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Sample records for amido por meio

  1. Cobalt - poly(amido amine) superparamagnetic nanocomposites.

    PubMed

    Atwater, James E; Akse, James R; Holtsnider, John T

    2008-06-30

    Metallic cobalt-dendrimer nanocomposites were prepared using generation 5 Poly(amido amine) dendrimers with primary amino termini. Cobalt loading of ~38 atoms per dendrimer was determined by atomic absorption spectrophotometry. Magnetic properties of the cobalt-dendrimer nanocomposites were investigated across the temperature range from 2-300 K by SQUID magnetometry. Magnetization as a function of temperature and applied field strength was studied in zero field cooled samples. Magnetization-demagnetization curves (hysteresis loops) were also acquired at temperatures between 10 - 300 K. These results clearly indicate superparamagnetism for the nanocomposites with a characteristic blocking temperature of ~50 K.

  2. Cobalt - poly(amido amine) superparamagnetic nanocomposites

    PubMed Central

    Atwater, James E.; Akse, James R.; Holtsnider, John T.

    2010-01-01

    Metallic cobalt-dendrimer nanocomposites were prepared using generation 5 Poly(amido amine) dendrimers with primary amino termini. Cobalt loading of ~38 atoms per dendrimer was determined by atomic absorption spectrophotometry. Magnetic properties of the cobalt-dendrimer nanocomposites were investigated across the temperature range from 2–300 K by SQUID magnetometry. Magnetization as a function of temperature and applied field strength was studied in zero field cooled samples. Magnetization-demagnetization curves (hysteresis loops) were also acquired at temperatures between 10 – 300 K. These results clearly indicate superparamagnetism for the nanocomposites with a characteristic blocking temperature of ~50 K. PMID:20352068

  3. An Efficient Synthesis of 5-Amido-3-Hydroxy-4-Pyrones as Inhibitors of Matrix Metalloproteinases

    PubMed Central

    Yan, Yi-Long; Cohen, Seth M.

    2008-01-01

    3-Hydroxy-4-pyrones are a class of important metal chelators with versatile medicinal applications. An efficient pathway for the preparation of new 5-amido-3-hydroxy-4-pyrone derivatives has been developed. The synthesized 5-amido-3-hydroxy-4-pyrones have been evaluated as inhibitors of matrix metalloproteinases. PMID:17521196

  4. Rare-Earth Metal Postmetallocene Catalysts with Chelating Amido Ligands

    NASA Astrophysics Data System (ADS)

    Li, Tianshu; Jenter, Jelena; Roesky, Peter W.

    This review deals with the synthesis and the catalytic application of noncyclopentadienyl complexes of the rare-earth elements. The main topics of the review are amido metal complexes with chelating bidentate ligands, which show the most similarities to cyclopentadienyl ligands. Benzamidinates and guanidinates will be reviewed in a separate contribution within this book. Beside the synthesis of the complexes, the broad potential of these compounds in homogeneous catalysis is demonstrated. Most of the reviewed catalytic transformations are either C-C multiple bond transformation such as the hydroamination and hydrosilylation or polymerization reaction of polar and nonpolar monomers. In this area, butadiene and isoprene, ethylene, as well as lactides and lactones were mostly used as monomers.

  5. Catalytic transformation of esters of 1,2-azido alcohols into α-amido ketones.

    PubMed

    Kim, Yongjin; Pak, Han Kyu; Rhee, Young Ho; Park, Jaiwook

    2016-05-05

    The esters of 1,2-azido alcohols were transformed into α-amido ketones without external oxidants through the Ru-catalyzed formation of N-H imines with the liberation of N2 followed by intramolecular migration of the acyl moiety. A wide range of α-amido ketones were obtained, and one-pot transformation into the corresponding oxazoles (or a thiazole) was demonstrated.

  6. A novel chiral yttrium complex with a tridentate linked amido-indenyl ligand for intramolecular hydroamination.

    PubMed

    Chai, Zhuo; Hua, Dezhi; Li, Kui; Chu, Jiang; Yang, Gaosheng

    2014-01-07

    A new chiral silicon-linked tridentate amido-indenyl ligand was developed from indene and enantiopure 1,2-cyclohexanediamine. Its yttrium complex was synthesized, characterized and applied to efficiently catalyze the intramolecular hydroamination of non-activated olefins with up to 97% ee.

  7. Isolable zirconium hydride species in the reaction of amido complexes with amine-boranes.

    PubMed

    Greño, Maider; Mena, Miguel; Pérez-Redondo, Adrián; Yélamos, Carlos

    2017-03-22

    Mono-, di- and trinuclear zirconium hydride species have been isolated in the treatment of amido complexes [Zr(η(5)-C5Me5)(NMe2)nCl3-n] (n = 3, 1) with amine-borane adducts NHR2BH3 (R2 = Me2, HtBu). The reactions involve the formation of amidoborane ligands with ZrH-B interactions which readily undergo β-hydride elimination to give hydride functions.

  8. Intermolecular insertion of ethylene and octene into a palladium-amide bond. Spectroscopic evidence for an ethylene amido intermediate.

    PubMed

    Hanley, Patrick S; Marković, Dean; Hartwig, John F

    2010-05-12

    We report a series of palladium diarylamido complexes containing a cyclometalated phosphine ligand and a coordinated THF that form enamine products from migratory insertion of ethylene and octene into the metal-nitrogen bond. The reactions of these complexes were sensitive to the electronic properties of the diarylamido group. The complex with the more electron-donating amido ligand reacted nearly 2 orders of magnitude faster than the complex with the least electron-donating amido group. The mechanism of the reactions with alkenes involves exchange of olefin for THF, as revealed by the positive order of the reaction in alkene and inverse order in the concentration of THF. A syn-aminopalladation that would result from migratory insertion was revealed by the stereochemistry of the enamine product resulting from reaction with cis-ethylene-d(2). Finally, a three-coordinate THF-free species was isolated from a synthesis of the amido complex in aromatic solvents, and spectroscopic evidence for an ethylene amido species was gained, in part by the addition of H(2)(13)C=(13)CH(2) to the three-coordinate amido complex at -100 degrees C.

  9. Relating the structure of geminal amido esters to their molecular hyperpolarizability

    DOE PAGES

    Cole, Jacqueline M.; Lin, Tze -Chia; Ashcroft, Christopher M.; ...

    2016-12-05

    Advanced organic non-linear optical (NLO) materials have attracted increasing attention due to their multitude of applications in modern telecommunication devices. Arguably the most important advantage of organic NLO materials, relative to traditionally used inorganic NLO materials, is their short optical response time. Geminal amido esters with their donor-x-acceptor (D-π-A) architecture exhibit high levels of electron delocalization and substantial intramolecular charge transfer, which should endow these materials with short optical response times and large molecular (hyper)polarizabilities. In order to test this hypothesis, the linear and second-order non-linear optical properties of five geminal amido esters, (E)-ethyl 3-(X-phenylamino)-2-(Y-phenylcarbamoyl)acrylate (1: X = 4-H,Y =more » 4-H; 2: X= 4-CH3, Y = 4-CH3; 3: X = 4-NO2, Y = 2,5-OCH3; 4: X = 2-Cl, Y = 2-Cl; 5: X = 4-Cl, Y = 4-Cl) were synthesized and characterized, whereby NLO structure-function relationships were established including intramolecular charge transfer characteristics, crystal field effects, and molecular first hyperpolarizabilities β. Given the typically large errors (10-30%) associated with the determination of (β) coefficients, three independent methods were used: i) density functional theory, ii) hyper-Rayleigh scattering, and iii) high-resolution X-ray diffraction data analysis based on multipolar modeling of electron densities at each atom. These three methods delivered consistent values of β, and based on these results, 3 should hold the most promise for NLO applications. In conclusion, the correlation between the molecular structure of these geminal amido esters and their linear and non-linear optical properties thus provide molecular design guidelines for organic NLO materials; this leads to the ultimate goal of generating bespoke organic molecules to suit a given NLO device application.« less

  10. Relating the structure of geminal amido esters to their molecular hyperpolarizability

    SciTech Connect

    Cole, Jacqueline M.; Lin, Tze -Chia; Ashcroft, Christopher M.; Perez-Moreno, Javier; Tan, Yizhou; Venkatesan, Perumal; Higginbotham, Andrew P.; Pattison, Philip; Edwards, Alison J.; Piltz, Ross O.; Clays, Koen; Ilangovan, Andivelu

    2016-12-05

    Advanced organic non-linear optical (NLO) materials have attracted increasing attention due to their multitude of applications in modern telecommunication devices. Arguably the most important advantage of organic NLO materials, relative to traditionally used inorganic NLO materials, is their short optical response time. Geminal amido esters with their donor-x-acceptor (D-π-A) architecture exhibit high levels of electron delocalization and substantial intramolecular charge transfer, which should endow these materials with short optical response times and large molecular (hyper)polarizabilities. In order to test this hypothesis, the linear and second-order non-linear optical properties of five geminal amido esters, (E)-ethyl 3-(X-phenylamino)-2-(Y-phenylcarbamoyl)acrylate (1: X = 4-H,Y = 4-H; 2: X= 4-CH3, Y = 4-CH3; 3: X = 4-NO2, Y = 2,5-OCH3; 4: X = 2-Cl, Y = 2-Cl; 5: X = 4-Cl, Y = 4-Cl) were synthesized and characterized, whereby NLO structure-function relationships were established including intramolecular charge transfer characteristics, crystal field effects, and molecular first hyperpolarizabilities β. Given the typically large errors (10-30%) associated with the determination of (β) coefficients, three independent methods were used: i) density functional theory, ii) hyper-Rayleigh scattering, and iii) high-resolution X-ray diffraction data analysis based on multipolar modeling of electron densities at each atom. These three methods delivered consistent values of β, and based on these results, 3 should hold the most promise for NLO applications. In conclusion, the correlation between the molecular structure of these geminal amido esters and their linear and non-linear optical properties thus provide molecular design guidelines for organic NLO materials; this leads to the ultimate goal of generating bespoke organic molecules to suit a given NLO device application.

  11. Amino Azaxylylenes Photogenerated from o-Amido Imines: Photoassisted Access to Complex Spiro-Poly-Heterocycles.

    PubMed

    Mukhina, Olga A; Kuznetsov, Dmitry M; Cowger, Teresa M; Kutateladze, Andrei G

    2015-09-21

    Upon irradiation, cyclic imines containing o-amido groups are shown to produce reactive intermediates, amino azaxylylenes, which undergo intramolecular cycloadditions to tethered unsaturated pendants to yield complex N,O-heterocycles having an additional spiro-connected nitrogen heterocyclic moiety. Modular assembly of the photoprecursors allows expeditious increase of the complexity of the target poly-heterocyclic scaffolds with a minimal number of experimentally simple reaction steps. The photocyclization and subsequent postphotochemical transformations are accompanied by an increase of Lovering's fsp3 factor, thus producing unprecedented three-dimensional molecular architectures, and offering extended sampling of chemical space.

  12. Bis(amidate)bis(amido) titanium complex: a regioselective intermolecular alkyne hydroamination catalyst.

    PubMed

    Yim, Jacky C-H; Bexrud, Jason A; Ayinla, Rashidat O; Leitch, David C; Schafer, Laurel L

    2014-03-07

    An efficient and selective bis(amidate)bis(amido) titanium precatalyst for the anti-Markovnikov hydroamination of alkynes is reported. Hydroamination of terminal and internal alkynes with primary alkylamines, arylamines, and hydrazines is promoted by 5-10 mol % of Ti catalyst. Various functional groups are tolerated including esters, protected alcohols, and imines. The in situ generated complex shows comparable catalytic activity, demonstrating its synthetic versatility for benchtop application. Applications of this catalyst for the synthesis of amino alcohols and a one-pot procedure for indole synthesis are described. A mechanistic proposal that invokes turnover-limiting protonolysis is presented to rationalize the observed regioselectivities.

  13. Formation of hierarchical molecular assemblies from poly(oxypropylene)-segmented amido acids under AFM tapping.

    PubMed

    Lin, Jiang-Jen; Tsai, Wei-Cheng; Wang, Chi-He

    2007-04-10

    Molecular self-aligning of amphiphilic molecules into bundles with a constant width of 7-13 nm was observed under tapping-mode atomic force microscopy (TM-AFM). The requisite amphiphile, a poly(oxypropylene)-trimellitic amido acid sodium salt, is constituted of a symmetric amido acid structure with potential noncovalent forces of ionic charges, hydrogen bonds, pi-pi aromatic stacking, and hydrophobic interactions for intermolecular interaction. The amphiphiles are able to self-align into orderly hierarchical assemblies after simply being dissolved in water and dried under spin-coated evaporation. Under the TM-AFM tapping process, the bundles increased their length from an initial 20 to 600 nm. A sequential TM-AFM scanning and interval heating process was designed to probe the morphological transformations from the molecular bundles to lengthy strips (nearly micrometer scale) and to columns (with 5-7 nm spacing between the parallel strips). The formation of hierarchical arrays via molecular stretching, aligning, and connecting to each other was simultaneously observed and accelerated under the TM-AFM vibration energy. The molecular self-alignment caused by vibrations is envisioned to be a potential methodology for manipulating molecules into assembled templates, sensors, and optoelectronic devices.

  14. Self-assembly of amido-ended hyperbranched polyester films with a highly ordered dendritic structure.

    PubMed

    Zhang, Daohong; Xu, Zhicai; Li, Junna; Chen, Sufang; Cheng, Juan; Zhang, Aiqing; Chen, Shenghui; Miao, Menghe

    2014-09-24

    Self-assemblies fabricated from dendrimers and amphiphilic polymers have demonstrated remarkable performances and a wide range of applications. Direct self-assembly of hyperbranched polymers into highly ordered macrostructures with heat-resistance remains a big challenge due to the weak amphiphilicity of the polymers. Here, we report the self-assembly of amphiphilic amido-ended hyperbranched polyester (HTDA-2) into millimeter-size dendritic films using combined hydrogen bond interaction and solvent induction. The self-assembly process and mechanism have been studied. Hydrogen bond interaction between amido-ended groups assists the aggregation of inner and outer chains of the HTDA-2, resulting in phase separation and micelle formation. Some micelles attach to and grow on the glass substrate like seedlings. Other micelles move to the seedlings and connect with their branches via solvent induction and hydrogen bond interaction, leading to the fabrication of highly ordered crystalline dendritic films that show high heat-resistance. HTDA-2 can further self-assemble into sheet crystals on the dendritic films.

  15. 3-Amido-3-aryl-piperidines: A Novel Class of Potent, Selective, and Orally Active GlyT1 Inhibitors.

    PubMed

    Pinard, Emmanuel; Alberati, Daniela; Alvarez-Sanchez, Ruben; Brom, Virginie; Burner, Serge; Fischer, Holger; Hauser, Nicole; Kolczewski, Sabine; Lengyel, Judith; Mory, Roland; Saladin, Christian; Schulz-Gasch, Tanja; Stalder, Henri

    2014-04-10

    3-Amido-3-aryl-piperidines were discovered as a novel structural class of GlyT1 inhibitors. The structure-activity relationship, which was developed, led to the identification of highly potent compounds exhibiting excellent selectivity against the GlyT2 isoform, drug-like properties, and in vivo activity after oral administration.

  16. 3-Amido-3-aryl-piperidines: A Novel Class of Potent, Selective, and Orally Active GlyT1 Inhibitors

    PubMed Central

    2014-01-01

    3-Amido-3-aryl-piperidines were discovered as a novel structural class of GlyT1 inhibitors. The structure–activity relationship, which was developed, led to the identification of highly potent compounds exhibiting excellent selectivity against the GlyT2 isoform, drug-like properties, and in vivo activity after oral administration. PMID:24900853

  17. Highly efficient hydrophosphonylation of aldehydes and unactivated ketones catalyzed by methylene-linked pyrrolyl rare earth metal amido complexes.

    PubMed

    Zhou, Shuangliu; Wu, Zhangshuan; Rong, Jiewei; Wang, Shaowu; Yang, Gaosheng; Zhu, Xiancui; Zhang, Lijun

    2012-02-27

    A series of rare earth metal amido complexes bearing methylene-linked pyrrolyl-amido ligands were prepared through silylamine elimination reactions and displayed high catalytic activities in hydrophosphonylations of aldehydes and unactivated ketones under solvent-free conditions for liquid substrates. Treatment of [(Me(3)Si)(2)N](3)Ln(μ-Cl)Li(THF)(3) with 2-(2,6-Me(2)C(6)H(3)NHCH(2))C(4)H(3)NH (1, 1 equiv) in toluene afforded the corresponding trivalent rare earth metal amides of formula {(μ-η(5):η(1)):η(1)-2-[(2,6-Me(2)C(6)H(3))NCH(2)](C(4)H(3)N)LnN(SiMe(3))(2)}(2) [Ln=Y (2), Nd (3), Sm (4), Dy (5), Yb (6)] in moderate to good yields. All compounds were fully characterized by spectroscopic methods and elemental analyses. The yttrium complex was also characterized by (1)H NMR spectroscopic analyses. The structures of complexes 2, 3, 4, and 6 were determined by single-crystal X-ray analyses. Study of the catalytic activities of the complexes showed that these rare earth metal amido complexes were excellent catalysts for hydrophosphonylations of aldehydes and unactivated ketones. The catalyzed reactions between diethyl phosphite and aldehydes in the presence of the rare earth metal amido complexes (0.1 mol%) afforded the products in high yields (up to 99%) at room temperature in short times of 5 to 10 min. Furthermore, the catalytic addition of diethyl phosphite to unactivated ketones also afforded the products in high yields of up to 99% with employment of low loadings (0.1 to 0.5 mol%) of the rare earth metal amido complexes at room temperature in short times of 20 min. The system works well for a wide range of unactivated aliphatic, aromatic or heteroaromatic ketones, especially for substituted benzophenones, giving the corresponding α-hydroxy diaryl phosphonates in moderate to high yields.

  18. Triclosan-loaded poly(amido amine) dendrimer for simultaneous treatment and remineralization of human dentine.

    PubMed

    Zhou, Yan; Yang, Jiaojiao; Lin, Zaifu; Li, Jiyao; Liang, Kunneng; Yuan, He; Li, Sheyu; Li, Jianshu

    2014-03-01

    In order to treat dental caries of damaged dentine, triclosan-loaded carboxyl-terminated poly(amido amine) dendrimer (PAMAM-COOH) is prepared and characterized. While being incubated in artificial saliva, triclosan-loaded PAMAM-COOH formulation can induce in situ remineralization of hydroxyapatite (HA) on etched dentine, and the regenerated HA has a similar crystal structure with natural dentine. It can also release the encapsulated triclosan for a long period. The interesting drug release profiles are controlled by both dendrimer encapsulation capability and the mineralization degree, which are ideal to obtain multifunctional properties of long-term release of anti-bacterial drug for local treatment during the remineralization process. The triclosan-loaded G4-COOH provides a general strategy to cure dental caries and repair damaged dentine at the same time, which forms a potential restorative material for dental repair.

  19. Bioreducible poly(amido amine)s with different branching degrees as gene delivery vectors.

    PubMed

    Zhang, Bo; Ma, Xinpeng; Murdoch, William; Radosz, Maciej; Shen, Youqing

    2013-03-01

    Based on the knowledge that cationic polymers with different topographical structures behave differently in gene transfection process, herein, we synthesized three biodegradable poly(amido amine)s (PAAs) with the same repeating units and molecular weights except for degree of branching: linear PAA (LPAA), low-branched PAA (LBPAA), and high-branched PAA (HBPAA). We found that LBPAA could more effectively compact pDNA into positively charged nanoparticles than both HBPAA and LPAA. LBPAA polyplexes had the highest transfection efficiency among the three PAA polyplexes, and the difference in transfection efficiency is mainly attributed to the endocytosis rate. The cytotoxicity of PAAs was negligible at the transfection doses, probably due to the degradable disulfide bonds. Therefore, we could use branching as a parameter to simply tune a polymer's cellular uptake behavior and transfection efficiency.

  20. Synthesis and cytotoxicity testing of new amido-substituted triazolopyrrolo[2,1-c][1,4]benzodiazepine (PBDT) derivatives.

    PubMed

    Sorra, Kumaraswamy; Chang, Chi-Fen; Pusuluri, Srinivas; Mukkanti, Khagga; Laiu, Min-Chiau; Bao, Bo-Ying; Su, Chia-Hao; Chuang, Ta-Hsien

    2012-07-25

    A series of amido-substituted triazolopyrrolo[2,1-c][1,4]benzodiazepine (PBDT) derivatives was synthesized from isatoic anhydride, and their cytotoxicity against the MRC-5 and Mahlavu cell lines was evaluated. The results suggest that compound PBDT-7i with the meta-trifluoromethylbenzoyl substituent can selectively inhibit the growth of Mahlavu cells and has low toxicity towards MRC-5 cells.

  1. Magnetically modified sheaths of Leptothrix sp. as an adsorbent for Amido black 10B removal

    NASA Astrophysics Data System (ADS)

    Angelova, Ralitsa; Baldikova, Eva; Pospiskova, Kristyna; Safarikova, Mirka; Safarik, Ivo

    2017-04-01

    The goal of this study was to assess the biosorption of Amido black 10B dye from aqueous solutions on magnetically modified sheaths of Leptothrix sp. in a batch system. The magnetic modification of the sheaths was performed using both microwave synthesized iron oxide nano- and microparticles and perchloric acid stabilized ferrofluid. The native and both magnetically modified sheaths were characterized by SEM. Various parameters significantly affecting the adsorption process, such as pH, contact time, temperature and initial concentration, were studied in detail using the adsorbent magnetized by both methods. The highest adsorption efficiency was achieved at pH 2. The maximum adsorption capacities of both types of magnetized material at room temperature were found to be 339.2 and 286.1 mg of dye per 1 g of ferrofluid modified and microwave synthesized particles modified adsorbent, respectively. Thermodynamic study of dye adsorption revealed a spontaneous and endothermic process in the temperature range between 279.15 and 313.15 K. The data were fitted to various equilibrium and kinetic models. Experimental data matched well with the pseudo-second-order kinetics and Freundlich isotherm model. The Leptothrix sheaths have excellent efficacy for dye adsorption. This material can be used as an effective, low-cost adsorbent.

  2. Poly(amido-amine)-based hydrogels with tailored mechanical properties and degradation rates for tissue engineering.

    PubMed

    Martello, Federico; Tocchio, Alessandro; Tamplenizza, Margherita; Gerges, Irini; Pistis, Valentina; Recenti, Rossella; Bortolin, Monica; Del Fabbro, Massimo; Argentiere, Simona; Milani, Paolo; Lenardi, Cristina

    2014-03-01

    Poly(amido-amine) (PAA) hydrogels containing the 2,2-bisacrylamidoacetic acid-4-amminobutyl guanidine monomeric unit have a known ability to enhance cellular adhesion by interacting with the arginin-glycin-aspartic acid (RGD)-binding αVβ3 integrin, expressed by a wide number of cell types. Scientific interest in this class of materials has traditionally been hampered by their poor mechanical properties and restricted range of degradation rate. Here we present the design of novel biocompatible, RGD-mimic PAA-based hydrogels with wide and tunable degradation rates as well as improved mechanical and biological properties for biomedical applications. This is achieved by radical polymerization of acrylamide-terminated PAA oligomers in both the presence and absence of 2-hydroxyethylmethacrylate. The degradation rate is found to be precisely tunable by adjusting the PAA oligomer molecular weight and acrylic co-monomer concentration in the starting reaction mixture. Cell adhesion and proliferation tests on Madin-Darby canine kidney epithelial cells show that PAA-based hydrogels have the capacity to promote cell adhesion up to 200% compared to the control. Mechanical tests show higher compressive strength of acrylic chain containing hydrogels compared to traditional PAA hydrogels.

  3. Monolayers of poly(amido amine) dendrimers on mica - In situ streaming potential measurements.

    PubMed

    Michna, Aneta; Adamczyk, Zbigniew; Sofińska, Kamila; Matusik, Katarzyna

    2017-01-01

    The deposition of poly(amido amine) dendrimers on mica at various pHs was studied by the atomic force microscopy (AFM) and in situ streaming potential measurements. Bulk characteristics of dendrimers were acquired by using the dynamic light scattering (DLS) and the laser Doppler velocimetry (LDV). The hydrodynamic radius derived from DLS measurements was 5.2nm for the ionic strength of 10(-2)M and pH range 4-10. The electrophoretic mobility, the zeta potential and the number of electrokinetic charges per molecule were derived as a function of pH from the LDV measurements. It was revealed that the dendrimers are positively charged for pH up to 10. This promoted their deposition on negatively charged mica substrate whose kinetics was quantitatively evaluated by direct AFM imaging and streaming potential measurements interpreted in terms of the electrokinetic model. The desorption kinetics of dendrimers under flowing conditions from monolayers of various coverage was also studied. It was revealed that dendrimer deposition was partially reversible for pH above 5.8. The acid-base properties of the dendrimer monolayers deposited on mica were characterized.

  4. Imido-pyridine Ti(IV) compounds: synthesis of unusual imido-amido heterobimetallic derivatives.

    PubMed

    Pedrosa, Sergio; Vidal, Fernando; Lee, Lucia Myongwon; Vargas-Baca, Ignacio; Gómez-Sal, Pilar; Mosquera, Marta E G

    2015-06-28

    The reaction of lithiated picolines and [TiCl3(η(5)-C5Me5)] leads to several bridging or terminal imido compounds, each of which can be selectively formed by controlling the stoichiometry and temperature. Specifically, the dinuclear imido-bridged [TiCl(η(5)-C5Me5)(μ-NR)]2 (1a, NR = 2-imido-3-picoline; 1b, NR = 2-imido-5-picoline) species and the unusual Ti-Li imido-amido heterobimetallic complex [{Li(THF)}{Ti(η(5)-C5Me5)(NR)(NHR)2}] (2a, NR = 2-imido-3-picoline; 2b, NR = 2-imido-5-picoline) were isolated. Compounds 2 are in effect the first structurally characterized examples of titanium(IV) coordinated to terminal imido-pyridines. DFT-D calculations for 2a denote a multiple bond character between titanium and the imido ligand and a strong polarization of the electron density by the alkali cation in spite of the lack of intermetallic bonding.

  5. Guanidinylated bioresponsive poly(amido amine)s designed for intranuclear gene delivery

    PubMed Central

    Yu, Jiankun; Zhang, Jinmin; Xing, Haonan; Yang, Zhen; Cai, Cuifang; Zhang, Conglu; Zhao, Xiaoyun; Wei, Minjie; Yang, Li; Ding, Pingtian

    2016-01-01

    Guanidinylated poly(amido amine)s with multiple disulfide linkages (Gua-SS-PAAs) were designed and constructed as nonviral gene carriers. The main chains of these novel carriers were synthesized based on monomers containing guanidino groups (guanidine hydrochloride and chlorhexidine), which could avoid complicated side-chain-modification reactions while introducing the guanidino groups. The synthesized Gua-SS-PAAs polymers were characterized by 1H nuclear magnetic resonance, molecular weight, and polydispersity. Furthermore, Gua-SS-PAAs polymers were complexed with pDNA, and the properties of the complexes were determined, including entrapment efficiency, particle size, ζ-potential, atomic force microscopy images, stability, DNA complexation ability, reduction sensitivity, cytotoxicity, and transfection efficiency. The new Gua-SS-PAAs carriers exhibited higher transfection efficiency and lower cytotoxicity compared with two widely used gene delivery carriers, polyethylenimine and lipofectamine 2000. Furthermore, the relationship between the side-chain structure and morphological/biological properties was extrapolated, and the results showed that guanidine in the side chain aids in the improvement of transfection efficiency. In addition, the introduction of guanidino group might confer the new carriers with nuclear localization function compared to carriers without it. PMID:27574429

  6. Inorganic base-catalyzed formation of antivirally active N-substituted benzamides from α-amido sulfones and N-nucleophile

    PubMed Central

    2011-01-01

    Background Heteronucleophiles as well as carbanionic reagents can be used to react with α-amido sulfones, thus giving the opportunity to prepare a large array of amino derivatives. Since, novel 1,3,4-oxadiazole-2-thiol derivatives can serve as potent nucleophiles, we employed 5-subsititued phenyl-1,3,4-oxadiazole-2-thiols as the nucleophilic source of nitrogen in the reaction with α-amido sulfones. Results A series of N-substituted benzamides bearing 1,3,4-oxadiazol unit were prepared for the first time by the reaction of in situ generated protected imine from α-amido sulfones with 5-subsititued phenyl-1,3,4-oxadiazole-2-thiols as the source of nitrogen nucleophile. Some of the synthesized products displayed favourable antiviral activity against cucumber mosaic virus (CMV) in preliminary antiviral activity tests. The title compounds 5c, 5o and 5r revealed curative activity of 42.2%, 48.7% and 40.5%, respectively against CMV (inhibitory rate) compared to the commercial standard Ningnanmycin (53.4%) at 500 μg/mL. Conclusion A practical synthetic route to N-benzoyl-α-amido sulfones by the reaction of 5-subsititued phenyl-1,3,4-oxadiazole-2-thiols as the source of nitrogen nucleophiles with in situ generated protected imine from N-benzoyl-α-amido sulfones is presented. The reaction catalyzed by an inorganic base has considerable significance to exploit the potential of α-amido sulfones in organic synthesis. PMID:21545729

  7. Diels-Alder Reactions of α-Amido Acrylates with N-Cbz-1,2-dihydropyridine and Cyclopentadiene.

    PubMed

    Abas, Hossay; Frampton, Christopher S; Spivey, Alan C

    2016-10-21

    Thermal Diels-Alder reactions of α-amido acrylates with N-Cbz-1,2-dihydropyridine and cyclopentadiene have been explored to investigate the factors influencing the endo/exo selectivity. For the dihydropyridine, steric factors allowed the diastereoselectivity to be modulated to favor either endo- or exo-ester adducts. For cyclopentadiene, the endo-ester adducts were favored regardless of steric perturbation, although catalysis by bulky Lewis acids increased the proportion of exo-ester adducts in some cases. These Lewis acids were incompatible with the dihydropyridine diene as they induced its decomposition.

