randall J.

    2016-01-01

    Single-nucleotide polymorphisms (SNPs) are the most common source of genetic variation within a species; however, few investigations demonstrate how naturally occurring SNPs may increase strain virulence. We recently used group A Streptococcus as a model pathogen to study bacteria strain genotype–patient disease phenotype relationships. Whole-genome sequencing of approximately 800 serotype M59 group A Streptococcus strains, recovered during an outbreak of severe invasive infections across North America, identified a disproportionate number of SNPs in the gene encoding multiple gene regulator of group A Streptococcus (mga). Herein, we report results of studies designed to test the hypothesis that the most commonly occurring SNP, encoding a replacement of arginine for histidine at codon 201 of Mga (H201R), significantly increases virulence. Whole transcriptome analysis revealed that the H201R replacement significantly increased expression of mga and 54 other genes, including many proven virulence factors. Compared to the wild-type strain, a H201R isogenic mutant strain caused significantly larger skin lesions in mice. Serial quantitative bacterial culture and noninvasive magnetic resonance imaging also demonstrated that the isogenic H201R strain was significantly more virulent in a nonhuman primate model of joint infection. These findings show that the H201R replacement in Mga increases the virulence of M59 group A Streptococcus and provide new insight to how a naturally occurring SNP in bacteria contributes to human disease phenotypes. PMID:25476528

  20. A naturally occurring single amino acid replacement in multiple gene regulator of group A Streptococcus significantly increases virulence.

    PubMed

    Sanson, Misu; O'Neill, Brian E; Kachroo, Priyanka; Anderson, Jeff R; Flores, Anthony R; Valson, Chandni; Cantu, Concepcion C; Makthal, Nishanth; Karmonik, Christof; Fittipaldi, Nahuel; Kumaraswami, Muthiah; Musser, James M; Olsen, Randall J

    2015-02-01

    Single-nucleotide polymorphisms (SNPs) are the most common source of genetic variation within a species; however, few investigations demonstrate how naturally occurring SNPs may increase strain virulence. We recently used group A Streptococcus as a model pathogen to study bacteria strain genotype-patient disease phenotype relationships. Whole-genome sequencing of approximately 800 serotype M59 group A Streptococcus strains, recovered during an outbreak of severe invasive infections across North America, identified a disproportionate number of SNPs in the gene encoding multiple gene regulator of group A Streptococcus (mga). Herein, we report results of studies designed to test the hypothesis that the most commonly occurring SNP, encoding a replacement of arginine for histidine at codon 201 of Mga (H201R), significantly increases virulence. Whole transcriptome analysis revealed that the H201R replacement significantly increased expression of mga and 54 other genes, including many proven virulence factors. Compared to the wild-type strain, a H201R isogenic mutant strain caused significantly larger skin lesions in mice. Serial quantitative bacterial culture and noninvasive magnetic resonance imaging also demonstrated that the isogenic H201R strain was significantly more virulent in a nonhuman primate model of joint infection. These findings show that the H201R replacement in Mga increases the virulence of M59 group A Streptococcus and provide new insight to how a naturally occurring SNP in bacteria contributes to human disease phenotypes. PMID:25476528

  1. Electron-Withdrawing Trifluoromethyl Groups in Combination with Hydrogen Bonds in Polyols: Brønsted Acids, Hydrogen-Bond Catalysts, and Anion Receptors

    SciTech Connect

    Shokri, Alireza; Wang, Xue B.; Kass, Steven R.

    2013-06-26

    Electron withdrawing trifluoromethyl groups were characterized in combination with hydrogen bond interactions in three polyols (i.e., CF3CH(OH)CH2CH(OH)CF3, 1; (CF3)2C(OH)C(OH)(CF3)2, 2; ((CF3)2C(OH)CH2)2CHOH, 3) by pKa measurements in DMSO and H2O, negative ion photoelectron spectroscopy and binding constant determinations with Cl–. Their catalytic behavior in several reactions were also examined and compared to a BrØnsted acid (HOAc) and a commonly employed thiourea ((3,5-(CF3)3C6H3NH)2CS). The combination of inductive stabilization and hydrogen bonds was found to afford potent acids which are effective catalysts. It also appears that hydrogen bonds can transmit the inductive effect over distance even in an aqueous environment, and this has far reaching implications.

  2. Polymeric nanostructures with pH-labile core for controlled drug release.

    PubMed

    Banerjee, Rakesh; Maiti, Saikat; Dey, Debabrata; Dhara, Dibakar

    2016-01-15

    Efficient and stimuli-triggered controlled delivery of therapeutics is one of the important issues in modern advanced therapy. In the present work, a versatile route for the synthesis of core cross-linked polymeric nanostructures (CLPN) through thiol-acrylate Michael addition reaction via the formation of β-thiopropionate has been described. The acid groups of the poly(acrylic acid) block of poly(ethylene glycol)-b-poly(N-isopropylacrylamide)-b-poly(acrylic acid) triblock copolymer were reacted with 2-hydroxyethyl acrylate (HEA) to yield the corresponding acrylate-functionalized copolymer (P1). Following this, P1 was reacted with a thiol functionalized cross-linker (CL) resulting in the formation of core cross-linked polymeric nanoparticles through acrylate-thiol Michael reaction. The ability of these nanoparticles to encapsulate drug molecules inside their core and their effective release following a pH-triggered controlled degradation of the core were demonstrated. The temperature sensitive release behaviour of the system was also studied. The non-toxic nature of the precursor polymers and the core cross-linked polymeric nanoparticles was also established, that further substantiated their potential as carriers for controlled release of drugs. PMID:26454376

  3. Improvement of oxygen-containing functional groups on olive stones activated carbon by ozone and nitric acid for heavy metals removal from aqueous phase.

    PubMed

    Bohli, Thouraya; Ouederni, Abdelmottaleb

    2016-08-01

    Recently, modification of surface structure of activated carbons in order to improve their adsorption performance toward especial pollutants has gained great interest. Oxygen-containing functional groups have been devoted as the main responsible for heavy metal binding on the activated carbon surface; their introduction or enhancement needs specific modification and impregnation methods. In the present work, olive stones activated carbon (COSAC) undergoes surface modifications in gaseous phase using ozone (O3) and in liquid phase using nitric acid (HNO3). The activated carbon samples were characterized using N2 adsorption-desorption isotherm, SEM, pHpzc, FTIR, and Boehm titration. The activated carbon parent (COSAC) has a high surface area of 1194 m(2)/g and shows a predominantly microporous structure. Oxidation treatments with nitric acid and ozone show a decrease in both specific surface area and micropore volumes, whereas these acidic treatments have led to a fixation of high amount of surface oxygen functional groups, thus making the carbon surface more hydrophilic. Activated carbon samples were used as an adsorbent matrix for the removal of Co(II), Ni(II), and Cu(II) heavy metal ions from aqueous solutions. Adsorption isotherms were obtained at 30 °C, and the data are well fitted to the Redlich-Peterson and Langmuir equation. Results show that oxidized COSACs, especially COSAC(HNO3), are capable to remove more Co(II), Cu(II), and Ni(II) from aqueous solution. Nitric acid-oxidized olive stones activated carbon was tested in its ability to remove metal ions from binary systems and results show an important maximum adsorbed amount as compared to single systems. PMID:25794582

  4. A united physicochemical description of the protonation and metal ion complexation equilibria of natural organic acids (humic and fulvic acids). 2. Influence of polyelectrolyte properties and functional group heterogeneity on the protonation equilibria of fulvic acid

    USGS Publications Warehouse

    Ephraim, J.; Alegret, S.; Mathuthu, A.; Bicking, M.; Malcolm, R.L.; Marinsky, J.A.

    1986-01-01

    Potentiometric studies of the neutralization of several fulvic acid sources with standard base in aqueous and nonaqueous media have been conducted. Analysis of the results with a recently developed unified physicochemical model has shown that the protonation behavior of these fulvic acid sources is a reflection of (1) their polyelectrolyte nature and (2) their heterogeneity. It has been possible to ascribe the polyelectrolyte properties observed to a rather inflexible fulvic acid molecule whose variably charged surface is impermeable to simple electrolyte. ?? 1986 American Chemical Society.

  5. Levels of Expression and Immunogenicity of Attenuated Salmonella enterica Serovar Typhimurium Strains Expressing Escherichia coli Mutant Heat-Labile Enterotoxin

    PubMed Central

    Covone, M. Giuseppina; Brocchi, Marcelo; Palla, Emanuela; da Silveira, W. Dias; Rappuoli, Rino; Galeotti, Cesira L.

    1998-01-01

    The effects of heterologous gene dosage as well as Salmonella typhimurium strain variability on immune response toward both the heterologous antigen, the nontoxic mutant of the Escherichia coli heat-labile enterotoxin LTK63, and the carrier Salmonella strain have been analyzed. Effects of a single integration into the host DNA and different-copy-number episomal vectors were compared in S. typhimurium Δcya Δcrp Δasd strains of two different serotypes, UK-1 and SR-11. Expression of the enterotoxin in the different Salmonella isolates in vitro was found to vary considerably and, for the episomal vectors, to correlate with the plasmid copy number. LTK63-specific serum immunoglobulin G (IgG) and mucosal immunoglobulin A (IgA) antibodies were highest in mice immunized with the high-level-expression strain. High anti-LTK63 IgG and IgA titers were found to correspond to higher anti-Salmonella immunity, suggesting that LTK63 exerts an adjuvant effect on response to the carrier. Statistically significant differences in anti-LTK63 immune response were observed between groups of mice immunized with the attenuated Δcya Δcrp UK-1 and SR-11 derivatives producing the antigen at the same rate. These data indicate that the same attenuation in S. typhimurium strains of different genetic backgrounds can influence significantly the immune response toward the heterologous antigen. Moreover, delivery of the LTK63 enterotoxin to the immune system by attenuated S. typhimurium strains is effective only when synthesis of the antigen is very high during the initial phase of invasion, while persistence of the S. typhimurium strain in deep tissues has only marginal influence. PMID:9423862

  6. Intranasal Immunization with SAG1 and Nontoxic Mutant Heat-Labile Enterotoxins Protects Mice against Toxoplasma gondii

    PubMed Central

    Bonenfant, C.; Dimier-Poisson, I.; Velge-Roussel, F.; Buzoni-Gatel, D.; Del Giudice, G.; Rappuoli, R.; Bout, D.

    2001-01-01

    Effective protection against intestinal pathogens requires both mucosal and systemic immune responses. Intranasal administration of antigens induces these responses but generally fails to trigger a strong protective immunity. Mucosal adjuvants can significantly enhance the immunogenicities of intranasally administered antigens. Cholera toxin (CT) and heat-labile enterotoxin (LT) are strong mucosal adjuvants with a variety of antigens. Moreover, the toxicities of CT and LT do not permit their use in humans. Two nontoxic mutant LTs, LTR72 and LTK63, were tested with Toxoplasma gondii SAG1 protein in intranasal vaccination of CBA/J mice. Vaccination with SAG1 plus LTR72 or LTK63 induced strong systemic (immunoglobulin G [IgG]) and mucosal (IgA) humoral responses. Splenocytes and mesenteric lymph node cells from mice immunized with LTR72 plus SAG1, but not those from mice immunized with LTK63 plus SAG1, responded to restimulation with a T. gondii lysate antigen in vitro. Gamma interferon and interleukin 2 (IL-2) production by splenocytes and IL-2 production by mesenteric lymph node cells were observed in vitro after antigen restimulation, underlying a Th1-like response. High-level protection as assessed by the decreased load of cerebral cysts after a challenge with the 76K strain of T. gondii was obtained in the group immunized with LTR72 plus SAG1 and LTK63 plus SAG1. They were as well protected as the mice immunized with the antigen plus native toxins. This is the first report showing protection against a parasite by using combinations of nontoxic mutant LTs and SAG1 antigen. These nontoxic mutant LTs are now attractive candidates for the development of mucosally delivered vaccines. PMID:11179334

  7. Crystal structure of a non-toxic mutant of heat-labile enterotoxin, which is a potent mucosal adjuvant.

    PubMed

    van den Akker, F; Pizza, M; Rappuoli, R; Hol, W G

    1997-12-01

    Two closely related bacterial toxins, heat-labile enterotoxin (LT-I) and cholera toxin (CT), not only invoke a toxic activity that affects many victims worldwide but also contain a beneficial mucosal adjuvant activity that significantly enhances the potency of vaccines in general. For the purpose of vaccine design it is most interesting that the undesirable toxic activity of these toxins can be eliminated by the single-site mutation Ser63Lys in the A subunit while the mucosal adjuvant activity is still present. The crystal structure of the Ser63Lys mutant of LT-I is determined at 2.0 A resolution. Its structure appears to be essentially the same as the wild-type LT-I structure. The substitution Ser63Lys was designed, based on the wild-type LT-I crystal structure, to decrease toxicity by interfering with NAD binding and/or catalysis. In the mutant crystal structure, the newly introduced lysine side chain is indeed positioned such that it could potentially obstruct the productive binding mode of the substrate NAD while at the same time its positive charge could possibly interfere with the critical function of nearby charged groups in the active site of LT-I. The fact that the Ser63Lys mutant of LT-I does not disrupt the wild-type LT-I structure makes the non-toxic mutant potentially suitable, from a structural point of view, to be used as a vaccine to prevent enterotoxigenic E. coli infections. The structural similarity of mutant and wild-type toxin might also be the reason why the inactive Ser63Lys variant retains its adjuvant activity. PMID:9416617

  8. Hereditary heat-labile hexosaminidase B: its implication for recognizing Tay-Sachs genotypes.

    PubMed

    Navon, R; Nutman, J; Kopel, R; Gaber, L; Gadoth, N; Goldman, B; Nitzan, M

    1981-11-01

    Two pairs of alleles, at the two loci of hexosaminidase (HEX), were found to segregate in an Arab inbred family: the normal and the mutant Tay-Sachs (TSD) alleles of HEX A, and the normal and a mutant allele of HEX B. Since the mutant HEX B is heat labile, no reliable identification of TSD genotypes can be obtained in its presence, as long as the proportions of HEX A and B are estimated by the routinely used heat-inactivation method. The genotypes may be correctly identified in such cases by separation of the two isoenzymes on ion-exchange chromatography, estimating their individual activities, and calculating the ratio between them. Of the nine genotype combinations possible with these two pairs of alleles, five have been identified in the reported family by this procedure. PMID:6459736

  9. Developmental Change and Intraindividual Variability: Relating Cognitive Aging to Cognitive Plasticity, Cardiovascular Lability, and Emotional Diversity

    PubMed Central

    Ram, Nilam; Gerstorf, Denis; Lindenberger, Ulman; Smith, Jacqui

    2010-01-01

    Repeated assessments obtained over years can be used to measure individuals’ developmental change, whereas repeated assessments obtained over a few weeks can be used to measure individuals’ dynamic characteristics. Using data from a burst of measurement embedded in the Berlin Aging Study (BASE: Baltes & Mayer, 1999), we illustrate and examine how long-term changes in cognitive ability are related to short-term changes in cognitive performance, cardiovascular function, and emotional experience. Our findings suggest that “better” cognitive aging over approximately13 years was associated with greater cognitive plasticity, less cardiovascular lability, and less emotional diversity over approximately 2 weeks at age 90 years. The study highlights the potential benefits of multi-time scale longitudinal designs for the study of individual function and development. PMID:21443355

  10. Significance of Isotopically Labile Organic Hydrogen in Thermal Maturation of Organic Matter

    SciTech Connect

    Arndt Schimmelmann; Maria Mastalerz

    2010-03-30

    Isotopically labile organic hydrogen in fossil fuels occupies chemical positions that participate in isotopic exchange and in chemical reactions during thermal maturation from kerogen to bitumen, oil and gas. Carbon-bound organic hydrogen is isotopically far less exchangeable than hydrogen bound to nitrogen, oxygen, or sulfur. We explore why organic hydrogen isotope ratios express a relationship with organic nitrogen isotope ratios in kerogen at low to moderate maturity. We develop and apply new techniques to utilize organic D/H ratios in organic matter fractions and on a molecular level as tools for exploration for fossil fuels and for paleoenvironmental research. The scope of our samples includes naturally and artificially matured substrates, such as coal, shale, oil and gas.

  11. Heat-labile enterotoxigenic Escherichia coli and intestinal protozoa in asymptomatic travellers.

    PubMed

    Echeverria, P; Cross, J H

    1977-12-01

    Thirty-two asymptomatic travellers who had recently journeyed in the Near, Middle, and Far East and had experienced a high incidence of diarrhoeal disease were screened for heat-labile enterotoxigenic Escherichia coli (ent+ E. coli) and other bacterial and parasitic pathogens. Six percent were colonized with ent+ E. coli and while other bacterial pathogens were not found, the intestinal protozoa Giardia lamblia (13%), Entamoeba histolytica (6%), Entamoeba coli (6%), Endolimax nana (6%), and Entamoeba hartmanni (3%) were detected in the stools. Ent+ E. coli, G. lamblia and E. histolytica should be considered in the differential diagnosis of gastrointestinal disease in travellers returning from the Orient. Furthermore, these travellers may be a potential source for the introduction of ent+ E. coli into communities where such organisms are relatively rare. PMID:351820

  12. Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C-N Bond Formation from Nonactivated Aliphatic Carboxylic Acids.

    PubMed

    Liu, Zhao-Jing; Lu, Xi; Wang, Guan; Li, Lei; Jiang, Wei-Tao; Wang, Yu-Dong; Xiao, Bin; Fu, Yao

    2016-08-01

    Copper-catalyzed directed decarboxylative amination of nonactivated aliphatic carboxylic acids is described. This intramolecular C-N bond formation reaction provides efficient access to the synthesis of pyrrolidine and piperidine derivatives as well as the modification of complex natural products. Moreover, this reaction presents excellent site-selectivity in the C-N bond formation step through the use of directing group. Our work can be considered as a big step toward controllable radical decarboxylative carbon-heteroatom cross-coupling. PMID:27439145

  13. Temporal Changes in Photochemically Labile DOM and Implications for Carbon Budgets in Peatland Aquatic Systems

    NASA Astrophysics Data System (ADS)

    Pickard, A.

    2015-12-01

    Aquatic systems in peatland catchments are subject to high loading of dissolved organic matter (DOM) from surrounding terrestrial environments. However the significance of photochemical transformation of DOM in peatland carbon budgets remains poorly constrained. In this study UV irradiation experiments were conducted on water samples collected over one year from two contrasting systems in Scotland: a stream draining a peatland with high levels of DOM and a reservoir draining a peat catchment with low levels of DOM. Further samples were collected from the high DOM system during two storm events. After experimental exposure, optical and chemical analyses were employed to determine photochemical lability of the DOM pool. At both sites irradiation-induced decreases in dissolved organic carbon (DOC) as a percentage of the total carbon pool were greatest in winter, suggesting that DOM was depleted in photo-reactive molecules in summer. Seasonal variability in DOC was high at the stream site and was positively correlated with CO₂ and CO photoproduction (r2 = 0.81 and 0.83, respectively; p<0.05). Lignin phenol analyses indicate considerable contribution of peat to the DOM pool at the stream site, particularly during summer. Whilst DOC concentrations did not vary greatly during storm events, UV-Vis absorbance indicators did, signifying changing DOM source material from activation of different hydrological pathways. The most photo-reactive DOM occurred 5-10 hours after peak discharge, suggesting that storms replenish photochemically labile DOM in headwater streams. Conservative estimates using data from this study suggest that up to 7% of the DOM pool of peatland streams can be lost (primarily as CO₂ and CO) upon exposure to 8 hours of environmentally representative UV irradiation. Further investigation in field campaigns under natural UV exposure are underway to assess the importance of photodegradation of DOM as a loss pathway of carbon based gases from aquatic systems.

  14. Labile and recalcitrant organic matter utilization by river biofilm under increasing water temperature.

    PubMed

    Ylla, Irene; Romaní, Anna M; Sabater, Sergi

    2012-10-01

    Microbial biofilms in rivers contribute to the decomposition of the available organic matter which typically shows changes in composition and bioavailability due to their origin, seasonality, and watershed characteristics. In the context of global warming, enhanced biofilm organic matter decomposition would be expected but this effect could be specific when either a labile or a recalcitrant organic matter source would be available. A laboratory experiment was performed to mimic the effect of the predicted increase in river water temperature (+4 °C above an ambient temperature) on the microbial biofilm under differential organic matter sources. The biofilm microbial community responded to higher water temperature by increasing bacterial cell number, respiratory activity (electron transport system) and microbial extracellular enzymes (extracellular enzyme activity). At higher temperature, the phenol oxidase enzyme explained a large fraction of respiratory activity variation suggesting an enhanced microbial use of degradation products from humic substances. The decomposition of hemicellulose (β-xylosidase activity) seemed to be also favored by warmer conditions. However, at ambient temperature, the enzymes highly responsible for respiration activity variation were β-glucosidase and leu-aminopeptidase, suggesting an enhanced microbial use of polysaccharides and peptides degradation products. The addition of labile dissolved organic carbon (DOC; dipeptide plus cellobiose) caused a further augmentation of heterotrophic biomass and respiratory activity. The changes in the fluorescence index and the ratio Abs(250)/total DOC indicated that higher temperature accelerated the rates of DOC degradation. The experiment showed that the more bioavailable organic matter was rapidly cycled irrespective of higher temperature while degradation of recalcitrant substances was enhanced by warming. Thus, pulses of carbon at higher water temperature might have consequences for DOC

  15. Collagenase-labile polyurethane urea synthesis and processing into hollow fiber membranes.

    PubMed

    Fu, Hui-Li; Hong, Yi; Little, Steven R; Wagner, William R

    2014-08-11

    As a means to stimulate wound healing, a hollow fiber membrane system might be placed within a wound bed to provide local and externally regulated controlled delivery of regenerative factors. After sufficient healing, it would be desirable to triggerably degrade these fibers as opposed to pulling them out. Accordingly, a series of enzymatically degradable thermoplastic elastomers was developed as potential hollow fiber base material. Polyurethane ureas (PUUs) were synthesized based on 1, 4-diisocyanatobutane, polycaprolactone (PCL) diol and polyethylene glycol (PEG) at different molar fractions as soft segments, and collagenase-sensitive peptide GGGLGPAGGK-NH2 as a chain extender (defined as PUU-CLxEGy-peptide, where x and y are the respective molar percents). In these polymers, PEG in the polymer backbone decreased tensile strengths and initial moduli of solvent-cast films in the wet state, while increasing water absorption. Collagenase degradation was observed at 75% relative PEG content in the soft segment. Control PUUs with putrescine or nonsense peptide chain extenders did not degrade acutely in collagenase. Conduits electrospun from PUU-CL25EG75-peptide and PUU-CL50EG50-peptide exhibited appropriate mechanical strength and sustained release of a model protein from the tube lumen for 7 days. Collapse of PUU-CL25EG75-peptide tubes occurred after collagenase degradation for 3 days. In conclusion, through molecular design, synthesis and characterization, a collagenase-labile PUU-CL25EG75-peptide polymer was identified that exhibited the desired traits of triggerable lability, processability, and the capacity to act as a membrane to facilitate controlled protein release. PMID:25003560

  16. The priming effect: Investigating the role of labile C quantity on subsoil C losses

    NASA Astrophysics Data System (ADS)

    Diochon, Amanda; Kellman, Lisa; Beltrami, Hugo

    2010-05-01

    In a study examining changes in soil organic carbon storage after clearcut harvesting, we previously reported a 50% decline in soil C stocks approximately 30 years after harvesting, with the greatest losses reported below 20 cm in the mineral soil. Physical and biological separation of organic matter indicated that the decline was greatest in the fractions of organic matter that are conceptually thought to be stable. Stable isotope analyses were consistent with increased mineralization post-harvest and we speculated that the deeper stores of C might have been primed by a flush of labile C post harvest. A recent review (Blagodatskyaya and Kuzyakov, 2008) reported that the direction (positive, negative, neutral) of the priming effect may be dependent not only upon the energy content of the added substrate, but the quantity of C added relative to microbial biomass carbon (MBC). In this study we test this hypothesis using a lab-based incubation of soils collected from the surface (0-10 cm) and subsoil (35-50 cm) of an 80 year old red spruce forest. We added 10, 100 and 1000 % C (glucose) relative to MBC and measured the rate of decomposition (microbial respiration) every 5 h for the first week, every 24 h for the second week, weekly for a month and biweekly for two months. After flushing the headspace with CO2 free air, we measured the rate of microbial respiration and the δ13C of the respired C using a Multiflow prep system with a Gilson autosampler coupled to an Isoprime mass spectrometer. We used an isotope-mixing model to partition the sources of respired C and determine the direction of priming. Our findings suggest that the quantity of added C can affect the direction of priming and that the relative priming effect differs between depths, suggesting that soil organic carbon stores in the subsoil are more sensitive to labile C additions.

  17. Modulation of arachidonic acid metabolism by phenols: relation to positions of hydroxyl groups and peroxyl radical scavenging properties.

    PubMed

    Alanko, J; Riutta, A; Mucha, I; Vapaatalo, H; Metsä-Ketelä, T

    1993-01-01

    We have shown earlier that catecholamines have opposite regulative effects on prostaglandin (PG)E2 and leukotriene (LT)B4 formation with a receptor-independent mechanism in human polymorphonuclear leukocytes (PMNs) and whole blood. To shed further light on the mechanisms involved and structure-action relationship, we tested the effects of phenols (catechol, hydroquinone, phenol, and resorcinol) on the synthesis of PGE2 and LTB4 in human A23187-stimulated PMNs. To study the mechanism of how phenols influence PGE2 and LTB4 synthesis, their peroxyl radical-scavenging properties were analyzed. In general, low concentrations of phenols stimulated (catechol > hydroquinone > phenol) and high concentrations inhibited (resorcinol > catechol > hydroquinone > phenol) PGE2 formation. Resorcinol was different from the other phenols: It did not stimulate PGE2 synthesis at all, but it was effective inhibitor at high concentrations. Phenols had only an inhibitory effect on LTB4 formation (catechol = hydroquinone > phenol > resorcinol). The order of both stochiometric factors and reactivities of phenols for scavenging peroxyl radicals was catechol > hydroquinone > resorcinol > phenol. According to these results, phenols having hydroxyl groups in ortho- or paraposition have the greatest stimulative effect on PGE2 synthesis, the highest inhibitory action on LTB4 synthesis, and are good antioxidants. Resorcinol, having hydroxyl groups in the metaposition, behaves differently. It neither stimulates PGE2 nor inhibits LTB4 formation, but it is the most potent inhibitor of PGE2 formation. In spite of resorcinol's two hydroxyl groups, it mimics as an antioxidant phenol more than catechol and hydroquinone. PMID:8384148

  18. A comparison of retrospective self-report versus ecological momentary assessment measures of affective lability in the examination of its relationship with bulimic symptomatology

    PubMed Central

    Anestis, Michael D.; Selby, Edward A.; Crosby, Ross D.; Wonderlich, Stephen A.; Engel, Scott G.; Joiner, Thomas E.

    2010-01-01

    Affective lability has been linked to several maladaptive behaviors (Anestis et al., 2009; Coccaro, 1991). Methodology for measuring affective lability varies and includes retrospective self-report and ecological momentary assessment (EMA). In this study, we sought to test these methodologies by examining which better predicted binge eating episodes and general eating disorder symptoms in a sample (n = 131) of women diagnosed with bulimia nervosa (BN). We hypothesized that, while the two forms of measurement would be correlated with one another and predict binge eating episodes, EMA affective lability would be the stronger predictor. Results supported several hypotheses. Specifically, both EMA affective lability and retrospective self-report affective lability significantly predicted global eating disorder symptoms, even when controlling for depression, age, body mass index, and level of education, EMA affective lability exhibited a significantly stronger correlation with binge eating episodes than did retrospective self-report affective lability, and EMA affective lability predicted number of binge eating episodes on any given day controlling for the same list of covariates. Limitations include the use of a clinical sample that may limit the generalizability of our findings. Findings highlight the importance of affect in such behavior. PMID:20392437

  19. A comparison of retrospective self-report versus ecological momentary assessment measures of affective lability in the examination of its relationship with bulimic symptomatology.