  8. Amido-Schiff base derivatives as colorimetric fluoride sensor: Effect of nitro substitution on the sensitivity and color change.

    PubMed

    Ghosh, Soumen; Alam, Md Akhtarul; Ganguly, Aniruddha; Guchhait, Nikhil

    2015-01-01

    A series of Schiff bases synthesized by the condensation of benzohydrazide and -NO2 substituted benzaldehyde have been used as selective fluoride ion sensor. Test paper coated with these synthetic Schiff bases (test kits) can detect fluoride ion selectively with a drastic color change and detection can be achieved by just using the naked-eye without the help of any optical instrument. Interestingly, the position of -NO2 group in the amido Schiff bases has an effect on the sensitivity as well as on the change of color of species.

  9. Preparation of polyelectrolyte complex nanoparticles of chitosan and poly(2-acry1amido-2-methylpropanesulfonic acid) for doxorubicin release.

    PubMed

    Zhang, Liping; Wang, Jie; Ni, Caihua; Zhang, Yanan; Shi, Gang

    2016-01-01

    A new kind of polyelectrolyte complex (PEC) based on cationic chitosan (CS) and anionic poly(2-acry1amido-2-methylpropanesulfonic acid) (PAMPS) was prepared using a polymer-monomer pair reaction system. Chitosan was mixed with 2-acry1amido-2-methylpropanesulfonic acid) (AMPS) in an aqueous solution, followed by polymerization of AMPS. The complex was formed by electrostatic interaction of NH3(+) groups of CS and SO3(-) groups of AMPS, leading to a formation of complex nanoparticles of CS-PAMPS. A series of nanoparticles were obtained by changing the weight ratio of CS to AMPS, the structure and properties of nanoparticles were investigated. It was observed that the nanoparticles possessed spherical morphologies with average diameters from 255 nm to 390 nm varied with compositions of the nanoparticles. The nanoparticles were used as drug vehicles for doxorubicin, displaying relative high drug loading rate and encapsulation rate. The vitro release profiles revealed that the drug release could be controlled by adjusting pH of the release media. The nanoparticles demonstrated apparent advantages such as simple preparation process, free of organic solvents, size controllable, good biodegradability and biocompatibility, and they could be potentially used in drug controlled release field.

  10. The amido-bridged zirconocene's reactivity and catalytic behavior for ethylene polymerization.

    PubMed

    Wang, Cun; van Meurs, Martin; Stubbs, Ludger P; Tay, Boon-Ying; Tan, Xiang-Jie; Aitipamula, Srinivasulu; Chacko, Jacob; Luo, He-Kuan; Wong, Pui-Kwan; Ye, Suming

    2010-01-21

    Reaction of the amido-bridged zirconium complex (CpSiMe(2)NSiMe(2)Cp)ZrCH(3) (1) (Cp = C(5)H(4)) with half an equivalent of B(C(6)F(5))(3) or Ph(3)CB(C(6)F(5))(4) afforded the binuclear zirconium complexes [(CpSiMe(2)NSiMe(2)Cp)Zr)(2)(mu-CH(3))][RB(C(6)F(5))(3)] (2a, R = CH(3), 2b, R = C(6)F(5)) with a methyl group as the bridge between the two zirconium atoms. In the presence of one equivalent of B(C(6)F(5))(3) or Ph(3)C(C(6)F(5))(4), 1 was transformed to the zwitterionic complexes [(CpSiMe(2)NSiMe(2)Cp)Zr][RB(C(6)F(5))(3)] (3a, R = CH(3), 3b, R = C(6)F(5)) which are free of a metal-bound sigma-alkyl ligand. 2b is stable with Me(3)Al while 3b combined with Me(3)Al to form a hetero-binuclear complex [(CpSiMe(2)NSiMe(2)Cp)Zr(mu-CH(3))]Al(CH(3))(2)][B(C(6)F(5))(4)] (4) as shown by NMR spectroscopy at room temperature. Treatment of 2a or 3a with an excess of Me(3)Al led to (CpSiMe(2)NSiMe(2)Cp)Zr(C(6)F(5)) (5) through a group exchange process. 2b, 3a and 5 have been characterized by X-ray diffraction studies. 2b, 2b, 3a and 3b were highly active catalysts for ethylene polymerization and copolymerization with 1-octene in the presence of trialkylaluminium, but the binuclear zirconium complexes (2a and 2b) showed higher activities than their mononuclear counterparts 3a and 3b. Polymerization activities varied with the trialkylaluminiums and increased with the trialkylaluminium concentration applied in the system. The product existed mainly in the form of Al(PE)(3) with polymeric chains, and its molecular weight and distribution were greatly influenced by the type and amount of trialkylaluminium applied in the catalytic system.

  11. Adsorption of Amido Black 10B from aqueous solutions onto Zr (IV) surface-immobilized cross-linked chitosan/bentonite composite

    NASA Astrophysics Data System (ADS)

    Zhang, Lujie; Hu, Pan; Wang, Jing; Huang, Ruihua

    2016-04-01

    Zr(IV) surface-immobilized cross-linked chitosan/bentonite composite was synthesized by immersing cross-linked chitosan/bentonite composite in zirconium oxychloride solution, and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Scanning electron microscopy techniques. The adsorption of an anionic dye, Amido Black 10B, from aqueous solution by Zr(IV) loaded cross-linked chitosan/bentonite composite was investigated as a function of loading amount of Zr(IV), adsorbent dosage, pH value of initial dye solution, and ionic strength. The removal of Amido Black 10B increased with an increase in loading amount of Zr(IV) and adsorbent dosage, but decreased with an increase in pH or ionic strength. The adsorption of AB10B onto Zr(IV) loaded cross-linked chitosan/bentonite composite was favored at lower pH values and higher temperatures. The Langmuir isotherm model fitted well with the equilibrium adsorption isotherm data and the maximum monolayer adsorption capacity was 418.4 mg/g at natural pH value and 298 K. The pseudo-second-order kinetic model well described the adsorption process of Amido Black 10B onto Zr(IV) loaded cross-linked chitosan/bentonite composite. The possible mechanisms controlling Amido Black 10B adsorption included hydrogen bonding and electrostatic interactions.

  12. Reactivity studies on [Cp'FeI]2: monomeric amido, phenoxo, and alkyl complexes.

    PubMed

    Walter, Marc D; White, Peter S

    2012-11-05

    A series of monomeric mono(cyclopentadienyl) iron amido, phenoxo, and alkyl complexes were synthesized, and their structure and reactivity are presented. The iron(II) centers in these 14VE one-legged piano stool complexes are high spin (S = 2) in solid state and solution independent of solvent. The silylamide compound [Cp'FeN(SiMe(3))(2)] (2a, Cp' = 1,2,4-(Me(3)C)(3)C(5)H(2)) is an excellent starting material for the reaction with more acidic substrates such as phenols. Sterically encumbered phenols 2,6-(Me(3)C)(2)(4-R)C(6)H(2)OH (R = H, Me, and tBu) were investigated. In all cases monomeric iron phenoxo half-sandwich complexes [Cp'FeOR'] (4-R) are initially formed. Rearrangement of 4-R to the diamagnetic oxocyclohexadienyl complex [Cp'Fe(η(5)-O═C(6)H(2)R'(2)R")] (5-R) is observed for 2,6-(Me(3)C)(2)(4-R)C(6)H(2)OH (R = H and Me) and the Gibbs free enthalpy of activation (ΔG(‡)) was determined. In contrast this rearrangement is inhibited when the 4-position is blocked by a tBu group. Removing the steric bulk from the 2,6-positions leads to the formation of a μ-phenoxo dimer, [Cp'Fe(μ-OC(6)H(3)tBu(2)-3,5)](2) (5). Density functional theory (DFT) was used to further elucidate the structure-reactivity relationship in these molecules. The one-legged piano stool anilido complex [Cp'Fe(NHC(6)H(2)tBu(3)-2,4,6)] (7) is not accessible via acid-base reaction between 2a and H(2)NC(6)H(2)tBu(3)-2,4,6, but can be prepared by conventional salt metathesis reaction from [Cp'FeI](2) and [Li(NHC(6)H(2)tBu(3)-2,4,6)(OEt(2))](2). In contrast, reaction of 2a with Ph(2)NH yields the bimetallic [Cp'Fe(N,C-κ(1),η(5)-C(6)H(5)NPh)Fe(N-κ(1)-NPh(2))Cp'] (8) which combines two iron centers in the same oxidation state (+2), but different spin-states (S = 0 and S = 2) which is reflected in very different Cp(cent)-Fe distances of 1.68 and 2.04 Å, respectively. A monomeric iron alkyl half-sandwich complex [Cp'FeCH(SiMe(3))(2)] (9) was prepared that exhibits no reactivity toward H(2), C

  13. Mixed amido-/imido-/guanidinato niobium complexes: synthesis and the effect of ligands on insertion reactions.

    PubMed

    Elorriaga, David; Carrillo-Hermosilla, Fernando; Antiñolo, Antonio; López-Solera, Isabel; Fernández-Galán, Rafael; Villaseñor, Elena

    2014-12-14

    The new monoguanidinato complexes [Nb(NMe2)2{N(2,6-(i)Pr2C6H3)}{(NR)(NR')C(NMe2)}] (R = R' = (i)Pr, 2; R = (t)Bu, R' = Et, 3) were obtained by the insertion reaction of either diisopropylcarbodiimide or 1-tert-butyl-3-ethylcarbodiimide with the triamido precursor [Nb(NMe2)3(N-2,6-(i)Pr2C6H3)] (1) bearing a bulky imido moiety. The μ-oxo derivative [{N(2,6-(i)Pr2C6H3)}{(N(i)Pr)2C(NMe2)}(NMe2)Nb]2(μ-O) (2a) was formed by an unexpected hydrolysis reaction of the amido niobium compound 2. Alternatively, monoguanidinato complexes [Nb(NMe2)2{N(2,6-(i)Pr2C6H3)}{(N(i)Pr)2C(NHR)}] (R = (i)Pr, 4, (n)Bu, 5) can be obtained by protonolysis of 1 with N,N',N''-alkylguanidines [(NH(i)Pr)2C(NR)] (R = (i)Pr, (n)Bu). Compound also reacts with either tert-butylisocyanide or 2,6-xylylisocyanide to give, by a migratory insertion reaction, the corresponding iminocarbamoyl compounds [Nb(NMe2)2{(NMe2)C=NR}{N(2,6-(i)Pr2C6H3)}] (R = (t)Bu, 6, Xy, 7). Addition of the neutral alkylguanidines to complex 6 results in a facile C-N bond cleavage at room temperature in a process directed by the formation of the stable chelate complex 4 or 5. Complex reacts with heterocumulenic CS2 to produce new imido dithiocarbamato complexes [Nb(NMe2){S2C(NMe2)}2{N(2,6-(i)Pr2C6H3)}] (8) and [Nb{S2C(NMe2)}3{N(2,6-(i)Pr2C6H3)}] (9). These complexes do not react with alkylguanines, although new mixed guanidinato dithiocarbamato complexes [Nb(NMe2){S2C(NMe2)}{(N(i)Pr)2C(NHiPr)}{N(2,6-(i)Pr2C6H3)}] (10) and [Nb{(S2C(NMe2)}2{(N(i)Pr)2C(NH(i)Pr)}{N(2,6-(i)Pr2C6H3)}] (11) can be obtained by reaction of complex 4 with one or two equivalents of CS2, respectively. All of the complexes were characterized spectroscopically and the dynamic behaviour of some of them was studied by variable-temperature NMR. The molecular structures of 2a, 3, 6 and 10 were also established by X-ray diffraction studies.

  14. Surface-functionalized hyperbranched poly(amido acid) magnetic nanocarriers for covalent immobilization of a bacterial γ-glutamyltranspeptidase.

    PubMed

    Juang, Tzong-Yuan; Kan, Shao-Ju; Chen, Yi-Yu; Tsai, Yi-Lin; Lin, Min-Guan; Lin, Long-Liu

    2014-04-22

    In this study, we synthesized water-soluble hyperbranched poly(amido acid)s (HBPAAs) featuring multiple terminal CO2H units and internal tertiary amino and amido moieties and then used them in conjunction with an in situ Fe2+/Fe3+ co-precipitation process to prepare organic/magnetic nanocarriers comprising uniformly small magnetic iron oxide nanoparticles (NP) incorporated within the globular HBPAAs. Transmission electron microscopy revealed that the HBPAA-γ-Fe2O3 NPs had dimensions of 6-11 nm, significantly smaller than those of the pristine γ-Fe2O3 (20-30 nm). Subsequently, we covalently immobilized a bacterial γ-glutamyltranspeptidase (BlGGT) upon the HBPAA-γ-Fe2O3 nanocarriers through the formation of amide linkages in the presence of a coupling agent. Magnetization curves of the HBPAA-γ-Fe2O3/BlGGT composites measured at 300 K suggested superparamagnetic characteristics, with a saturation magnetization of 52 emu g⁻¹. The loading capacity of BlGGT on the HBPAA-γ-Fe2O3 nanocarriers was 16 mg g⁻¹ support; this sample provided a 48% recovery of the initial activity. The immobilized enzyme could be recycled 10 times with 32% retention of the initial activity; it had stability comparable with that of the free enzyme during a storage period of 63 days. The covalent immobilization and stability of the enzyme and the magnetization provided by the HBPAA-γ-Fe2O3 NPs suggests that this approach could be an economical means of depositing bioactive enzymes upon nanocarriers for BlGGT-mediated bio-catalysis.

  15. Lanthanide amido complexes incorporating amino-coordinate-lithium bridged bis(indolyl) ligands: synthesis, characterization, and catalysis for hydrophosphonylation of aldehydes and aldimines.

    PubMed

    Zhu, Xiancui; Wang, Shaowu; Zhou, Shuangliu; Wei, Yun; Zhang, Lijun; Wang, Fenhua; Feng, Zhijun; Guo, Liping; Mu, Xiaolong

    2012-07-02

    Two series of new lanthanide amido complexes supported by bis(indolyl) ligands with amino-coordinate-lithium as a bridge were synthesized and characterized. The interactions of [(Me(3)Si)(2)N](3)Ln(III)(μ-Cl)Li(THF)(3) with 2 equiv of 3-(CyNHCH(2))C(8)H(5)NH in toluene produced the amino-coordinate-lithium bridged bis(indolyl) lanthanide amides [μ-{[η(1):η(1):η(1):η(1)-3-(CyNHCH(2))Ind](2)Li}Ln[N(SiMe(3))(2)](2)] (Cy = cyclohexyl, Ind = Indolyl, Ln = Sm (1), Eu (2), Dy (3), Yb (4)) in good yields. Treatment of [μ-{[η(1):η(1):η(1):η(1)-3-(CyNHCH(2))Ind](2)Li}Ln[N(SiMe(3))(2)](2)] with THF gave new lanthanide amido complexes [μ-{[η(1):η(1)-3-(CyNHCH(2))Ind](2)Li(THF)}Ln[N(SiMe(3))(2)](2)] (Ln = Eu (5), Dy (6), Yb (7)), which can be transferred to amido complexes 2, 3, and 4 by reflux the corresponding complexes in toluene. Thus, two series of rare-earth-metal amides could be reciprocally transformed easily by merely changing the solvent in the reactions. All new complexes 1-7 are fully characterized including X-ray structural determination. The catalytic activities of these new lanthanide amido complexes for hydrophosphonylation of both aromatic and aliphatic aldehydes and various substituted aldimines were explored. The results indicated that these complexes displayed a high catalytic activity for the C-P bond formation with employment of low catalyst loadings (0.1 mol % for aldehydes and 1 mol % for aldimines) under mild conditions. Thus, it provides a convenient way to prepare both α-hydroxy and α-amino phosphonates.

  16. Investigation on the reactivity of α-azidochalcones with carboxylic acids: Formation of α-amido-1,3-diketones and highly substituted 2-(trifluoromethyl)oxazoles

    PubMed Central

    Rajaguru, Kandasamy; Mariappan, Arumugam; Suresh, Rajendran; Manivannan, Periasamy

    2015-01-01

    Summary The reaction of α-azidochalcones with carboxylic acids has been investigated resulting in the formation of α-amido-1,3-diketones under microwave irradiation via in situ formation of 2H-azirine intermediates. An interesting reaction is described wherein, with trifluoroacetic acid at lower temperature, it affords highly substituted 2-(trifluoromethyl)oxazoles. These flexible transformations proceed under solvent free conditions in good to excellent yields without any catalyst. PMID:26664623

  17. A Novel Tool for Studying Auxin-Metabolism: The Inhibition of Grapevine Indole-3-Acetic Acid-Amido Synthetases by a Reaction Intermediate Analogue

    PubMed Central

    Böttcher, Christine; Dennis, Eric G.; Booker, Grant W.; Polyak, Steven W.; Boss, Paul K.; Davies, Christopher

    2012-01-01

    An important process for the regulation of auxin levels in plants is the inactivation of indole-3-acetic acid (IAA) by conjugation to amino acids. The conjugation reaction is catalysed by IAA-amido synthetases belonging to the family of GH3 proteins. Genetic approaches to study the biological significance of these enzymes have been hampered by large gene numbers and a high degree of functional redundancy. To overcome these difficulties a chemical approach based on the reaction mechanism of GH3 proteins was employed to design a small molecule inhibitor of IAA-amido synthetase activity. Adenosine-5′-[2-(1H-indol-3-yl)ethyl]phosphate (AIEP) mimics the adenylated intermediate of the IAA-conjugation reaction and was therefore proposed to compete with the binding of MgATP and IAA in the initial stages of catalysis. Two grapevine IAA-amido synthetases with different catalytic properties were chosen to test the inhibitory effects of AIEP in vitro. GH3-1 has previously been implicated in the grape berry ripening process and is restricted to two amino acid substrates, whereas GH3-6 conjugated IAA to 13 amino acids. AIEP is the most potent inhibitor of GH3 enzymes so far described and was shown to be competitive against MgATP and IAA binding to both enzymes with Ki-values 17-68-fold lower than the respective Km-values. AIEP also exhibited in vivo activity in an ex planta test system using young grape berries. Exposure to 5–20 µM of the inhibitor led to decreased levels of the common conjugate IAA-Asp and reduced the accumulation of the corresponding Asp-conjugate upon treatment with a synthetic auxin. AIEP therefore represents a novel chemical probe with which to study IAA-amido synthetase function. PMID:22649546

  18. Solvent-dependent intramolecular charge transfer dual fluorescence of p-dimethylaminobenzanilide bearing steric ortho,ortho-dimethyl substituents at amido aniline.

    PubMed

    Zhang, Xuan; Jiang, Yun-Bao

    2011-11-01

    Intramolecular charge transfer (ICT) dual fluorescence was observed in various organic solvents with p-dimethylaminobenzanilide (DMBA) derivatives bearing ortho-methyl (DMOMBA) and ortho,ortho-dimethyl (DMDMBA) substituents at amido aniline moiety. Ab initio calculation and absorption spectral data indicated that high steric hindrance was introduced by the ortho,ortho-dimethyl substitutions. It was found that, with DMDMBA, the CT emission initially shifted to the red with increasing solvent polarity from cyclohexane (CHX, 480 nm) to diethyl ether (DEE, 520 nm), similar to those of DMBA derivatives with the ortho-, meta- or para-methyl substitutions at amido aniline moiety. However, there is a characteristic blue-shift of the long wavelength emission between DEE and tetrahydrofuran (THF, 424 nm) then a bathochromic shift again in highly polar solvent acetonitrile (ACN, 484 nm). The unusual solvent-dependent CT emission was ascribed to two competitive CT channels. One is benzanilide (BA)-like CT, whose CT reaction occurs from amido aniline to benzoyl moiety in nonpolar solvent CHX and DEE; the other one is p-dimethylaminobenzamide (DMABA)-like, whose CT reaction occurs from dimethylamino to benzanilide moiety in highly polar solvent THF and ACN. These findings revealed the steric effect plays an important role in the ICT process, which may alter the properties of the electron donor and/or acceptor, but also change the reaction potential.

  19. Piano-Stool Lutetium Amido and Imido Compounds Supported by a Constrained Bis(oxazoline)cyclopentadienyl Ligand.

    PubMed

    Lampland, Nicole L; Zhu, Jing; Hovey, Megan; Jana, Barun; Ellern, Arkady; Sadow, Aaron D

    2015-07-20

    {Bo(M)Cp(tet)}Lu(CH2Ph)2 (1; Bo(M)Cp(tet) = MeC(Ox(Me2))2C5Me4; Ox(Me2) = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of Bo(M)Cp(tet)H and Lu(CH2Ph)3THF3. Compound 1 reacts with 1 or 2 equiv of H2NCH2R (R = C6H5, 1-C10H7) to give the corresponding imido complexes [{Bo(M)Cp(tet)}LuNCH2R]2 (R = C6H5 (2a), 1-C10H7 (2b)) or amido complexes {Bo(M)Cp(tet)}Lu(NHCH2R)2 (R = C6H5 (3a), 1-C10H7 (3b)). Once isolated, the imido species are insoluble in nonprotic organic solvents. Crystallographic characterization reveals dimeric [{Bo(M)Cp(tet)}LuNCH2(1-C10H7)]2 in the solid state. The reaction of 1 and NH3B(C6F5)3 affords crystallographically characterized {Bo(M)Cp(tet)}Lu{NHB(C6F5)2}C6F5. This species is proposed to form via a transient lutetium imido, which undergoes C6F5 migration to the lutetium center.

  20. Piano-stool lutetium amido and imido compounds supported by a constrained bis(oxazoline)cyclopentadienyl ligand

    DOE PAGES

    Lampland, Nicole L.; Zhu, Jing; Hovey, Megan; ...

    2015-06-25

    {BoMCptet}Lu(CH2Ph)2 (1; BoMCptet = MeC(OxMe2 2C5Me4; OxMe2 = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of BoMCptetH and Lu(CH2Ph)3THF3. Compound 1 reacts with 1 or 2 equiv of H2NCH2R (R = C6H5, 1-C10H7) to give the corresponding imido complexes [{BoMCptet}LuNCH2R]2 (R = C6H5 (2a), 1-C10H7 (2b)) or amido complexes {BoMCptet}Lu(NHCH2R)2 (R = C6H5 (3a), 1-C10H7 (3b)). When isolated, the imido species are insoluble in nonprotic organic solvents. Crystallographic characterization reveals dimeric [{BoMCptet}LuNCH2(1-C10H7)]2 in the solid state. The reaction of 1 and NH3B(C6F5)3 affords crystallographically characterized {BoMCptet}Lu{NHB(C6F5)2}C6F5. This species is proposed to form via a transient lutetium imido, whichmore » undergoes C6F5 migration to the lutetium center.« less

  1. Synthesis and Biological Evaluation of Some Novel 5-[(3-Aralkyl Amido/Imidoalkyl) Phenyl]-1,2,4-Triazolo[3,4-b]-1,3,4-Thiadiazines as Antiviral Agents

    PubMed Central

    Pandey, Vinod Kumar; Tusi, Zehra; Tusi, Sumerah; Joshi, Madhawanand

    2012-01-01

    A series of novel 4-amino-5-mercapto-3-[(3-aralkyl amido/imidoalkyl) phenyl]-1,2,4-triazoles (5a-d) were obtained by treating m-(aralkyl amido/imidoalkyl) benzoic acid hydrazides (3a-d) with carbon disulphide in alcoholic KOH and hydrazine hydrate, respectively. These triazole derivatives were employed in the synthesis of 5-[(3′-aralkyl amido/imidoalkyl) phenyl]-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazines (6a-d). The newly synthesized compounds were evaluated for their antiviral activity against two animal viruses, namely, Japanese encephalitis virus (JEV) strain P20778 and herpes simplex virus-1 (HSV-1) strain 753166. PMID:24052850

  2. Synthesis, structure, and catalytic activity of novel trinuclear rare-earth metal amido complexes incorporating μ-η5:η1 bonding indolyl and μ3-oxo groups.

    PubMed

    Yang, Song; Zhu, Xiancui; Zhou, Shuangliu; Wang, Shaowu; Feng, Zhijun; Wei, Yun; Miao, Hui; Guo, Liping; Wang, Fenhua; Zhang, Guangchao; Gu, Xiaoxia; Mu, Xiaolong

    2014-02-14

    The reactions of different pyrrolyl-functionalized indoles with rare-earth metal(III) amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Er, Dy, Eu, Y) produced different kinds of rare-earth metal amido complexes. Reactions of N-((1H-pyrrol-2-yl)methylene)-2-(1H-indol-3-yl)ethanamine with rare-earth metal amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Er, Dy, Eu, Y) in toluene or THF at temperatures of 75-80 °C afforded the novel trinuclear rare-earth metal amido complexes incorporating the indolyl ligand in μ-η(5):η(1) bonding modes and a μ3-O group, which is believed to originate from cleavage of the THF ring based on experimental results. Reactions of 2-(1H-indol-3-yl)-N-((1-methyl-1H-pyrrol-2-yl)methylene)ethanamine with rare-earth metal(III) amides [(Me3Si)2N]3RE(III)(μ-Cl)Li(THF)3 (RE = Yb, Dy) produced mononuclear ytterbium and dysprosium amides having the indolyl ligand in an η(1) bonding fashion. The results indicate that substituents not only have an influence on reactivity, but also have an influence on the bonding of the indolyl ligands with metals. The catalytic activities of the novel lanthanide amido complexes for the hydrophosphonylation of both aromatic and aliphatic aldehydes and ketones were explored. The results indicate that these complexes display a high catalytic activity for the C-P bond formation under mild conditions when using low catalyst loadings (0.1 mol% for aldehydes and ketones). Thus, it provides a potential way to prepare α-hydroxy phosphonates.

  3. A chromatographic estimate of the degree of surface heterogeneity of RPLC packing materials. III. Endcapped amido-embedded reversed phase

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2006-01-01

    The difference in adsorption behavior between a conventional monomeric endcapped C{sub 18} stationary phase (3.43 {micro}mol/m{sup 2}) and an endcapped polymeric RP-Amide phase (3.31 {micro}mol/m{sup 2}) was investigated. The adsorption isotherms of four compounds (phenol, caffeine, sodium 2-naphthalene sulfonate, and propranololium chloride) were measured by frontal analysis (FA) and the degree of heterogeneity of each phase for each solute was characterized by their adsorption energy distributions (AED), derived using the Expectation-Maximization method. The results show that only certain analytes (phenol and 2-naphthalene sulfonate) are sensitive to the presence of the polar embedded amide groups within the RP phase. Their binding constants on the amide-bonded phase are significantly higher than on conventional RPLC phases. Furthermore, an additional type of adsorption sites was observed for these two compounds. However, these sites having a low density, their presence does not affect much the retention factors of the two analytes. On the other hand, the adsorption behavior of the other two analytes (caffeine and propranololium chloride) is almost unaffected by the presence of the amide group in the bonded layer. Strong selective interactions may explain these observations. For example, hydrogen-bond interactions between an analyte (e.g., phenol or naphthalene sulfonate) and the carbonyl group (acceptor) or the nitrogen (donor) of the amido-embedded group may take place. No such interactions may take place with either caffeine or the cation propranololium chloride. This study confirms the hypothesis that analytes have ready access to locations deep inside the bonded layer, where the amide groups are present.

  4. Reactions of bis[bis(trimethylsilyl)amido] zinc with amides of sulfonimidic acids. Crystal structure and NMR studies of bischelate zinc complex

    NASA Astrophysics Data System (ADS)

    Guzyr, Olexandr I.; Markovskii, Leonid N.; Povolotskii, Mark I.; Roesky, Herbert W.; Chernega, Alexander N.; Rusanov, Eduard B.

    2006-05-01

    Reactions of bis[bis(trimethylsilyl)amido] zinc with amides of sulfonimidic acids are leading to the corresponding bischelate complexes 1- 3. Compounds 1- 3 were characterized by means of NMR spectroscopy and elemental analysis. The X-ray analysis of [ p-MeC 6H 4S(O)(N t-Bu) 2] 2Zn ( 3) demonstrates a tetrahedral environment of the Zn atom in the solid state and dynamic 1H NMR studies showed interconvention between two conformers in solution at high temperatures.

  5. Dual functional AuNRs@MnMEIOs nanoclusters for magnetic resonance imaging and photothermal therapy.

    PubMed

    Chuang, Yao-Chen; Lin, Chia-Jung; Lo, Shih-Feng; Wang, Jei-Lin; Tzou, Shey-Cherng; Yuan, Shyng-Shiou; Wang, Yun-Ming

    2014-05-01

    A novel dual functional theranosis platform is developed based on manganese magnetism-engineered iron oxide (MnMEIO) and gold nanorods (AuNRs) to combine magnetic resonance (MR) imaging and photothermal therapy in one nanocluster. The platform showed improved T2-weighted MR imaging and exhibited a near-infrared (NIR) induced temperature elevation due to the unique characteristics of AuNRs@MnMEIOs nanoclusters. The obtained dual functional spherical-shaped nanoclusters showed low cytotoxicity, and high cellular uptake efficiency. The AuNRs@MnMEIOs nanoclusters also demonstrated a 1.9 and 2.2 folds r2 relaxivity value higher than those of monodispersed MnMEIO and Resovist. In addition, in vivo MR imaging study found that the contrast enhancements were - 70.4 ± 4.3% versus - 7.5 ± 3.0% in Her-2/neu overexpression tumors as compared to the control tumors. More importantly, NIR laser irradiation to the tumor site resulted in outstanding photothermal therapeutic efficacy and without damage to the surrounding tissue. In additional, the prepared dual functional AuNRs@MnMEIOs display high stability and furthermore disperse even in the presence of external magnet, showing that AuNRs@MnMEIOs nanoclusters can be manipulated by an external magnetic field. Therefore, such nanoclusters combined MR imaging and photothermal therapeutic functionality can be developed as a promising nanosystem for effective cancer diagnosis and therapy.