    PubMed

    Anestis, Michael D; Selby, Edward A; Crosby, Ross D; Wonderlich, Stephen A; Engel, Scott G; Joiner, Thomas E

    2010-07-01

    Affective lability has been linked to several maladaptive behaviors (Anestis et al., 2009; Coccaro, 1991). Methodology for measuring affective lability varies and includes retrospective self-report and ecological momentary assessment (EMA). In this study, we sought to test these methodologies by examining which better predicted binge eating episodes and general eating disorder symptoms in a sample (n = 131) of women diagnosed with bulimia nervosa (BN). We hypothesized that, while the two forms of measurement would be correlated with one another and predict binge eating episodes, EMA affective lability would be the stronger predictor. Results supported several hypotheses. Specifically, both EMA affective lability and retrospective self-report affective lability significantly predicted global eating disorder symptoms, even when controlling for depression, age, body mass index, and level of education, EMA affective lability exhibited a significantly stronger correlation with binge eating episodes than did retrospective self-report affective lability, and EMA affective lability predicted number of binge eating episodes on any given day controlling for the same list of covariates. Limitations include the use of a clinical sample that may limit the generalizability of our findings. Findings highlight the importance of affect in such behavior. PMID:20392437

  20. Thermal Analysis of Labile Trace Elements in CM and CV Carbonaceous Chondrites Using Inductively Coupled Plasma-Mass Spectrometry

    NASA Technical Reports Server (NTRS)

    Lauretta, D. S.; Klaue, B.; Blum, J. D.; Buseck, P. R.

    2001-01-01

    We developed a technique to measure the thermal release profiles of a suite of labile elements (Zn, As, Se, Cd, In, Sn, Sb, Te, Pt, Hg, Au, Tl, Pb, Bi). Conclusions are reached about the behavior of each element during parent-body alteration. Additional information is contained in the original extended abstract.

  1. ReCLIP (Reversible Cross-Link Immuno-Precipitation): An Efficient Method for Interrogation of Labile Protein Complexes

    PubMed Central

    Smith, Andrew L.; Friedman, David B.; Yu, Huapeng; Carnahan, Robert H.; Reynolds, Albert B.

    2011-01-01

    The difficulty of maintaining intact protein complexes while minimizing non-specific background remains a significant limitation in proteomic studies. Labile interactions, such as the interaction between p120-catenin and the E-cadherin complex, are particularly challenging. Using the cadherin complex as a model-system, we have developed a procedure for efficient recovery of otherwise labile protein-protein interactions. We have named the procedure “ReCLIP” (Reversible Cross-Link Immuno-Precipitation) to reflect the primary elements of the method. Using cell-permeable, thiol-cleavable crosslinkers, normally labile interactions (i.e. p120 and E-cadherin) are stabilized in situ prior to isolation. After immunoprecipitation, crosslinked binding partners are selectively released and all other components of the procedure (i.e. beads, antibody, and p120 itself) are discarded. The end result is extremely efficient recovery with exceptionally low background. ReCLIP therefore appears to provide an excellent alternative to currently available affinity-purification approaches, particularly for studies of labile complexes. PMID:21283770

  2. Production of Escherichia coli heat labile toxin (LT) B subunit in soybean seed and analysis of its immunogenicity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Expression of the heat-labile toxin B subunit of enterotoxigenic Escherichia coli (LT) B was directed to the endoplasmic reticulum (ER) of soybean seed storage parenchyma cells for immunogen sequestration in de novo synthesized, ER-derived protein accretions in transgenic seed. Pentameric LTB accumu...

  3. Plant-Soil Relationships of Bromus tectorum L.: Interactions among Labile Carbon Additions, Soil Invasion Status, and Fertilizer.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Invasion of western North America by the annual exotic grass Bromus tectorum L. (cheatgrass) has been an ecological disaster. High soil bioavailability of nitrogen is a contributing factor in the invasive potential of B. tectorum. Application of labile carbon sources to the soil can immobilize soil ...

  4. Dynamics of labile and recalcitrant soil carbon pools in a sorghum Free-Air Co2 Enrichment (FACE) agroecosystem

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Experimentation with dynamics of soil carbon pools as affected by elevated CO2 can better define the ability of terrestrial ecosystems to sequester global carbon. In the present study, 6 N HCl hydrolysis and stable-carbon isotopic analysis ('13C) were used to investigate the labile and recalcitrant ...

  5. Emotional Lability in Children and Adolescents with Attention Deficit/Hyperactivity Disorder (ADHD): Clinical Correlates and Familial Prevalence

    ERIC Educational Resources Information Center

    Sobanski, Esther; Banaschewski, Tobias; Asherson, Philip; Buitelaar, Jan; Chen, Wai; Franke, Barbara; Holtmann, Martin; Krumm, Bertram; Sergeant, Joseph; Sonuga-Barke, Edmund; Stringaris, Argyris; Taylor, Eric; Anney, Richard; Ebstein, Richard P.; Gill, Michael; Miranda, Ana; Mulas, Fernando; Oades, Robert D.; Roeyers, Herbert; Rothenberger, Aribert; Steinhausen, Hans-Christoph; Faraone, Stephen V.

    2010-01-01

    Background: The goal of this study was to investigate the occurrence, severity and clinical correlates of emotional lability (EL) in children with attention deficit/hyperactivity disorder (ADHD), and to examine factors contributing to EL and familiality of EL in youth with ADHD. Methods: One thousand, one hundred and eighty-six children with ADHD…

  6. Tillage and rotational effects on exchangeable and enzyme-labile phosphorus forms in conventional and organic cropping systems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The transformations of crop residues and bio-fertilizers used as primary sources of nutrients for organic grain and forage production are influenced by soil management practices. The effects of management of the near-surface zone on labile phosphorus (P) forms were studied in soil under three organ...

  7. Affective lability and difficulties with regulation are differentially associated with amygdala and prefrontal response in women with Borderline Personality Disorder.

    PubMed

    Silvers, Jennifer A; Hubbard, Alexa D; Biggs, Emily; Shu, Jocelyn; Fertuck, Eric; Chaudhury, Sadia; Grunebaum, Michael F; Weber, Jochen; Kober, Hedy; Chesin, Megan; Brodsky, Beth S; Koenigsberg, Harold; Ochsner, Kevin N; Stanley, Barbara

    2016-08-30

    The present neuroimaging study investigated two aspects of difficulties with emotion associated with Borderline Personality Disorder (BPD): affective lability and difficulty regulating emotion. While these two characteristics have been previously linked to BPD symptomology, it remains unknown whether individual differences in affective lability and emotion regulation difficulties are subserved by distinct neural substrates within a BPD sample. To address this issue, sixty women diagnosed with BPD were scanned while completing a task that assessed baseline emotional reactivity as well as top-down emotion regulation. More affective instability, as measured by the Affective Lability Scale (ALS), positively correlated with greater amygdala responses on trials assessing emotional reactivity. Greater difficulties with regulating emotion, as measured by the Difficulties with Emotion Regulation Scale (DERS), was negatively correlated with left Inferior Frontal Gyrus (IFG) recruitment on trials assessing regulatory ability. These findings suggest that, within a sample of individuals with BPD, greater bottom-up amygdala activity is associated with heightened affective lability. By contrast, difficulties with emotion regulation are related to reduced IFG recruitment during emotion regulation. These results point to distinct neural mechanisms for different aspects of BPD symptomology. PMID:27379614

  8. A Longitudinal Study of Emotion Regulation, Emotion Lability-Negativity, and Internalizing Symptomatology in Maltreated and Nonmaltreated Children

    ERIC Educational Resources Information Center

    Kim-Spoon, Jungmeen; Cicchetti, Dante; Rogosch, Fred A.

    2013-01-01

    The longitudinal contributions of emotion regulation and emotion lability-negativity to internalizing symptomatology were examined in a low-income sample (171 maltreated and 151 nonmaltreated children, from age 7 to 10 years). Latent difference score models indicated that for both maltreated and nonmaltreated children, emotion regulation was a…

  9. On the Labile Memory Buffer in the Attentional Blink: Masking the T2 Representation by Onset Transients Mediates the AB

    ERIC Educational Resources Information Center

    Jannati, Ali; Spalek, Thomas M.; Di Lollo, Vincent

    2011-01-01

    Report of a second target (T2) is impaired when presented within 500 ms of the first (T1). This attentional blink (AB) is known to cause a delay in T2 processing during which T2 must be stored in a labile memory buffer. We explored the buffer's characteristics using different types of masks after T2. These characteristics were inferred by…

  10. Influence of group A streptococcal acid glycoprotein on expression of major virulence factors and internalization by epithelial cells.

    PubMed

    Marouni, Mehran J; Ziomek, Edmund; Sela, Shlomo

    2003-08-01

    A single transposon insertion upstream to the open-reading-frame identified as the streptococcal acid glycoprotein (sagp) gene rendered a Tn916 isolate of Streptococcus pyogenes with elevated susceptibility to internalization by the epithelial cells. The role of SAGP in S. pyogenes internalization was further studied using isogenic mutant containing an in-frame deletion within the sagp gene. The sagp mutant displayed slower growth-rate and showed 5-fold higher internalization efficiency than the parent strain. Transcription of sagp at the logarithmic phase, but not at the stationary phase of the growth was repressed by csrR, the global regulator gene. At the same time, mutation of the sagp gene partially decreased the transcription of hasA, a gene that is required for capsule synthesis. The mutation had no effect on transcription of the emm3 gene, encoding for the M protein. The most striking effect of the sagp mutation was a down-regulation of the streptococcal pyrogenic exotoxin B (SpeB) at both translational and transcriptional level. Treatment of the SAGP mutant cells with the exogenous mSpeB (mature protease) only partially reduced their susceptibility to internalization. The exogenous mSpeB was more effective in reducing the internalization efficiency of a speB mutant and brought it to the level observed for the parent strain. In overall, results show that CsrR, directly or indirectly, affects the expression of SAGP, and that the SAGP modulates expression of not only SpeB, but also other genes that facilitate S. pyogenes internalization. PMID:12901845

  11. The GH67 α-glucuronidase of Paenibacillus curdlanolyticus B-6 removes hexenuronic acid groups and facilitates biodegradation of the model xylooligosaccharide hexenuronosyl xylotriose.

    PubMed

    Septiningrum, Krisna; Ohi, Hiroshi; Waeonukul, Rattiya; Pason, Patthra; Tachaapaikoon, Chakrit; Ratanakhanokchai, Khanok; Sermsathanaswadi, Junjarus; Deng, Lan; Prawitwong, Panida; Kosugi, Akihiko

    2015-04-01

    4-O-Methylglucuronic acid (MeGlcA) side groups attached to the xylan backbone through α-1,2 linkages are converted to hexenuronic acid (HexA) during alkaline pulping. α-Glucuronidase (EC 3.2.1.139) hydrolyzes 1,2-linked MeGlcA from xylooligosaccharides. To determine whether α-glucuronidase can also hydrolyze HexA-decorated xylooligosaccharides, a gene encoding α-glucuronidase (AguA) was cloned from Paenibacillus curdlanolyticus B-6. The purified protein degraded hexenuronosyl xylotriose (ΔX3), a model substrate prepared from kraft pulp. AguA released xylotriose and HexA from ΔX3, but the Vmax and kcat values for ΔX3 were lower than those for MeGlcA, indicating that HexA side groups may affect the hydrolytic activity. To explore the potential for biological bleaching, ΔX3 degradation was performed using intracellular extract from P. curdlanolyticus B-6. The intracellular extract, with synergistic α-glucuronidase and β-xylosidase activities, degraded ΔX3 to xylose and HexA. These results indicate that α-glucuronidase can be used to remove HexA from ΔX3 derived from pulp, reducing the need for chemical treatments in the pulping process. PMID:25765307

  12. Muscle antioxidant (vitamin E) and major fatty acid groups, lipid oxidation and retail colour of meat from lambs fed a roughage based diet with flaxseed or algae.

    PubMed

    Ponnampalam, Eric N; Burnett, Viv F; Norng, Sorn; Hopkins, David L; Plozza, Tim; Jacobs, Joe L

    2016-01-01

    The effect of feeding flaxseed or algae supplements to lambs on muscle antioxidant potential (vitamin E), major fatty acid groups, lipid oxidation and retail colour was investigated. Lambs (n=120) were randomly allocated to one of 4 dietary treatments according to liveweight and fed the following diets for eight weeks: Annual ryegrass hay [60%]+subterranean clover hay [40%] pellets=Basal diet; Basal diet with flaxseed (10.7%)=Flax; Basal diet with algae (1.8%)=Algae; Basal diet with flaxseed (10.7%) and algae (1.8%)=FlaxAlgae. Flaxseed or algae supplementation significantly affected major fatty acid groups in muscle. The addition of algae (average of Algae and FlaxAlgae) resulted in lower vitamin E concentration in muscle (P<0.003; 1.0 vs 1.3mg/kg of muscle) compared with lambs fed a diet without algae (average of Basal and Flax). Increasing muscle EPA+DHA by algae supplementation significantly increased lipid oxidation, but retail display colour of fresh meat was not affected. PMID:26409038

  13. Removal of the side-chain glucose groups from schizophyllan improves the thermal stability of the polycytidylic acid complexes under the physiological conditions.

    PubMed

    Koumoto, Kazuya; Karinaga, Ryouji; Mizu, Masami; Anada, Takahisa; Sakurai, Kazuo; Kunitake, Toyoki; Shinkai, Seiji

    2004-12-01

    Thermal stabilization of the complex between polycytidylic acid [poly(C)] and the modified schizophyllan (SPG) whose hydrophilic side-chain glucose groups are selectively removed utilizing mild Smith-degradation has been investigated. With the decrease in the side-chain glucose groups of schizophyllan, the complex with poly(C) can be considerably stabilized compared with unmodified SPG; for example, the T(m) value after the removal of the side-chain glucose groups from 33.3 (unmodified) to 1.0 is enhanced by 14 degrees C. In addition, the thermal stabilization effect is even operative under the physiological conditions ([NaCl] = 0.15 mol dm(-3)). This effect is exerted owing to the construction of the hydrophobic atmosphere around the complex. Although schizophyllan lost the side-chain glucose groups, it still kept the protection effect of the bound poly(C) chain against RNaseA-mediated hydrolysis as observed for unmodified schizophyllan. The assessment of the cytotoxicity for A375:human malignant melanoma, and HL60:human promyelocytic leukemia revealed that the modified schizophyllan scarcely increases the cytotoxicity. These results indicate that the present modification for schizophyllan is of great significance in a viewpoint to develop the practical gene carriers operative even under the physiological conditions. PMID:15457435

  14. Sorbents based on asbestos with a layer of an hydroxyethylcyclam derivative of PVC containing aquacomplexes of sulfuric acid or sodium hydroxide with aza-crown groups

    NASA Astrophysics Data System (ADS)

    Tsivadze, A. Yu.; Fridman, A. Ya.; Morozova, E. M.; Sokolova, N. P.; Voloshchuk, A. M.; Petukhova, G. A.; Bardyshev, I. I.; Gorbunov, A. M.; Polyakova, I. Ya.; Titova, V. N.; Yavich, A. A.; Novikov, A. K.; Petrova, N. V.