  6. Piano-stool lutetium amido and imido compounds supported by a constrained bis(oxazoline)cyclopentadienyl ligand

    SciTech Connect

    Lampland, Nicole L.; Zhu, Jing; Hovey, Megan; Jana, Barun; Ellern, Arkady; Sadow, Aaron D.

    2015-06-25

    {BoMCptet}Lu(CH2Ph)2 (1; BoMCptet = MeC(OxMe2 2C5Me4; OxMe2 = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of BoMCptetH and Lu(CH2Ph)3THF3. Compound 1 reacts with 1 or 2 equiv of H2NCH2R (R = C6H5, 1-C10H7) to give the corresponding imido complexes [{BoMCptet}LuNCH2R]2 (R = C6H5 (2a), 1-C10H7 (2b)) or amido complexes {BoMCptet}Lu(NHCH2R)2 (R = C6H5 (3a), 1-C10H7 (3b)). When isolated, the imido species are insoluble in nonprotic organic solvents. Crystallographic characterization reveals dimeric [{BoMCptet}LuNCH2(1-C10H7)]2 in the solid state. The reaction of 1 and NH3B(C6F5)3 affords crystallographically characterized {BoMCptet}Lu{NHB(C6F5)2}C6F5. This species is proposed to form via a transient lutetium imido, which undergoes C6F5 migration to the lutetium center.

  7. Introduction of ester and amido functions in tetrairon(III) single-molecule magnets: synthesis and physical characterization.

    PubMed

    Rodriguez-Douton, Maria Jesus; Cornia, Andrea; Sessoli, Roberta; Sorace, Lorenzo; Barra, Anne-Laure

    2010-07-07

    Tetrairon(III) complexes with a propeller-like structure derived from [Fe(4)(OMe)(6)(dpm)(6)] (1) (Hdpm = 2,2,6,6-tetramethylheptane-3,5-dione) are providing a growing class of Single Molecule Magnets (SMMs) displaying unprecedented synthetic flexibility and ease of functionalization. Herein we report the synthesis, crystal structures and magnetic properties of two novel tetrairon(III) SMMs, [Fe(4)(esterC5)(2)(dpm)(6)] (2) and [Fe(4)(amideC5)(2)(dpm)(6)].Et(2)O.4MeOH (3.Et(2)O.4MeOH), in which functionalization of the cluster core is achieved using ester and amido linkages, respectively. To this aim, two new tripodal ligands were prepared by acylation of pentaerythritol (2,2-bis(hydroxymethyl)propane-1,3-diol) and TRIS (2-amino-2-(hydroxymethyl)propane-1,3-diol), namely H(3)esterC5 = RC(O)OCH(2)C(CH(2)OH)(3) and H(3)amideC5 = RC(O)NHC(CH(2)OH)(3) with R = n-butyl. The compounds were structurally investigated by single-crystal XRD, which demonstrated coordination of the tripodal ligands to the cluster core. The products display SMM behavior with anisotropy barriers U(eff)/k(B) congruent with 11 K due to a high-spin (S = 5) ground state and an easy axis anisotropy, described by D = -0.421 cm(-1) in 2 and -0.414 cm(-1) in 3.Et(2)O.4MeOH. The departure of U(eff) from the total splitting of the S = 5 ground multiplet, U/k(B) congruent with 15 K, has to be ascribed to the sizeable rhombic anisotropy that characterizes the two compounds (E = 0.021 cm(-1) in 2 and 0.019 cm(-1) in 3.Et(2)O.4MeOH), as confirmed by master matrix calculations of the temperature-dependent relaxation time.

  8. One-pot chemical synthesis of small ubiquitin-like modifier protein-peptide conjugates using bis(2-sulfanylethyl)amido peptide latent thioester surrogates.

    PubMed

    Boll, Emmanuelle; Drobecq, Hervé; Ollivier, Nathalie; Blanpain, Annick; Raibaut, Laurent; Desmet, Rémi; Vicogne, Jérôme; Melnyk, Oleg

    2015-02-01

    Small ubiquitin-like modifier (SUMO) post-translational modification (PTM) of proteins has a crucial role in the regulation of important cellular processes. This protocol describes the chemical synthesis of functional SUMO-peptide conjugates. The two crucial stages of this protocol are the solid-phase synthesis of peptide segments derivatized by thioester or bis(2-sulfanylethyl)amido (SEA) latent thioester functionalities and the one-pot assembly of the SUMO-peptide conjugate by a sequential native chemical ligation (NCL)/SEA native peptide ligation reaction sequence. This protocol also enables the isolation of a SUMO SEA latent thioester, which can be attached to a target peptide or protein in a subsequent step. It is compatible with 9-fluorenylmethoxycarbonyl (Fmoc) chemistry, and it gives access to homogeneous, reversible and functional SUMO conjugates that are not easily produced using living systems. The synthesis of SUMO-peptide conjugates on a milligram scale takes 20 working days.

  9. Synthesis of [3]ferrocenophane-bridged Cp-amido zirconium complexes and ansa-zirconocene complexes and their use in catalytic polymerisation reactions.

    PubMed

    Unverhau, Kerstin; Kehr, Gerald; Fröhlich, Roland; Erker, Gerhard

    2011-04-14

    Starting from 1,1'-diacetylferrocene the ortho-amino,α-dimethylamino[3]ferrocenophane system 3 was prepared. This was converted to the o-imino,α-Cp-derivative 6. Subsequent treatment with e.g. an excess of methyllithium followed by ZrCl(2)(NMe(2))(2)(thf)(2) and Me(2)SiCl(2) eventually gave the [3]ferrocenophane based Cp-amido zirconium complex 11b. In a similar way the [3]ferrocenophane derived fluorenyl-Cp ansa-zirconocene dichloride complex 20 was obtained. The 20-methylalumoxane (MAO) system is an active homogeneous Ziegler-Natta catalyst for ethylene polymerization. The 11b-MAO system reacts efficiently with an ethene-1-octene mixture to yield a mixture of linear polyethylene plus the ethene-1-octene copolymer. The compounds 5, 8, 10b, 11b, 13, 14, and 20 were characterized by X-ray diffraction.

  10. Crystal structure of tris­(di­methyl­amido-κN)­bis­(di­methyl­amine-κN)­zirconium(IV) iodide

    PubMed Central

    Clark, Wesley D.; Akurathi, Gopalakrishna; Valle, Henry U.; Hollis, T. Keith

    2016-01-01

    Zirconium amides have become increasingly popular and useful due to their widespread use as precursors to other zirconium complexes and their use in the production of solid oxide fuel cells (SOFCs). Herein we report the mol­ecular structure of tris­(di­methyl­amido)­bis­(di­methyl­amine)­zirconium(IV) iodide, [Zr(C2H6N)3(C2H7N)2]I. The bond lengths and bond angles are consistent with a slightly distorted trigonal–bipyramidal coordination geometry around the metal atom. N⋯I contacts of 3.6153 (15) and 3.5922 (14) Å are consistent with the presence of N—H⋯I inter­actions. These N—H⋯I inter­actions link the complex cations and iodide anions into extended chains that propagate parallel to the a axis. PMID:26870590

  11. Synthesis and characterization of anionic rare-earth metal amides stabilized by phenoxy-amido ligands and their catalytic behavior for the polymerization of lactide.

    PubMed

    Lu, Min; Yao, Yingming; Zhang, Yong; Shen, Qi

    2010-10-28

    A dianionic phenoxyamido ligand was the first to be used to stabilize organo-rare-earth metal amido complexes. Amine elimination reaction of Nd[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) (TMS = SiMe(3)) with aminophenol [HNOH] {[HNOH] = N-p-methylphenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine} in a 1 : 1 molar-ratio gave the anionic phenoxyamido neodymium amide [NO](2)Nd[N(TMS)(2)][Li(THF)](2) (2) in a low isolated yield. A further study revealed that the stoichiometric reactions of Ln[N(TMS)(2)](3)(μ-Cl)Li(THF)(3) with the lithium aminophenoxy [HNOLi(THF)](2) (1) in tetrahydrofuran (THF) gave the anionic rare-earth metal amido complexes [NO](2)Ln[N(TMS)(2)][Li(THF)](2) [Ln = Nd (2), Sm (3), Yb (4), Y (5)] in high isolated yields. All of these complexes are fully characterized. X-Ray structure determination revealed that complex 1 has a solvated dimeric structure, and complexes 2-5 are isostructural, and have solvated monomeric structures. Each of the rare-earth metal ions is coordinated by two oxygen atoms and two nitrogen atoms from two phenoxyamido ligands and one nitrogen atom from the N(TMS)(2) group to form a distorted trigonal bipyramidal geometry. Each of the lithium atoms in complexes 2-5 is coordinated with one oxygen atom and one nitrogen atom from two different phenoxyamido groups, and one oxygen atom from one THF molecule to form a trigonal planar geometry. Furthermore, the catalytic behavior of complexes 2-5 for the ring-opening polymerization of l-lactide was explored.

  12. Carbohydrate-interactive pDNA and siRNA gene vectors based on boronic acid functionalized poly(amido amine)s.

    PubMed

    Piest, Martin; Ankoné, Marc; Engbersen, Johan F J

    2013-08-10

    In order to evaluate the influence of incorporation of boronic acid groups on the properties of poly(amido amine)s as gene vectors, a novel poly(amido amine) copolymer p(CBA-ABOL/2AMPBA) containing ortho-aminomethylphenylboronic acid (2AMPBA) moieties was prepared by Michael-type polyaddition of a mixture of 1,4-aminobutanol (ABOL) and 2-((4-aminobutylamino)methyl)phenyl boronic acid to N,N'-cystamine bisacrylamide (CBA). It appeared that the presence of the boronic acid moieties as side groups along the polymer chain strongly enhances the stability of the self-assembled nanoparticles and nanosized polyplexes formed from this polymer; no aggregation was observed after storage for 6days at 37°C. This strong stabilization can be attributed to intermolecular Lewis acid-base interactions between the 2AMPBA groups and the alcohol and amine groups present in the polymer, leading to dynamical (reversible) crosslinking in the nanoparticles. Moreover, since the boronic acids can reversibly form boronic esters with vicinal diol groups, the presence of the 2AMPBA groups add carbohydrate-interactive properties to these polymers that strongly influence their behavior as gene delivery vectors. DNA transfection with p(CBA-ABOL/2AMPBA) polyplexes gave transfection efficiencies that were approximately similar to commercial PEI in different cell lines (COS-7, HUH-6 and H1299-Fluc), but lower than those obtained with reference polyplexes from p(CBA-ABOL). It is hypothesized that the uptake of the boronated polyplexes is suppressed by binding to the glycocalyx of the cells. This is supported by the observation that addition of sorbitol or dextran to the transfection medium significantly enhances the transfection efficiency, which can be attributed to increased cellular uptake of the polyplexes due to boronic ester formation with these agents. AFM, SEM and confocal microscopy showed that polyplexes of p(CBA-ABOL/2AMPBA) become decorated with a dextran layer in the presence of 0.9% (w

  13. Low-temperature CVD of iron, cobalt, and nickel nitride thin films from bis[di(tert-butyl)amido]metal(II) precursors and ammonia

    SciTech Connect

    Cloud, Andrew N.; Abelson, John R.; Davis, Luke M.; Girolami, Gregory S.

    2014-03-15

    Thin films of late transition metal nitrides (where the metal is iron, cobalt, or nickel) are grown by low-pressure metalorganic chemical vapor deposition from bis[di(tert-butyl)amido]metal(II) precursors and ammonia. These metal nitrides are known to have useful mechanical and magnetic properties, but there are few thin film growth techniques to produce them based on a single precursor family. The authors report the deposition of metal nitride thin films below 300 °C from three recently synthesized M[N(t-Bu){sub 2}]{sub 2} precursors, where M = Fe, Co, and Ni, with growth onset as low as room temperature. Metal-rich phases are obtained with constant nitrogen content from growth onset to 200 °C over a range of feedstock partial pressures. Carbon contamination in the films is minimal for iron and cobalt nitride, but similar to the nitrogen concentration for nickel nitride. X-ray photoelectron spectroscopy indicates that the incorporated nitrogen is present as metal nitride, even for films grown at the reaction onset temperature. Deposition rates of up to 18 nm/min are observed. The film morphologies, growth rates, and compositions are consistent with a gas-phase transamination reaction that produces precursor species with high sticking coefficients and low surface mobilities.

  14. Atomic layer deposition of TiO2 from tetrakis-dimethyl-amido titanium or Ti isopropoxide precursors and H2O

    NASA Astrophysics Data System (ADS)

    Xie, Qi; Jiang, Yu-Long; Detavernier, Christophe; Deduytsche, Davy; Van Meirhaeghe, Roland L.; Ru, Guo-Ping; Li, Bing-Zong; Qu, Xin-Ping

    2007-10-01

    Atomic layer deposition (ALD) of TiO2 thin films using Ti isopropoxide and tetrakis-dimethyl-amido titanium (TDMAT) as two kinds of Ti precursors and water as another reactant was investigated. TiO2 films with high purity can be grown in a self-limited ALD growth mode by using either Ti isopropoxide or TDMAT as Ti precursors. Different growth behaviors as a function of deposition temperature were observed. A typical growth rate curve-increased growth rate per cycle (GPC) with increasing temperatures was observed for the TiO2 film deposited by Ti isopropoxide and H2O, while surprisingly high GPC was observed at low temperatures for the TiO2 film deposited by TDMAT and H2O. An energetic model was proposed to explain the different growth behaviors with different precursors. Density functional theory (DFT) calculation was made. The GPC in the low temperature region is determined by the reaction energy barrier. From the experimental results and DFT calculation, we found that the intermediate product stability after the ligand exchange is determined by the desorption behavior, which has a huge effect on the width of the ALD process window.

  15. Poly(amido)amine dendrimers generation 4.0 (PAMAM G4) reduce blood hyperglycaemia and restore impaired blood-brain barrier permeability in streptozotocin diabetes in rats.

    PubMed

    Karolczak, Kamil; Rozalska, Sylwia; Wieczorek, Marek; Labieniec-Watala, Magdalena; Watala, Cezary

    2012-10-15

    We hypothesized that BBB is impaired in rat model of streptozotocin-induced diabetes and can be sealed by poly(amido)amine dendrimers G4.0 (PAMAM G4), which reveal anti-glycation activity. The BBB permeabilization was monitored in rats with the 60-day streptozotocin-diabetes and non-diabetic animals, using three fluorescent dyes (given intraperitoneally) differing in molecular weight: fluorescein, fluorescein isothiocyanate (FITC)-dextran and Evans blue. All animals were administered for 2 months with either PAMAM G4 dendrimer or placebo. The fluorescence intensities of the injected fluorescent markers were recorded in the homogenates of selected brain regions. The highest accumulations of the used fluorescent dyes were observed for fluorescein, predominantly in thalamus, hippocampus, frontal cortex, striatum and cerebellum. FITC-dextran leaked to much smaller extent, however, higher permeabilization for FITC-dextran was revealed in pons-medulla oblongata, frontal and parietal cortex of diabetic compared to control animals. Evans blue leaked very slowly into striatum and pons-medulla oblongata in diabetic rats. The treatment of diabetic animals with PAMAM G4 significantly reduced blood glucose concentration and hallmarks of late diabetic complications, compared to non-treated diabetic animals. PAMAM G4 significantly reduced diabetes-induced permeabilization of BBB, which remained in line with the reduced blood glucose and the amelioration of the biochemical hallmarks of severe hyperglycaemia.

  16. Saturable and reverse saturable absorption and nonlinear refraction in nanoclustered Amido Black dye-polymer films under low power continuous wave He-Ne laser light excitation

    NASA Astrophysics Data System (ADS)

    Sreekumar, G.; Louie Frobel, P. G.; Muneera, C. I.; Sathiyamoorthy, K.; Vijayan, C.; Mukherjee, Chandrachur

    2009-12-01

    We report an observed transition from a saturable absorption type of behaviour to a reverse saturable absorption one for solid films of a guest-host system constituted by an organic chromophore, Amido Black 10B, embedded in a vinyl polymer, polyvinyl alcohol, and comprising a uniform distribution of aggregated nanoclusters, as studied using the standard Z-scan technique under low intensity continuous wave laser light excitation at 632 nm, while increasing the concentration of the dye content. This is attributed to the presence of higher aggregates of the dye molecules in the sample. Besides this, the samples also displayed complex nonlinear refraction behaviour, yielding a net negative nonlinearity, explained on the basis of a possible, simultaneous occurrence of refractive nonlinearities of different origin, in addition to the obvious effect of absorption. The estimated values of the effective coefficients of nonlinear absorption, nonlinear refraction and third-order nonlinear susceptibility, |χ(3)|, compared to those reported for continuous wave laser light excitation, measure up to the highest among them. These nonlinear effects could be the basis for possible applications of this new reverse saturable absorption material, sensitive even to low power excitation, as an efficient material for use in nonlinear optical devices.

  17. Synthesis of biologically active 1'-(2-oxo-2H-benzopyran-6-yl)- 5'-hydroxy-2'-methylindole-3'-amido-2"-phenyl-thiazolidene-4"-ones.

    PubMed

    Mulwad, Vinata V; Parmar, Hitesh T; Mir, Abid A

    2011-01-01

    6-Aminocoumarins on refluxing with ethyl acetoacetate in 1,2-dichloroethane gave two products: 3'-(2-oxo-2H-benzopyran-6-yl-amino)-but-2'-enoic acid ethyl ester 2a-c and N-(-2-oxo-2H-benzopyran-6-yl)-3'-oxo-butyramide 3a-c. Compounds 2a-c on treatment with 1,4-benzoquinone in N2-atmosphere yielded 1'-( 2-oxo-2H-benzopyran-6-yl)-5'-hydroxy-2'-methyl-3'-carbethoxyindoles 4a-c, which on further treatment with hydrazine hydrate gave 1'-(2-oxo-2H-benzopyran-6-yl)-5'-hydroxy-2'-methylindole-3'-acid hydrazides 5a-c. These acid hydrazides were treated with benzaldehyde to give 1'-(2-oxo-2H-benzopyran-6-yl)-5'-hydroxy-2'-methylindole-3'-benzylidene hydrazides 6a-c, which on further treatment with mercaptoacetic acid in 1,4-dioxane yielded 1'-(2-oxo-2H-benzopyran-6-yl)-5'-hydroxy-2'-methylindole-3'-amido-2"-phenylthiazolidene-4"-ones 7a-c. The structures of the compounds have been established on the basis of spectral and analytical data. All compounds have been screened for their antimicrobial activity and have been found to exhibit significant antibacterial and antifungal activities.

  18. Body Size Versus Depth: Regional and Taxonomical Variation in Deep-Sea Meio- and Macrofaunal Organisms.

    PubMed

    van der Grient, Jesse M A; Rogers, Alex D

    2015-01-01

    Body size (weight per individual) is an important concept in ecology. It has been studied in the deep sea where a decrease in size with increasing depth has often been found. This has been explained as an adaptation to food limitation where size reduction results in a lowered metabolic rate and a decreased energetic requirement. However, observations vary, with some studies showing an increase in size with depth, and some finding no depth correlation at all. Here, we collected data from peer-reviewed studies on macro- and meiofaunal abundance and biomass, creating two datasets allowing statistical comparison of factors expected to influence body size in meio- and macrofaunal organisms. Our analyses examined the influence of region, taxonomic group and sampling method on the body size of meiofauna and macrofauna in the deep sea with increasing depth, and the resulting models are presented. At the global scale, meio- and macrofaunal communities show a decrease in body size with increasing depth as expected with the food limitation hypothesis. However, at the regional scale there were differences in trends of body size with depth, either showing a decrease (e.g. southwest Pacific Ocean; meio- and macrofauna) or increase (e.g. Gulf of Mexico; meiofauna only) compared to a global mean. Taxonomic groups also showed differences in body size trends compared to total community average (e.g. Crustacea and Bivalvia). Care must be taken when conducting these studies, as our analyses indicated that sampling method exerts a significant influence on research results. It is possible that differences in physiology, lifestyle and life history characteristics result in different responses to an increase in depth and/or decrease in food availability. This will have implications in the future as food supply to the deep sea changes as a result of climate change (e.g. increased ocean stratification at low to mid latitudes and reduced sea ice duration at high latitudes).

  19. The Systemic Acquired Resistance Regulator OsNPR1 Attenuates Growth by Repressing Auxin Signaling through Promoting IAA-Amido Synthase Expression1[OPEN

    PubMed Central

    2016-01-01

    Systemic acquired resistance is a long-lasting and broad-spectrum disease resistance to pathogens. Our previous study demonstrated that overexpression of NONEXPRESSOR OF PATHOGENESIS-RELATED GENES1 (OsNPR1), a master gene for systemic acquired resistance in rice (Oryza sativa), greatly enhanced resistance to bacterial blight caused by Xanthomonas oryzae pv oryzae. However, the growth and development of the OsNPR1 overexpression (OsNPR1-OX) plants were restrained, and the mechanism remained elusive. In this study, we dissected the OsNPR1-induced growth inhibition. We found that the OsNPR1-OX lines displayed phenotypes mimicking auxin-defective mutants, with decreases in root system, seed number and weight, internode elongation, and tiller number. Whole-genome expression analysis revealed that genes related to the auxin metabolism and signaling pathway were differentially expressed between the OsNPR1-OX and wild-type plants. Consistently, the indole-3-acetic acid (IAA) content was decreased and the auxin distribution pattern was altered in OsNPR1-OX plants. Importantly, we found that some GH3 family members, in particular OsGH3.8 coding IAA-amido synthetase, were constitutively up-regulated in OsNPR1-OX plants. Decreased OsGH3.8 expression by RNA interference could partially restore IAA level and largely rescue the restrained growth and development phenotypes but did not affect the disease resistance of OsNPR1-OX plants. Taken together, we revealed that OsNPR1 affects rice growth and development by disrupting the auxin pathway at least partially through indirectly up-regulating OsGH3.8 expression. PMID:27378815

  20. Rare-earth metal alkyl, amido, and cyclopentadienyl complexes supported by imidazolin-2-iminato ligands: synthesis, structural characterization, and catalytic application.

    PubMed

    Trambitas, Alexandra G; Panda, Tarun K; Jenter, Jelena; Roesky, Peter W; Daniliuc, Constantin; Hrib, Cristian G; Jones, Peter G; Tamm, Matthias

    2010-03-01

    The rare earth metal dichlorides [(1)MCl(2)(THF)(3)] (2a, M = Sc; 2b, M = Y; 2c, M = Lu) and the gadolinium complex [(1)GdCl(2)(THF)(2)] x [LiCl(THF)(2)] (2d), containing the 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato ligand 1, proved to be versatile starting materials for the preparation of trimethylsilylmethyl ("neosilyl") and bis(trimethylsilyl)amido complexes [(1)M(CH(2)SiMe(3))(2)(THF)(2)] (3a-3d) and [(1)M(HMDS)(2)(THF)] [4a-4d, HMDS = hexamethyldisilazide, N(SiMe(3))(2)] and for the preparation of the benzyl complex [(1)Lu(CH(2)Ph)(2)(THF)(2)] (5c) by the reaction with LiCH(2)SiMe(3), Na[N(SiMe(3))(2)], and KCH(2)Ph, respectively. Treatment of 2a-2c with KCp* afforded the mono(pentamethylcyclopentadienyl) complexes [(1)Sc(Cp*)Cl(THF)] (6a), [(1)Y(Cp*)Cl(THF)(2)] (6b), and [(1)Lu(Cp*)Cl(THF)] (6c). In contrast, the gadolinocene complex [(1)Gd(Cp*)(2)(THF)] (7) was isolated from the reaction of 2d with 2 equiv of KCp*. The molecular structures of 3a-3d, 4b.THF, 4d, 5c, 6a, 6c, and 7 x THF were determined by X-ray diffraction analyses, revealing the presence of exceptionally short metal-nitrogen bonds. The neosilyl complexes 3b and 3c showed high catalytic activity in the intramolecular hydroamination of aminoalkenes and aminoalkynes and in the hydrosilylation of 1-hexene and 1-octene with PhSiH(3).

  1. Poly (amido amine) and nano-calcium phosphate bonding agent to remineralize tooth dentin in cyclic artificial saliva/lactic acid.

    PubMed

    Liang, Kunneng; Weir, Michael D; Reynolds, Mark A; Zhou, Xuedong; Li, Jiyao; Xu, Hockin H K

    2017-03-01

    The objectives of this study were to develop a novel method to remineralize dentin lesions, and investigate the remineralization effects of poly (amido amine) (PAMAM) dendrimer plus a bonding agent with nanoparticles of amorphous calcium phosphate (NACP) in a cyclic artificial saliva/lactic acid environment for the first time. Dentin lesions were produced via phosphoric acid. Four groups were tested: (1) dentin control, (2) dentin with PAMAM, (3) dentin with NACP bonding agent, and (4) dentin with PAMAM plus NACP bonding agent. Specimens were treated with cyclic artificial saliva/lactic acid. The remineralized dentin was examined using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), hardness and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). NACP bonding agent yielded a dentin shear bond strength similar to commercial controls (Prime & Bond NT, Dentsply; Scotchbond Multi-purpose, 3M) (p>0.1). Increasing NACP in bonding agent from 0 to 40% did not affect bond strength. NACP bonding agent neutralized the acid and released Ca ions with concentrations of 4 to 20mmol/L, and P ions of 2 to 9mmol/L. PAMAM or NACP bonding agent alone achieved slight remineralization. The PAMAM+NACP group achieved the greatest dentin remineralization p<0.05). At 20days, PAMAM+NACP increased the hardness of pre-demineralized dentin to reach the normal dentin hardness (p>0.1). In conclusion, superior remineralization of PAMAM+NACP bonding agent was demonstrated for the first time. PAMAM+NACP bonding agent induced dentin remineralization under acid challenge, when conventional remineralization methods such as PAMAM alone did not work well. The novel PAMAM+NACP bonding agent method is promising to improve the longevity of resin-dentin bonds, inhibit caries, and protect teeth.

  2. The Systemic Acquired Resistance Regulator OsNPR1 Attenuates Growth by Repressing Auxin Signaling through Promoting IAA-Amido Synthase Expression.

    PubMed

    Li, Xiaozun; Yang, Dong-Lei; Sun, Li; Li, Qun; Mao, Bizeng; He, Zuhua

    2016-09-01

    Systemic acquired resistance is a long-lasting and broad-spectrum disease resistance to pathogens. Our previous study demonstrated that overexpression of NONEXPRESSOR OF PATHOGENESIS-RELATED GENES1 (OsNPR1), a master gene for systemic acquired resistance in rice (Oryza sativa), greatly enhanced resistance to bacterial blight caused by Xanthomonas oryzae pv oryzae However, the growth and development of the OsNPR1 overexpression (OsNPR1-OX) plants were restrained, and the mechanism remained elusive. In this study, we dissected the OsNPR1-induced growth inhibition. We found that the OsNPR1-OX lines displayed phenotypes mimicking auxin-defective mutants, with decreases in root system, seed number and weight, internode elongation, and tiller number. Whole-genome expression analysis revealed that genes related to the auxin metabolism and signaling pathway were differentially expressed between the OsNPR1-OX and wild-type plants. Consistently, the indole-3-acetic acid (IAA) content was decreased and the auxin distribution pattern was altered in OsNPR1-OX plants. Importantly, we found that some GH3 family members, in particular OsGH3.8 coding IAA-amido synthetase, were constitutively up-regulated in OsNPR1-OX plants. Decreased OsGH3.8 expression by RNA interference could partially restore IAA level and largely rescue the restrained growth and development phenotypes but did not affect the disease resistance of OsNPR1-OX plants. Taken together, we revealed that OsNPR1 affects rice growth and development by disrupting the auxin pathway at least partially through indirectly up-regulating OsGH3.8 expression.

  3. A Highly Efficient Diversification of 2-Amino/Amido-1,3,4-oxadiazole and 1,3,4-Thiadiazole Derivatives via Reagent-Based Cyclization of Thiosemicarbazide Intermediate on Solid-Phase.

    PubMed

    Yang, Seung-Ju; Choe, Ji-Hye; Abdildinova, Aizhan; Gong, Young-Dae

    2015-12-14

    A 2-amino/amido-1,3,4-oxadiazole and 1,3,4-thiadiazole library has been constructed on solid-phase organic synthesis. The key step on this solid-phase synthesis involves the preparation of polymer-bound 2-amino-1,3,4-oxadiazole and 1,3,4-thiadiazole core skeleton resin by cyclization of thiosemicarbazide with EDC·HCl and p-TsCl, respectively. The resulting core skeleton undergoes functionalization reaction with various electrophiles such as alkyl halides, and acid chlorides to generate N-alkylamino and N-acylamino-1,3,4-oxadiazole, and 1,3,4-thiadiazole resin, respectively. Finally, the 2-amino and 2-amido-1,3,4-oxadiazole and 1,3,4-thiadiazole library was then generated in good yields and high purities by cleavage of the respective resin under trifluoroacetic acid(TFA) in dichloromethane(DCM). The constructed library shows reasonable, oral bioavailability drug properties as determine by using the Lipinski's Rule and similar parameters.

  4. The metabolic fate of the amido-N group of glutamine in the tissues of the gastrointestinal tract in 24 h-fasted sheep.