    2016-07-01

    Aquacomplexes of sulfuric acid and sodium hydroxide with aza-crown groups are synthesized in cavities of a sorbent from the porous layer of a PVC cyclam-derivative grafted onto fibers of asbestos fabric. The structure of sorbents with complexes is studied and their adsorption characteristics are determined. It is shown that the affinity of the developed surface toward ethanol, benzene, and hexane depends on the nature of complexes in the pore walls, and the volume of cavities formed as a result of the pores on the developed asbestos surface being coated with networks of aza-crown groups is larger than that of cavities with walls of aza-crown groups in the layers of a PVC cyclam derivative. Indicators of H+- and OH--conductivity of sorbents with complexes as electrochemical bridges are determined. It is shown that the major part of H+- and OH--ions moves through complexes with aza-crown groups in the region of cavities formed of pores on the surface of asbestos.

  15. Salmonella enterica serovar enteritidis ghosts carrying the Escherichia coli heat-labile enterotoxin B subunit are capable of inducing enhanced protective immune responses.

    PubMed

    Jawale, Chetan V; Lee, John Hwa

    2014-06-01

    The Escherichia coli heat-labile enterotoxin B subunit (LTB) is a potent vaccine adjuvant. Salmonella enterica serovar Enteritidis ghosts carrying LTB (S. Enteritidis-LTB ghosts) were genetically constructed using a novel plasmid, pJHL187-LTB, designed for the coexpression of the LTB and E lysis proteins. S. Enteritidis-LTB ghosts were characterized using scanning electron microscopy to visualize their transmembrane tunnel structures. The expression of LTB in S. Enteritidis-LTB ghost preparations was confirmed by immunoblot and enzyme-linked immunosorbent assays. The parenteral adjuvant activity of LTB was demonstrated by immunizing chickens with either S. Enteritidis-LTB ghosts or S. Enteritidis ghosts. Chickens were intramuscularly primed at 5 weeks of age and subsequently boosted at 8 weeks of age. In total, 60 chickens were equally divided into three groups (n = 20 for each): group A, nonvaccinated control; group B, immunized with S. Enteritidis-LTB ghosts; and group C, immunized with S. Enteritidis ghosts. Compared with the nonimmunized chickens (group A), the immunized chickens (groups B and C) exhibited increased titers of plasma IgG and intestinal secretory IgA antibodies. The CD3(+) CD4(+) subpopulation of T cells was also significantly increased in both immunized groups. Among the immunized chickens, those in group B exhibited significantly increased titers of specific plasma IgG and intestinal secretory IgA (sIgA) antibodies compared with those in group C, indicating the immunomodulatory effects of the LTB adjuvant. Furthermore, both immunized groups exhibited decreased bacterial loads in their feces and internal organs. These results indicate that parenteral immunization with S. Enteritidis-LTB ghosts can stimulate superior induction of systemic and mucosal immune responses compared to immunization with S. Enteritidis ghosts alone, thus conferring efficient protection against salmonellosis. PMID:24671556

  16. Synthesis of the very acid-sensitive Fmoc-Cys(Mmt)-OH and its application in solid-phase peptide synthesis.

    PubMed

    Barlos, K; Gatos, D; Hatzi, O; Koch, N; Koutsogianni, S

    1996-03-01

    S-4-methoxytrityl cysteine was synthesized and converted into the corresponding Fmoc-Cys(Mmt)-OH by its reaction with Fmoc-OSu. As compared to the corresponding Fmoc-Cys(Trt)-OH, the S-Mmt-function was found to be considerably more acid labile. Quantitative S-Mmt-removal occurs selectively in the presence of groups of the tert butyl type and S-Trt by treatment with 0.5-1.0% TFA. The new derivative was successfully utilized in the SPPS of Tyr1-somatostatin on 2-chlorotrityl resin. In this synthesis groups of the Trt-type were exclusively used for amino acid side-chain protection. Quantitative cleavage from the resin and complete deprotection was performed by treatment with 3% TFA in DCM-TES (95:5) for 30 min at RT. We observed no reduction of tryptophan under these conditions. PMID:8740963

  17. Evidence for the enhanced lability of dissolved organic matter following permafrost slope disturbance in the Canadian High Arctic

    NASA Astrophysics Data System (ADS)

    Woods, Gwen C.; Simpson, Myrna J.; Pautler, Brent G.; Lamoureux, Scott F.; Lafrenière, Melissa J.; Simpson, André J.

    2011-11-01

    Arctic landscapes are believed to be highly sensitive to climate change and accelerated disturbance of permafrost is expected to significantly impact the rate of carbon cycling. While half the global soil organic matter (SOM) is estimated to reside in Arctic soils, projected warmer temperatures and permafrost disturbance will release much of this SOM into waterways in the form of dissolved organic matter (DOM). The spring thaw and subsequent flushing of soils releases the highest contributions of DOM annually but has historically been undersampled due to the difficulties of sampling during this period. In this study, passive samplers were placed throughout paired High Arctic watersheds during the duration of the 2008 spring flush in Nunavut, Canada. The watersheds are very similar with the exception of widespread active layer detachments (ALDs) that occurred within one of the catchments during a period of elevated temperatures in the summer of 2007. DOM samples were analyzed for structural and spectral characteristics via nuclear magnetic resonance (NMR) and fluorescence spectroscopy as well as vulnerability to degradation with simulated solar exposure. Lignin-derived phenols were further assessed utilizing copper(II) oxide (CuO) oxidation and gas chromatography/mass spectrometry (GC/MS). The samples were found to have very low dissolved lignin phenol content (˜0.07% of DOC) and appear to originate from primarily non-woody angiosperm vegetation. The acid/aldehyde ratios for dissolved vanillyl phenols were found to be high (up to 3.6), indicating the presence of highly oxidized lignin. Differences between DOM released from the ALD vs. the undisturbed watershed suggest that these shallow detachment slides have significantly impacted the quality of Arctic DOM. Although material released from the disturbed catchment was found to be highly oxidized, DOM in the lake into which this catchment drained had chemical characteristics indicating high contributions from

  18. Increasing Superoxide Production and the Labile Iron Pool in Tumor Cells may Sensitize Them to Extracellular Ascorbate

    PubMed Central

    McCarty, Mark Frederick; Contreras, Francisco

    2014-01-01

    ascorbic acid with oxygen. An increased pool of labile iron in cancer cells may contribute to the selective susceptibility of many cancers to i.v. ascorbate; antagonism of NF-kappaB activity with salicylate, and intravenous iron administration, could be employed to further elevate free iron in cancers. PMID:25279352

  19. A spermine conjugated stearic acid-g-chitosan oligosaccharide polymer with different types of amino groups for efficient p53 gene therapy.

    PubMed

    Meng, Tingting; Wu, Jie; Yi, Hanxi; Liu, Jingwen; Lu, Binbin; Yuan, Ming; Huang, Xuan; Yuan, Hong; Hu, Fuqiang

    2016-09-01

    The effect of various amino groups on gene vector is different. In order to combine their effect in one vector and finally promote the transfection efficiency, a biogenic tetra-amine spermine was introduced to modify the stearic acid-grafted chitosan oligosaccharide (CSOSA) polymer to build a new gene delivery system. The spermine linked CSOSA (SP-CSOSA) polymer consists two types of amino groups with 73.3%, 19.3% of all nitrogen atoms for primary and secondary amine groups, respectively. The SP modified CSOSA showed strong DNA condensation capability and obviously enhanced proton binding ability especially at about pH 5.0, which significantly promoted the escape of SP-CSOSA/pDNA complexes from endo-lysosoms. Moreover, the transfection efficiency at the N/P ratio of 10 could compete with that of Lipofectamine 2000 and PEI 25K, but with lower cytotoxicities. The therapeutic wild type p53 gene transfected by the SP-CSOSA polymer restored the function of aberrant p53 gene and induced obvious cell apoptosis and G1 phase arrest. We concluded that the new vector SP-CSOSA polymer proved to be a potential delivery system for gene therapy. PMID:27289311

  20. Polymethyl methacrylate-co-methacrylic acid coatings with controllable concentration of surface carboxyl groups: A novel approach in fabrication of polymeric platforms for potential bio-diagnostic devices

    NASA Astrophysics Data System (ADS)

    Hosseini, Samira; Ibrahim, Fatimah; Djordjevic, Ivan; Koole, Leo H.

    2014-05-01

    The generally accepted strategy in development of bio-diagnostic devices is to immobilize proteins on polymeric surfaces as a part of detection process for diseases and viruses through antibody/antigen coupling. In that perspective, polymer surface properties such as concentration of functional groups must be closely controlled in order to preserve the protein activity. In order to improve the surface characteristics of transparent polymethacrylate plastics that are used for diagnostic devices, we have developed an effective fabrication procedure of polymethylmetacrylate-co-metacrylic acid (PMMA-co-MAA) coatings with controlled number of surface carboxyl groups. The polymers were processed effectively with the spin-coating technique and the detailed control over surface properties is here by demonstrated through the variation of a single synthesis reaction parameter. The chemical structure of synthesized and processed co-polymers has been investigated with nuclear magnetic resonance spectroscopy (NMR) and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-ToF-MS). The surface morphology of polymer coatings have been analyzed with atomic force microscopy (AFM) and scanning electron microscopy (SEM). We demonstrate that the surface morphology and the concentration of surface -COOH groups (determined with UV-vis surface titration) on the processed PMMA-co-MAA coatings can be precisely controlled by variation of initial molar ratio of reactants in the free-radical polymerization reaction. The wettability of developed polymer surfaces also varies with macromolecular structure.

  1. Ultrafast photochemistry of polyatomic molecules containing labile halogen atoms in solution

    NASA Astrophysics Data System (ADS)

    Mereshchenko, Andrey S.

    Because breaking and making of chemical bonds lies at the heart of chemistry, this thesis focuses on dynamic studies of labile molecules in solutions using ultrafast transient absorption spectroscopy. Specifically, my interest is two-fold: (i) novel reaction intermediates of polyhalogenated carbon, boron and phosphorus compounds; (ii) photophysics and photochemistry of labile copper(II) halide complexes. Excitation of CH2Br2, CHBr3, BBr 3, and PBr3 into n(Br)sigma*(X-Br) states, where X=C, B, or P, leads to direct photoisomerization with formation of isomers having Br-Br bonds as well as rupture of one of X-Br bonds with the formation of a Br atom and a polyatomic radical fragment, which subsequently recombine to form similar isomer products. Nonpolar solvation stabilizes the isomers, consistent with intrinsic reaction coordinate calculations of the isomer ground state potential energy surfaces at the density functional level of theory, and consequently, the involvement of these highly energetic species on chemically-relevant time scales needs to be taken into account. Monochlorocomplexes in methanol solutions promoted to the ligand-to-metal charge transfer (LMCT) excited state predominantly undergo internal conversion via back electron transfer, giving rise to vibrationally hot ground-state parent complexes. Copper-chloride homolitical bond dissociation yielding the solvated copper(I) and Cl- atom/solvent CT complexes constitutes a minor pathway. Insights into ligand substitution mechanisms were acquired by monitoring the recovery of monochloro complexes at the expense of two unexcited dichloro- and unsubstituted forms of Cu(II) complexes also present in the solution. Detailed description of ultrafast excited-state dynamics of CuCl 42- complexes in acetonitrile upon excitation into all possible Ligand Field (LF) excited states and two most intense LMCT transitions is reported. The LF states were found to be nonreactive with lifetimes remarkably longer than those

  2. Preservation of labile organic matter in soils of drained thaw lakes in Northern Alaska

    NASA Astrophysics Data System (ADS)

    Mueller, Carsten W.; Rethemeyer, Janet; Kao-Kniffin, Jenny; Löppmann, Sebastian; Hinkel, Kenneth; Bockheim, James

    2014-05-01

    A large number of studies predict changing organic matter (OM) dynamics in arctic soils due to global warming. In contrast to rather slowly altering bulk soil properties, single soil organic matter (SOM) fractions can provide a more detailed picture of the dynamics of differently preserved SOM pools in climate sensitive arctic regions. By the study of the chemical composition of such distinctive SOM fractions using nuclear magnetic resonance spectroscopy (NMR) together with radiocarbon analyses it is possible to evaluate the stability of the major OM pools. Approximately 50-75% of Alaska's Arctic Coastal Plain is covered with thaw lakes and drained thaw lakes that follow a 5,000 yr cycle of development (between creation and final drainage), thus forming a natural soil chronosequence. The drained thaw lakes offer the possibility to study SOM dynamics affected by permafrost processes over millennial timescales. In April 2010 we sampled 16 soil cores (including the active and permanent layer) reaching from young drained lakes (0-50 years since drainage) to ancient drained lakes (3000-5500 years since drainage). Air dried soil samples from soil horizons of the active and permanent layer were subjected to density fractionation in order to differentiate particulate OM and mineral associated OM. The chemical composition of the SOM fractions was analyzed by 13C CPMAS NMR spectroscopy. For a soil core of a young and an ancient drained thaw lake basin we also analyzed the 14C content. For the studied soils we can show that up to over 25 kg OC per square meter are stored mostly as labile, easily degradable organic matter rich in carbohydrates. In contrast only 10 kg OC per square meter were sequestered as presumably more stable mineral associated OC dominated by aliphatic compounds. Comparable to soils of temperate regions, we found small POM (< 20 µm) occluded in aggregated soil structures which differed in the chemical composition from larger organic particles. This was

  3. Familial giant cell hepatitis associated with synthesis of 3 beta, 7 alpha-dihydroxy-and 3 beta,7 alpha, 12 alpha-trihydroxy-5-cholenoic acids.

    PubMed Central

    Clayton, P T; Leonard, J V; Lawson, A M; Setchell, K D; Andersson, S; Egestad, B; Sjövall, J

    1987-01-01

    Urinary bile acids from a 3-mo-old boy with cholestatic jaundice were analyzed by ion exchange chromatography and gas chromatography-mass spectrometry (GC-MS). This suggested the presence of labile sulfated cholenoic acids with an allylic hydroxyl group, a conclusion supported by analysis using fast atom bombardment mass spectrometry (FAB-MS). The compounds detected by FAB-MS were separated by thin layer chromatography and high performance liquid chromatography. The sulfated bile acids could be solvolyzed in acidified tetrahydrofuran, and glycine conjugates were partially hydrolyzed by cholylglycine hydrolase. Following solvolysis, deconjugation, and methylation with diazomethane, the bile acids were identified by GC-MS of trimethylsilyl derivatives. The major bile acids in the urine were 3 beta,7 alpha-dihydroxy-5-cholenoic acid 3-sulfate, 3 beta,7 alpha,12 alpha-trihydroxy-5-cholenoic acid monosulfate, and their glycine conjugates. Chenodeoxycholic acid and cholic acid were undetectable in urine and plasma. The family pedigree suggested that abnormal bile acid synthesis was an autosomal recessive condition leading to cirrhosis in early childhood. PMID:3470305

  4. pH-responsive ion transport in polyelectrolyte multilayers of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(4-styrenesulfonic acid-co-maleic acid) (PSS-MA) bearing strong- and weak anionic groups.