    PubMed

    Gate, J J; Parker, D S; Lobley, G E

    1999-04-01

    Whole-body and gastrointestinal tract (GIT) metabolism of [5-(15)N]glutamine were monitored in lambs (33 kg live weight) fasted for 24 h. Animals were previously prepared with vascular catheters across the mesenteric-(MDV) and portal-drained viscera (PDV) to permit quantification of mass and isotopic transfers of metabolites by arterio-venous difference. Continuous infusions of [5-(15)N]glutamine into the jugular vein were conducted for 10 h and integrated blood samples withdrawn over 75 min intervals for the last 5 h of infusion. The lambs were then killed and portions from various tissues of the digestive tract and other body organs removed for determination of 15N enrichment in RNA, DNA and protein (the latter obtained by difference using total acid-precipitable N). Whole-body glutamine flux was 108 mumol/min of which 23 and 47% could be attributed to MDV and PDV metabolism (P < 0.001) respectively. There was a small net production of glutamine across the MDV. GIT blood-flows and NH3 production were partitioned 3:2 between MDV and non-MDV components. Less than 5% of the NH3 produced was derived from the amido-N of glutamine, while across the small intestine (MDV) 26% of the glutamine flux was converted to NH3, compared with 18% for non-MDV transfers. The 15N enrichments in protein were of the order jejunum > duodenum > ileum with mucosal cells more labelled than serosal (P < 0.001). Lesser enrichments were observed for other GIT tissues (abomasum > caecum > rumen) while liver and lymph were comparable with the abomasum; kidney, spleen and muscle were lower still (P < 0.05). Enrichments of RNA were similar to that of protein and followed the same pattern, except for higher relative values for liver, spleen and lymphoid tissue. The lowest enrichments were observed for DNA, but again the pattern order was similar except for increased label in lymph, caecum and the spleen. For the MDV there was reasonable agreement between 15N-disappearance as glutamine and

  5. CD44-Targeted Hyaluronic Acid-Coated Redox-Responsive Hyperbranched Poly(amido amine)/Plasmid DNA Ternary Nanoassemblies for Efficient Gene Delivery.

    PubMed

    Gu, Jijin; Chen, Xinyi; Ren, Xiaoqing; Zhang, Xiulei; Fang, Xiaoling; Sha, Xianyi

    2016-07-20

    Hyaluronic acid (HA), which can specifically bind to CD44 receptor, is a specific ligand for targeting to CD44-overexpressing cancer cells. The current study aimed to develop ternary nanoassemblies based on HA-coating for targeted gene delivery to CD44-positive tumors. A novel reducible hyperbranched poly(amido amine) (RHB) was assembled with plasmid DNA (pDNA) to form RHB/pDNA nanoassemblies. HA/RHB/pDNA nanoassemblies were fabricated by coating HA on the surface of the RHB/pDNA nanoassembly core through electrostatic interaction. After optimization, HA/RHB/pDNA nanoassemblies were spherical, core-shell nanoparticles with nanosize (187.6 ± 11.4 nm) and negative charge (-9.1 ± 0.3 mV). The ternary nanoassemblies could efficiently protect the condensed pDNA from enzymatic degradation by DNase I, and HA could significantly improve the stability of nanoassemblies in the sodium heparin solution or serum in vitro. As expected, HA significantly decreased the cytotoxicity of RHB/pDNA nanoassemblies due to the negative surface charges. Moreover, it revealed that HA/RHB/pDNA nanoassemblies showed higher transfection activity than RHB/pDNA nanoassemblies in B16F10 cells, especially in the presence of serum in vitro. Because of the active recognition between HA and CD44 receptor, there was significantly different transfection efficiency between B16F10 (CD44+) and NIH3T3 (CD44-) cells after treatment with HA/RHB/pDNA nanoassemblies. In addition, the cellular targeting and transfection activity of HA/RHB/pDNA nanoassemblies were further evaluated in vivo. The results indicated that the interaction between HA and CD44 receptor dramatically improved the accumulation of HA/RHB/pDNA nanoassemblies in CD44-positive tumor, leading to higher gene expression than RHB/pDNA nanoassemblies. Therefore, HA/RHB/pDNA ternary nanoassemblies may be a potential gene vector for delivery of therapeutic genes to treat CD44-overexpressing tumors in vivo.

  6. Rare-earth dichloro and bis(alkyl) complexes supported by bulky amido-imino ligand. Synthesis, structure, reactivity and catalytic activity in isoprene polymerization.

    PubMed

    Kissel, Alexander A; Lyubov, Dmitry M; Mahrova, Tatyana V; Fukin, Georgy K; Cherkasov, Anton V; Glukhova, Tatyana A; Cui, Dongmei; Trifonov, Alexander A

    2013-07-07

    A monoanionic amido-imino ligand system [(2,6-iPr2C6H3)N=C(Me)C(=CH2)N(C6H3-2,6-iPr2)](-) was successfully employed for the synthesis of monomeric dichloro [(2,6-iPr2C6H3)N=C(Me)C(=CH2)N(C6H3-2,6-iPr2)]LnCl2(THF)2 (Ln = Y, 2Y; Lu, 2Lu) and bis(alkyl) [(2,6-iPr2C6H3)N=C(Me)C(=CH2)N(C6H3-2,6-iPr2)]Ln(CH2SiMe3)2(THF) (Ln = Y, 4Y; Lu, 4Lu) species of yttrium and lutetium. Dichloro complexes 2Y and 2Lu turned out to be unstable in aromatic solvents. The ligand symmetrization reaction in the case of 2Y affords the yttrium complex coordinated by dianionic [(2,6-iPr2C6H3)NC(=CH2)C(=CH2)N(C6H3-2,6-iPr2)](2-) ligand, (2,6-iPr2C6H3)N=C(Me)C(Me)=N(C6H3-2,6-iPr2) and YCl3. On the contrary, bis(alkyl) species 4Y and 4Lu are rather stable and do not undergo such a transformation or thermal decomposition. The treatment of complex 4Y with DME resulted in C-O bond cleavage and the formation of a dimeric methoxy-alkyl species {[(2,6-iPr2C6H3)N=C(Me)C(=CH2)N(C6H3-2,6-iPr2)]Y(CH2SiMe3)(μ-OMe)}2 (5). The ternary systems 4Ln/AliBu3/borate (borate = [HNMe2Ph][B(C6F5)4] and [CPh3][B(C6F5)4]; molar ratio 1 : 10 : 1) performed high catalytic activity in isoprene polymerization and ability to convert into polymer 1000-5000 equivalents of isoprene in 20-120 min with quantitative conversion. The obtained polyisoprenes possessed high molecular weights (2.9 × 10(4)-4.1 × 10(4)) and moderate polydispersities (2.14-3.52). Predominant 3,4-regioselectivity (up to 78%) was observed.

  7. Portable exhausters POR-004 SKID B, POR-005 SKID C, POR-006 SKID D storage plan

    SciTech Connect

    Nelson, O.D.

    1997-09-04

    This document provides a storage plan for portable exhausters POR-004 SKID B, POR-005 SKID C, AND POR-006 SKID D. The exhausters will be stored until they are needed by the TWRS (Tank Waste Remediation Systems) Saltwell Pumping Program. The storage plan provides criteria for portable exhauster storage, periodic inspections during storage, and retrieval from storage.

  8. Astronomia cultural e meio ambiente segundo uma abordagem holística

    NASA Astrophysics Data System (ADS)

    Jafelice, L. C.

    2003-08-01

    Neste trabalho ampliamos a discussão da abordagem holística para o ensino de astronomia que temos desenvolvido nos últimos anos, analisamos novos resultados e apresentamos exemplos práticos para interessados em experimentá-la. A constatação básica a orientar este enfoque é que cursos introdutórios em astronomia costumam ser excessiva e prematuramente técnicos, além de assumirem uma visão tradicional, muito estreita, do que seja educação científica, herdada da era cartesiana e positivista da ciência. Fundamentamos porque é importante que elementos de astronomia cultural ofereçam o mote e constituam o eixo norteador daqueles cursos e porque é urgente revermos a visão que temos da relação entre astronomia e meio ambiente. Um ponto central nesta abordagem é explorar formas de reativar e atualizar uma relação orgânica com o meio e excitar a consciência de nossa inevitável e profunda interdependência com ele em nível cósmico. Neste trabalho exemplificamos a possibilidade de concretização desta proposta em três diferentes situações: disciplinas de cursos de licenciatura em geografia e em física; escolas de nível fundamental; e, neste caso ainda a ser implementada, comunidades carentes. Estes casos envolvem públicos e espaços diferenciados para educação formal e não-formal. Dos casos já implementados, destacamos os resultados alcançados pelos alunos: enriquecimento cultural, aprendizagem significativa de conteúdos astronômicos tradicionais; mudanças de comportamento, incorporando contato diário com o céu; e freqüentes vivências de sentimentos empáticos que redirecionam a relação com a natureza e a consciência ecológica global. Além disto, para interessados em aplicar esta proposta, também socializamos procedimentos e cuidados para a implementação de ações alternativas consonantes com a mesma. (PPGECNM/UFRN; PRONEX/FINEP; NUPA/USP; Temáticos/FAPESP)

  9. Di and trinuclear rare-earth metal complexes supported by 3-amido appended indolyl ligands: synthesis, characterization and catalytic activity towards isoprene 1,4-cis polymerization.

    PubMed

    Zhang, Guangchao; Deng, Baojia; Wang, Shaowu; Wei, Yun; Zhou, Shuangliu; Zhu, Xiancui; Huang, Zeming; Mu, Xiaolong

    2016-10-21

    Different di and trinuclear rare-earth metal complexes supported by 3-amido appended indolyl ligands were synthesized and their catalytic activities towards isoprene polymerization were investigated. Treatment of [RE(CH2SiMe3)3(thf)2] with 1 equiv. of 3-(CyN[double bond, length as m-dash]CH)C8H5NH in toluene or in THF afforded dinuclear rare-earth metal alkyl complexes having indolyl ligands in different hapticities with central metals {[η(2):η(1)-μ-η(1)-3-(CyNCH(CH2SiMe3))Ind]RE-(thf)(CH2SiMe3)}2 (Cy = cyclohexyl, Ind = Indolyl, RE = Yb (1), Er (2), Y (3)) or {[η(1)-μ-η(1)-3-(CyNCH(CH2SiMe3))Ind]RE-(thf)2(CH2SiMe3)}2 (RE = Yb (4), Er (5), Y (6), Gd (7)), respectively. These two series of dinuclear complexes could be transferred to each other easily by only changing the solvents in the process. Reaction of [Er(CH2SiMe3)3(thf)2] with 1 equiv. of 3-t-butylaminomethylindole 3-((t)BuNHCH2)C8H5NH in THF afforded the unexpected trinuclear erbium alkyl complex [η(2):η(1)-μ-η(1)-3-((t)BuNCH2)Ind]4Er3(thf)5(CH2SiMe3) (8), which can also be prepared by reaction of 3 equiv. of [Er(CH2SiMe3)3(thf)2] with 4 equiv. of 3-((t)BuNHCH2)C8H5NH in THF. Accordingly, complexes [η(2):η(1)-μ-η(1)-3-((t)BuNCH2)Ind]4RE3(thf)5(CH2SiMe3) (RE = Y (9), Dy (10)) were prepared by reactions of 3 equiv. of [RE(CH2SiMe3)3(thf)2] with 4 equiv. of 3-((t)BuNHCH2)C8H5NH in THF. Reactions of [RE(CH2SiMe3)3(thf)2] with 1 equiv. of 3-t-butylaminomethylindole 3-((t)BuNHCH2)C8H5NH in THF, followed by treatment with 1 equiv. of [(2,6-(i)Pr2C6H3)N[double bond, length as m-dash]CHNH(C6H3(i)Pr2-2,6)] afforded, after workup, the dinuclear rare-earth metal complexes [η(1)-μ-η(1):η(1)-3-((t)BuNCH2)Ind][η(1)-μ-η(1):η(3)-3-((t)BuNCH2)Ind]RE2(thf)[(η(3)-2,6-(i)Pr2C6H3)NCHN(C6H3(i)Pr2-2,6)]2(RE = Er (11), Y (12)) having the indolyl ligands bonded with the rare-earth metal in different ligations. All new complexes 1-12 were fully characterized by spectroscopic methods and elemental analyses, and

  10. Dehydrogenation of secondary amines: synthesis, and characterization of rare-earth metal complexes incorporating imino- or amido-functionalized pyrrolyl ligands.

    PubMed

    Li, Qinghai; Zhou, Shuangliu; Wang, Shaowu; Zhu, Xiancui; Zhang, Lijun; Feng, Zhijun; Guo, Liping; Wang, Fenhua; Wei, Yun

    2013-02-28

    The dehydrogenation of pyrrolyl-functionalized secondary amines initiated by rare-earth metal amides was systematically studied. Reactions of the rare-earth metal amides [(Me(3)Si)(2)N](3)RE(μ-Cl)Li(THF)(3) with pyrrolyl-functionalized secondary amines 2-(t)BuNHCH(2)-5-R-C(4)H(2)NH (R = H (1), R = (t)Bu (2)) led to dehydrogenation of the secondary amines with isolation of imino-functionalized pyrrolyl rare-earth metal complexes [2-(t)BuN=CH-5-R-C(4)H(2)N](2)REN(SiMe(3))(2) (R = H, RE = Y (3a), Dy (3b), Yb (3c), Eu (3d); R = (t)Bu, RE = Y (4a), Dy (4b), Er (4c)). The mixed ligands erbium complex [2-(t)BuNCH(2)-5-(t)Bu-C(4)H(2)N]Er[2-(t)BuN=CH-5-(t)BuC(4)H(2)N](2)ClLi(2)(THF) (4c') was isolated in a short reaction time for the synthesis of complex 4c. Reaction of the deuterated pyrrolyl-functionalized secondary amine 2-((t)BuNHCHD)C(4)H(3)NH with yttrium amide [(Me(3)Si)(2)N](3)Y(μ-Cl)Li(THF)(3) further proved that pyrrolyl-amino ligands were transferred to pyrrolyl-imino ligands. Treatment of 2-((t)BuNHCH(2))C(4)H(3)NH (1) with excess (Me(3)Si)(2)NLi gave the only pyrrole deprotonated product {[η(5):η(2):η(1)-2-((t)BuNHCH(2))C(4)H(3)N]Li(2)N(SiMe(3))(2)}(2) (5), indicating that LiN(SiMe(3))(2) could not dehydrogenate the secondary amines to imines and rare-earth metal ions had a decisive effect on the dehydrogenation. The reaction of the rare-earth metal amides [(Me(3)Si)(2)N](3)RE(μ-Cl)Li(THF)(3) with 1 equiv. of more bulky pyrrolyl-functionalized secondary amine 2-[(2,6-(i)Pr(2)C(6)H(3))NHCH(2)](C(4)H(3)NH) (6) in toluene afforded the only amine and pyrrole deprotonated dinuclear rare-earth metal amido complexes {(μ-η(5):η(1)):η(1)-2-[(2,6-(i)Pr(2)C(6)H(3))NCH(2)]C(4)H(3)N]LnN(SiMe(3))(2)}(2) (RE = Nd (7a), Sm (7b), Er (7c)), no dehydrogenation of secondary amine to imine products were observed. On the basis of experimental results, a plausible mechanism for the dehydrogenation of secondary amines to imines was proposed.

  11. The evaluation of the biomedical effectiveness of poly(amido)amine dendrimers generation 4.0 as a drug and as drug carriers: a systematic review and meta-analysis.

    PubMed

    Jędrych, Marian; Borowska, Katarzyna; Galus, Ryszard; Jodłowska-Jędrych, Barbara

    2014-02-28

    The purpose of this study was to investigate the evaluation of the biomedical effectiveness of poly(amido)amine dendrimers generation 4.0 (PAMAM G4) as a drug and as drug carriers by a systematic review of literature and meta-analysis. The results obtained from meta-analysis concluded that drug therapy reduces the change of parameters in relation to the control. The impact of the drug administered to change the test parameters are dependent on the type of tissue. PAMAM G4 may be effective in vitro and in vivo as a drug and drug carriers and may have appropriate applications in various fields of medicine. PAMAM G4 dendrimers hold promises for nanomedicine.

  12. The amide C-N bond of isatins as the directing group and the internal oxidant in Ru-catalyzed C-H activation and annulation reactions: access to 8-amido isocoumarins.

    PubMed

    Kaishap, Partha Pratim; Sarma, Bipul; Gogoi, Sanjib

    2016-07-28

    The N-O, N-N and O-O bonds are the frequently used internally oxidative directing groups used in various redox-neutral coupling reactions. The sole use of the C-N bond as the oxidizing directing group was reported recently by Li X. and co-workers for the Rh(iii)-catalyzed C-H activation of phenacyl ammonium salts. Herein, we report the use of the amide C-N bond of isatins as the oxidizing directing group for the Ru(ii)-catalyzed redox-neutral C-H activation and annulation reactions with alkynes which afford 8-amido isocoumarins. The reaction also features excellent regioselectivity with alkyl aryl substituted alkynes.

  13. Synthesis, physical-chemical characterisation and biological evaluation of novel 2-amido-3-hydroxypyridin-4(1H)-ones: Iron chelators with the potential for treating Alzheimer's disease.

    PubMed

    Gaeta, Alessandra; Molina-Holgado, Francisco; Kong, Xiao L; Salvage, Sarah; Fakih, Sarah; Francis, Paul T; Williams, Robert J; Hider, Robert C

    2011-02-01

    A novel class of 2-amido-3-hydroxypyridin-4-one iron chelators is described. These compounds have been designed to behave as suitable molecular probes which will improve our knowledge of the role of iron in neurodegenerative conditions. Neurodegenerative disorders, such as Alzheimer's disease (AD) and Parkinson disease (PD), can be considered as diverse pathological conditions sharing critical metabolic processes such as protein aggregation and oxidative stress. Interestingly, both these metabolic alterations seem to be associated with the involvement of metal ions, including iron. Iron chelation is therefore a potential therapeutic approach. The physico-chemical (pK(a), pFe(3+) and logP) and biological properties (inhibition of iron-containing enzymes) of these chelators have been investigated in order to obtain a suitable profile for the treatment of neurodegenerative conditions. Studies with neuronal cell cultures confirm that the new iron chelators are neuroprotective against β-amyloid-induced toxicity.

  14. Combined use of meio- and macrobenthic indices to assess complex chemical impacts on a stream ecosystem

    NASA Astrophysics Data System (ADS)

    McKnight, Ursula S.; Sonne, Anne T.; Rasmussen, Jes J.; Traunspurger, Walter; Höss, Sebastian; Bjerg, Poul L.

    2016-04-01

    habitats for overall ecosystem health, many biological indices tend only to reflect the ecological quality of surface water, rather than of the sedimentary zones where the accumulation of pollutants is often highest. To address this issue, we monitored meiobenthic (i.e. nematodes) and macrobenthic invertebrate communities along a pollution gradient in order to assess the impact of multiple stressors on a groundwater-fed stream, and thus quantify the link between chemical and ecological status. The studied stressors included point source pollutants originating from contaminated groundwater and aquaculture, and diffuse source pollutants originating from conventional agriculture and urban areas. The use of macrofauna is now well-accepted for assessing ecological integrity in aquatic ecosystems, but less is known about the application of meiofaunal community indicators. High abundance and ubiquitous distribution are two potential advantages for including meiofaunal indicators, and notably - for the case of groundwater-surface water interactions - they are particularly suitable for identifying changes in environmental conditions over smaller spatial scales. The results indicate a change in community composition for both meio- and macrobenthic fauna, pointing towards the presence of a local impact resulting from the discharging contaminated groundwater, which extends downstream along a dilution gradient of the groundwater contaminants. Ecological impacts could be linked to xenobiotic compounds coming from groundwater (both chlorinated solvents and pharmaceuticals), as well as the presence of trace metals of diffuse and/or biogenic origin.

  15. Dynamic sedimentary environments of an Arctic glacier-fed river estuary (Adventfjorden, Svalbard). II: Meio- and macrobenthic fauna

    NASA Astrophysics Data System (ADS)

    Włodarska-Kowalczuk, Maria; Szymelfenig, Maria; Zajiczkowski, Marek

    2007-08-01

    The paper examines the meio- and macrobenthic responses to physical disturbance and sediment instabilities in a small Arctic glacier-fed river estuary. Zajiczkowski and Włodarska-Kowalczuk [Zajiczkowski, M., Włodarska-Kowalczuk, M., 2007. Dynamic sedimentary environments of Arctic glacier-fed river estuary (Adventfjorden, Svalbard). I. Flux, deposition, and sediment dynamics. Estuarine, Coastal and Shelf Science 74(1-2), 285-296] distinguished three zones in Adventfjorden (west Spitsbergen) estuary: the tidal flat, the slope (high sedimentation, frequent sediment slides), the central basin (low sedimentation, stable sediments). The numbers of individuals and species of meio- and macrofauna were very low on the tidal flat. The total densities of meio- and macrofauna were significantly lower on the slope of the glacio-fluvial delta than in the central basin. Only the macrofauna responded to sediment instabilities on the slope by a significant decrease in total biomass. Nematodes inhabiting the slope sediments were larger than those in the central basin, although there was no significant difference in the size of harpacticoids in the two zones. The frequently disturbed, resuspended, and redeposited slope sediments were colonized by the opportunistic polychaete Capitella capitata agg. and by the high sedimentation resistant polychaetes Chaetozone setosa agg. and Cossura longocirrata. Tube-dwelling, sedentary, or suspension-feeding fauna only occurred at the central basin stations. The species richness and ratio of surface-dwelling to burrowing deposit-feeders in the macrobenthic communities decreased towards the river mouths. The differences in the taxonomic composition of communities inhabiting the sediments of the slope and the central basin were less pronounced in meiofauna (studied at a higher taxonomic level) than in the macrofauna (identified to the species level). Nevertheless, the differences were significant for both benthic compartments (ANOSIM test, P < 0

  16. pH-responsive polymeric micelle based on PEG-poly(β-amino ester)/(amido amine) as intelligent vehicle for magnetic resonance imaging in detection of cerebral ischemic area.

    PubMed

    Gao, Guang Hui; Lee, Jae Won; Nguyen, Minh Khanh; Im, Geun Ho; Yang, Jehoon; Heo, Hyejung; Jeon, Pyoung; Park, Tae Gwan; Lee, Jung Hee; Lee, Doo Sung

    2011-10-10

    A series of pH-responsive polymeric micelles is developed to act as intelligent carriers to deliver iron oxide (Fe(3)O(4)) nanoparticles and respond rapidly to an acidic stimuli environment for magnetic resonance imaging (MRI). The polymeric micelle can be self-assembled at physiological pH by a block copolymer, consisting of a hydrophilic methoxy poly(ethylene glycol) (PEG) and a pH-responsive poly(β-amino ester)/(amido amine) block. Consequently, the Fe(3)O(4) nanoparticles can be well encapsulated into polymeric micelles due to the hydrophobic interaction, shielded by a PEG coronal shell. In an acidic environment, however, the pH-responsive component, which has ionizable tert-amino groups on its backbone, can become protonated to be soluble and release the hydrophobic Fe(3)O(4) nanoparticles. The Fe(3)O(4)-loaded polymeric micelle was measured by dynamic light scattering (DLS), superconducting quantum interference device (SQUID) and a 3.0T MRI scanner. To assess the ability of this MRI probe as a pH-triggered agent, we utilize a disease rat model of cerebral ischemia that produces acidic tissue due to its pathologic condition. We found gradual accumulation of Fe(3)O(4) nanoparticles in the brain ischemic area, indicating that the pH-triggered MRI probe may be effective for targeting the acidic environment and diagnostic imaging of pathologic tissue.

  17. Use of S-[2,3-bispalmitoyiloxy-(2R)-propyl]-R-cysteinyl-amido-monomethoxy polyethylene glycol as an adjuvant improved protective immunity associated with a DNA vaccine encoding Cu,Zn superoxide dismutase of Brucella abortus in mice.

    PubMed

    Retamal-Díaz, Angello; Riquelme-Neira, Roberto; Sáez, Darwin; Rivera, Alejandra; Fernández, Pablo; Cabrera, Alex; Guzmán, Carlos A; Oñate, Angel

    2014-11-01

    This study was conducted to evaluate the immunogenicity and protective efficacy of a DNA vaccine encoding Brucella abortus Cu,Zn superoxide dismutase (SOD) using the Toll-like receptor 2/6 agonist S-[2,3-bispalmitoyiloxy-(2R)-propyl]-R-cysteinyl-amido-monomethoxy polyethylene glycol (BPPcysMPEG) as an adjuvant. Intranasal coadministration of BPPcysMPEG with a plasmid carrying the SOD-encoding gene (pcDNA-SOD) into BALB/c mice elicited antigen-specific humoral and cellular immune responses. Humoral responses were characterized by the stimulation of IgG2a and IgG1 and by the presence of SOD-specific secretory IgA in nasal and bronchoalveolar lavage fluids. Furthermore, T-cell proliferative responses and increased production of gamma interferon were also observed upon splenocyte restimulation with recombinant SOD. Cytotoxic responses were also stimulated, as demonstrated by the lysis of RB51-SOD-infected J774.A1 macrophages by cells recovered from immunized mice. The pcDNA-SOD/BPPcysMPEG formulation induced improved protection against challenge with the virulent strain B. abortus 2308 in BALB/c mice over that provided by pcDNA-SOD, suggesting the potential of this vaccination strategy against Brucella infection.

  18. How do the full-generation poly(amido)amine (PAMAM) dendrimers activate blood platelets? Activation of circulating platelets and formation of "fibrinogen aggregates" in the presence of polycations.

    PubMed

    Watala, Cezary; Karolczak, Kamil; Kassassir, Hassan; Talar, Marcin; Przygodzki, Tomasz; Maczynska, Katarzyna; Labieniec-Watala, Magdalena

    2016-04-30

    Direct use of poly(amido)amine (PAMAM) dendrimers as drugs may be limited, due to uncertain (cyto)toxicity. Peripheral blood components, which constitute the first line of a contact with administered pharmaceuticals, may become vastly affected by PAMAM dendrimers. The aim of this study was to explore how PAMAMs' polycationicity might affect blood platelet activation and reactivity, and thus trigger various haemostatic events. We monitored blood platelet reactivity in rats with experimental diabetes upon a long-term administration of the unmodified PAMAM dendrimers. In parallel, the effects on blood flow in a systemic circulation was recorded intravitally in mice administered with PAMAM G2, G3 or G4. Compounding was the in vitro approach to monitor the impact of PAMAM dendrimers on blood platelet activation and reactivity and on selected haemostatic and protein conformation parameters. We demonstrated the activating effects of polycations on blood platelets. Some diversity of the revealed outcomes considerably depended on the used approach and the particular technique employed to monitor blood platelet function. We discovered undesirable impact of plain PAMAM dendrimers on primary haemostasis and their prothrombotic influence. We emphasize the need of a more profound verifying of all the promising findings collected for PAMAMs with the use of well-designed in vivo preclinical studies.

  19. The Meio 1498 earthquake and tsunami : driving force of abrupt environmental change in the Hamana floodplain, Shizuoka prefecture, Japan.

    NASA Astrophysics Data System (ADS)

    Heyvaert, Vanessa M. A.; Fujiwara, Osamu; Umitsu, Masatomo; Sato, Yoshiki; Ono, Einsuke; Yata, Toshifumi

    2013-04-01

    The objective of this research is to study the role of a tsunami, generated by the 1498 Meio earthquake (M8.2 - 8.4) along the eastern Nankai on the geomorphological evolution of the Hamana river floodplain, located along the Pacific coastline of Central Japan (Shizuoka prefecture). Historical sources document a sudden decline at the end of the 15th century of the harbour town Hashimoto, located along the river Hamana. Before the 15th century, this river connected the Pacific Ocean with an enclosed coastal embayment separated by a sand barrier (i.e. the present-day Hamana lake) from the Pacific. The reconstruction of the palaeocourse of the Hamana river was carried out on the basis of detailed facies and diatom analyses of undisturbed sediment cores (geoslicer and drilling). The palaeochannel was detected along the western side of the present-day coastal embayment. It seems that the river's mouth was abruptly sealed off due to the migration of huge volumes of sand that initiated the development of a marsh environment upstream along the channel. The identification and radiocarbon dating of these sandy high-energy flow deposits in several cores (thick sand bed of marine origin intercalated at the estuarine - marsh environmental change boundary) suggests that the river mouth closure was initated by mass sediment transport by a storm surge or tsunami (1498 Meio tsunami and/or 1498 and 1499 large storm surges along the Hamana coastline). The same process, of sudden river mouth sealing by tsunami-transported sediments, was recently observed in the northeast of Japan during the great 2011 Sendai tsunami (Uda, T., 2011). Historical sources document that after the 1498 Meio tsunami, the Hamana back-barrier sheltered environment was reconnected to the Pacific Ocean due to breaching of its sand barrier. Both environmental changes (river mouth closure and barrier breaching)are synchronous with the sudden decline of the harbour town Hashimoto. These data suggest that disruption

  20. Size matters at deep-sea hydrothermal vents: different diversity and habitat fidelity patterns of meio- and macrofauna.

    PubMed

    Gollner, Sabine; Govenar, Breea; Fisher, Charles R; Bright, Monika

    2015-02-03

    Species with markedly different sizes interact when sharing the same habitat. Unravelling mechanisms that control diversity thus requires consideration of a range of size classes. We compared patterns of diversity and community structure for meio- and macrofaunal communities sampled along a gradient of environmental stress at deep-sea hydrothermal vents on the East Pacific Rise (9° 50' N) and neighboring basalt habitats. Both meio- and macrofaunal species richnesses were lowest in the high-stress vent habitat, but macrofaunal richness was highest among intermediate-stress vent habitats. Meiofaunal species richness was negatively correlated with stress, and highest on the basalt. In these deep-sea basalt habitats surrounding hydrothermal vents, meiofaunal species richness was consistently higher than that of macrofauna. Consideration of the physiological capabilities and life history traits of different-sized animals suggests that different patterns of diversity may be caused by different capabilities to deal with environmental stress in the 2 size classes. In contrast to meiofauna, adaptations of macrofauna may have evolved to allow them to maintain their physiological homeostasis in a variety of hydrothermal vent habitats and exploit this food-rich deep-sea environment in high abundances. The habitat fidelity patterns also differed: macrofaunal species occurred primarily at vents and were generally restricted to this habitat, but meiofaunal species were distributed more evenly across proximate and distant basalt habitats and were thus not restricted to vent habitats. Over evolutionary time scales these contrasting patterns are likely driven by distinct reproduction strategies and food demands inherent to fauna of different sizes.