    PubMed

    Maza, Eliana; Tuninetti, Jimena S; Politakos, Nikolaos; Knoll, Wolfgang; Moya, Sergio; Azzaroni, Omar

    2015-11-28

    The layer-by-layer construction of interfacial architectures displaying stimuli-responsive control of mass transport is attracting increasing interest in materials science. In this work, we describe the creation of interfacial architectures displaying pH-dependent ionic transport properties which until now have not been observed in polyelectrolyte multilayers. We describe a novel approach to create pH-controlled ion-rectifying systems employing polyelectrolyte multilayers assembled from a copolymer containing both weakly and strongly charged pendant groups, poly(4-styrenesulfonic acid-co-maleic acid) (PSS-MA), alternately deposited with poly(diallyldimethylammonium chloride) (PDADMAC). The conceptual framework is based on the very contrasting and differential interactions of PSS and MA units with PDADMAC. In our setting, sulfonate groups play a structural role by conferring stability to the multilayer due to the strong electrostatic interactions with the polycations, while the weakly interacting MA groups remain "silent" within the film and then act as on-demand pH-responsive units. When these multilayers are combined with a strong cationic capping layer that repels the passage of cationic probes, a pH-gateable rectified transport of anions is observed. Concomitantly, we also observed that these functional properties are significantly affected when multilayers are subjected to extensive pH cycling as a consequence of irreversible morphological changes taking place in the film. We envision that the synergy derived from combining weak and strong interactions within the same multilayer will play a key role in the construction of new interfacial architectures displaying tailorable ion transport properties. PMID:26489595

  5. Development of a Gene Knockout System Using Mobile Group II Introns (Targetron) and Genetic Disruption of Acid Production Pathways in Clostridium beijerinckii

    PubMed Central

    Wang, Yi; Li, Xiangzhen; Milne, Caroline B.; Janssen, Holger; Lin, Weiyin; Phan, Gloria; Hu, Huiying; Jin, Yong-Su; Price, Nathan D.

    2013-01-01

    Clostridium beijerinckii is a well-known solvent-producing microorganism with great potential for biofuel and biochemical production. To better understand and improve the biochemical pathway to solvents, the development of genetic tools for engineering C. beijerinckii is highly desired. Based on mobile group II intron technology, a targetron gene knockout system was developed for C. beijerinckii in this study. This system was successfully employed to disrupt acid production pathways in C. beijerinckii, leading to pta (encoding phosphotransacetylase)- and buk (encoding butyrate kinase)-negative mutants. In addition to experimental characterization, the mutant phenotypes were analyzed in the context of our C. beijerinckii genome-scale model. Compared to those of the parental strain (C. beijerinckii 8052), acetate production in the pta mutant was substantially reduced and butyrate production was remarkably increased, while solvent production was dependent on the growth medium. The pta mutant also produced much higher levels of lactate, suggesting that disrupting pta influenced the energy generation and electron flow pathways. In contrast, acetate and butyrate production in the buk mutant was generally similar to that of the wild type, but solvent production was consistently 20 to 30% higher and glucose consumption was more rapid and complete. Our results suggest that the acid and solvent production of C. beijerinckii can be effectively altered by disrupting the acid production pathways. As the gene disruption method developed in this study does not leave any antibiotic marker in a disrupted allele, multiple and high-throughput gene disruption is feasible for elucidating genotype and phenotype relationships in C. beijerinckii. PMID:23872562

  6. In silico modification of Zn2+ binding group of suberoylanilide hydroxamic acid (SAHA) by organoselenium compounds as Homo sapiens class II HDAC inhibitor of cervical cancer

    NASA Astrophysics Data System (ADS)

    Sumo Friend Tambunan, Usman; Bakri, Ridla; Aditya Parikesit, Arli; Ariyani, Titin; Dyah Puspitasari, Ratih; Kerami, Djati

    2016-02-01

    Cervical cancer is the most common cancer in women, and ranks seventh of all cancers worldwide, with 529000 cases in 2008 and more than 85% cases occur in developing countries. One way to treat this cancer is through the inhibition of HDAC enzymes which play a strategic role in the regulation of gene expression. Suberoyl Anilide Hydroxamic Acid (SAHA) or Vorinostat is a drug which commercially available to treat the cancer, but still has some side effects. This research present in silico SAHA modification in Zinc Binding Group (ZBG) by organoselenium compound to get ligands which less side effect. From molecular docking simulation, and interaction analysis, there are five best ligands, namely CC27, HA27, HB28, IB25, and KA7. These five ligands have better binding affinity than the standards, and also have interaction with Zn2+ cofactor of inhibited HDAC enzymes. This research is expected to produce more potent HDAC inhibitor as novel drug for cervical cancer treatment.

  7. From solution to in-cell study of the chemical reactivity of acid sensitive functional groups: a rational approach towards improved cleavable linkers for biospecific endosomal release.

    PubMed

    Jacques, Sylvain A; Leriche, Geoffray; Mosser, Michel; Nothisen, Marc; Muller, Christian D; Remy, Jean-Serge; Wagner, Alain

    2016-06-01

    pH-Sensitive linkers designed to undergo selective hydrolysis at acidic pH compared to physiological pH can be used for the selective release of therapeutics at their site of action. In this paper, the hydrolytic cleavage of a wide variety of molecular structures that have been reported for their use in pH-sensitive delivery systems was examined. A wide variety of hydrolytic stability profiles were found among the panel of tested chemical functionalities. Even within a structural family, a slight modification of the substitution pattern has an unsuspected outcome on the hydrolysis stability. This work led us to establish a first classification of these groups based on their reactivities at pH 5.5 and their relative hydrolysis at pH 5.5 vs. pH 7.4. From this classification, four representative chemical functions were selected and studied in-vitro. The results revealed that only the most reactive functions underwent significant lysosomal cleavage, according to flow cytometry measurements. These last results question the acid-based mechanism of action of known drug release systems and advocate for the importance of an in-depth structure-reactivity study, using a tailored methodology, for the rational design and development of bio-responsive linkers. PMID:27169758

  8. Synthesis and characterization of novel sulfonated poly(arylene ether ketone) copolymers with pendant carboxylic acid groups for proton exchange membranes

    NASA Astrophysics Data System (ADS)

    Zhang, Yang; Cui, Zhiming; Zhao, Chengji; Shao, Ke; Li, Hongtao; Fu, Tiezhu; Na, Hui; Xing, Wei

    A series of novel side-chain-type sulfonated poly(arylene ether ketone)s with pendant carboxylic acid groups copolymers (C-SPAEKs) were synthesized by direct copolymerization of sodium 5,5‧-carbonyl-bis(2-fluorobenzenesulfonate), 4,4‧-difluorobenzophenone and 4,4‧-bis(4-hydroxyphenyl) valeric acid (DPA). The expected structure of the sulfonated copolymers was confirmed by FT-IR and 1H NMR. Membranes with good thermal and mechanical stability could be obtained by solvent cast process. It should be noted that the proton conductivity of these copolymers with high sulfonatation degree (DS > 0.6) was higher than 0.03 S cm -1 and increased with increasing temperature. At 80 °C, the conductivity of C-SPAEK-3 (DS = 0.6) and C-SPAEK-4 (DS = 0.8) reached up to 0.12 and 0.16 S cm -1, respectively, which were higher than that of Nafion 117 (0.10 S cm -1). Moreover, their methanol permeability was much lower than that of Nafion 117. These results showed that the synthesized materials might have potential applications as the proton exchange membranes for DMFCs.

  9. Mercapturic Acids Derived from the Toxicants Acrolein and Crotonaldehyde in the Urine of Cigarette Smokers from Five Ethnic Groups with Differing Risks for Lung Cancer

    PubMed Central

    Park, Sungshim L.; Carmella, Steven G.; Chen, Menglan; Patel, Yesha; Stram, Daniel O.; Haiman, Christopher A.; Le Marchand, Loic; Hecht, Stephen S.

    2015-01-01

    The Multiethnic Cohort epidemiology study has clearly demonstrated that, compared to Whites and for the same number of cigarettes smoked, African Americans and Native Hawaiians have a higher risk for lung cancer whereas Latinos and Japanese Americans have a lower risk. Acrolein and crotonaldehyde are two important constituents of cigarette smoke which have well documented toxic effects and could play a role in lung cancer etiology. Their urinary metabolites 3-hydroxypropylmercapturic acid (3-HPMA) and 3-hydroxy-1-methylpropylmercapturic acid (HMPMA), respectively, are validated biomarkers of acrolein and crotonaldehyde exposure. We quantified levels of 3-HPMA and HMPMA in the urine of more than 2200 smokers from these five ethnic groups, and also carried out a genome wide association study using blood samples from these subjects. After adjusting for age, sex, creatinine, and total nicotine equivalents, geometric mean levels of 3-HPMA and HMPMA were significantly different in the five groups (P<0.0001). Native Hawaiians had the highest and Latinos the lowest geometric mean levels of both 3-HPMA and HMPMA. Levels of 3-HPMA and HMPMA were 3787 and 2759 pmol/ml urine, respectively, in Native Hawaiians and 1720 and 2210 pmol/ml urine in Latinos. These results suggest that acrolein and crotonaldehyde may be involved in lung cancer etiology, and that their divergent levels may partially explain the differing risks of Native Hawaiian and Latino smokers. No strong signals were associated with 3-HPMA in the genome wide association study, suggesting that formation of the glutathione conjugate of acrolein is mainly non-enzymatic, while the top significant association with HMPMA was located on chromosome 12 near the TBX3 gene, but its relationship to HMPMA excretion is not clear. PMID:26053186

  10. Mercapturic Acids Derived from the Toxicants Acrolein and Crotonaldehyde in the Urine of Cigarette Smokers from Five Ethnic Groups with Differing Risks for Lung Cancer.

    PubMed

    Park, Sungshim L; Carmella, Steven G; Chen, Menglan; Patel, Yesha; Stram, Daniel O; Haiman, Christopher A; Le Marchand, Loic; Hecht, Stephen S

    2015-01-01

    The Multiethnic Cohort epidemiology study has clearly demonstrated that, compared to Whites and for the same number of cigarettes smoked, African Americans and Native Hawaiians have a higher risk for lung cancer whereas Latinos and Japanese Americans have a lower risk. Acrolein and crotonaldehyde are two important constituents of cigarette smoke which have well documented toxic effects and could play a role in lung cancer etiology. Their urinary metabolites 3-hydroxypropylmercapturic acid (3-HPMA) and 3-hydroxy-1-methylpropylmercapturic acid (HMPMA), respectively, are validated biomarkers of acrolein and crotonaldehyde exposure. We quantified levels of 3-HPMA and HMPMA in the urine of more than 2200 smokers from these five ethnic groups, and also carried out a genome wide association study using blood samples from these subjects. After adjusting for age, sex, creatinine, and total nicotine equivalents, geometric mean levels of 3-HPMA and HMPMA were significantly different in the five groups (P < 0.0001). Native Hawaiians had the highest and Latinos the lowest geometric mean levels of both 3-HPMA and HMPMA. Levels of 3-HPMA and HMPMA were 3787 and 2759 pmol/ml urine, respectively, in Native Hawaiians and 1720 and 2210 pmol/ml urine in Latinos. These results suggest that acrolein and crotonaldehyde may be involved in lung cancer etiology, and that their divergent levels may partially explain the differing risks of Native Hawaiian and Latino smokers. No strong signals were associated with 3-HPMA in the genome wide association study, suggesting that formation of the glutathione conjugate of acrolein is mainly non-enzymatic, while the top significant association with HMPMA was located on chromosome 12 near the TBX3 gene, but its relationship to HMPMA excretion is not clear. PMID:26053186

  11. Sample storage-induced changes in the quantity and quality of soil labile organic carbon

    PubMed Central

    Sun, Shou-Qin; Cai, Hui-Ying; Chang, Scott X.; Bhatti, Jagtar S.

    2015-01-01

    Effects of sample storage methods on the quantity and quality of labile soil organic carbon are not fully understood even though their effects on basic soil properties have been extensively studied. We studied the effects of air-drying and frozen storage on cold and hot water soluble organic carbon (WSOC). Cold- and hot-WSOC in air-dried and frozen-stored soils were linearly correlated with those in fresh soils, indicating that storage proportionally altered the extractability of soil organic carbon. Air-drying but not frozen storage increased the concentrations of cold-WSOC and carbohydrate in cold-WSOC, while both increased polyphenol concentrations. In contrast, only polyphenol concentration in hot-WSOC was increased by air-drying and frozen storage, suggesting that hot-WSOC was less affected by sample storage. The biodegradability of cold- but not hot-WSOC was increased by air-drying, while both air-drying and frozen storage increased humification index and changed specific UV absorbance of both cold- and hot-WSOC, indicating shifts in the quality of soil WSOC. Our results suggest that storage methods affect the quantity and quality of WSOC but not comparisons between samples, frozen storage is better than air-drying if samples have to be stored, and storage should be avoided whenever possible when studying the quantity and quality of both cold- and hot-WSOC. PMID:26617054

  12. Isolation and evolution of labile sulfur allotropes via kinetic encapsulation in interactive porous networks.

    PubMed

    Kitagawa, Hakuba; Ohtsu, Hiroyoshi; Cruz-Cabeza, Aurora J; Kawano, Masaki

    2016-07-01

    The isolation and characterization of small sulfur allotropes have long remained unachievable because of their extreme lability. This study reports the first direct observation of disulfur (S2) with X-ray crystallography. Sulfur gas was kinetically trapped and frozen into the pores of two Cu-based porous coordination networks containing interactive iodide sites. Stabilization of S2 was achieved either through physisorption or chemisorption on iodide anions. One of the networks displayed shape selectivity for linear molecules only, therefore S2 was trapped and remained stable within the material at room temperature and higher. In the second network, however, the S2 molecules reacted further to produce bent-S3 species as the temperature was increased. Following the thermal evolution of the S2 species in this network using X-ray diffraction and Raman spectroscopy unveiled the generation of a new reaction intermediate never observed before, the cyclo-tri-sulfur dication (cyclo-S3 (2+)). It is envisaged that kinetic guest trapping in interactive crystalline porous networks will be a promising method to investigate transient chemical species. PMID:27437110

  13. GM1 erythroimmunoassay for detection and titration of Escherichia coli heat-labile enterotoxin.

    PubMed

    Germani, Y; Bégaud, E; Guesdon, J L; Moreau, J P

    1986-11-01

    A GM1 ganglioside erythroimmunoassay for the detection of heat-labile Escherichia coli enterotoxin (LT) was developed for use in poorly equipped laboratories in developing countries. This assay is based on the immunological similarity between Vibrio cholerae toxin and LT and uses cholera toxin antiserum and sheep anti-rabbit immunoglobulin covalently coupled to sheep erythrocytes as conjugate. This assay has the following advantages over other currently available techniques: the reagents it uses are stable, in particular, tanned and sensitized sheep erythrocytes; GM1 ganglioside is commercially available; erythro-adsorption can be read with the naked eye; the test can be completed in 1 day; and as little as 4 ng of V. cholerae toxin or LT per ml can be detected accurately. The GM1 ganglioside erythroimmunoassay showed good quantitative and qualitative correlation with the Vero cell assay and the conventional GM1 enzyme-linked immunosorbent assay. The GM1 ganglioside erythroimmunoassay was somewhat less sensitive than the GM1 enzyme-linked immunosorbent assay but more sensitive than the Vero cell assay. Results obtained for 12 LT-positive and 138 LT-negative E. coli strains correlated with results obtained with GM1 enzyme-linked immunosorbent and Vero cell assays. PMID:3533985

  14. Heat-labile enterotoxin of Escherichia coli promotes intestinal colonization of Salmonella enterica.

    PubMed

    Verbrugghe, Elin; Van Parys, Alexander; Leyman, Bregje; Boyen, Filip; Arnouts, Sven; Lundberg, Urban; Ducatelle, Richard; Van den Broeck, Wim; Yekta, Maryam Atef; Cox, Eric; Haesebrouck, Freddy; Pasmans, Frank

    2015-12-01

    Enterotoxigenic Escherichia coli (ETEC) is an important cause of infantile and travellers' diarrhoea, which poses a serious health burden, especially in developing countries. In addition, ETEC bacteria are a major cause of illness and death in neonatal and recently weaned pigs. The production of a heat-labile enterotoxin (LT) promotes the colonization and pathogenicity of ETEC and may exacerbate co-infections with other enteric pathogens such as Salmonella enterica. We showed that the intraintestinal presence of LT dramatically increased the intestinal Salmonella Typhimurium load in experimentally inoculated pigs. This could not be explained by direct alteration of the invasion or survival capacity of Salmonella in enterocytes, in vitro. However, we demonstrated that LT affects the enteric mucus layer composition in a mucus-secreting goblet cell line by significantly decreasing the expression of mucin 4. The current results show that LT alters the intestinal mucus composition and aggravates a Salmonella Typhimurium infection, which may result in the exacerbation of the diarrhoeal illness. PMID:26616654

  15. Uncaria tomentosa (Willd. ex. Roem. & Schult.) DC. and Eucalyptus globulus Labill. interactions when administered with diazepam.

    PubMed

    Quílez, A M; Saenz, M T; García, M D

    2012-03-01

    The safety of natural drugs is defined by their side effects and toxicity as well as any interactions that may occur if taken together with other drugs. In particular, it is essential to identify synergies, antagonisms and other types of interference with other drugs so that the correct choice can be made from the range of phytomedicines available. The aim of this work was to investigate changes in the pharmacological effect of diazepam (2 mg/kg) on the CNS when administered together with a medicinal plant: Eucalyptus globulus Labill. (eucalyptus 6 mg/kg and 3.25 mg/kg) or Uncaria tomentosa (Willd. ex Roem. & Schult). DC. (cat's claw, 7.14 mg/kg and 3.54 mg/kg). Various different psychopharmacological effects were evaluated through assessing exploratory behavior, muscle relaxation and spontaneous motor activity. Both phytodrugs interacted with the benzodiazepine. Eucalyptus had an inhibitory effect at both doses and could be useful at the highest dose in cases where the desired effect of the depressant is moderate anxiolytic activity without marked muscle relaxation. Cat's claw, at both doses, enhanced the action of diazepam on spontaneous motor activity and, at the lowest dose, exploratory ability. These herbal drugs could be useful for their antiinflammatory activity in musculoskeletal pathologies treated with benzodiazepines. PMID:21928376

  16. Assessing the labile arsenic pool in contaminated paddy soils by isotopic dilution techniques and simple extractions.

    PubMed

    Stroud, Jacqueline L; Khan, M Asaduzzman; Norton, Gareth J; Islam, M Rafiqul; Dasgupta, Tapash; Zhu, Yong-Guan; Price, Adam H; Meharg, Andrew A; McGrath, Steve P; Zhao, Fang-Jie

    2011-05-15

    Arsenic (As) contamination of paddy soils threatens rice cultivation and the health of populations relying on rice as a staple crop. In the present study, isotopic dilution techniques were used to determine the chemically labile (E value) and phytoavailable (L value) pools of As in a range of paddy soils from Bangladesh, India, and China and two arable soils from the UK varying in the degree and sources of As contamination. The E value accounted for 6.2-21.4% of the total As, suggesting that a large proportion of soil As is chemically nonlabile. L values measured with rice grown under anaerobic conditions were generally larger than those under aerobic conditions, indicating increased potentially phytoavailable pool of As in flooded soils. In an incubation study, As was mobilized into soil pore water mainly as arsenite under flooded conditions, with Bangladeshi soils contaminated by irrigation of groundwater showing a greater potential of As mobilization than other soils. Arsenic mobilization was best predicted by phosphate-extractable As in the soils. PMID:21504212

  17. Dissolved organic carbon lability and stable isotope shifts during microbial decomposition in a tropical river system

    NASA Astrophysics Data System (ADS)

    Geeraert, N.; Omengo, F. O.; Govers, G.; Bouillon, S.

    2016-01-01

    A significant amount of carbon is transported to the ocean as dissolved organic carbon (DOC) in rivers. During transport, it can be transformed through microbial consumption and photochemical oxidation. In dark incubation experiments with water from the Tana River, Kenya, we examined the consumption of DOC through microbial decomposition and the associated change in its carbon stable isotope composition (δ13C). In 15 of the 18 incubations, DOC concentrations decreased significantly by 10 to 60 %, with most of the decomposition taking place within the first 24-48 h. After 8 days, the remaining DOC was up to 3 ‰ more depleted in 13C compared with the initial pool, and the change in δ13C correlated strongly with the fraction of DOC remaining. We hypothesize that the shift in δ13C is consistent with greater microbial lability of DOC originating from herbaceous C4 vegetation than DOC derived from woody C3 vegetation in the semi-arid lower Tana. The results complement earlier findings that the stable isotope concentration of riverine DOC does not necessarily reflect the proportion of C3 and C4-derived DOC in the catchment: besides spatial distribution patterns of different vegetation types, processing within the river can further influence the δ13C of riverine OC.

  18. An improved high pressure freezing and freeze substitution method to preserve the labile vaccinia virus nucleocapsid.

    PubMed

    Jesus, Desyree Murta; Moussatche, Nissin; Condit, Richard C

    2016-07-01

    In recent years, high pressure freezing and freeze substitution have been widely used for electron microscopy to reveal viral and cellular structures that are difficult to preserve. Vaccinia virus, a member of the Poxviridae family, presents one of the most complex viral structures. The classical view of vaccinia virus structure consists of an envelope surrounding a biconcave core, with a lateral body in each concavity of the core. This classical view was challenged by Peters and Muller (1963), who demonstrated the presence of a folded tubular structure inside the virus core and stated the difficulty in visualizing this structure, possibly because it is labile and cannot be preserved by conventional sample preparation. Therefore, this tubular structure, now called the nucleocapsid, has been mostly neglected over the years. Earlier studies were able to preserve the nucleocapsid, but with low efficiency. In this study, we report the protocol (and troubleshooting) that resulted in preservation of the highest numbers of nucleocapsids in several independent preparations. Using this protocol, we were able to demonstrate an interdependence between the formation of the virus core wall and the nucleocapsid, leading to the hypothesis that an interaction exists between the major protein constituents of these compartments, A3 (core wall) and L4 (nucleocapsid). Our results show that high pressure freezing and freeze substitution can be used in more in-depth studies concerning the nucleocapsid structure and function. PMID:27155322

  19. An intermetallic Au24Ag20 superatom nanocluster stabilized by labile ligands.

    PubMed

    Wang, Yu; Su, Haifeng; Xu, Chaofa; Li, Gang; Gell, Lars; Lin, Shuichao; Tang, Zichao; Häkkinen, Hannu; Zheng, Nanfeng

    2015-04-01

    An intermetallic nanocluster containing 44 metal atoms, Au24Ag20(2-SPy)4(PhC≡C)20Cl2, was successfully synthesized and structurally characterized by single-crystal analysis and density funtional theory computations. The 44 metal atoms in the cluster are arranged as a concentric three-shell Au12@Ag20@Au12 Keplerate structure having a high symmetry. For the first time, the co-presence of three different types of anionic ligands (i.e., phenylalkynyl, 2-pyridylthiolate, and chloride) was revealed on the surface of metal nanoclusters. Similar to thiolates, alkynyls bind linearly to surface Au atoms using their σ-bonds, leading to the formation of two types of surface staple units (PhC≡C-Au-L, L = PhC≡C(-) or 2-pyridylthiolate) on the cluster. The co-presence of three different surface ligands allows the site-specific surface and functional modification of the cluster. The lability of PhC≡C(-) ligands on the cluster was demonstrated, making it possible to keep the metal core intact while removing partial surface capping. Moreover, it was found that ligand exchange on the cluster occurs easily to offer various derivatives with the same metal core but different surface functionality and thus different solubility. PMID:25803406

  20. Thermodynamic N-donor trans influence in labile pseudo-octahedral zinc complexes: a delusion?

    PubMed

    Aboshyan-Sorgho, Lilit; Lathion, Timothée; Guénée, Laure; Besnard, Céline; Piguet, Claude

    2014-12-15

    While the forces responsible for the chelate effect are well-established in coordination chemistry, the origin and implementation of the related thermodynamic trans influence remains debatable. This work illustrates a simple approach for quantifying this effect in labile pseudo-octahedral [Zn(Lk)3](2+) complexes lacking stereochemical preferences (Lk = L1–L4 are unsymmetrical didentate α,α′-diimine ligands). In line with statistics, the triply degenerated meridional isomers mer-[Zn(Lk)3](2+) are stabilized by 0.8 ≤ ΔGexch(mer→fac) ≤ 4.2 kJ/mol over their nondegenerated facial analogues fac-[Zn(Lk)3](2+) and therefore display no apparent trans influence at room temperature. However, the dissection of the free energy terms into opposite enthalpic (favoring the facial isomers) and entropic (favoring the meridional isomers) contributions reveals a trans influence assigned to solvation processes occurring in polar solvents. Altogether, the thermodynamic trans influence operating in [Zn(α,α′-diimine)3](2+) complexes is 1–2 orders of magnitude smaller than the chelate effect. A weak templating effect provided by a noncovalent lanthanide tripod is thus large enough to produce the wanted facial isomer at room temperature. PMID:25407515

  1. Isolation and evolution of labile sulfur allotropes via kinetic encapsulation in interactive porous networks

    PubMed Central

    Kitagawa, Hakuba; Ohtsu, Hiroyoshi; Cruz-Cabeza, Aurora J.; Kawano, Masaki

    2016-01-01

    The isolation and characterization of small sulfur allotropes have long remained unachievable because of their extreme lability. This study reports the first direct observation of disulfur (S2) with X-ray crystallography. Sulfur gas was kinetically trapped and frozen into the pores of two Cu-based porous coordination networks containing interactive iodide sites. Stabilization of S2 was achieved either through physisorption or chemisorption on iodide anions. One of the networks displayed shape selectivity for linear molecules only, therefore S2 was trapped and remained stable within the material at room temperature and higher. In the second network, however, the S2 molecules reacted further to produce bent-S3 species as the temperature was increased. Following the thermal evolution of the S2 species in this network using X-ray diffraction and Raman spectroscopy unveiled the generation of a new reaction intermediate never observed before, the cyclo-tri­sulfur dication (cyclo-S3 2+). It is envisaged that kinetic guest trapping in interactive crystalline porous networks will be a promising method to investigate transient chemical species. PMID:27437110

  2. Moist-heat sterilization and the chemical stability of heat-labile parenteral solutions.

    PubMed

    Li, L C; Parasrampuria, J; Bommireddi, A; Pec, E; Dudleston, A; Mayoral, J

    1998-01-01

    The impact of moist-heat sterilization (autoclaving) on the chemical stability of parenteral solutions was examined using two heat-labile products, clindamycin phosphate and succinylcholine chloride injections, as examples. A nonisothermal kinetic model was used to predict the extent of product degradation during autoclaving. The predicted results were found to be in close agreement with the experimental data. For the same peak temperature, a greater loss of product was shown by using a cycle with a higher F0. On the other hand, a higher peak-temperature cycle resulted in less product degradation for the same F0 value. The benefit of a high-temperature cycle was further illustrated by the fact that less chemical degradation for both products was produced by a 122 degrees C cycle with an F0 of 11 as compared to that which occurred during a 116.5 degrees C cycle with an F0 of 8. Although clindamycin phosphate was found to be highly unstable during a conventional autoclaving process, predicted data indicate that a UHT (Ultra-High Temperature) process may be used to sterilize this product with acceptable degradation. PMID:15605602

  3. Oxidation-labile subfraction of human plasma low density lipoprotein isolated by ion-exchange chromatography.

    PubMed

    Shimano, H; Yamada, N; Ishibashi, S; Mokuno, H; Mori, N; Gotoda, T; Harada, K; Akanuma, Y; Murase, T; Yazaki, Y