  1. Size matters at deep-sea hydrothermal vents: different diversity and habitat fidelity patterns of meio- and macrofauna

    PubMed Central

    Gollner, Sabine; Govenar, Breea; Fisher, Charles R.; Bright, Monika

    2015-01-01

    Species with markedly different sizes interact when sharing the same habitat. Unravelling mechanisms that control diversity thus requires consideration of a range of size classes. We compared patterns of diversity and community structure for meio- and macrofaunal communities sampled along a gradient of environmental stress at deep-sea hydrothermal vents on the East Pacific Rise (9° 50′ N) and neighboring basalt habitats. Both meio- and macrofaunal species richnesses were lowest in the high-stress vent habitat, but macrofaunal richness was highest among intermediate-stress vent habitats. Meiofaunal species richness was negatively correlated with stress, and highest on the basalt. In these deep-sea basalt habitats surrounding hydrothermal vents, meiofaunal species richness was consistently higher than that of macrofauna. Consideration of the physiological capabilities and life history traits of different-sized animals suggests that different patterns of diversity may be caused by different capabilities to deal with environmental stress in the 2 size classes. In contrast to meiofauna, adaptations of macrofauna may have evolved to allow them to maintain their physiological homeostasis in a variety of hydrothermal vent habitats and exploit this food-rich deep-sea environment in high abundances. The habitat fidelity patterns also differed: macrofaunal species occurred primarily at vents and were generally restricted to this habitat, but meiofaunal species were distributed more evenly across proximate and distant basalt habitats and were thus not restricted to vent habitats. Over evolutionary time scales these contrasting patterns are likely driven by distinct reproduction strategies and food demands inherent to fauna of different sizes. PMID:26166922

  2. Acyl substrate preferences of an IAA-amido synthetase account for variations in grape (Vitis vinifera L.) berry ripening caused by different auxinic compounds indicating the importance of auxin conjugation in plant development.

    PubMed

    Böttcher, Christine; Boss, Paul K; Davies, Christopher

    2011-08-01

    Nine Gretchen Hagen (GH3) genes were identified in grapevine (Vitis vinifera L.) and six of these were predicted on the basis of protein sequence similarity to act as indole-3-acetic acid (IAA)-amido synthetases. The activity of these enzymes is thought to be important in controlling free IAA levels and one auxin-inducible grapevine GH3 protein, GH3-1, has previously been implicated in the berry ripening process. Ex planta assays showed that the expression of only one other GH3 gene, GH3-2, increased following the treatment of grape berries with auxinic compounds. One of these was the naturally occurring IAA and the other two were synthetic, α-naphthalene acetic acid (NAA) and benzothiazole-2-oxyacetic acid (BTOA). The determination of steady-state kinetic parameters for the recombinant GH3-1 and GH3-2 proteins revealed that both enzymes efficiently conjugated aspartic acid (Asp) to IAA and less well to NAA, while BTOA was a poor substrate. GH3-2 gene expression was induced by IAA treatment of pre-ripening berries with an associated increase in levels of IAA-Asp and a decrease in free IAA levels. This indicates that GH3-2 responded to excess auxin to maintain low levels of free IAA. Grape berry ripening was not affected by IAA application prior to veraison (ripening onset) but was considerably delayed by NAA and even more so by BTOA. The differential effects of the three auxinic compounds on berry ripening can therefore be explained by the induction and acyl substrate specificity of GH3-2. These results further indicate an important role for GH3 proteins in controlling auxin-related plant developmental processes.

  3. Antitumor effects of a tetradentate amido-carboxylate ligands and corresponding square-planar palladium(II) complexes toward some cancer cells. Crystal structure, DFT modeling and ligand to DNA probe docking simulation.

    PubMed

    Matović, Zoran D; Mrkalić, Emina; Bogdanović, Gordana; Kojić, Vesna; Meetsma, Auke; Jelić, Ratomir

    2013-04-01

    Novel square-planar palladium(II) complexes with O-N-N-O-type ligands H4mda (H4mda=malamido-N,N'-diacetic acid) and H4obp (H4obp=oxamido-N,N'-di-3-propionic acid) were prepared and characterized. The ligands coordinate to the palladium(II) ion via two pairs of deprotonated ligating atoms with square chelation. A four coordinate, square-planar geometry was verified crystallographicaly for the K2[Pd(mda)]·H2O complex. The binary and ternary systems of Pd(II) ion with H4mda or H4obp (L) as primary ligands and guanosine (A) as secondary ligand were studied in aqueous solutions in 0.1 M NaCl ionic medium at 25 °C by potentiometric titrations. In addition, calculations based on density functional methods (DFT) were carried out. A natural bonding orbital analysis indicated that the Pd-N bonds are three-centric in nature and mainly governed by charge transfer via a strong delocalization of the oxygen lone pair with "p" character into the bonding Pd-N orbital. Mononuclear palladium(II) complexes together with amido acid N,O-containing ligands were tested against several tumor cells and reveal significant antitumor activity and lower resistance of tumor cells in vitro than cisplatin. In this paper, interactions of palladium complexes with DNA are discussed in order to provide guidance and determine structure and antitumor activity relationships for continuing studies of these systems. Docking simulation on DNA dodecamer or 29-mer (Lippard solved crystal structures), suggests several favorable interactions with the hydrogen pocket/binding site for the incoming ligands. These results support amidoacids/Pd complexes as novel antitumor drugs and suggest that their potent cell life inhibition may contribute to its anti-cancer efficacy.

  4. Acyl substrate preferences of an IAA-amido synthetase account for variations in grape (Vitis vinifera L.) berry ripening caused by different auxinic compounds indicating the importance of auxin conjugation in plant development

    PubMed Central

    Böttcher, Christine; Boss, Paul K.; Davies, Christopher

    2011-01-01

    Nine Gretchen Hagen (GH3) genes were identified in grapevine (Vitis vinifera L.) and six of these were predicted on the basis of protein sequence similarity to act as indole-3-acetic acid (IAA)-amido synthetases. The activity of these enzymes is thought to be important in controlling free IAA levels and one auxin-inducible grapevine GH3 protein, GH3-1, has previously been implicated in the berry ripening process. Ex planta assays showed that the expression of only one other GH3 gene, GH3-2, increased following the treatment of grape berries with auxinic compounds. One of these was the naturally occurring IAA and the other two were synthetic, α-naphthalene acetic acid (NAA) and benzothiazole-2-oxyacetic acid (BTOA). The determination of steady-state kinetic parameters for the recombinant GH3-1 and GH3-2 proteins revealed that both enzymes efficiently conjugated aspartic acid (Asp) to IAA and less well to NAA, while BTOA was a poor substrate. GH3-2 gene expression was induced by IAA treatment of pre-ripening berries with an associated increase in levels of IAA-Asp and a decrease in free IAA levels. This indicates that GH3-2 responded to excess auxin to maintain low levels of free IAA. Grape berry ripening was not affected by IAA application prior to veraison (ripening onset) but was considerably delayed by NAA and even more so by BTOA. The differential effects of the three auxinic compounds on berry ripening can therefore be explained by the induction and acyl substrate specificity of GH3-2. These results further indicate an important role for GH3 proteins in controlling auxin-related plant developmental processes. PMID:21543520

  5. Reaction Mechanism of the Symmetry-Forbidden [2+2] Addition of Ethylene and Acetylene to Amido-Substituted Digermynes and Distannynes Ph2N-EE-NPh2, (E = Ge, Sn): A Theoretical Study.

    PubMed

    Zhao, Lili; Jones, Cameron; Frenking, Gernot

    2015-08-24

    Quantum chemical calculations of reaction mechanisms for the formal [2+2] addition of ethylene and acetylene to the amido-substituted digermyne and distannyne Ph2N-EE-NPh2 (E = Ge, Sn) have been carried out by using density functional theory at the BP86/def2-TZVPP level. The nature and bonding situations were studied with the NBO method and with the charge and energy decomposition analysis EDA-NOCV. The addition of ethylene to Ph2N-EE-NPh2 takes place through an initial [2+1] addition to one metal atom and consecutive rearrangement to four-membered cyclic species, which feature a weak E-E bond. Rotation about the C-C bond with concomitant rupture of the E-E bond leads to the 1,2-disubstituted ethanes, which have terminal E(NPh2) groups. The overall reaction Ph2N-EE-NPh2+C2H4→(Ph2N)E-C2H4-E(NPh2) has very low activation barriers and is slightly exergonic for E = Ge but slightly endergonic for E = Sn. The analysis of the electronic structure shows that there is charge donation of nearly one electron to the ethylene moiety already in the first part of the reaction. The energy partitioning analysis suggests that the HOMO(Ph2N-EE-NPh2)→LUMO(C2H4) interaction has a similar strength as the HOMO(C2H4)→LUMO(Ph2N-EE-NPh2) interaction. The [2+2] addition of acetylene to Ph2N-EE-NPh2 also takes place through an initial [2+1] approach, which eventually leads to 1,2-disubstituted olefins (Ph2N)E-C2H2-E(NPh2). The formation of the energetically lowest lying conformations of cis-(Ph2N)E-C2H2-E(NPh2), which occurs with very low activation barriers, is clearly exergonic for the germanium and the tin compound. The trans-coordinated isomers of (Ph2N)E-C2H2-E(NPh2) are slightly lower in energy than the cis form but they are separated by a substantial energy barrier for the rotation about the C-C bond. The energy decomposition analysis indicates that the initial reaction takes place under formation of electron-sharing bonds between triplet fragments rather than HOMO

  6. Tetrakis-amido high flux membranes

    DOEpatents

    McCray, Scott B.

    1989-01-01

    Composite RO membranes of a microporous polymeric support and a polyamide reaction product of a tetrakis-aminomethyl compound and a polyacylhalide are disclosed, said membranes exhibiting high flux and good chlorine resistance.

  7. Tetrakis-amido high flux membranes

    DOEpatents

    McCray, S.B.

    1989-10-24

    Composite RO membranes of a microporous polymeric support and a polyamide reaction product of a tetrakis-aminomethyl compound and a polyacylhalide are disclosed, said membranes exhibiting high flux and good chlorine resistance.

  8. Influence of filled d pi-manifold and L/L' ligands on the structure, basicity, and bond rotations of the octahedral and d(6) amido complexes TpRu(L)(L')(NHPh) (Tp = hydridotris(pyrazolyl)borate; L = L' = PMe(3) or P(OMe)(3), or L = CO and L' = PPh(3)): solid-state structures of [TpRu(PMe(3))(2)(NH(2)Ph)][OTf], [TpRu[P(OMe)(3)](2)(NH(2)Ph)][OTf], and TpRu[P(OMe)(3)](2)(NHPh).

    PubMed

    Conner, David; Jayaprakash, K N; Gunnoe, T Brent; Boyle, Paul D

    2002-06-03

    It has been suggested that the reactivity of pi-donating ligands bound to late-transition-metal complexes is heightened due to high d-electron counts. Herein, the synthesis and characterization of the Ru(II) amine and Ru(II) amido complexes [TpRuL(2)(NH(2)Ph)][OTf] (OTf = trifluoromethanesulfonate) and TpRuL(2)(NHPh) (L = PMe(3) or P(OMe)(3)) are presented, including solid-state X-ray diffraction studies of [TpRu(PMe(3))(2)(NH(2)Ph)][OTf], [TpRu[P(OMe)(3)](2)(NH(2)Ph)][OTf], and TpRu[P(OMe)(3)](2)(NHPh). The pK(a)'s of the Ru(II) amine complexes and the previously reported [TpRu(CO)(PPh(3))(NH(2)Ph)](+) have been estimated to be comparable to that of malononitrile in methylene chloride. In addition, the impact of the filled dpi-manifold (i.e., Ru(II) and d(6) octahedral systems) on barriers to rotation of the Ru-NHPh moieties has been studied. For TpRu(PMe(3))(2)(NHPh) and TpRu[P(OMe)(3)](2)(NHPh), evidence for hindered rotation about the amido nitrogen and phenyl ipso carbon has been observed, and the relative N-C and Ru-N bond rotational barriers for the series of three amido complexes are discussed in terms of the pi-conflict.

  9. Direct Spectroscopic Observation of Large Quenching of First Order Orbital Angular Momentum with Bending in Monomeric, Two-Coordinate Fe(II) Primary Amido Complexes and the Profound Magnetic Effects of the Absence of Jahn- and Renner-Teller Distortions in Rigorously Linear Coordination

    PubMed Central

    Merrill, W. Alexander; Stich, Troy A.; Brynda, Marcin; Yeagle, Gregory J.; Fettinger, James C.; De Hont, Raymond; Reiff, William M.; Schulz, Charles E.; Britt, R. David; Power, Philip P.

    2009-01-01

    The monomeric iron(II) amido derivatives Fe{N(H)Ar*}2 (1), Ar* = C6H3-2,6-(C6H2-2,4,6-Pri3)2, and Fe{N(H)Ar#}2 (2), Ar# = C6H3-2,6-(C6H2-2,4,6-Me3)2, were synthesized and studied in order to determine the effects of geometric changes on their unusual magnetic properties. The compounds, which are the first stable homoleptic primary amides of iron(II), were obtained by the transamination of Fe{N(SiMe3)2}2, with HN(SiMe3)2 elimination, by the primary amines H2NAr* or H2NAr#. X-ray crystallography shows that they have either strictly linear (1) or bent (2, N–Fe–N = 140.9(2)°) iron coordination. Variable temperature magnetization and applied magnetic field Mössbauer spectroscopy studies reveal a very large dependence of the magnetic properties on the metal coordination geometry. At ambient temperature, the linear 1 displayed an effective magnetic moment in the range 7.0 to 7.50 μB, consistent with essentially free ion magnetism. There is a very high internal orbital field component, HL ≈ 170 T which is only exceeded by a HL ≈ 203 T of Fe{C(SiMe3)3}2. In contrast, the strongly bent 2 displays a significantly lower μeff value in the range 5.25 to 5.80 μB at ambient temperature and a much lower orbital field HL value of 116 T. The data for the two amido complexes demonstrate a very large quenching of the orbital magnetic moment upon bending the linear geometry. In addition, a strong correlation of HL with overall formal symmetry is confirmed. ESR spectroscopy supports the existence of large orbital magnetic moments in 1 and 2, and DFT calculations provide good agreement with the physical data. PMID:19670870

  10. Structural Insights into the PorK and PorN Components of the Porphyromonas gingivalis Type IX Secretion System

    PubMed Central

    Gorasia, Dhana G.; Veith, Paul D.; Hanssen, Eric G.; Glew, Michelle D.; Sato, Keiko; Yukitake, Hideharu; Nakayama, Koji; Reynolds, Eric C.

    2016-01-01

    The type IX secretion system (T9SS) has been recently discovered and is specific to Bacteroidetes species. Porphyromonas gingivalis, a keystone pathogen for periodontitis, utilizes the T9SS to transport many proteins including the gingipain virulence factors across the outer membrane and attach them to the cell surface via a sortase-like mechanism. At least 11 proteins have been identified as components of the T9SS including PorK, PorL, PorM, PorN and PorP, however the precise roles of most of these proteins have not been elucidated and the structural organization of these components is unknown. In this study, we purified PorK and PorN complexes from P. gingivalis and using electron microscopy we have shown that PorN and the PorK lipoprotein interact to form a 50 nm diameter ring-shaped structure containing approximately 32–36 subunits of each protein. The formation of these rings was dependent on both PorK and PorN, but was independent of PorL, PorM and PorP. PorL and PorM were found to form a separate stable complex. PorK and PorN were protected from proteinase K cleavage when present in undisrupted cells, but were rapidly degraded when the cells were lysed, which together with bioinformatic analyses suggests that these proteins are exposed in the periplasm and anchored to the outer membrane via the PorK lipid. Chemical cross-linking and mass spectrometry analyses confirmed the interaction between PorK and PorN and further revealed that they interact with the PG0189 outer membrane protein. Furthermore, we established that PorN was required for the stable expression of PorK, PorL and PorM. Collectively, these results suggest that the ring-shaped PorK/N complex may form part of the secretion channel of the T9SS. This is the first report showing the structural organization of any T9SS component. PMID:27509186

  11. Structural Insights into the PorK and PorN Components of the Porphyromonas gingivalis Type IX Secretion System.

    PubMed

    Gorasia, Dhana G; Veith, Paul D; Hanssen, Eric G; Glew, Michelle D; Sato, Keiko; Yukitake, Hideharu; Nakayama, Koji; Reynolds, Eric C

    2016-08-01

    The type IX secretion system (T9SS) has been recently discovered and is specific to Bacteroidetes species. Porphyromonas gingivalis, a keystone pathogen for periodontitis, utilizes the T9SS to transport many proteins including the gingipain virulence factors across the outer membrane and attach them to the cell surface via a sortase-like mechanism. At least 11 proteins have been identified as components of the T9SS including PorK, PorL, PorM, PorN and PorP, however the precise roles of most of these proteins have not been elucidated and the structural organization of these components is unknown. In this study, we purified PorK and PorN complexes from P. gingivalis and using electron microscopy we have shown that PorN and the PorK lipoprotein interact to form a 50 nm diameter ring-shaped structure containing approximately 32-36 subunits of each protein. The formation of these rings was dependent on both PorK and PorN, but was independent of PorL, PorM and PorP. PorL and PorM were found to form a separate stable complex. PorK and PorN were protected from proteinase K cleavage when present in undisrupted cells, but were rapidly degraded when the cells were lysed, which together with bioinformatic analyses suggests that these proteins are exposed in the periplasm and anchored to the outer membrane via the PorK lipid. Chemical cross-linking and mass spectrometry analyses confirmed the interaction between PorK and PorN and further revealed that they interact with the PG0189 outer membrane protein. Furthermore, we established that PorN was required for the stable expression of PorK, PorL and PorM. Collectively, these results suggest that the ring-shaped PorK/N complex may form part of the secretion channel of the T9SS. This is the first report showing the structural organization of any T9SS component.

  12. Intermitência alfvênica gerada por caos na atmosfera solar e no vento solar

    NASA Astrophysics Data System (ADS)

    Rempel, E. L.; Chian, A. C.-L.; Macau, E. E. N.; Rosa, R. R.

    2003-08-01

    Dados medidos no vento solar rápido proveniente dos buracos coronais revelam que os plasmas no meio interplanetário são dominados por flutuações Alfvênicas, caracterizadas por uma alta correlação entre as variações do campo magnético e da velocidade do plasma. As flutuações exibem muitas características esperadas em turbulência magneto-hidrodinâmica totalmente desenvolvida, tais como intermitência e espectros contínuos. Contudo, os mecanismos responsáveis pela evolução de turbulência Alfvênica intermitente não são completamente compreendidos. Neste trabalho a teoria de caos é usada para explicar como sistemas Alfvênicos, modelados pela equação Schrödinger não-linear derivativa e pela equação Kuramoto-Sivashinsky, podem se tornar fortemente caóticos à medida em que parâmetros do plasma são variados. Pequenas perturbações no parâmetro de dissipação podem fazer com que o sistema mude bruscamente de um regime periódico, ou fracamente caótico, para um regime fortemente caótico. As séries temporais das flutuações do campo magnético nos regimes fortemente caóticos exibem comportamento intermitente, em que fases laminares ou fracamente caóticas são interrompidas por fortes estouros caóticos. É mostrado que o regime fortemente caótico é atingido quando as soluções periódicas ou fracamente caóticas globalmente estáveis interagem com soluções do sistema que são fortemente caóticas, mas globalmente instáveis. Estas soluções globalmente instáveis são conjuntos caóticos não-atrativos conhecidos como selas caóticas, e são responsáveis pelos fortes estouros nos regimes intermitentes. Selas caóticas têm sido detectadas experimentalmente em uma grande variedade de sistemas, sendo provável que elas desempenhem um papel importante na turbulência intermitente observada em plasmas espaciais.

  13. New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses, X-ray diffraction structures of TaCl(NMe2)(3)[N(TMS)NMe2] and Ta(NMe2)(4)[N(TMS)NMe2], and fluxional behavior of the amido and hydrazido ligands in solution

    SciTech Connect

    Huang, Shih-Huang Huang; Pilvi, Tero; Wang, Xiaoping; Leskela,, Markku; Richmond, Michael G.

    2010-01-01

    The synthesis and structural characterization of new tantalum(V) compounds containing a single hydrazido(1) ligand are reported. Hydrazinolysis of TaCl(NMe2)(4) using trimethylsilyl(dimethyl)hydrazine affords the compound TaCl(NMe2)(3)[N(TMS)NMe2] in essentially quantitative yield. Metathetical replacement of the chloride ligand in TaCl(NMe2)(3)]N(TMS)NMe2] by LiNMe2 gives the all-nitrogen coordinated compound Ta(NMe2)(4)[N(TMS)NMe2]. VT H-1 NMR studies support the existence of low-energy pathways involving rotation about the Ta-N bonds of the ancillary amido and hydrazido ligands in both hydrazido-substituted compounds. X-ray crystallographic analyses confirm the octahedral disposition about the tantalum metal in TaCl(NMe2)(3)[N(TMS)NMe2] and Ta(NMe2)(4)[N(TMS)NMe2] and the presence of an mu(2)-hydrazido(1) ligand. Preliminary data using Ta(NMe2)(4)[N(TMS)NMe2] as an ALD precursor for the preparation of tantalum nitride and tantalum oxide thin films are presented.

  14. Análise dos Conceitos Astronômicos Apresentados por Professores de Algumas Escolas Estaduais Brasileiras

    NASA Astrophysics Data System (ADS)

    Voelzke, Marcos Rincon; Gonzaga, Edson Pereira

    2011-12-01

    A razão para o desenvolvimento deste trabalho baseia-se no fato de que muitos professores da Educação Básica (EB) não lidam com conceitos relacionados à astronomia, e quando o fazem eles simplesmente seguem livros didáticos que podem conter erros conceituais. Como é de conhecimento geral a astronomia é um dos conteúdos a serem ensinados na EB fazendo parte dos Parâmetros Curriculares Nacionais e das Propostas Curriculares do Estado de São Paulo, mas é um fato, que vários pesquisadores apontam, a existência de muitos problemas no ensino da astronomia. Com o propósito de minimizar algumas dessas deficiências foi realizado um trabalho de pesquisa com a utilização de questionários pré e pós pesquisa, para tanto foi desenvolvido um Curso de Extensão Universitária para professores da Diretoria de Ensino Regional (DE) que abrange Mauá, Ribeirão Pires e Rio Grande da Serra (no Estado de São Paulo) com os seguintes objetivos: levantar concepções alternativas; subsidiar os professores por meio de palestras, debates e workshops, e verificar o sucesso da aprendizagem após o curso, adotando-se como referência, para a análise dos resultados, os dicionários de Língua Portuguesa (FERREIRA, 2004) e Enciclopédico de Astronomia e Astronáutica (MOURĀO, 1995). Portanto, dezesseis questões foram aplicadas antes e após o curso, assim pode-se verificar após a pesquisa que 100,0% dos professores sabiam os nomes das fases da Lua, 97,0% entenderam que o Sistema Solar é composto por oito planetas, 78,1% foram capazes de explicar como ocorre um eclipse lunar, um eclipse solar e um solstício, 72,7% sabiam como explicar a ocorrência das estações do ano; 64,5% explicaram corretamente a ocorrência do equinócio, 89,7% foram capazes de definir adequadamente o termo cometa; 63,6% definiram asteróide, 54,5% meteoro, 58,1% galáxia, e 42,4% planeta. Os resultados obtidos indicam uma aprendizagem significativa por parte dos participantes.

  15. The PorX Response Regulator of the Porphyromonas gingivalis PorXY Two-Component System Does Not Directly Regulate the Type IX Secretion Genes but Binds the PorL Subunit

    PubMed Central

    Vincent, Maxence S.; Durand, Eric; Cascales, Eric

    2016-01-01

    The Type IX secretion system (T9SS) is a versatile multi-protein complex restricted to bacteria of the Bacteriodetes phylum and responsible for the secretion or cell surface exposition of diverse proteins that participate to S-layer formation, gliding motility or pathogenesis. The T9SS is poorly characterized but a number of proteins involved in the assembly of the secretion apparatus in the oral pathogen Porphyromonas gingivalis have been identified based on genome substractive analyses. Among these proteins, PorY, and PorX encode typical two-component system (TCS) sensor and CheY-like response regulator respectively. Although the porX and porY genes do not localize at the same genetic locus, it has been proposed that PorXY form a bona fide TCS. Deletion of porX in P. gingivalis causes a slight decrease of the expression of a number of other T9SS genes, including sov, porT, porP, porK, porL, porM, porN, and porY. Here, we show that PorX and the soluble cytoplasmic domain of PorY interact. Using electrophoretic mobility shift, DNA-protein co-purification and heterologous host expression assays, we demonstrate that PorX does not bind T9SS gene promoters and does not directly regulate expression of the T9SS genes. Finally, we show that PorX interacts with the cytoplasmic domain of PorL, a component of the T9SS membrane core complex and propose that the CheY-like PorX protein might be involved in the dynamics of the T9SS. PMID:27630829

  16. Diphenyl (p-tolyl­amido)­phosphate

    PubMed Central

    Pourayoubi, Mehrdad; Zargaran, Poorya; Ghammamy, Shahriar; Eshtiagh-Hosseini, Hossein

    2010-01-01

    The P atom in the title compound, C19H18NO3P, exhibits a distorted tetra­hedral configuration while the N atom shows a planar coordination. In the crystal, inter­molecular N—H⋯O hydrogen bonds form centrosymmetric dimers. PMID:21589626

  17. System design description for portable 1,000 CFM exhauster Skids POR-007/Skid E and POR-008/Skid F

    SciTech Connect

    Nelson, O.D.

    1998-07-25

    The primary purpose of the two 1,000 CFM Exhauster Skids, POR-007-SKID E and POR-008-SKID F, is to provide backup to the waste tank primary ventilation systems for tanks 241-C-106 and 241-AY-102, and the AY-102 annulus in the event of a failure during the sluicing of tank 241-C-106 and subsequent transfer of sluiced waste to 241-AY-102. This redundancy is required since both of the tank ventilation systems have been declared as Safety Class systems.

  18. Click-chemistry approach to study mycoloylated proteins: Evidence for PorB and PorC porins mycoloylation in Corynebacterium glutamicum.

    PubMed

    Issa, Hanane; Huc-Claustre, Emilie; Reddad, Thamila; Bonadé Bottino, Nolwenn; Tropis, Maryelle; Houssin, Christine; Daffé, Mamadou; Bayan, Nicolas; Dautin, Nathalie

    2017-01-01

    Protein mycoloylation is a recently identified, new form of protein acylation. This post-translational modification consists in the covalent attachment of mycolic acids residues to serine. Mycolic acids are long chain, α-branched, β-hydroxylated fatty acids that are exclusively found in the cell envelope of Corynebacteriales, a bacterial order that includes important genera such as Mycobacterium, Nocardia or Corynebacterium. So far, only 3 mycoloylated proteins have been identified: PorA, PorH and ProtX from C. glutamicum. Whereas the identity and function of ProtX is unknown, PorH and PorA associate to form a membrane channel, the activity of which is dependent upon PorA mycoloylation. However, the exact role of mycoloylation and the generality of this phenomenon are still unknown. In particular, the identity of other mycoloylated proteins, if any, needs to be determined together with establishing whether such modification occurs in Corynebacteriales genera other than Corynebacterium. Here, we tested whether a metabolic labeling and click-chemistry approach could be used to detect mycoloylated proteins. Using a fatty acid alkyne analogue, we could indeed label PorA, PorH and ProtX and determine ProtX mycoloylation site. Importantly, we also show that two other porins from C. glutamicum, PorB and PorC are mycoloylated.

  19. Click-chemistry approach to study mycoloylated proteins: Evidence for PorB and PorC porins mycoloylation in Corynebacterium glutamicum

    PubMed Central

    Issa, Hanane; Huc-Claustre, Emilie; Reddad, Thamila; Bonadé Bottino, Nolwenn; Tropis, Maryelle; Houssin, Christine; Daffé, Mamadou; Bayan, Nicolas

    2017-01-01

    Protein mycoloylation is a recently identified, new form of protein acylation. This post-translational modification consists in the covalent attachment of mycolic acids residues to serine. Mycolic acids are long chain, α-branched, β-hydroxylated fatty acids that are exclusively found in the cell envelope of Corynebacteriales, a bacterial order that includes important genera such as Mycobacterium, Nocardia or Corynebacterium. So far, only 3 mycoloylated proteins have been identified: PorA, PorH and ProtX from C. glutamicum. Whereas the identity and function of ProtX is unknown, PorH and PorA associate to form a membrane channel, the activity of which is dependent upon PorA mycoloylation. However, the exact role of mycoloylation and the generality of this phenomenon are still unknown. In particular, the identity of other mycoloylated proteins, if any, needs to be determined together with establishing whether such modification occurs in Corynebacteriales genera other than Corynebacterium. Here, we tested whether a metabolic labeling and click-chemistry approach could be used to detect mycoloylated proteins. Using a fatty acid alkyne analogue, we could indeed label PorA, PorH and ProtX and determine ProtX mycoloylation site. Importantly, we also show that two other porins from C. glutamicum, PorB and PorC are mycoloylated. PMID:28199365

  20. Por La Vida intervention model for cancer prevention in Latinas.

    PubMed

    Navarro, A M; Senn, K L; Kaplan, R M; McNicholas, L; Campo, M C; Roppe, B

    1995-01-01

    Our goal was to describe the development and implementation of an intervention on cancer prevention for Latinas in San Diego, Calif. Thirty-six lay community workers ("consejeras") were recruited and trained to conduct educational group sessions. Each consejera recruited approximately 14 peers from the community to participate in the program (total number = 512). Half of the consejeras were randomly assigned to a control group, in which they participated in an equally engaging program entitled "Community Living Skills." Implementation of the intervention was assessed by qualitative and quantitative methods. Preintervention and postintervention self-report information was obtained from project participants on access to health care services, cancer knowledge, preventive measures, and previous cancer-screening examinations. Base-line data suggest that lack of knowledge, costs of cancer-screening tests, and the lack of a regular health care provider are the major obstacles against obtaining cancer-screening tests. Predisposing factors, such as fear and embarrassment, also constitute barriers to getting regular cervical cancer screening. Preliminary analysis indicates that the Por La Vida intervention increases use of cancer-screening tests in comparison to a community living skills control group. Universal access to health care would remove some of the major financial barriers to cancer screening. The Por La Vida program attempts to overcome the substantial barriers by reaching out to low-income Latinas and by providing information regarding the availability, acceptability, and preventive nature of cancer-screening tests.