    1991-05-01

    We isolated subfractions of human plasma low density lipoprotein (LDL) using ion-exchange chromatography. Plasma LDL from normolipidemic subjects were applied to a DEAE Sepharose 6B column. After elution of the bulk of LDL at 150 mM NaCl (the major fraction), the residual LDL was eluted at 500 mM NaCl and designated as the minor fraction. The minor fraction, only less than 1% of total LDL, tended to be somewhat similar in certain properties to oxidized LDL, e.g., an increased negative charge, higher protein/cholesterol ratio, and a higher flotation density than native LDL. These results were consistent with data reported by Avogaro et al. (1988. Arteriosclerosis. 8: 79-87). However, assays of 125I-labeled LDL binding activity for LDL receptors equal to that of the major fraction. Incorporation of [14C]oleate into cholesteryl ester [acyl-CoA:cholesterol acyltransferase (ACAT) activity] in mouse peritoneal macrophages incubated with the minor fraction was only slightly greater than that with the major fraction. Incubation of the minor fraction with 0.5 microM Cu2+ caused a remarkable stimulation of ACAT activity, while stimulation by the major fraction required incubation with 5 microM Cu2+, suggesting that the minor fraction was relatively labile to oxidation. The minor but definite presence of a plasma LDL subfraction more negative and susceptible to oxidation implicates the possibility of its association with atherogenesis. PMID:2072039

  4. Sample storage-induced changes in the quantity and quality of soil labile organic carbon.

    PubMed

    Sun, Shou-Qin; Cai, Hui-Ying; Chang, Scott X; Bhatti, Jagtar S

    2015-01-01

    Effects of sample storage methods on the quantity and quality of labile soil organic carbon are not fully understood even though their effects on basic soil properties have been extensively studied. We studied the effects of air-drying and frozen storage on cold and hot water soluble organic carbon (WSOC). Cold- and hot-WSOC in air-dried and frozen-stored soils were linearly correlated with those in fresh soils, indicating that storage proportionally altered the extractability of soil organic carbon. Air-drying but not frozen storage increased the concentrations of cold-WSOC and carbohydrate in cold-WSOC, while both increased polyphenol concentrations. In contrast, only polyphenol concentration in hot-WSOC was increased by air-drying and frozen storage, suggesting that hot-WSOC was less affected by sample storage. The biodegradability of cold- but not hot-WSOC was increased by air-drying, while both air-drying and frozen storage increased humification index and changed specific UV absorbance of both cold- and hot-WSOC, indicating shifts in the quality of soil WSOC. Our results suggest that storage methods affect the quantity and quality of WSOC but not comparisons between samples, frozen storage is better than air-drying if samples have to be stored, and storage should be avoided whenever possible when studying the quantity and quality of both cold- and hot-WSOC. PMID:26617054

  5. [Evaluation of the actual traceability of labile blood products using medical records].

    PubMed

    Ingrand, P; Salmi, L R; Benz-Lemoine, E; Dupuis, M

    1998-12-01

    The traceability of blood products is an essential part of haemovigilance and transfusion safety. A pilot survey assessed the actual traceability by analysing transfusion information collected from medical records of a representative sample of 390 labile blood products transfused in a French university hospital. Transfusion and distribution forms were missing in 2.3% and 6.9% respectively. Availability and validity of transfusion information varied according to the nature of the expected information, elements of patients' records and types of wards. The location where the transfusion was performed was false or ambiguous in 38% of cases in surgery. Crude traceability, evaluated by the feedback of validated distribution forms, was estimated at 85.2% whereas actual traceability was estimated at 81.9% (SD 1.7%). High availability (98.7%) of at least one of the two sheets of the distribution form in medical records, or in the blood bank, revealed that a significant improvement of traceability should come from a better compliance to the rules of information transmission. The actual traceability differed significantly according to clinical services (worse in surgery) and was lower in case of autologous or absence of previous transfusion. An analysis of markers of good traceability should suggest efficient evolution of organization and information systems. This pilot study shows the relevance and feasibility of this kind of survey which could interestingly be performed on a large national representative random sample. PMID:9894331

  6. Sample storage-induced changes in the quantity and quality of soil labile organic carbon

    NASA Astrophysics Data System (ADS)

    Sun, Shou-Qin; Cai, Hui-Ying; Chang, Scott X.; Bhatti, Jagtar S.

    2015-11-01

    Effects of sample storage methods on the quantity and quality of labile soil organic carbon are not fully understood even though their effects on basic soil properties have been extensively studied. We studied the effects of air-drying and frozen storage on cold and hot water soluble organic carbon (WSOC). Cold- and hot-WSOC in air-dried and frozen-stored soils were linearly correlated with those in fresh soils, indicating that storage proportionally altered the extractability of soil organic carbon. Air-drying but not frozen storage increased the concentrations of cold-WSOC and carbohydrate in cold-WSOC, while both increased polyphenol concentrations. In contrast, only polyphenol concentration in hot-WSOC was increased by air-drying and frozen storage, suggesting that hot-WSOC was less affected by sample storage. The biodegradability of cold- but not hot-WSOC was increased by air-drying, while both air-drying and frozen storage increased humification index and changed specific UV absorbance of both cold- and hot-WSOC, indicating shifts in the quality of soil WSOC. Our results suggest that storage methods affect the quantity and quality of WSOC but not comparisons between samples, frozen storage is better than air-drying if samples have to be stored, and storage should be avoided whenever possible when studying the quantity and quality of both cold- and hot-WSOC.

  7. Anger induced by interferon-alpha is moderated by ratio of arachidonic acid to omega-3 fatty acids

    PubMed Central

    Lotrich, Francis E.; Sears, Barry; McNamara, Robert K.

    2013-01-01

    Objective Anger worsens in some patients during interferon-alpha (IFN-α) therapy. Elevated anger has also been associated with lower long-chain omega-3 (LCn-3) fatty acid levels. We examined whether fatty acids could influence vulnerability to anger during IFN-α exposure. Methods Plasma arachidonic acid (AA), eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA) levels were determined prior to IFN-α therapy by mass spectroscopy. Repeated-measure analyses examined the relationship between AA/EPA+DHA and the subsequent development of labile anger and irritability in 82 subjects who prospectively completed the Anger, Irritability, and Assault Questionnaire (AIAQ) during the first eight weeks of IFN-α therapy. Results Prior to IFN-α therapy, AA/EPA+DHA did not correlate with either labile anger or irritability. Pre-treatment AA/EPA+DHA did correlate with the subsequent maximal increase in labile anger during IFN-α therapy (r=0.33; p=0.005). Over time, labile anger increased more in subjects with above median AA/EPA+DHA ratios (p<0.05). Of the 17 subjects ultimately requiring psychiatric intervention for anger, 14/17 had above-median AA/EPA+DHA ratios (p=0.009). There was also an interaction with the tumor necrosis factor-alpha (TNF-α) promoter polymorphism (A-308G), such that only those with both elevated AA/EPA+DHA and the A allele had increased labile anger (p=0.001). In an additional 18 subjects, we conversely observed that selective serotonin reuptake inhibitor treatment was associated with increased irritability during IFN-α therapy. Conclusion LCn-3 fatty acid status may influence anger development during exposure to elevated inflammatory cytokines, and may interact with genetic risk for increased brain TNF-α. LCn-3 supplements may be one strategy for minimizing this adverse side effect of IFN-α. PMID:24182638

  8. DGT-labile As, Cd, Cu and Ni monitoring in freshwater: toward a framework for interpretation of in situ deployment.

    PubMed

    Buzier, Rémy; Charriau, Adeline; Corona, David; Lenain, Jean-François; Fondanèche, Patrice; Joussein, Emmanuel; Poulier, Gaëlle; Lissalde, Sophie; Mazzella, Nicolas; Guibaud, Gilles

    2014-09-01

    The use of the Diffusive Gradient in Thin Film sampler (DGT) as a monitoring tool for regulatory programs is currently evaluated. In this context, the impact of commonly followed procedures on the accuracy of DGT-labile As, Cd, Cu, and Ni quantification was studied. Initial sampler contamination yields to define quantification limits instead of using blank subtraction, thus avoiding artifact concentrations. Not considering the alteration of element diffusion by the filter membrane leads to significant underestimation. However, diffusion coefficients determined on a non-fouled membrane were found to be suitable for the studied site, making it possible to use data from the literature. When diffusive boundary layer formation is neglected, no loss of accuracy is recorded provided the layer is thinner than 0.5 mm. Finally, exploration of potential biases allowed initiating a framework that might help limit inaccuracies in DGT-labile concentration estimation and interpretation, especially in a low contamination context. PMID:24886969

  9. Encapsulation of microbiologically labile compounds within macromolecular organic matter in sedimentary systems as a means of preservation

    SciTech Connect

    Hatcher, P.G.; Knicker, H.; Rio, J.C. del

    1996-12-31

    The preservation of microbiologically labile organic compounds in the sedimentary geological record for times that are longer than what would be expected is a phenomenon recently touted as being due to physical entrapment within mesopores of mineral particles. Presumably, the mesopores offer protection from the action of microbial enzymes. Our recent studies of the preservation of organic compounds in mineral-free sediments indicates that protection from the action of enzymes can also be afforded by encapsulation within macromolecular organic matter, especially if this organic matter is strongly hydrophobic. The basis of this conclusion centers upon the observation that labile proteinaceous materials survive in these sediments for extended periods of time as deduced by solid-state {sup 15}N NMR and thermochemolysis with tetramethylammonium hydroxide.

  10. Mutants of Escherichia coli heat-labile toxin lacking ADP-ribosyltransferase activity act as nontoxic, mucosal adjuvants.

    PubMed

    Douce, G; Turcotte, C; Cropley, I; Roberts, M; Pizza, M; Domenghini, M; Rappuoli, R; Dougan, G

    1995-02-28

    A nontoxic mutant (LTK7) of the Escherichia coli heat-labile enterotoxin (LT) lacking ADP-ribosylating activity but retaining holotoxin formation was constructed. By using site-directed mutagenesis, the arginine at position 7 of the A subunit was replaced with lysine. This molecule, which was nontoxic in several assays, was able to bind to eukaryotic cells and acted as a mucosal adjuvant for co-administered proteins; BALB/c mice immunized intranasally with LTK7 and ovalbumin developed high levels of serum and local antibodies to ovalbumin and toxin. In addition, mice immunized intranasally with fragment C of tetanus toxin and LTK7 were protected against lethal challenge with tetanus toxin. Thus nontoxic mutants of heat-labile toxin can act as effective intranasal mucosal adjuvants. PMID:7878032

  11. Analysis of Phosphorus in Soil Humic Acid Fractions by Enzymatic Hydrolysis and Ultraviolet Irradiation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Humic acid is an important soil component which influences chemical, biological, and physical soil properties. In this study, we investigated lability of phosphorus (P) in the mobile humic acid (MHA) and calcium humate (CaHA) fractions of four soils by orthophosphate-releasing enzymatic hydrolysis a...

  12. Orientation preferences of backbone secondary amide functional groups in peptide nucleic acid complexes: quantum chemical calculations reveal an intrinsic preference of cationic D-amino acid-based chiral PNA analogues for the P-form.

    PubMed

    Topham, Christopher M; Smith, Jeremy C

    2007-02-01

    Geometric descriptions of nonideal interresidue hydrogen bonding and backbone-base water bridging in the minor groove are established in terms of polyamide backbone carbonyl group orientation from analyses of residue junction conformers in experimentally determined peptide nucleic acid (PNA) complexes. Two types of interresidue hydrogen bonding are identified in PNA conformers in heteroduplexes with nucleic acids that adopt A-like basepair stacking. Quantum chemical calculations on the binding of a water molecule to an O2 base atom in glycine-based PNA thymine dimers indicate that junctions modeled with P-form backbone conformations are lower in energy than a dimer comprising the predominant conformation observed in A-like helices. It is further shown in model systems that PNA analogs based on D-lysine are better able to preorganize in a conformation exclusive to P-form helices than is glycine-based PNA. An intrinsic preference for this conformation is also exhibited by positively charged chiral PNA dimers carrying 3-amino-D-alanine or 4-aza-D-leucine residue units that provide for additional rigidity by side-chain hydrogen bonding to the backbone carbonyl oxygen. Structural modifications stabilizing P-form helices may obviate the need for large heterocycles to target DNA pyrimidine bases via PNA.DNA-PNA triplex formation. Quantum chemical modeling methods are used to propose candidate PNA Hoogsteen strand designs. PMID:17071666

  13. Dual, differential isotope labeling shows the preferential movement of labile plant constituents into mineral-bonded soil organic matter.

    PubMed

    Haddix, Michelle L; Paul, Eldor A; Cotrufo, M Francesca

    2016-06-01

    The formation and stabilization of soil organic matter (SOM) are major concerns in the context of global change for carbon sequestration and soil health. It is presently believed that lignin is not selectively preserved in soil and that chemically labile compounds bonding to minerals comprise a large fraction of the SOM. Labile plant inputs have been suggested to be the main precursor of the mineral-bonded SOM. Litter decomposition and SOM formation are expected to have temperature sensitivity varying with the lability of plant inputs. We tested this framework using dual (13) C and (15) N differentially labeled plant material to distinguish the metabolic and structural components within a single plant material. Big Bluestem (Andropogon gerardii) seedlings were grown in an enriched (13) C and (15) N environment and then prior to harvest, removed from the enriched environment and allowed to incorporate natural abundance (13) C-CO2 and (15) N fertilizer into the metabolic plant components. This enabled us to achieve a greater than one atom % difference in (13) C between the metabolic and structural components within the plant litter. This differentially labeled litter was incubated in soil at 15 and 35 °C, for 386 days with CO2 measured throughout the incubation. After 14, 28, 147, and 386 days of incubation, the soil was subsequently fractionated. There was no difference in temperature sensitivity of the metabolic and structural components with regard to how much was respired or in the amount of litter biomass stabilized. Only the metabolic litter component was found in the sand, silt, or clay fraction while the structural component was exclusively found in the light fraction. These results support the stabilization framework that labile plant components are the main precursor of mineral-associated organic matter. PMID:27142168

  14. Molecular Imaging of Labile Iron(II) Pools in Living Cells with a Turn-On Fluorescent Probe

    PubMed Central

    Au-Yeung, Ho Yu; Chan, Jefferson; Chantarojsiri, Teera; Chang, Christopher J.