  1. Meio-Socks & Other Genetic Yarns

    ERIC Educational Resources Information Center

    Stravroulakis, Anthea M.

    2005-01-01

    As a teacher, the author is always interested in novel pedagogical methods for presenting complex concepts and material in genetics that interest and engage the students, while helping them understand and recall the lesson. In this article, she describes sock and yarn models that allow students the opportunity to examine the meiotic process in a…

  2. Compton imaging with the PorGamRays spectrometer

    NASA Astrophysics Data System (ADS)

    Judson, D. S.; Boston, A. J.; Coleman-Smith, P. J.; Cullen, D. M.; Hardie, A.; Harkness, L. J.; Jones, L. L.; Jones, M.; Lazarus, I.; Nolan, P. J.; Pucknell, V.; Rigby, S. V.; Seller, P.; Scraggs, D. P.; Simpson, J.; Slee, M.; Sweeney, A.; PorGamRays Collaboration

    2011-10-01

    The PorGamRays project aims to develop a portable gamma-ray detection system with both spectroscopic and imaging capabilities. The system is designed around a stack of thin Cadmium Zinc Telluride (CZT) detectors. The imaging capability utilises the Compton camera principle. Each detector is segmented into 100 pixels which are read out through custom designed Application Specific Integrated Circuits (ASICs). This device has potential applications in the security, decommissioning and medical fields. This work focuses on the near-field imaging performance of a lab-based demonstrator consisting of two pixelated CZT detectors, each of which is bonded to a NUCAM II ASIC. Measurements have been made with point 133Ba and 57Co sources located ˜35 mm from the surface of the scattering detector. Position resolution of ˜20 mm FWHM in the x and y planes is demonstrated.

  3. Gliding motility and Por secretion system genes are widespread among members of the phylum bacteroidetes.

    PubMed

    McBride, Mark J; Zhu, Yongtao

    2013-01-01

    The phylum Bacteroidetes is large and diverse, with rapid gliding motility and the ability to digest macromolecules associated with many genera and species. Recently, a novel protein secretion system, the Por secretion system (PorSS), was identified in two members of the phylum, the gliding bacterium Flavobacterium johnsoniae and the nonmotile oral pathogen Porphyromonas gingivalis. The components of the PorSS are not similar in sequence to those of other well-studied bacterial secretion systems. The F. johnsoniae PorSS genes are a subset of the gliding motility genes, suggesting a role for the secretion system in motility. The F. johnsoniae PorSS is needed for assembly of the gliding motility apparatus and for secretion of a chitinase, and the P. gingivalis PorSS is involved in secretion of gingipain protease virulence factors. Comparative analysis of 37 genomes of members of the phylum Bacteroidetes revealed the widespread occurrence of gliding motility genes and PorSS genes. Genes associated with other bacterial protein secretion systems were less common. The results suggest that gliding motility is more common than previously reported. Microscopic observations confirmed that organisms previously described as nonmotile, including Croceibacter atlanticus, "Gramella forsetii," Paludibacter propionicigenes, Riemerella anatipestifer, and Robiginitalea biformata, exhibit gliding motility. Three genes (gldA, gldF, and gldG) that encode an apparent ATP-binding cassette transporter required for F. johnsoniae gliding were absent from two related gliding bacteria, suggesting that the transporter may not be central to gliding motility.

  4. An investigation of exploitation versus exploration in GBEA optimization of PORS 15 and 16 Problems

    SciTech Connect

    Koch, Kaelynn

    2012-01-01

    It was hypothesized that the variations in time to solution are driven by the competing mechanisms of exploration and exploitation.This thesis explores this hypothesis by examining two contrasting problems that embody the hypothesized tradeoff between exploration and exploitation. Plus one recall store (PORS) is an optimization problem based on the idea of a simple calculator with four buttons: plus, one, store, and recall. Integer addition and store are classified as operations, and one and memory recall are classified as terminals. The goal is to arrange a fixed number of keystrokes in a way that maximizes the numerical result. PORS 15 (15 keystrokes) represents the subset of difficult PORS problems and PORS 16 (16 keystrokes) represents the subset of PORS problems that are easiest to optimize. The goal of this work is to examine the tradeoff between exploitation and exploration in graph based evolutionary algorithm (GBEA) optimization. To do this, computational experiments are used to examine how solutions evolve in PORS 15 and 16 problems when solved using GBEAs. The experiment is comprised of three components; the graphs and the population, the evolutionary algorithm rule set, and the example problems. The complete, hypercube, and cycle graphs were used for this experiment. A fixed population size was used.

  5. Crystallographic analysis of Neisseria meningitidis PorB extracellular loops potentially implicated in TLR2 recognition

    PubMed Central

    Kattner, Christof; Toussi, Deana; Zaucha, Jan; Wetzler, Lee M.; Rüppel, Nadine; Zachariae, Ulrich; Massari, Paola; Tanabe, Mikio

    2014-01-01

    Among all Neisseriae species, N. meningitidis and N. gonorrhoeae are the only human pathogens, causative agents of bacterial meningitis and gonorrhoea, respectively. PorB, a pan-Neisseriae trimeric porin that mediates diffusive transport of essential molecules across the bacterial outer membrane, is also known to activate host innate immunity via Toll-like receptor 2 (TLR2)-mediated signaling. The molecular mechanism of PorB binding to TLR2 is not known, but it has been hypothesized that electrostatic interactions contribute to ligand/receptor binding. Strain-specific sequence variability in the surface-exposed loops of PorB which are potentially implicated in TLR2 binding, may explain the difference in TLR2-mediated cell activation in vitro by PorB homologs from the commensal N. lactamica and the pathogen N. meningitidis. Here, we report a comparative structural analysis of PorB from N. meningitidis serogroup B strain 8765 (63% sequence homology with PorB from N. meningitidis serogroup W135) and a mutant in which amino acid substitutions in the extracellular loop 7 lead to significantly reduced TLR2-dependent activity in vitro. We observe that this mutation both alters the loop conformation and causes dramatic changes of electrostatic surface charge, both of which may affect TLR2 recognition and signalling. PMID:24361688

  6. Por Secretion System-Dependent Secretion and Glycosylation of Porphyromonas gingivalis Hemin-Binding Protein 35

    PubMed Central

    Shoji, Mikio; Sato, Keiko; Yukitake, Hideharu; Kondo, Yoshio; Narita, Yuka; Kadowaki, Tomoko; Naito, Mariko; Nakayama, Koji

    2011-01-01

    The anaerobic Gram-negative bacterium Porphyromonas gingivalis is a major pathogen in severe forms of periodontal disease and refractory periapical perodontitis. We have recently found that P. gingivalis has a novel secretion system named the Por secretion system (PorSS), which is responsible for secretion of major extracellular proteinases, Arg-gingipains (Rgps) and Lys-gingipain. These proteinases contain conserved C-terminal domains (CTDs) in their C-termini. Hemin-binding protein 35 (HBP35), which is one of the outer membrane proteins of P. gingivalis and contributes to its haem utilization, also contains a CTD, suggesting that HBP35 is translocated to the cell surface via the PorSS. In this study, immunoblot analysis of P. gingivalis mutants deficient in the PorSS or in the biosynthesis of anionic polysaccharide-lipopolysaccharide (A-LPS) revealed that HBP35 is translocated to the cell surface via the PorSS and is glycosylated with A-LPS. From deletion analysis with a GFP-CTD[HBP35] green fluorescent protein fusion, the C-terminal 22 amino acid residues of CTD[HBP35] were found to be required for cell surface translocation and glycosylation. The GFP-CTD fusion study also revealed that the CTDs of CPG70, peptidylarginine deiminase, P27 and RgpB play roles in PorSS-dependent translocation and glycosylation. However, CTD-region peptides were not found in samples of glycosylated HBP35 protein by peptide map fingerprinting analysis, and antibodies against CTD-regions peptides did not react with glycosylated HBP35 protein. These results suggest both that the CTD region functions as a recognition signal for the PorSS and that glycosylation of CTD proteins occurs after removal of the CTD region. Rabbits were used for making antisera against bacterial proteins in this study. PMID:21731719

  7. Molecular characterisation of Porcine rubulavirus (PorPV) isolates from different outbreaks in Mexico.

    PubMed

    Cuevas-Romero, S; Rivera-Benítez, J F; Blomström, A-L; Ramliden, M; Hernández-Baumgarten, E; Hernández-Jáuregui, P; Ramírez-Mendoza, H; Berg, M

    2016-02-01

    Since the report of the initial outbreak of Porcine rubulavirus (PorPV) infection in pigs, only one full-length genome from 1984 (PorPV-LPMV/1984) has been characterised. To investigate the overall genetic variation, full-length gene nucleotide sequences of current PorPV isolates were obtained from different clinical cases of infected swine. Genome organisation and sequence analysis of the encoded proteins (NP, P, F, M, HN and L) revealed high sequence conservation of the NP protein and the expression of the P and V proteins in all PorPV isolates. The V protein of one isolate displayed a mutation that has been implicated to antagonise the antiviral immune responses of the host. The M protein indicated a variation in a short region that could affect the electrostatic charge and the interaction with the membrane. One PorPV isolate recovered from the lungs showed a mutation at the cleavage site (HRKKR) of the F protein that could represent an important factor to determine the tissue tropism and pathogenicity of this virus. The HN protein showed high sequence identity through the years (up to 2013). Additionally, a number of sequence motifs of very high amino acid conservation among the PorPV isolates important for polymerase activity of the L protein have been identified. In summary, genetic comparisons and phylogenetic analyses indicated that three different genetic variants of PorPV are currently spreading within the swine population, and a new generation of circulating virus with different characteristics has begun to emerge.

  8. In silico studies of outer membrane of Neisseria meningitidis por a: its expression and immunogenic properties.

    PubMed

    Behrouzi, Ava; Bouzari, Saeid; Siadat, Seyed Davar; Irani, Shiva

    2014-01-01

    Neisseria meningitidis is a major causative agent of bacterial septicemia and meningitis in humans. Currently, there are no vaccines to prevent disease caused by strains of N.meningitidis serogroup B. The Class 1 Outer Membrane Protein (OMP) has been named porA which is a cation selective transmembrane protein of 45 KDa that forms trimeric pore in the meningococcal outer membrane. PorA from serogroup B N. meningitidis was cloned into prokaryotic expression vector pBAD-gIIIA. Recombinant protein was expressed with arabinose and affinity purified by Ni-NTA agarose, SDS-PAGE and western blotting were performed for protein determination and verification. BALB/c mice were immunized subcutaneously with purified rPorA together with alum adjuvant. Serum antibody responses to serogroups B N.meningitidis were determined by ELISA. Serum IgG response significantly increased in the group immunized with rPorA together with alum adjuvant in comparison with control groups. These results suggest that rPorA can be a potential vaccine candidate for serogroup B N.meningitidis.

  9. In Silico Studies of Outer Membrane of Neisseria Meningitidis Por A: Its Expression and Immunogenic Properties

    PubMed Central

    Behrouzi, Ava; Bouzari, Saeid; Siadat, Seyed Davar; Irani, Shiva

    2014-01-01

    Neisseria meningitidis is a major causative agent of bacterial septicemia and meningitis in humans. Currently, there are no vaccines to prevent disease caused by strains of N.meningitidis serogroup B. The Class 1 Outer Membrane Protein (OMP) has been named porA which is a cation selective transmembrane protein of 45 KDa that forms trimeric pore in the meningococcal outer membrane. PorA from serogroup B N. meningitidis was cloned into prokaryotic expression vector pBAD-gIIIA. Recombinant protein was expressed with arabinose and affinity purified by Ni-NTA agarose, SDS-PAGE and western blotting were performed for protein determination and verification. BALB/c mice were immunized subcutaneously with purified rPorA together with alum adjuvant. Serum antibody responses to serogroups B N.meningitidis were determined by ELISA. Serum IgG response significantly increased in the group immunized with rPorA together with alum adjuvant in comparison with control groups. These results suggest that rPorA can be a potential vaccine candidate for serogroup B N.meningitidis. PMID:25317403

  10. PorA Represents the Major Cell Wall Channel of the Gram-Positive Bacterium Corynebacterium glutamicum

    PubMed Central

    Costa-Riu, Noelia; Burkovski, Andreas; Krämer, Reinhard; Benz, Roland

    2003-01-01

    The cell wall of the gram-positive bacterium Corynebacterium glutamicum contains a channel (porin) for the passage of hydrophilic solutes. The channel-forming polypeptide PorA is a 45-amino-acid acidic polypeptide with an excess of four negatively charged amino acids, which is encoded by the 138-bp gene porA. porA was deleted from the chromosome of C.glutamicum wild-type strain ATCC 13032 to obtain mutant ATCC 13032ΔporA. Southern blot analysis demonstrated that porA was deleted. Lipid bilayer experiments revealed that PorA was not present in the cell wall of the mutant strain. Searches within the known chromosome of C. glutamicum by using National Center for Biotechnology Information BLAST and reverse transcription-PCR showed that no other PorA-like protein is encoded on the chromosome or is expressed in the deletion strain. The porA deletion strain exhibited slower growth and longer growth times than the C. glutamicum wild-type strain. Experiments with different antibiotics revealed that the susceptibility of the mutant strain was much lower than that of the wild-type C. glutamicum strain. The results presented here suggest that PorA represents a major hydrophilic pathway through the cell wall and that C. glutamicum contains cell wall channels which are not related to PorA. PMID:12896997

  11. Oral administration of recombinant Neisseria meningitidis PorA genetically fused to H. pylori HpaA antigen increases antibody levels in mouse serum, suggesting that PorA behaves as a putative adjuvant

    PubMed Central

    Vasquez, Abel E; Manzo, Ricardo A; Soto, Daniel A; Barrientos, Magaly J; Maldonado, Aurora E; Mosqueira, Macarena; Avila, Anastasia; Touma, Jorge; Bruce, Elsa; Harris, Paul R; Venegas, Alejandro

    2015-01-01

    The Neisseria meningitidis outer membrane protein PorA from a Chilean strain was purified as a recombinant protein. PorA mixed with AbISCO induced bactericidal antibodies against N. meningitidis in mice. When PorA was fused to the Helicobacter pylori HpaA antigen gene, the specific response against H. pylori protein increased. Splenocytes from PorA-immunized mice were stimulated with PorA, and an increase in the secretion of IL-4 was observed compared with that of IFN-γ. Moreover, in an immunoglobulin sub-typing analysis, a substantially higher IgG1 level was found compared with IgG2a levels, suggesting a Th2-type immune response. This study revealed a peculiar behavior of the purified recombinant PorA protein per se in the absence of AbISCO as an adjuvant. Therefore, the resistance of PorA to proteolytic enzymes, such as those in the gastrointestinal tract, was analyzed, because this is an important feature for an oral protein adjuvant. Finally, we found that PorA fused to the H. pylori HpaA antigen, when expressed in Lactococcus lactis and administered orally, could enhance the antibody response against the HpaA antigen approximately 3 fold. These observations strongly suggest that PorA behaves as an effective oral adjuvant. PMID:25750999

  12. Variation in the Neisseria lactamica porin, and its relationship to meningococcal PorB.

    PubMed

    Bennett, Julia S; Callaghan, Martin J; Derrick, Jeremy P; Maiden, Martin C J

    2008-05-01

    One potential vaccine strategy in the fight against meningococcal disease involves the exploitation of outer-membrane components of Neisseria lactamica, a commensal bacterium closely related to the meningococcus, Neisseria meningitidis. Although N. lactamica shares many surface structures with the meningococcus, little is known about the antigenic diversity of this commensal bacterium or the antigenic relationships between N. lactamica and N. meningitidis. Here, the N. lactamica porin protein (Por) was examined and compared to the related PorB antigens of N. meningitidis, to investigate potential involvement in anti-meningococcal immunity. Relationships among porin sequences were determined using distance-based methods and F(ST), and maximum-likelihood analyses were used to compare the selection pressures acting on the encoded proteins. These analyses demonstrated that the N. lactamica porin was less diverse than meningococcal PorB and although it was subject to positive selection, this was not as strong as the positive selection pressures acting on the meningococcal porin. In addition, the N. lactamica porin gene sequences and the protein sequences of the loop regions predicted to be exposed to the human immune system were dissimilar to the corresponding sequences in the meningococcus. This suggests that N. lactamica Por, contrary to previous suggestions, may have limited involvement in the development of natural immunity to meningococcal disease and might not be effective as a meningococcal vaccine component.

  13. Detección y estudio mediante Fluorescencia Inducida por Láser de radicales libres formados por Disociación Multifotónica Infrarroja

    NASA Astrophysics Data System (ADS)

    Santos, M.; Díaz, L.; Torresano, J. A.; Rubio, L.; Samoudi, B.

    Una de las principales aplicaciones actuales de los procesos de disociación multifotónica inducidos por radiación láser infrarroja (DMI) es la producción de radiales libres, con el fin de estudiar sus propiedades cinéticas y espectroscópicas. La disociación de moléculas poliatómicas en el IR con láseres de CO2 tiene lugar desde la superficie de energía molecular mas baja y conduce generalmente a la formación de fragmentos en el estado electrónico fundamental, con diversos grados de excitación vibracional. En el Grupo de Procesos Multifotónicos del Instituto de Estructura de la Materia del C.S.I.C. hemos puesto a punto la técnica de Fluorescencia Inducida por Láser (LIF) para la detección y análisis en tiempo real de los fragmentos producidos en la DMI inducida mediante uno o dos campos láseres de diferentes longitudes de onda. Objetivos de nuestro trabajo han sido el estudio de los canales de disociación mayoritarios y de las especies transitoria producidas, así como de la distribución de energía interna con que éstas son generadas. En particular hemos detectado mediante LIF las especies: C2, CF, CH, SiH2, CF2, CH2, SiHCl, y CF3 a partir de la disociación de, entre otras, las siguientes moléculas: C2H3Br, C3F6, C4H8Si, C2H5ClSi y CH5ClSi. En este trabajo presentamos algunos de los resultados obtenidos mediante el estudio por LIF de estos radicales: estudio temporal de la señal LIF obtenida con determinación de tiempos de vida, espectros de excitación y fluorescencia, temperaturas vibracionales de formación, variación de la intensidad LIF con el tiempo de retraso entre los láseres de disociación y prueba, etc.

  14. Methodology for obtaining stakeholder assessments of obesity policy options in the PorGrow project.

    PubMed

    Stirling, A; Lobstein, T; Millstone, E

    2007-05-01

    The Policy Options for Responding to the Growing Challenge of Obesity Research Project (PorGrow) study provided a unique opportunity to develop a large-scale application of a semi-quantitative technique for exploring interviewees' views on options to tackle obesity, using multi-criteria mapping. This 'heuristic' approach utilizes the advantages of a structured interviews framework by predefining a set of options for appraisal, while leaving interviewees free to select their own criteria for making their judgements. Additional information can be gleaned from the interview transcripts and related materials to set the appraisals in their policy context, and allowing interviewees to express their views on the options presented and their own appraisals. The PorGrow study team agreed a predefined set of 20 options for appraisal, and interviewed sets of stakeholders representing more than 20 aspects of policy development in each of the nine participating countries. The details of the methodology adopted are set out in this paper.

  15. Tris(bis(trimethylsilyl)amido)uranium: Compounds with tri-, tetra-, and penta-valent uranium

    SciTech Connect

    Stewart, J.L.

    1988-04-01

    This trivalent uranium compound, serves as a precursor to new tri-, tetra-, and penta-valent uranium species. The geometry about the U atom is pyramidal. Lewis-base coordination compounds of U(N(SiMe/sub 3/)/sub 2/)/sub 3/ with a one-to-one- ratio of Lewis base to uranium were isolated with pyridine, 4-dimethylamino-pyridine, 2,6-Me/sub 2/-C/sub 6/H/sub 3/NC, and TPO. Two-to-one coordination compounds were obtained with t-butylnitrile and t-butylisocyanide. Compounds with more sterically demanding bases could not be isolated. The expected decrease in U-N(SiMe/sub 3/)/sub 2/ bond length with increase in oxidation state is not observed. Reaction of ClU(N(SiMe/sub 3/)/sub 2/)/sub 3/and Li(NH(p-tolyl)) yields the uranium (IV) dimer, U/sub 2/(N(SiMe/sub 3/)/sub 2/)/sub 4/(..mu..-N(p-tolyl))/sub 2/. Reaction with 2,4,6-triemethylaniline produces a dimer. Analogous substitution products could not be obtained with aniline or p-toluidine. t-Bu/sub 3/CO/sup /minus//, t-Bu/sub 2/CHO/sup /minus//, and t-Bu/sub 3/SiO/sup /minus// are used to synthesize new tetravalent, mononuclear uranium compounds. Reaction of ClU(tritox)/sub 3/ with alkyllithium reagents leads to isolation of RU(tritox)/sub 3/. The reaction of U(ditox)/sub 4/ with MeLi affords the addition product U(ditox)/sub 4/(Me)Li, whose crystal structure is described. Preparation of uranium silox compounds is reported. 97 refs., 26 figs., 39 tabs.

  16. The “Speedy” Synthesis of Atom-Specific 15N Imino/Amido-Labeled RNA

    PubMed Central

    Kreutz, Christoph; Micura, Ronald

    2016-01-01

    Although numerous reports on the synthesis of atom-specific 15N-labeled nucleosides exist, fast and facile access to the corresponding phosphoramidites for RNA solid-phase synthesis is still lacking. This situation represents a severe bottleneck for NMR spectroscopic investigations on functional RNAs. Here, we present optimized procedures to speed up the synthesis of 15N(1) adenosine and 15N(1) guanosine amidites, which are the much needed counterparts of the more straightforward-to-achieve 15N(3) uridine and 15N(3) cytidine amidites in order to tap full potential of 1H/15N/15N-COSY experiments for directly monitoring individual Watson–Crick base pairs in RNA. Demonstrated for two preQ1 riboswitch systems, we exemplify a versatile concept for individual base-pair labeling in the analysis of conformationally flexible RNAs when competing structures and conformational dynamics are encountered. PMID:26237536

  17. Discovery of amido-benzisoxazoles as potent c-Kit inhibitors

    SciTech Connect

    Kunz, Roxanne K.; Rumfelt, Shannon; Chen, Ning; Zhang, Dawei; Tasker, Andrew S.; Bürli, Roland; Hungate, Randall; Yu, Violeta; Nguyen, Yen; Whittington, Douglas A.; Meagher, Kristin L.; Plant, Matthew; Tudor, Yanyan; Schrag, Michael; Xu, Yang; Ng, Gordon Y.; Hu, Essa

    2010-01-12

    Deregulation of the receptor tyrosine kinase c-Kit is associated with an increasing number of human diseases, including certain cancers and mast cell diseases. Interference of c-Kit signaling with multi-kinase inhibitors has been shown clinically to successfully treat gastrointestinal stromal tumors and mastocytosis. Targeted therapy of c-Kit activity may provide therapeutic advantages against off-target effects for non-oncology applications. A new structural class of c-Kit inhibitors is described, including in vitro c-Kit potency, kinase selectivity, and the observed binding mode.

  18. Synthesis and structural characterization of amido scorpionate rare earth metals complexes.

    PubMed

    Márquez-Segovia, Isabel; Lara-Sánchez, Agustín; Otero, Antonio; Fernández-Baeza, Juan; Castro-Osma, José Antonio; Sánchez-Barba, Luis F; Rodríguez, Ana M

    2014-07-07

    The reactivity of hybrid scorpionate/cyclopentadienyl ligands in the form of the protio derivatives as a mixture of two regioisomers, namely bpzcpH [1-{2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl}-1,3-cyclopentadiene and 2-{2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl}-1,3-cyclopentadiene] and bpztcpH [1-{2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethyl}-1,3-cyclopentadiene and 2-{2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethyl}-1,3-cyclopentadiene], with the tris(silylamide) precursors [M{N(SiHMe2)2}3(thf)x] of rare earth metals (including the group 3 metals scandium and yttrium) is related to the atomic radii of the metal centres. The reaction with the precursor containing the smallest ion, [Sc{N(SiHMe2)2}3(thf)], did not proceed even heating at reflux temperature in toluene. The reaction with the precursors that contain a medium-sized metal ion, i.e., [M{N(SiHMe2)2}3(thf)2] (M = Y, Lu), proceeded only at high temperature and gave good yields of the silylenediamide-containing derivatives [M{κ(2)-NN-Me2Si(NSiHMe2)2}(bpzcp)] (M = Y , Lu ) and [M{κ(2)-NN-Me2Si(NSiHMe2)2}(bpztcp)] (M = Y , Lu ) by an double activation of Si-H and Si-N bonds. However, the reaction with the precursors that contained the largest metal ions, i.e., [M{N(SiHMe2)2}3(thf)2] (M = Nd, Sm), proceeded rapidly at room temperature to afford the bis(silylamide) complexes [M{N(SiHMe2)2}2(bpzcp)] (M = Nd , Sm ) and [M{N(SiHMe2)2}2(bpztcp)] (M = Nd , Sm ). Additionally, the alkyl heteroscorpionate yttrium and lutetium complexes [M(CH2SiMe3)2(NNCp)] (M = Y, Lu) reacted with an excess of HN(SiHMe2)2 to give the mixed alkyl/amide derivatives [M{N(SiHMe2)2}(CH2SiMe3)(bpzcp)] (M = Y , Lu ) and [M{N(SiHMe2)2}(CH2SiMe3)(bpztcp)] (M = Y , Lu ). The structures of the complexes were determined by spectroscopic methods and the X-ray crystal structures of , and were also established.

  19. Reaction products of amido-amine and epoxide useful as fuel additives

    SciTech Connect

    Efner, H.F.

    1988-04-12

    A method for reducing engine deposits in an internal combustion engine is described comprising the addition of a detergent fuel additive package to a hydrocarbon fuel for the engine. The fuel detergent is added in an amount effective to reduce deposits and the hydrocarbon fuel is used with detergent additive as fuel in an internal combustion engine. The detergent fuel additive package comprises: (1) a fuel detergent additive that is the reaction product prepared by reacting (a) vegetable oil or (b) higher carboxylic acid chosen from (i) aliphatic fatty acids having 10-25 carbon atoms and (ii) aralkyl acids having 12-42 carbon atoms with (c) multiamine to obtain a fist product mixture with the first product mixture reacted with alklylene oxide to produce a second product mixture and (2) a fuel detergent additive solvent compatible with the fuels.

  20. CRYSTAL AND MOLECULAR STRUCTURE OF HYDRIDOTIS (BIS(TRIMETHYLSILYL)AMIDO]URANIUM(IV)

    SciTech Connect

    Andersen, Richard A.; Zalkin, Allen; Templeton, David H.

    1980-05-01

    New hydride derivatives of thorium (IV) and uranium (IV), HM[N(SiMe{sub 3}){sub 2}]{sub 3}, have recently been prepared. This paper describes the crystal structure of the uranium species, though the hydride-ion was not located, and shows that the thorium analogue is isostructural. The reaction chemistry and spectroscopy leave no doubt that these derivatives are authentic examples of four-coordinate, monomeric hydride, compounds.

  1. Nucleophilic aromatic substitution on aryl-amido ligands promoted by oxidizing osmium(IV) centers.

    PubMed

    Soper, Jake D; Saganic, Erik; Weinberg, David; Hrovat, David A; Benedict, Jason B; Kaminsky, Werner; Mayer, James M

    2004-09-20

    Addition of amine nucleophiles to acetonitrile solutions of the OsIV anilido complex TpOs(NHPh)Cl2 (1) [Tp = hydrotris(1-pyrazolyl)borate] gives products with derivatized anilido ligands, i.e., TpOs[NH-p-C6H4(N(CH2)5)]Cl2 (2) from piperidine and TpOs[NH-p-C6H4N(CH2)4]Cl2 (3) from pyrrolidine. These materials are formed in approximately 30% yield under anaerobic conditions, together with approximately 60% yields of the OsIII aniline complex TpOs(NH2Ph)Cl2 (5). Formation of the para-substituted materials 2 or 3 from 1 involves oxidative removal of two hydrogen atoms (two H+ and two e-). The oxidation can be accomplished by 1, forming 5, or by O2. Related reactions have been observed with other amines and with the 2-naphthylamido derivative, which gives an ortho-substituted product. Kinetic studies indicate an addition-elimination mechanism involving initial attack of the amine nucleophile on the anilido ligand. These are unusual examples of nucleophilic aromatic substitution of hydrogen. Ab initio calculations on 1 show that the LUMO has significant density at the ortho and para positions of the anilido ligand, resembling the LUMO of nitrobenzene. By analogy with nucleophilic aromatic substitution, 2 is quantitatively formed from piperidine and the p-chloroanilide TpOs(NH-p-C6H4Cl)Cl2 (7). Binding the anilide ligands to an oxidizing OsIV center thus causes a remarkable umpolung or inversion of chemical character from a typically electron-rich anilido to an electron-deficient aromatic functionality. This occurs because of the coupling of redox changes at the TpOsIV center with bond formation at the coordinated ligand.

  2. p-Tolyl bis­(o-tolyl­amido)­phosphinate

    PubMed Central

    Sabbaghi, Fahimeh; Mancilla Percino, Teresa; Pourayoubi, Mehrdad; Leyva, Marco A.

    2010-01-01

    In the title compound, C21H23N2O2P, the P atom has a distorted tetra­hedral configuration. The O atom of the OC6H4-4-CH3 group and the N atoms show sp 2 character. In the crystal, adjacent mol­ecules are linked by N—H⋯O hydrogen bonds into helical chains parallel to the b axis. PMID:21587971

  3. Improved purification of native meningococcal porin PorB and studies on its structure/function.

    PubMed

    Massari, Paola; King, Carol A; MacLeod, Heather; Wetzler, Lee M

    2005-12-01

    The outer membrane protein PorB of Neisseria meningitidis is a pore-forming protein which has various effects on eukaryotic cells. It has been shown to (1) up-regulate the surface expression of the co-stimulatory molecule CD86 and of MHC class II (which are TLR2/MyD88 dependent and related to the porin's immune-potentiating ability), (2) be involved in prevention of apoptosis by modulating the mitochondrial membrane potential, and (3) form pores in eukaryotic cells. As an outer membrane protein, its native trimeric form isolation is complicated by its insoluble nature, requiring the presence of detergent throughout the whole procedure, and by its tight association with other outer membrane components, such as neisserial LOS or lipoproteins. In this study, an improved chromatographic purification method to obtain an homogeneous product free of endotoxin and lipoprotein is described, without loss of any of the above-mentioned properties of the porin. Furthermore, we have investigated the requirement of the native trimeric structure for the porin's activity. Inactivation of functional PorB trimers into non-functional monomers was achieved by incubation on ice. Thus, routine long- and medium-term storage at low temperature may be a cause of porin inactivation.

  4. Diagnóstico diferencial en la encefalitis por anticuerpos contra el receptor NMDA

    PubMed Central

    González-Valcárcel, J.; Rosenfeld, M.R.; Dalmau, J.

    2011-01-01

    Resumen Introducción La encefalitis por anticuerpos contra el receptor de NMDA (NMDAR) suele desarrollarse como un síndrome característico de evolución multifásica y diagnóstico diferencial amplio. Pacientes Presentamos a 2 pacientes diagnosticadas de encefalitis por anticuerpos NMDAR con un cuadro clínico típico, pero que inicialmente señaló otras etiologías. Discusión La afectación frecuente de pacientes jóvenes con manifestaciones psiquiátricas prominentes indica frecuentemente otras consideraciones diagnósticas; las más frecuentes son las encefalitis virales, los procesos psiquiátricos y el síndrome neuroléptico maligno. Varios síndromes previamente definidos de manera parcial o descriptiva en adultos y pacientes pediátricos probablemente eran casos de encefalitis anti-NMDAR. Conclusiones La encefalitis anti-NMDAR debe considerarse en pacientes jóvenes con manifestaciones psiquiátricas subagudas, movimientos anormales y alteraciones autonómicas. La caracterización clínica e inmunológica de esta enfermedad ha llevado a la identificación de nuevos anticuerpos que afectan a procesos de memoria, aprendizaje, conducta y psicosis. PMID:20964986

  5. Effect of SPM-based cleaning POR on EUV mask performance

    NASA Astrophysics Data System (ADS)

    Choi, Jaehyuck; Lee, Han-shin; Yoon, Jinsang; Shimomura, Takeya; Friz, Alex; Montgomery, Cecilia; Ma, Andy; Goodwin, Frank; Kang, Daehyuk; Chung, Paul; Shin, Inkyun; Cho, H.

    2011-11-01

    EUV masks include many different layers of various materials rarely used in optical masks, and each layer of material has a particular role in enhancing the performance of EUV lithography. Therefore, it is crucial to understand how the mask quality and patterning performance can change during mask fabrication, EUV exposure, maintenance cleaning, shipping, or storage. The fact that a pellicle is not used to protect the mask surface in EUV lithography suggests that EUV masks may have to undergo more cleaning cycles during their lifetime. More frequent cleaning, combined with the adoption of new materials for EUV masks, necessitates that mask manufacturers closely examine the performance change of EUV masks during cleaning process. We have investigated EUV mask quality and patterning performance during 30 cycles of Samsung's EUV mask SPM-based cleaning and 20 cycles of SEMATECH ADT exposure. We have observed that the quality and patterning performance of EUV masks does not significantly change during these processes except mask pattern CD change. To resolve this issue, we have developed an acid-free cleaning POR and substantially improved EUV mask film loss compared to the SPM-based cleaning POR.

  6. Multiple active site residues are important for photochemical efficiency in the light-activated enzyme protochlorophyllide oxidoreductase (POR).

    PubMed

    Menon, Binuraj R K; Hardman, Samantha J O; Scrutton, Nigel S; Heyes, Derren J

    2016-08-01

    Protochlorophyllide oxidoreductase (POR) catalyzes the light-driven reduction of protochlorophyllide (Pchlide), an essential, regulatory step in chlorophyll biosynthesis. The unique requirement of the enzyme for light has provided the opportunity to investigate how light energy can be harnessed to power biological catalysis and enzyme dynamics. Excited state interactions between the Pchlide molecule and the protein are known to drive the subsequent reaction chemistry. However, the structural features of POR and active site residues that are important for photochemistry and catalysis are currently unknown, because there is no crystal structure for POR. Here, we have used static and time-resolved spectroscopic measurements of a number of active site variants to study the role of a number of residues, which are located in the proposed NADPH/Pchlide binding site based on previous homology models, in the reaction mechanism of POR. Our findings, which are interpreted in the context of a new improved structural model, have identified several residues that are predicted to interact with the coenzyme or substrate. Several of the POR variants have a profound effect on the photochemistry, suggesting that multiple residues are important in stabilizing the excited state required for catalysis. Our work offers insight into how the POR active site geometry is finely tuned by multiple active site residues to support enzyme-mediated photochemistry and reduction of Pchlide, both of which are crucial to the existence of life on Earth.

  7. Reconstrução tridimensional de arcos magnéticos por tomografia

    NASA Astrophysics Data System (ADS)

    Simões, P. J. A.; Costa, J. E. R.

    2003-08-01

    Uma explosão solar é uma variação súbita do brilho que ocorre nas regiões ativas da atmosfera solar. Estas regiões são constituídas por um plasma magnetizado com intensa indução magnética e em cenários bem complexos como visto recentemente através de experimentos embarcados em satélites operando instrumentos em raios X moles e ultra-violeta distante. A energia magnética, que pode ser armazenada por um período de horas até dias em configurações magnéticas estressadas, é subitamente lançada na atmosfera solar e transferida para partículas como elétrons, prótons e núcleos pesados, que são acelerados e/ou aquecidos, produzindo radiação eletromagnética. A proposta final deste projeto é determinar as características espaciais de alta resolução da emissão e polarização girossincrotrônica de explosões solares em ambientes complexos de campos magnéticos. Os recentes resultados da emissão difusa em EUV apresentado pelos satélites TRACE e SOHO dos arcos magnéticos conectando as diferentes polaridades magnéticas sobre as regiões ativas possibilitam novas abordagens sobre o papel do campo magnético na emissão em rádio. Nesta etapa apresentamos os resultados da reconstrução da geometria tridimensional das linhas de força destes arcos utilizando técnicas tomográficas, a partir de imagens de alta resolução espacial obtidas pelo instrumento EIT (Extreme ultraviolet Imaging Telescope), além da modelagem das induções magnéticas por um campo dipolar e as densidades de partículas aceleradas. Utilizamos para a reconstrução geométrica, imagens tomadas em vários ângulos dos arcos devido à rotacão solar. Com estes resultados, daremos continuidade ao projeto, com os cálculos da transferência radiativa nos modos ordinário e extraordinário de propagação da radiação girossincrotrônica de explosões solares.

  8. Geometry sensing through POR1 regulates Rac1 activity controlling early osteoblast differentiation in response to nanofiber diameter.

    PubMed

    Higgins, A M; Banik, B L; Brown, J L

    2015-02-01

    Bone grafting procedures in the United States rely heavily upon autografts and allografts, which are donor-dependent, cause donor site pain, and can transmit disease. Synthetic bone grafts can reduce these risks; however, synthetics lack the bone differentiating (osteoinductive) abilities of auto- and allografts. Achieving innate osteoinductive properties of synthetics through surface modifications is currently under investigation. This study focuses on nanofibers, with emphasis on how fiber diameter and the potential curvature sensor POR1 affect the activation of the signaling molecules Rac1 and Arf1, and leading to expression of alkaline phosphatase (ALP), an osteoinductive marker. Diameters of 0.1, 0.3, and 1.0 μm were compared against a flat control. The highest level of Rac1 activation was achieved on the smallest fibers (0.1 μm), a trend that was lost in POR1 knockdowns. This supports the hypothesis that on small nanofibers, POR1 favorably binds to highly curved cell membranes, which allows Rac1 to subsequently dissociate and activate. When the curvature is insufficient to bind POR1, POR1 binds to inactive Rac1 and competitively inhibits its activation. Arf1 activation followed an opposite trend, with the largest nanofibers exhibiting the highest activity. This trend reinforces the known interaction between Rac1 and Arf1 through the GIT-PIX complex, an Arf1 GAP and Rac1 GEF, respectively. Large, (1.0 μm), nanofibers demonstrated the highest ALP activity, indicating that ALP expression is inversely dependent on Rac1 activation. Knockdown of POR1 resulted in increased ALP activity across the substrates but without regard to the curvature sensing trend seen previously. Thus, POR1 senses curvature and increases Rac1 activity, which negatively regulates bone differentiation.

  9. Using the PORS Problems to Examine Evolutionary Optimization of Multiscale Systems

    SciTech Connect

    Reinhart, Zachary; Molian, Vaelan; Bryden, Kenneth

    2013-01-01

    Nearly all systems of practical interest are composed of parts assembled across multiple scales. For example, an agrodynamic system is composed of flora and fauna on one scale; soil types, slope, and water runoff on another scale; and management practice and yield on another scale. Or consider an advanced coal-fired power plant: combustion and pollutant formation occurs on one scale, the plant components on another scale, and the overall performance of the power system is measured on another. In spite of this, there are few practical tools for the optimization of multiscale systems. This paper examines multiscale optimization of systems composed of discrete elements using the plus-one-recall-store (PORS) problem as a test case or study problem for multiscale systems. From this study, it is found that by recognizing the constraints and patterns present in discrete multiscale systems, the solution time can be significantly reduced and much more complex problems can be optimized.

  10. jPOR: An ImageJ macro to quantify total optical porosity from blue-stained thin sections

    NASA Astrophysics Data System (ADS)

    Grove, Clayton; Jerram, Dougal A.

    2011-11-01

    A fast and effective method has been developed to measure total optical porosity (TOP) of blue resin-impregnated thin sections. This utilises a macro file (jPOR.txt) for ImageJ, which can be used on digital photomicrographs of thin sections. The method requires no specialised scientific equipment and can be run entirely using free to download software. Digital images are acquired from blue resin-impregnated thin sections using a conventional film scanner in the present study, though the technique can be applied to any high resolution colour digital acquired by different means (e.g., flat bed scanning, digital capture). Images are preprocessed using a newly developed custom 8-bit palette and analysed for porosity in ImageJ using the simple to use jPOR macro. Our method rapidly calculates TOP for batches of images with or without the option of user adjustment. Results are compared with conventional methods (e.g., to point counting), and tested with several users to estimate any user variability. jPOR provided comparable results to more time-consuming point counting, but with significantly less "counting error" and less interoperator variability than published point counting studies. The jPOR macro has been integrated into a macro tool set that can be configured to be run on ImageJ start up.

  11. [Professor Frantisek Por MD and Professor Robert Klopstock MD, students at Budapest and Prague Faculties of Medicine].

    PubMed

    Mydlík, M; Derzsiová, K

    2010-11-01

    Professor Frantisek Por MD and Professor Robert Klopstock MD were contemporaries, both born in 1899, one in Zvolen, the other in Dombovar, at the time of Austro-Hungarian Monarchy. Prof. Por attended the Faculty of Medicine in Budapest from 1918 to 1920, and Prof. Klopstock studied at the same place between 1917 and 1919. From 1920 until graduation on 6th February 1926, Prof. Por continued his studies at the German Faculty of Medicine, Charles University in Prague. Prof. Klopstock had to interrupt his studies in Budapest due to pulmonary tuberculosis; he received treatment at Tatranske Matliare where he befriended Franz Kafka. Later, upon Kafka's encouragement, he changed institutions and continued his studies at the German Faculty of Medicine, Charles University in Prague, where he graduated the first great go. It is very likely that, during their studies in Budapest and Prague, both professors met repeatedly, even though their life paths later separated. Following his graduation, Prof. Por practiced as an internist in Prague, later in Slovakia, and from 1945 in Kosice. In 1961, he was awarded the title of university professor of internal medicine at the Faculty of Medicine, Pavol Jozef Safarik University in Kosice, where he practiced until his death in 1980. Prof. Klopstock continued his studies in Kiel and Berlin. After his graduation in 1933, he practiced in Berlin as a surgeon and in 1938 left for USA. In 1962, he was awarded the title of university professor of pulmonary surgery in NewYork, where he died in 1972.

  12. Unidas por la Vida (United for Life): implementing a culturally-tailored, community-based, family-oriented lifestyle intervention.

    PubMed

    Sorkin, Dara H; Biegler, Kelly A; Peyreda, Margarita; Kilgore, David; Dow, Emily; Ngo-Metzger, Quyen

    2013-01-01

    Unidas por la Vida, a behavioral weight-loss program, was developed for use among low-income, Mexican-American women with diabetes and their overweight/obese adult daughters. The program leverages community resources in a partnership between primary care and community-based organizations. This paper describes the program's implementation, lessons learned, and implications for sustainability.

  13. Global Microlending in Education Reform: Enseñá Por Argentina and the Neoliberalization of the Grassroots

    ERIC Educational Resources Information Center

    Friedrich, Daniel S.

    2010-01-01

    This article examines the workings and underlying assumptions behind Enseñá por Argentina (Teach for Argentina), one specific program that takes part in the larger and expanding network of Teach for All, by thinking about the ways in which a global push for redefining teaching and teacher education encounters local characteristics and histories,…

  14. Inversor Resonante de Tres Elementos L-LC con Caracteristica Cortocircuitable para Aplicaciones de Calentamiento por Induccion

    NASA Astrophysics Data System (ADS)

    Espi Huerta, Jose Miguel

    Los generadores de calentamiento por induccion son puentes inversores con carga resonante, cuya mision es basicamente crear una corriente sinusoidal de gran amplitud sobre la "bobina de caldeo", que forma parte del tanque resonante. En el interior de esta bobina se introduce la pieza que se desea calentar. EI campo magnetico creado induce corrientes superficiales (corrientes de Foucault) sobre la pieza, que producen su calentamiento. Los tanques resonantes (tambien llamados osciladores) utilizados en la actualidad son el resonante serie y el resonante paralelo. Aunque ya desde hace algun tiempo se vienen construyendo generadores de alta potencia basados en estos dos osciladores, el exito nunca ha. sido completo en ninguno de los dos casos. Tal y como se explica en la introduccion de esta memoria, los puentes inversores utilizados deben operar sobre una carga inductiva (corriente retrasada) para evitar el fenomeno de la recuperacion inversa de sus diodos y la consiguiente ruptura de los transistores. De la restriccion topologica anterior se deduce que el generador paralelo debe conmutar a frecuencias inferiores a la resonancia, y el serie a frecuencias superiores. A esta restriccion topologica hay que unir otra que es exclusiva del calentamiento por induccion: La corriente por la bobina de caldeo debe ser sinusoidal. De no ser asi, resultaria imposible disponer toda la potencia de calentamiento sobre la pieza en el espesor requerido por la aplicacion. Como consecuencia, los inversores no pueden operar por debajo de la frecuencia de resonancia del oscilador, pues en ese caso se amplifican los armonicos de orden superior de la tension/corriente de entrada situados sobre la resonancia, con la consiguiente distorsion de la corriente de salida. La conjuncion de las dos restricciones anteriores obligan al inversor paralelo a funcionar a la frecuencia de resonancia del oscilador. Esto imposibilita un control por variacion de frecuencia, regulandose la potencia desde la

  15. The amino acid sequence of Neisseria lactamica PorB surface-exposed loops influences Toll-like receptor 2-dependent cell activation.

    PubMed

    Toussi, Deana N; Carraway, Margaretha; Wetzler, Lee M; Lewis, Lisa A; Liu, Xiuping; Massari, Paola

    2012-10-01

    Toll-like receptors (TLRs) play a major role in host mucosal and systemic defense mechanisms by recognizing a diverse array of conserved pathogen-associated molecular patterns (PAMPs). TLR2, with TLR1 and TLR6, recognizes structurally diverse bacterial products such as lipidated factors (lipoproteins and peptidoglycans) and nonlipidated proteins, i.e., bacterial porins. PorB is a pan-neisserial porin expressed regardless of organisms' pathogenicity. However, commensal Neisseria lactamica organisms and purified N. lactamica PorB (published elsewhere as Nlac PorB) induce TLR2-dependent proinflammatory responses of lower magnitude than N. meningitidis organisms and N. meningitidis PorB (published elsewhere as Nme PorB). Both PorB types bind to TLR2 in vitro but with different apparent specificities. The structural and molecular details of PorB-TLR2 interaction are only beginning to be unraveled and may be due to electrostatic attraction. PorB molecules have significant strain-specific sequence variability within surface-exposed regions (loops) putatively involved in TLR2 interaction. By constructing chimeric recombinant PorB loop mutants in which surface-exposed loop residues have been switched between N. lactamica PorB and N. meningitidis PorB, we identified residues in loop 5 and loop 7 that influence TLR2-dependent cell activation using HEK cells and BEAS-2B cells. These loops are not uniquely responsible for PorB interaction with TLR2, but NF-κB and MAP kinases signaling downstream of TLR2 recognition are likely influenced by a hypothetical "TLR2-binding signature" within the sequence of PorB surface-exposed loops. Consistent with the effect of purified PorB in vitro, a chimeric N. meningitidis strain expressing N. lactamica PorB induces lower levels of interleukin 8 (IL-8) secretion than wild-type N. meningitidis, suggesting a role for PorB in induction of host cell activation by whole bacteria.

  16. Encefalitis por anticuerpos contra el receptor de NMDA: experiencia con seis pacientes pediátricos. Potencial eficacia del metotrexato

    PubMed Central

    Bravo-Oro, Antonio; Abud-Mendoza, Carlos; Quezada-Corona, Arturo; Dalmau, Josep; Campos-Guevara, Verónica

    2016-01-01

    Introducción La encefalitis por anticuerpos contra el receptor de N-metil-D-aspartato (NMDA) es una entidad cada vez más diagnosticada en edad pediátrica. A diferencia de los adultos, en muchos casos no se asocia a tumores y las manifestaciones iniciales en niños más frecuentes son crisis convulsivas y trastornos del movimiento, mientras que en los adultos predominan las alteraciones psiquiátricas. Casos clínicos Presentamos seis casos pediátricos confirmados con anticuerpos contra la subunidad NR1 del receptor de NMDA en suero y líquido cefalorraquídeo. Cinco de los casos comenzaron con crisis convulsivas como manifestación clínica inicial antes de desarrollar el cuadro clásico de esta entidad. En todos los casos se utilizaron esteroides como primera línea de tratamiento, con los que sólo se observó control de las manifestaciones en uno, por lo que el resto de los pacientes requirió inmunomoduladores de segunda línea. Todos los pacientes recibieron metotrexato como tratamiento inmunomodulador para evitar recaídas y la evolución fue a la mejoría en todos ellos. Conclusiones En nuestra serie de pacientes con encefalitis por anticuerpos contra el receptor de NMDA, ninguno se asoció a tumores. Todos los casos recibieron metotrexato por lo menos durante un año, no observamos eventos adversos clínicos ni por laboratorio, ni hubo secuelas neurológicas ni recaídas durante el tratamiento. Aunque es una serie pequeña y es deseable incrementar el número y tiempo de evolución, consideramos el metotrexato una excelente alternativa como tratamiento inmunomodulador para esta patología. PMID:24150952

  17. Prevalencia y tamizaje del Trastorno por Déficit de Atención con Hiperactividad en Costa Rica

    PubMed Central

    Weiss, Nicholas T.; Schuler, Jovita; Monge, Silvia; McGough, James J.; Chavira, Denise; Bagnarello, Monica; Herrera, Luis Diego; Mathews, Carol A.

    2015-01-01

    Resumen La investigación tuvo como propósito estimar la prevalencia del Trastorno por Déficit de Atención con Hiperactividad (TDAH) en Costa Rica y determinar si la versión en español del cuestionario Swanson Nolan and Pelham Scale IV (SNAP-IV) es un instrumento de tamizaje útil en una población de niños y niñas escolares costarricenses. El instrumento fue entregado a padres y maestros de 425 niños entre 5 y 13 años de edad (promedio = 8.8). Todos fueron evaluados con el instrumento Swanson, Kotkin, Agler, M-Flynn and Pelham Scale (SKAMP). Su diagnóstico fue confirmado con una entrevista clínica. La sensibilidad y la especificidad del SNAP-IV fueron evaluadas como predictores de criterios de diagnóstico según el DSM-IV. La prevalencia puntual en la muestra del TDAH fue del 5%. El tamizaje más preciso lo hizo el SNAP-IV completado por el maestro en un corte de 20%, con una sensibilidad de 96% y una especificidad de un 82%. La sensibilidad de los instrumentos completados por los padres fue más baja que aquella de los maestros. El SNAP-IV completado por las maestras con un corte aislando el 20% de los mayores puntajes categorizó correctamente a un 87% de los sujetos. PMID:22432094

  18. Racism in digital era: Development and initial validation of the Perceived Online Racism Scale (PORS v1.0).

    PubMed

    Keum, Brian TaeHyuk; Miller, Matthew J

    2017-04-01

    The purpose of this study was to develop the Perceived Online Racism Scale (PORS) to assess perceived online racist interpersonal interactions and exposure to online racist content among people of color. Items were developed through a multistage process involving a comprehensive literature review, focus-groups, qualitative data collection, and survey of online racism experiences. Based on a sample of 1,023 racial minority participants, exploratory and confirmatory factor analyses provided support for a 30-item bifactor model accounted by the general factor and the following 3 specific factors: (a) personal experience of racial cyber-aggression, (b) vicarious exposure to racial cyber-aggression, and (c) online-mediated exposure to racist reality. The PORS demonstrated measurement invariance across racial/ethnic groups in our sample. Internal reliability estimates for the total and subscale scores of the PORS were above .88 and the 4-week test-retest reliability was adequate. Limitations and future directions for research are discussed. (PsycINFO Database Record

  19. Chlorophyll Synthesis in a Deetiolated (det340) Mutant of Arabidopsis without NADPH-Protochlorophyllide (PChlide) Oxidoreductase (POR) A and Photoactive PChlide-F655.

    PubMed Central

    Lebedev, N.; Van Cleve, B.; Armstrong, G.; Apel, K.

    1995-01-01

    Chlorophyll (Chl) synthesis in Arabidopsis is controlled by two light-dependent NADPH-protochlorophyllide (PChlide) oxidoreductases (PORs), one (POR A) that is active transiently in etiolated seedlings at the beginning of illumination and another (POR B) that also operates in green plants. The function of these two enzymes during the light-induced greening of dark-grown seedlings has been studied in the wild type and a deetiolated (det340) mutant of Arabidopsis. One of the consequences of the det mutation is that POR A is constitutively down-regulated, and therefore, synthesis of the POR A enzyme is shut off. When grown in the dark, the det340 mutant lacks POR A and the photoactive PChlide-F655 species but maintains the second PChlide reductase, POR B. Previously, photoactive PChlide-F655 has often been considered to be the only PChlide form that leads to Chl formation. Despite its deficiency in POR A and photoactive PChlide-F655, the det340 mutant is able to green when placed in the light. Chl accumulation, however, proceeds abnormally. At the beginning of illumination, seedlings of det340 mutants are extremely susceptible to photooxidative damage and accumulate Chl only at extremely low light intensities. They form core complexes of photosystems I and II but are almost completely devoid of light-harvesting structures. The results of this study demonstrate that in addition to the route of Chl synthesis that has been studied extensively in illuminated dark-grown wild-type plants, a second branch of Chl synthesis exists that is driven by POR B and does not require POR A. PMID:12242369

  20. The PorB porin from commensal Neisseria lactamica induces Th1 and Th2 immune responses to ovalbumin in mice and is a potential immune adjuvant.

    PubMed

    Liu, Xiuping; Wetzler, Lee M; Massari, Paola

    2008-02-06

    Porins from pathogenic Neisseriae are among several bacterial products with immune adjuvant activity. Neisseria meningitidis (Nme) PorB, has been shown to induce immune cells activation in a TLR2-dependent manner and acts as a vaccine immune adjuvant. The PorB porin from Neisseria lactamica (Nlac), a common nasopharyngeal commensal, shares significant structural and functional similarities with Nme PorB. In this work we ask whether the immune adjuvant ability of porins from pathogenic Neisserial strains is a characteristic shared with porins from non-pathogenic Neisserial species or whether it is unique for bacterial products derived from microorganisms capable of inducing inflammation and disease. We evaluated the potential immune adjuvant effect of Nlac PorB in mice using ovalbumin (OVA) as a prototype antigen. Immunization with Nlac PorB/OVA induced high OVA-specific IgG and IgM titers compared to OVA alone, similar to other adjuvants such as Nme PorB and alum. High titers of IgG1 and IgG2b were detected as well as production of IL-4, IL-10, IL-12 and INF-gamma in response to Nlac PorB, consistent with induction of both a Th1-type and a Th2-type immune response. OVA-specific proliferation was also determined in splenocytes from Nlac PorB/OVA-immunized mice. In addition, B cell activation in vitro and cytokine production in response to Nlac PorB was found to be mediated by TLR2, in a similar manner to Nme PorB.

  1. CYP2C9*2 allele increases risk for hypoglycemia in POR*1/*1 type 2 diabetic patients treated with sulfonylureas.

    PubMed

    Ragia, G; Tavridou, A; Elens, L; Van Schaik, R H N; Manolopoulos, V G

    2014-01-01

    It is previously shown that carriers of the defective allele CYP2C9*3 that leads to impaired sulfonylurea metabolism are at increased sulfonylurea-induced hypoglycemia risk due to diminished drug metabolism, whereas no effect of CYP2C9*2 allele was found. Recently, a polymorphism in P450 oxidoreductase (POR) gene, assigned as POR*28 allele, was associated with increased CYP2C9 activity. The aim of this study was to assess i) the effect of POR*28 allele on sulfonylurea-induced hypoglycemia risk and ii) the association of CYP2C9*2 allele with hypoglycemia risk in non-carriers of POR*28 allele. The study group consisted of 176 patients with diagnosed type 2 diabetes mellitus (T2DM) treated with sulfonylureas, of whom 92 patients had experienced at least one drug-associated hypoglycemic event (cases), while 84 had never experienced a hypoglycemic event (controls). POR*28 allele was detected by use of real-time TaqMan PCR. POR*28 allele was not associated with sulfonyl-urea-induced hypoglycemia. In POR*1/*1 patients, CYP2C9*1/*2 genotype was more common in cases than in controls (32.7 vs. 14.3%, p=0.041). In a model adjusted for age, BMI, duration of T2DM and renal function, and POR*1/*1 entered as a selection variable, CYP2C9*2 allele increased the hypoglycemia risk in response to sulfonylurea (odds ratio: 3.218, p=0.031). In conclusion, our results suggest that POR*28 allele is masking the association of CYP2C9*2 allele with sulfonyl-urea-induced hypoglycemia. Therefore, POR*28 allele is an important source of CYP2C9 activity variability and combined with CYP2C9 gene poly-morphisms may explain individual variability in the effect of sulfonylureas.

  2. Flavobacterium johnsoniae PorV is required for secretion of a subset of proteins targeted to the type IX secretion system.

    PubMed

    Kharade, Sampada S; McBride, Mark J

    2015-01-01

    Flavobacterium johnsoniae exhibits gliding motility and digests many polysaccharides, including chitin. A novel protein secretion system, the type IX secretion system (T9SS), is required for gliding and chitin utilization. The T9SS secretes the cell surface motility adhesins SprB and RemA and the chitinase ChiA. Proteins involved in secretion by the T9SS include GldK, GldL, GldM, GldN, SprA, SprE, and SprT. Porphyromonas gingivalis has orthologs for each of these that are required for secretion of gingipain protease virulence factors by its T9SS. P. gingivalis porU and porV have also been linked to T9SS-mediated secretion, and F. johnsoniae has orthologs of these. Mutations in F. johnsoniae porU and porV were constructed to determine if they function in secretion. Cells of a porV deletion mutant were deficient in chitin utilization and failed to secrete ChiA. They were also deficient in secretion of the motility adhesin RemA but retained the ability to secrete SprB. SprB is involved in gliding motility and is needed for formation of spreading colonies on agar, and the porV mutant exhibited gliding motility and formed spreading colonies. However, the porV mutant was partially deficient in attachment to glass, apparently because of the absence of RemA and other adhesins on the cell surface. The porV mutant also appeared to be deficient in secretion of numerous other proteins that have carboxy-terminal domains associated with targeting to the T9SS. PorU was not required for secretion of ChiA, RemA, or SprB, indicating that it does not play an essential role in the F. johnsoniae T9SS.