    2013-01-01

    Iron is an essential metal for living organisms, but misregulation of its homeostasis at the cellular level can trigger detrimental oxidative and/or nitrosative stress and damage events. Motivated to help study the physiological and pathological consequences of biological iron regulation, we now report a reaction-based strategy for monitoring labile Fe2+ pools in aqueous solution and in living cells. Iron Probe 1 (IP1) exploits a bioinspired, iron-mediated oxidative C–O bond cleavage reaction to achieve a selective turn-on response to Fe2+ over a range of cellular metal ions in their bioavailable forms. We show that this first-generation chemical tool for fluorescence Fe2+ detection can visualize changes in exchangeable iron stores in living cells upon iron supplementation or depletion, including labile iron pools at endogenous, basal levels. Moreover, IP1 can be used to identify reversible expansion of labile iron pools by stimulation with vitamin C or the iron regulatory hormone hepcidin, providing a starting point for further investigations of iron signaling and stress events in living systems as well as future probe development. PMID:24063668

  15. Typing of heat-stable and heat-labile antigens of Campylobacter jejuni and Campylobacter coli by coagglutination.

    PubMed Central

    Wong, K H; Skelton, S K; Patton, C M; Feeley, J C; Morris, G

    1985-01-01

    A coagglutination system has been devised for typing heat-stable and heat-labile antigens of Campylobacter jejuni and C. coli. The use of protein A-positive Staphylococcus aureus cells carrying Campylobacter sp. serotype antibody and the treatment of Campylobacter sp. cells with DNase in the antigen suspension permitted rapid and specific coagglutination of rough (autoagglutinable) as well as smooth cultures. Cells of S. aureus were sensitized with Campylobacter sp. serotype antisera. Four to five types of sensitized S. aureus cells were pooled. A strain of Campylobacter sp. was first tested with the pools and then typed with the individual reagents of the reactive pool. After the described procedures, 68 serotype strains tested blindly as unknowns were correctly typed according to their heat-stable or heat-labile antigens. The two most commonly used typing schemes which are based separately on the heat-stable or the heat-labile antigens as assayed by passive hemagglutination and slide agglutination, respectively, can be utilized simultaneously in the coagglutination system for strain characterization. The coagglutination system is simple, yields results rapidly, conserves typing reagents, and offers the flexibility of formulating the pools of reagents according to the experimental design or the prevalence of serotypes in a geographic location. It should be a practical system for the typing of Campylobacter spp. in public health or clinical laboratories. PMID:3998098

  16. Fate of microbial nitrogen, carbon, hydrolysable amino acids, monosaccharides, and fatty acids in sediment

    NASA Astrophysics Data System (ADS)

    Veuger, Bart; van Oevelen, Dick; Middelburg, Jack J.

    2012-04-01

    The fate of microbial carbon, nitrogen, hydrolysable amino acids (HAAs), monosaccharides, and fatty acids in sediment was investigated experimentally. The microbial community of a tidal flat sediment was labeled with 13C-enriched glucose and 15N-enriched ammonium, and sediment was incubated for up to 371 days. Analysis of total concentrations and 13C- and 15N content of bulk sediment, hydrolysable amino acids (including D-alanine), monosaccharides, total fatty acids (TFAs), and phospholipid-derived fatty acids (PLFAs) allowed us to trace the fate of microbial biomass and -detritus and the major biochemical groups therein (proteins, carbohydrates, and lipids) over intermediate time scales (weeks-months). Moreover, the unidentified fraction of the labeled material (i.e. not analyzed as HAA, FA, or carbohydrate) provided information on the formation and fate of molecularly uncharacterizable organic matter. Loss of 13C and 15N from the sediment was slow (half live of 433 days) which may have been due to the permanently anoxic conditions in the experiment. Loss rates for the different biochemical groups were also low with the following order of loss rate constants: PLFA > TFA > HAA > monosaccharides. The unidentified 13C-pool was rapidly formed (within days) and then decreased relatively slowly, resulting in a gradual relative accumulation of this pool over time. Degradation and microbial reworking of the labeled material resulted in subtle, yet consistent, diagenetic changes within the different biochemical groups. In the HAA pool, glycine, lysine, and proline were lost relatively slowly (i.e. best preserved) while there was no accumulation of D-alanine relative to L-alanine, indicating no relative accumulation of bacterial macromolecules rich in D-alanine. In the fatty acid pool, there was very little difference between PLFAs and TFAs, indicating a very similar lability of these pools. Differences between individual fatty acids included a relatively slow loss of i15

  17. Comparison of a live attenuated Salmonella Enteritidis vaccine candidate secreting Escherichia coli heat-labile enterotoxin B subunit with a commercial vaccine for efficacy of protection against internal egg contamination by Salmonella in hens

    PubMed Central

    Nandre, Rahul M.; Eo, Seong Kug; Park, Sang Youel; Lee, John Hwa

    2015-01-01

    This study compared a new live attenuated Salmonella Enteritidis vaccine candidate secreting Escherichia coli heat-labile enterotoxin B subunit (SE-LTB) with a commercial Salmonella Enteritidis (SE) vaccine for efficacy of protection against SE infection in laying hens. Chickens were divided into 3 groups of 20 each. Group A chickens were inoculated orally with phosphate-buffered saline and served as controls, group B chickens were inoculated orally with the vaccine candidate, and group C chickens were inoculated intramuscularly with a commercial vaccine, the primary inoculation in groups B and C being at 10 wk of age and the booster at 16 wk. Groups B and C showed significantly higher titers of plasma immunoglobulin G, intestinal secretory immunoglobulin A, and egg yolk immunoglobulin Y antibodies compared with the control group, and both vaccinated groups showed a significantly elevated cellular immune response. After virulent challenge, group B had significantly lower production of thin-shelled and/or malformed eggs and a significantly lower rate of SE contamination of eggs compared with the control group. Furthermore, the challenge strain was detected significantly less in all of the examined organs of group B compared with the control group. Group C had lower gross lesion scores only in the spleen and had lower bacterial counts only in the spleen, ceca, and ovary. These findings indicate that vaccination with the SE-LTB vaccine candidate can efficiently reduce internal egg and internal organ contamination by Salmonella and has advantages over the commercial vaccine. PMID:26130857

  18. Type II heat-labile enterotoxins from 50 diverse Escherichia coli isolates belong almost exclusively to the LT-IIc family and may be prophage encoded.

    PubMed

    Jobling, Michael G; Holmes, Randall K

    2012-01-01

    Some enterotoxigenic Escherichia coli (ETEC) produce a type II heat-labile enterotoxin (LT-II) that activates adenylate cyclase in susceptible cells but is not neutralized by antisera against cholera toxin or type I heat-labile enterotoxin (LT-I). LT-I variants encoded by plasmids in ETEC from humans and pigs have amino acid sequences that are ≥ 95% identical. In contrast, LT-II toxins are chromosomally encoded and are much more diverse. Early studies characterized LT-IIa and LT-IIb variants, but a novel LT-IIc was reported recently. Here we characterized the LT-II encoding loci from 48 additional ETEC isolates. Two encoded LT-IIa, none encoded LT-IIb, and 46 encoded highly related variants of LT-IIc. Phylogenetic analysis indicated that the predicted LT-IIc toxins encoded by these loci could be assigned to 6 subgroups. The loci corresponding to individual toxins within each subgroup had DNA sequences that were more than 99% identical. The LT-IIc subgroups appear to have arisen by multiple recombinational events between progenitor loci encoding LT-IIc1- and LT-IIc3-like variants. All loci from representative isolates encoding the LT-IIa, LT-IIb, and each subgroup of LT-IIc enterotoxins are preceded by highly-related genes that are between 80 and 93% identical to predicted phage lysozyme genes. DNA sequences immediately following the B genes differ considerably between toxin subgroups, but all are most closely related to genomic sequences found in predicted prophages. Together these data suggest that the LT-II loci are inserted into lambdoid type prophages that may or may not be infectious. These findings raise the possibility that production of LT-II enterotoxins by ETEC may be determined by phage conversion and may be activated by induction of prophage, in a manner similar to control of production of Shiga-like toxins by converting phages in isolates of enterohemmorhagic E. coli. PMID:22242186

  19. Bipolar mass spectrometry of labile coordination complexes, redox active inorganic compounds, and proteins using a glass nebulizer for sonic-spray ionization.

    PubMed

    Antonakis, Manolis M; Tsirigotaki, Alexandra; Kanaki, Katerina; Milios, Constantinos J; Pergantis, Spiros A

    2013-08-01

    In this study, we report on the development of a novel nebulizer configuration for sonic-spray ionization (SSI) mass spectrometry (MS), more specifically for a version of SSI that is referred to as Venturi easy ambient sonic-spray ionization (V-EASI) MS. The developed nebulizer configuration is based on a commercially available pneumatic glass nebulizer that has been used extensively for aerosol formation in atomic spectrometry. In the present study, the nebulizer was modified in order to achieve efficient V-EASI-MS operation. Upon evaluating this system, it has been demonstrated that V-EASI-MS offers some distinct advantages for the analysis of coordination compounds and redox active inorganic compounds over the predominantly used electrospray ionization (ESI) technique. Such advantages, for this type of compounds, are demonstrated here for the first time. More specifically, a series of labile heptanuclear heterometallic [Cu(II) 6Ln(III)] clusters held together with artificial amino acid ligands, in addition to easily oxidized inorganic oxyanions of selenium and arsenic, were analyzed. The observed advantages pertain to V-EASI appearing to be a "milder" ionization source than ESI, not requiring electrical potentials for gas phase ion formation, thus eliminating the possibility of unwanted redox transformations, allowing for the "simultaneous" detection of negative and positive ions (bipolar analysis) without the need to change source ionization conditions, and also not requiring the use of syringes and delivery pumps. Because of such features, especially because of the absence of ionization potentials, EASI can be operated with minimal requirements for source parameter optimization. We observed that source temperature and accelerating voltage do not seem to affect labile compounds to the extent they do in ESI-MS. In addition, bipolar analysis of proteins was demonstrated here by acquiring both positive and negative ion mass spectra from the same protein solutions

  20. A pH- and thermo-responsive poly(amino acid)-based drug delivery system.

    PubMed

    Liu, Na; Li, Bingqiang; Gong, Chu; Liu, Yuan; Wang, Yanming; Wu, Guolin

    2015-12-01

    A pH- and thermo-responsive poly(amino acid)-based amphiphilic copolymer was developed, functioning as a tumour targeting drug delivery system with good biocompatibility and biodegradability. To provide multi-stimuli sensitivity characteristics to the poly(amino acid)s, the polyaspartamide scaffold has been functionalized with N,N-diisopropylamide groups via aminolysis reaction of polysuccinimide. PEG chains have also been chemically grafted to the poly(amino acid) backbone through acid-labile hydrazone linkages, providing a removable shield for the poly(amino acid) based nanoparticles. Furthermore, doxorubicin was chemically linked to the copolymer chain via hydrazone bonds, acting as the hydrophobic moiety to drive the polymeric self-assembly. Free doxorubicin molecules could be encapsulated into the self-assembled nanoparticles via hydrophobic interactions and molecular π-π stacking. The results obtained show that the drug release can be triggered by the temperature with a significantly increased release being observed under acidic conditions. The cytotoxicity behaviour of the copolymers and drug-loaded nanoparticles was investigated in vitro at varying pH values and different temperatures. In doing so, superior characteristics concerning compatibility and anti-cancer activity could be observed. PMID:26454546

  1. Conformational Switching and Nanoscale Assembly of Human Prion Protein into Polymorphic Amyloids via Structurally Labile Oligomers.

    PubMed

    Dalal, Vijit; Arya, Shruti; Bhattacharya, Mily; Mukhopadhyay, Samrat

    2015-12-29

    Conformational switching of the prion protein (PrP) from an α-helical normal cellular form (PrP(C)) to an aggregation-prone and self-propagating β-rich scrapie form (PrP(Sc)) underlies the molecular basis of pathogenesis in prion diseases. Anionic lipids play a critical role in the misfolding and conformational conversion of the membrane-anchored PrP into the amyloidogenic pathological form. In this work, we have used a diverse array of techniques to interrogate the early intermediates during amyloid formation from recombinant human PrP in the presence of a membrane mimetic anionic detergent such as sodium dodecyl sulfate. We have been able to detect and characterize two distinct types of interconvertible oligomers. Our results demonstrate that highly ordered large β-oligomers represent benign off-pathway intermediates that lack the ability to mature into amyloid fibrils. On the contrary, structurally labile small oligomers are capable of switching to an ordered amyloid-state that exhibits profound toxicity to mammalian cells. Our fluorescence resonance energy transfer measurements revealed that the partially disordered PrP serves as precursors to small amyloid-competent oligomers. These on-pathway oligomers are eventually sequestered into higher order supramolecular assemblies that conformationally mature into polymorphic amyloids possessing varied nanoscale morphology as evident by the atomic force microscopy imaging. The nanoscale diversity of fibril architecture is attributed to the heterogeneous ensemble of early obligatory oligomers and offers a plausible explanation for the existence of multiple prion strains in vivo. PMID:26645611

  2. Parenteral Adjuvant Effects of an Enterotoxigenic Escherichia coli Natural Heat-Labile Toxin Variant

    PubMed Central

    Braga, Catarina J. M.; Rodrigues, Juliana F.; Medina-Armenteros, Yordanka; Farinha-Arcieri, Luís E.; Ventura, Armando M.; Boscardin, Silvia B.; Sbrogio-Almeida, Maria E.; Ferreira, Luís C. S.

    2014-01-01

    Native type I heat-labile toxins (LTs) produced by enterotoxigenic Escherichia coli (ETEC) strains exert strong adjuvant effects on both antibody and T cell responses to soluble and particulate antigens following co-administration via mucosal routes. However, inherent enterotoxicity and neurotoxicity (following intra-nasal delivery) had reduced the interest in the use of these toxins as mucosal adjuvants. LTs can also behave as powerful and safe adjuvants following delivery via parenteral routes, particularly for activation of cytotoxic lymphocytes. In the present study, we evaluated the adjuvant effects of a new natural LT polymorphic form (LT2), after delivery via intradermal (i.d.) and subcutaneous (s.c.) routes, with regard to both antibody and T cell responses. A recombinant HIV-1 p24 protein was employed as a model antigen for determination of antigen-specific immune responses while the reference LT (LT1), produced by the ETEC H10407 strain, and a non-toxigenic LT form (LTK63) were employed as previously characterized LT types. LT-treated mice submitted to a four dose-base immunization regimen elicited similar p24-specific serum IgG responses and CD4+ T cell activation. Nonetheless, mice immunized with LT1 or LT2 induced higher numbers of antigen-specific CD8+ T cells and in vivo cytotoxic responses compared to mice immunized with the non-toxic LT derivative. These effects were correlated with stronger activation of local dendritic cell populations. In addition, mice immunized with LT1 and LT2, but not with LTK63, via s.c. or i.d. routes developed local inflammatory reactions. Altogether, the present results confirmed that the two most prevalent natural polymorphic LT variants (LT1 or LT2) display similar and strong adjuvant effects for subunit vaccines administered via i.d. or s.c. routes. PMID:24432018

  3. Labile sleep promotes awareness of abstract knowledge in a serial reaction time task

    PubMed