  3. Room Temperature Synthesis and Antibacterial Activity of New Sulfonamides Containing N,N-Diethyl-Substituted Amido Moieties

    PubMed Central

    Ajani, Olayinka O.; Familoni, Oluwole B.; Wu, Feipeng; Echeme, Johnbull O.; Sujiang, Zheng

    2012-01-01

    Sulfonamide drugs which have brought about an antibiotic revolution in medicine are associated with a wide range of biological activities. We have synthesized a series of α-tolylsulfonamide, 1–11 and their substituted N,N-diethyl-2-(phenylmethylsulfonamido) alkanamide derivatives, 12–22 in improved and excellent yields in aqueous medium at room temperature through highly economical synthetic routes. The chemical structures of the synthesized compounds 1–22 were confirmed by analytical and spectral data such as IR, 1H- and 13C-NMR, and mass spectra. The in vitro antibacterial activity of these compounds along with standard clinical reference, streptomycin, was investigated on two key targeted organisms. It was observed that 1-(benzylsulfonyl)pyrrolidine-2-carboxylic acid, 2 emerged as the most active compound against Staphylococcus aureus at MIC value of 1.8 μg/mL while 4-(3-(diethylamino)-3-oxo-2-(phenylmethylsulfonamido) propyl)phenyl phenylmethanesulfonate, 22 was the most active sulfonamide scaffold on Escherichia coli at MIC value of 12.5 μg/mL. PMID:25374686

  4. 4-[3-(4-Methyl­piperidin-1-yl)propan­amido]­benzene­sulfonamide monohydrate

    PubMed Central

    Türkmen, Hasan; Yalçın, Şerife Pınar; Durgun, Mustafa; Akkurt, Mehmet

    2012-01-01

    In the title compound, C15H23N3O3S·H2O, the piperidine ring has a chair conformation. In the crystal, the sulfonamide mol­ecules are linked by N—H⋯O hydrogen bonds, forming a layer parallel to (10-1). The layers are inter­connected via N—H⋯Ow, Ow—H⋯N and Ow—H⋯O (w = water) hydrogen bonds, forming a three-dimensional network. PMID:23476289

  5. Poly(amido)amine (PAMAM) dendrimer-cisplatin complexes for chemotherapy of cisplatin-resistant ovarian cancer cells

    NASA Astrophysics Data System (ADS)

    Yellepeddi, Venkata Kashyap; Vangara, Kiran Kumar; Palakurthi, Srinath

    2013-09-01

    Dendrimer-cisplatin complexes were prepared using PAMAM dendrimers with terminal -NH2 and -COOH groups as well as biotin-conjugated dendrimers. Preformulation parameters of dendrimer-cisplatin complexes were studied using differential scanning calorimetry (DSC) and inductively coupled plasma-mass spectrometry (ICP-MS). Cytotoxicity and mechanism of cytotoxicity of dendrimer-cisplatin complexes was investigated in OVCAR-3, SKOV, A2780 and cisplatin-resistant CP70 human ovarian cancer cell lines. The loading of cisplatin in dendrimers was 11 % (w/w). PAMAM G4 dendrimers with amine surface groups (biotinylated and native) have shown 2.5- to 3.0-fold reduction in IC50 values in ovarian cancer cells when compared with carboxylate surface dendrimers ( p < 0.05). A correlation was observed among cytotoxicity of the complexes, cellular uptake, and platinum-DNA adduct formation. Treatment with dendrimer-cisplatin complexes resulted in a 7.0-fold increase ( p < 0.05) in expression of apoptotic genes ( Bcl2, Bax, p53) and 13.2- to 27.1-fold increase ( p < 0.05) in the activity of caspases 3, 8, and 9 in vitro. Results suggest that PAMAM dendrimers can be used as potential carrier for cisplatin chemotherapy of ovarian cancer.

  6. Preparation and crystal structure of the 1,2-dimethoxyethane complex of bis[bis(trimethylsilyl)amido]dichlorouranium(IV)

    SciTech Connect

    McCullough, Laughlin G.; Turner, Howard W.; Andersen, Richard A.; Zalkin, Allan.; Templeton, David H.

    1981-09-01

    The complex [(Me3Si)2N]2UCl2(1,2-dimethoxyethane) has been prepared for this study from uranium tetrachloride and two molar equivalents of sodium bis(trimethylsilyl)amide in 1,2-dimethoxyethane. It may also be prepared from uranium tetrachloride and two molar equivalents of sodium bis(trimethylsilyl)amide in tetrahydrofuran followed by addition of 1,2-dimethyoxyethane. The green pentane-soluble complex crystallizes in space group Pbca with cell dimensions a = 15.207(4) Å, b= 12.021(3) Å, and c = 33.429(9) Å, Z = 8, and dx = 1.57 g cm-3. The uranium atom, which has approximate C2 symmetry, is coordinated to two nitrogen atoms from the amide groups, two oxygen atoms from the dimethoxyethane group, and two chlorine atoms. Lastly, the average U-N, U-O, and U-Cl distances are 2.23, 2.59, and 2.64 Å, respectively.

  7. Crystal structure of 2-benzene­sulfon­amido-3-hy­droxy­propanoic acid

    PubMed Central

    Jabeen, Nabila; Mushtaq, Misbah; Danish, Muhammad; Tahir, Muhammad Nawaz; Raza, Muhammad Asam

    2015-01-01

    In the title compound, C9H11NO5S, the O=S=O plane of the sulfonyl group is twisted at a dihedral angle of 52.54 (16)° with respect to the benzene ring. The dihedral angle between the carb­oxy­lic acid group and the benzene ring is 49.91 (16)°. In the crystal, C—H⋯O, N—H⋯O and O—H⋯O hydrogen bonds link the mol­ecules into (001) sheets. PMID:26594589

  8. Structural and functional probing of PorZ, an essential bacterial surface component of the type-IX secretion system of human oral-microbiomic Porphyromonas gingivalis.

    PubMed Central

    Lasica, Anna M.; Goulas, Theodoros; Mizgalska, Danuta; Zhou, Xiaoyan; de Diego, Iñaki; Ksiazek, Mirosław; Madej, Mariusz; Guo, Yonghua; Guevara, Tibisay; Nowak, Magdalena; Potempa, Barbara; Goel, Apoorv; Sztukowska, Maryta; Prabhakar, Apurva T.; Bzowska, Monika; Widziolek, Magdalena; Thøgersen, Ida B.; Enghild, Jan J.; Simonian, Mary; Kulczyk, Arkadiusz W.; Nguyen, Ky-Anh; Potempa, Jan; Gomis-Rüth, F. Xavier

    2016-01-01

    Porphyromonas gingivalis is a member of the human oral microbiome abundant in dysbiosis and implicated in the pathogenesis of periodontal (gum) disease. It employs a newly described type-IX secretion system (T9SS) for secretion of virulence factors. Cargo proteins destined for secretion through T9SS carry a recognition signal in the conserved C-terminal domain (CTD), which is removed by sortase PorU during translocation. Here, we identified a novel component of T9SS, PorZ, which is essential for surface exposure of PorU and posttranslational modification of T9SS cargo proteins. These include maturation of enzyme precursors, CTD removal and attachment of anionic lipopolysaccharide for anchorage in the outer membrane. The crystal structure of PorZ revealed two β-propeller domains and a C-terminal β-sandwich domain, which conforms to the canonical CTD architecture. We further documented that PorZ is itself transported to the cell surface via T9SS as a full-length protein with its CTD intact, independently of the presence or activity of PorU. Taken together, our results shed light on the architecture and possible function of a novel component of the T9SS. Knowledge of how T9SS operates will contribute to our understanding of protein secretion as part of host-microbiome interactions by dysbiotic members of the human oral cavity. PMID:27883039

  9. Influence of Various Polymorphic Variants of Cytochrome P450 Oxidoreductase (POR) on Drug Metabolic Activity of CYP3A4 and CYP2B6

    PubMed Central

    Naranmandura, Hua; Zeng, Su; Chen, Shu Qing

    2012-01-01

    Cytochrome P450 oxidoreductase (POR) is known as the sole electron donor in the metabolism of drugs by cytochrome P450 (CYP) enzymes in human. However, little is known about the effect of polymorphic variants of POR on drug metabolic activities of CYP3A4 and CYP2B6. In order to better understand the mechanism of the activity of CYPs affected by polymorphic variants of POR, six full-length mutants of POR (e.g., Y181D, A287P, K49N, A115V, S244C and G413S) were designed and then co-expressed with CYP3A4 and CYP2B6 in the baculovirus-Sf9 insect cells to determine their kinetic parameters. Surprisingly, both mutants, Y181D and A287P in POR completely inhibited the CYP3A4 activity with testosterone, while the catalytic activity of CYP2B6 with bupropion was reduced to approximately ∼70% of wild-type activity by Y181D and A287P mutations. In addition, the mutant K49N of POR increased the CLint (Vmax/Km) of CYP3A4 up to more than 31% of wild-type, while it reduced the catalytic efficiency of CYP2B6 to 74% of wild-type. Moreover, CLint values of CYP3A4-POR (A115V, G413S) were increased up to 36% and 65% of wild-type respectively. However, there were no appreciable effects observed by the remaining two mutants of POR (i.e., A115V and G413S) on activities of CYP2B6. In conclusion, the extent to which the catalytic activities of CYP were altered did not only depend on the specific POR mutations but also on the isoforms of different CYP redox partners. Thereby, we proposed that the POR-mutant patients should be carefully monitored for the activity of CYP3A4 and CYP2B6 on the prescribed medication. PMID:22719896

  10. "Estudio tribologico de aceros para moldes. Aplicacion al moldeo por inyeccion de polibutilentereftalato reforzado con fibra de vidrio"

    NASA Astrophysics Data System (ADS)

    Martinez Mateo, Isidoro Jose

    Mould materials for injection moulding of polymers and polymer-matrix composites represent a relevant industrial economic sector due to the large quantity of pieces and components processed. The material selection for mould manufacturing, its composition and heat treatment, the hardening procedures and machining and finishing processes determine the service performance and life of the mould. In the first part of the present study, the relationship between the hardness and microstructure and the wear resistance of mould steels from large blocks has been studied by pin-on-disc tests, studying the main wear mechanisms. In order to determine the surface damage on mould steels under real injection conditions, different commercial steels have been studied by measuring the variation of surface roughness with the number of injected pieces with different reinforcement percentages and different mould geometries, by using optical profilometry and scanning electron microscopy techniques. It was important to determine the variation of surface roughness of the moulded pieces with the number of injection operations. The materials used were polybutyleneterephthalate pure and reinforced with either 20% or 50% glass fibre. For the different mould designs, the evolution of the glass fibre orientation with injection flow has been determined by image analysis and related to roughness changes and surface damage, both of the composite parts and of the mould steel surface. Finally, the abrasion resistance of the composite parts has been studied by scratch tests as a function of the number of injected parts and of the scratch direction with respect to injection flow and glass fibre orientation. Los materiales para moldes de inyeccion de polimeros y materiales compuestos representan un sector economicamente muy relevante debido al gran aumento del numero de componentes fabricados a partir de materiales polimericos obtenidos mediante moldeo por inyeccion. La seleccion del material para la

  11. Crystallization and preliminary X-ray analysis of the C-terminal fragment of PorM, a subunit of the Porphyromonas gingivalis type IX secretion system

    PubMed Central

    Stathopulos, Julien; Cambillau, Christian; Cascales, Eric; Roussel, Alain; Leone, Philippe

    2015-01-01

    PorM is a membrane protein involved in the assembly of the type IX secretion system (T9SS) from Porphyromonas gingivalis, a major bacterial pathogen responsible for periodontal disease in humans. The periplasmic domain of PorM was overexpressed in Escherichia coli and purified. A fragment of the purified protein was obtained by limited proteolysis. Crystals of this fragment belonged to the tetragonal space group P43212. Native and MAD data sets were recorded to 2.85 and 3.1 Å resolution, respectively, using synchrotron radiation. PMID:25615973

  12. Community-based education in nutrition and cancer: the Por La Vida Cuidándome curriculum.

    PubMed

    Navarro, A M; Rock, C L; McNicholas, L J; Senn, K L; Moreno, C

    2000-01-01

    The Por La Vida (PLV) intervention model relies on community lay health advisors trained to conduct education sessions among members of their existing social networks. PLV Cuidándome was funded by the NCI to develop, implement, and evaluate the PLV model with respect to nutrition and cancer prevention, as well as early detection of breast and cervical cancers. The target population is the Latino community, for which substantial barriers to health care access exist. This article presents the curriculum that guides the sessions and describes its development, which was based on semi-structured interviews with Latina lay-health community workers to explore relevant attitudes and behaviors. Also key to the process was the work of the educational materials committee, whose members offered community representation as well as expertise in nutritional sciences, educational technologies, and community-based health promotion interventions and research. The 12-session curriculum's goal was to increase both the variety and the quality of fruits and/or vegetables consumed. It included information about consumption of fiber and fat in the importance of balance between energy intake and physical activity. The program has been well received. An ongoing study examines how it enhances nutrition and cancer prevention.

  13. El proceso hacia la integracion de la equidad por genero al curriculo.(The Process of the Integration of Gender Equity in the Curriculum.)

    ERIC Educational Resources Information Center

    Rivera-Bermudez, Carmen D.

    "El Proyecto Colaborativo de Equidad por Genero en la Educacion," or the Collaborative Project for Gender Equity in Education, was undertaken in Puerto Rico between 1990 and 1992 to study how to facilitate the integration of gender equity themes in the curriculum through the direct action of participating teachers. A study examined the…

  14. P(O)R2-directed Pd-catalyzed C-H functionalization of biaryl derivatives to synthesize chiral phosphorous ligands.

    PubMed

    Hu, Rong-Bin; Wang, Hong-Li; Zhang, Hong-Yu; Zhang, Heng; Ma, Yan-Na; Yang, Shang-Dong

    2014-01-01

    Chiral phosphorus ligands have been widely used in transition metal-catalyzed asymmetric reactions. Herein, we report a new synthesis approach of chiral biaryls containing a phosphorus moiety using P(O)R2-directed Pd-catalyzed C-H activation; the functionalized products are produced with good enantioselectivity.

  15. Estimaciones de Prevalencia del VIH por Género y Grupo de Riesgo en Tijuana, México: 2006

    PubMed Central

    Iñiguez-Stevens, Esmeralda; Brouwer, Kimberly C.; Hogg, Robert S.; Patterson, Thomas L.; Lozada, Remedios; Magis-Rodriguez, Carlos; Elder, John P.; Viani, Rolando M.; Strathdee, Steffanie A.

    2010-01-01

    OBJETIVO Estimar la prevalencia del VIH en adultos de 15-49 años de edad en Tijuana, México - en la población general y en subgrupos de riesgo en el 2006. METODOS Se obtuvieron datos demográficos del censo Mexicano del 2005, y la prevalencia del VIH se obtuvo de la literatura. Se construyó un modelo de prevalencia del VIH para la población general y de acuerdo al género. El análisis de sensibilidad consistió en estimar errores estándar del promedio-ponderado de la prevalencia del VIH y tomar derivados parciales con respecto a cada parámetro. RESULTADOS La prevalencia del VIH es 0.54%(N = 4,347) (Rango: 0.22%–0.86%, (N = 1,750–6,944)). Esto sugiere que 0.85%(Rango: 0.39%–1.31%) de los hombres y 0.22%(Rango: 0.04%–0.40%) de las mujeres podrían ser VIH-positivos. Los hombres que tienen sexo con hombres (HSH), las trabajadoras sexuales usuarias de drogas inyectables (MTS-UDI), MTS-noUDI, mujeres UDI, y los hombres UDI contribuyeron las proporciones más elevadas de personas infectadas por el VIH. CONCLUSIONES El número de adultos VIH-positivos entre subgrupos de riesgo en la población de Tijuana es considerable, marcando la necesidad de enforcar las intervenciones de prevención en sus necesidades específicas. El presente modelo estima que hasta 1 en cada 116 adultos podrían ser VIH-positivos. PMID:19685824

  16. Adjuvant effects elicited by novel oligosaccharide variants of detoxified meningococcal lipopolysaccharides on Neisseria meningitidis recombinant PorA protein: a comparison in mice.

    PubMed

    Mehta, Ojas H; Norheim, Gunnstein; Hoe, J Claire; Rollier, Christine S; Nagaputra, Jerry C; Makepeace, Katherine; Saleem, Muhammad; Chan, Hannah; Ferguson, David J P; Jones, Claire; Sadarangani, Manish; Hood, Derek W; Feavers, Ian; Derrick, Jeremy P; Pollard, Andrew J; Moxon, E Richard

    2014-01-01

    Neisseria meningitidis lipopolysaccharide (LPS) has adjuvant properties that can be exploited to assist vaccine immunogenicity. The modified penta-acylated LPS retains the adjuvant properties of hexa-acylated LPS but has a reduced toxicity profile. In this study we investigated whether two modified glycoform structures (LgtE and IcsB) of detoxified penta-acylated LPS exhibited differential adjuvant properties when formulated as native outer membrane vesicles (nOMVs) as compared to the previously described LgtB variant. Detoxified penta-acylated LPS was obtained by disruption of the lpxL1 gene (LpxL1 LPS), and three different glycoforms were obtained by disruption of the lgtB, lgtE or icsB genes respectively. Mice (mus musculus) were immunized with a recombinant PorA P1.7-2,4 (rPorA) protein co-administered with different nOMVs (containing a different PorA serosubtype P1.7,16), each of which expressed one of the three penta-acylated LPS glycoforms. All nOMVs induced IgG responses against the rPorA, but the nOMVs containing the penta-acylated LgtB-LpxL1 LPS glycoform induced significantly greater bactericidal activity compared to the other nOMVs or when the adjuvant was Alhydrogel. Compared to LgtE or IcsB LPS glycoforms, these data support the use of nOMVs containing detoxified, modified LgtB-LpxL1 LPS as a potential adjuvant for future meningococcal protein vaccines.

  17. Astronomy in the Classroom: Why? (Spanish Title: Astronomía en la Clase: ¿Por Qué?) Astronomia na Sala de Aula: Por Quê?

    NASA Astrophysics Data System (ADS)

    Daros Gama, Leandro; Bagdonas Henrique, Alexandre

    2010-07-01

    There are many discussions about the relevance of the topics covered in classes. One subject in particular is the focus of this essay: astronomy. In what sense and to what extent it would be worth to teach it in science or other kind of classes? In this paper we discuss some aspects of the advantages of dealing with this area of knowledge in schools, taking into account the epistemological and axiological dimensions of astronomy, in light of the vision of science as an intelligent dialogue with the world (Bachelard), in addition to the "problematization" knowledge of Paulo Freire. We propose that in fact the Astronomy does not need to be seen as just a new set of contents to be taught, but appears as a set of motivational contents for historical-philosophical discussions, and permit the discussion of concepts of other disciplines. Numerosas discusiones se están llevando a cabo acerca de la pertinencia de los temas tradicionalmente tratados en las clases. Uno de los temas, en particular, es el foco de este ensayo: la astronomía. ¿En qué sentido y en qué medida sería conveniente tratarla en clase, ya sea en clases de ciencias naturales, específicamente en las de astronomía o asignaturas afines? Elaboramos en este artículo algunos aspectos de las ventajas de tratar esta área del conocimiento en las escuelas, teniendo en cuenta las dimensiones epistemológica y axiológica de la astronomía, a la luz de la visión de la ciencia como un diálogo inteligente con el mundo (Bachelard), además de la propuesta del conocimiento "problematizador" de Paulo Freire. Proponemos que en realidad la astronomía no tiene por qué ser vista sólo como un nuevo conjunto de contenidos que se enseñan, sino que aparece como un conjunto de temas de motivación para el debate histórico-filosófico y para permitir la discusión de los conceptos típicos de otras disciplinas. Muitas discussões vêm acontecendo sobre a relevância dos temas abordados em sala de aula. Um tema, em

  18. Obtención de la curva de luz en la ocultación de 35 Sgr por Júpiter el 6 de marzo de 1996

    NASA Astrophysics Data System (ADS)

    Paolantonio, S.; Duffard, R.; Carranza, G.

    La ocultación de la estrella de quinta magnitud 35 Sgr por Júpiter, se produjo el 6 de Marzo de 1996 a las 13 hs. TU. El objetivo era medir el cambio del flujo de la estrella en el ingreso y egreso por el limbo del planeta. Con estos datos se pueden determinar parámetros físicos del planeta (radio, eccentricidad) y de su atmósfera (escala de altura, temperatura, densidad, presión) Para lograr ésto se programó la cámara CCD TH 7896 1024 x 1025 instalada en el telescopio de 1.54 m de Bosque Alegre con el objetivo de lograr 2 imágenes por segundo. De esta forma se obtuvieron 2100 imágenes de la inmersión y otras tantas de la emersión. Hubo que tener grandes precauciones para evitar la saturación del CCD ya que la observación se realizó de día. En este momento las imágenes se encuentran en el Department of Planetary Sciences, Lunar and Planetary Laboratory, University of Arizona, para su reducción.

  19. Pincharse sin infectarse: estrategias para prevenir la infección por el VIH y el VHC entre usuarios de drogas inyectables

    PubMed Central

    MATEU-GELABERT, P.; FRIEDMAN, S.; SANDOVAL, M.

    2011-01-01

    Resumen Objetivo Desde principios de los noventa, en la ciudad de Nueva York se han implementado con éxito programas para reducir la incidencia del virus de la inmunodeficiencia humana (VIH) y, en menor medida, del virus de la hepatitis C (VHC). A pesar de ello, aproximadamente el 70% de los usuario de drogas inyectables (UDI) están infectados por el VHC. Queremos investigar cómo el 30% restante se las ha arreglado para no infectarse. El Staying safe (nombre original del estudio) explora los comportamientos y mecanismos que ayudan a evitar la infección por el VHC y el VIH a largo plazo. Material y métodos Hemos utilizado el concepto de «desviación positiva» aplicado en otros campos de salud pública. Estudiamos las estrategias, prácticas y tácticas de prevención de aquellos UDI que, viviendo en contextos de alta prevalencia, se mantienen sin infectar por VIH y el VHC, a pesar de haberse inyectado heroína durante años. Los resultados preliminares presentados en este artículo incluyen el análisis de las entrevistas realizadas a 25 UDI (17 doble negativos, 3 doble positivos y 5 con infección por el VHC y sin infección por el VIH). Se usaron entrevistas semiestructuradas que exploraban con detalle la historia de vida de los sujetos, incluyendo su consumo de drogas, redes sociales, contacto con instituciones, relaciones sexuales y estrategias de protección y vigilancia. Resultados La intencionalidad es importante para no infectarse, especialmente durante períodos de involución (períodos donde hay un deterioro económico y/o social que llevan al que se inyecta a situaciones de mayor riesgo). Presentamos tres dimensiones independientes de intencionalidad que conllevan comportamientos que pueden ayudar a prevenir la infección: a) evitar «el mono» (síntomas de abstención) asegurando el acceso a la droga; b) «llevarlo bien» para no convertirse en un junkie y así evitar la «muerte social» y la falta de acceso a los recursos, y c) seguir sin

  20. PAH effects on meio- and microbial benthic communities strongly depend on bioavailability.

    PubMed

    Lindgren, J Fredrik; Hassellöv, Ida-Maja; Dahllöf, Ingela

    2014-01-01

    The effects of anthropogenic pollutants in dissimilar habitats can vary depending on differences in bioavailability. The factors determining bioavailability are not yet fully understood. This study was performed to evaluate whether analysis of total PAH concentrations in sediments is a satisfactory measurement to indicate environmental effects or if bioavailability is needed to be taken into account. We have here performed a 60-day experiment, where nominal PAH concentrations of 1,300 μg/kg sediment were added to three different marine sediments. Meiofaunal and microbial communities were analyzed for alterations in community response at 30 and 60 days. Results showed that bioavailability of PAHs varied between the three different sediments. Nonetheless, the petroleum addition gave rise to significant negative effects on all three sediments at both time points. The two direct measurements of toxicity on the microbial community, potential nitrification and denitrification, displayed a lower effect of the PAH addition in the muddy sediment at both time points, compared to the other two sediment types. No effects were seen in the analysis of meiofaunal community structure. Measurements of PAH bioavailability in the three sediment types concurred with the results from the microbial community, revealing a lower bioavailability in the muddy sediment compared to the other two sediment types, 34% compared to sandy and 18% compared to organic at day 0. At day 60 it was 61% lower compared to sandy and 20% lower compared to organic. The negative effects of the PAH addition on the microbial nitrogen cycle were in six out of eight cases best correlated to the amount of alkylated bioavailable PAH in the sediments, and thus microbial nitrogen cycle is a possible good indicator for assessing PAH-induced stress. The results presented here have implications for risk analysis studies of petroleum-contaminated marine sediments; consequently, sediment characteristics and its effects on bioavailability are important to include. In addition, these results add to the understanding that bioavailability measurements of PAHs are a more correct assessment compared to measurements of total PAH concentrations, and need to be included when estimating effects of PAHs in marine benthic communities.

  1. A survey of homopteran species (Auchenorrhyncha) from coffee shrubs and poró and laurel trees in shaded coffee plantations, in Turrialba, Costa Rica.

    PubMed

    Rojas, L; Godoy, C; Hanson, P; Hilje, L

    2001-01-01

    A survey of homopteran species (Auchenorryncha) was conducted in coffee plantations with no shade (C), and in those with shade of either poró (Erythrina poeppigiana) (CP) or poró plus laurel (Cordia alliodora) (CPL), in Turrialba, Costa Rica. A total of 130 species in ten families were collected, dominated by Cicadellidae (82 species). Species richness was highest in the CP system (88), followed by CPL (74) and C systems (60). Five most common species for all systems were Fusigonalia lativittata, Hebralebra nicaraguensis, Neocoelidia sp., Oliarus sp. and Clastoptera sp. Diversification of the coffee agroecosystem favors some species while limiting others, and have no effect on the majority of species. Thus, only F. lativittata, Neocoelidia sp. and Scaphytopius ca. latidens were well represented in all systems, but were more abundant in coffee shrubs. Additionally, the following were the dominant species in each system: Graphocephala sp. 1 (C), F. lativittata (CP) and H. nicaraguensis (CPL). Four species abundant on laurel trees, including H. nicaraguensis, appeared almost exclusively on these tree species. Species similarity was highest on the CP and CPL systems (51% of the species in common), followed by the C and CP (39%) and the C and CPL systems (38%). These findings show that even disturbed systems can harbor many insect species, so that they deserve attention from conservation advocates and biologists.

  2. A Fast Real-Time Polymerase Chain Reaction Method for Sensitive and Specific Detection of the Neisseria gonorrhoeae porA Pseudogene

    PubMed Central

    Hjelmevoll, Stig Ove; Olsen, Merethe Elise; Sollid, Johanna U. Ericson; Haaheim, Håkon; Unemo, Magnus; Skogen, Vegard

    2006-01-01

    Ever since the advent of molecular methods, the diagnostics of Neisseria gonorrhoeae has been troubled by false negative and false positive results compared with culture. Commensal Neisseria species and Neisseria meningitidis are closely related to N. gonorrhoeae and may cross-react when using molecular tests comprising too-low specificity. We have devised a real-time polymerase chain reaction (PCR), including an internal amplification control, that targets the N. gonorrhoeae porA pseudogene. DNA was automatically isolated on a BioRobot M48. Our subsequent PCR method amplified all of the different N. gonorrhoeae international reference strains (n = 34) and N. gonorrhoeae clinical isolates (n = 176) but not isolates of the 13 different nongonococcal Neisseria species (n = 68) that we tested. Furthermore, a panel of gram-negative bacterial (n = 18), gram-positive bacterial (n = 23), fungal (n = 1), and viral (n = 4) as well as human DNA did not amplify. The limit of detection was determined to be less than 7.5 genome equivalents/PCR reaction. In conclusion, the N. gonorrhoeae porA pseudogene real-time PCR developed in the present study is highly sensitive, specific, robust, rapid and reproducible, making it suitable for diagnosis of N. gonorrhoeae infection. PMID:17065426

  3. Prevalencia y factores de riesgo para infecciones del tracto urinario de inicio en la comunidad causadas por Escherichia coli productor de betalactamasas de espectro extendido en Colombia

    PubMed Central

    Blanco, Victor M.; Maya, Juan J.; Correa, Adriana; Perenguez, Marcela; Muñoz, Juan S.; Motoa, Gabriel; Pallares, Christian J.; Rosso, Fernando; Matta, Lorena; Celis, Yamile; Garzon, Martha; Villegas, y María V.

    2016-01-01

    RESUMEN Introducción Las infecciones del tracto urinario (ITU) son frecuentes en la comunidad. Sin embargo, la información de aislamientos resistentes en este contexto es limitada en Latinoamérica. Este estudio tiene como objetivo determinar la prevalencia y los factores de riesgo asociados con ITU de inicio en la comunidad (ITU-IC) causadas por Escherichia coli productor de betalactamasas de espectro extendido (BLEE) en Colombia. Materiales y métodos Entre agosto y diciembre de 2011 se realizó un estudio de casos y controles en 3 instituciones de salud de tercer nivel en Colombia. Se invitó a participar a todos los pacientes admitidos a urgencias con diagnóstico probable de ITU-IC, y se les pidió una muestra de orina. En los aislamien-tos de E. coli se realizaron pruebas confirmatorias para BLEE, susceptibilidad antibiótica, caracterización molecular (PCR en tiempo real para genes bla, repetitive element palindromic PCR [rep-PCR], multilocus sequence typing [MLST] y factores de virulencia por PCR). Se obtuvo información clínica y epidemiológica, y posteriormente se realizó el análisis estadístico. Resultados De los 2.124 pacientes seleccionados, 629 tuvieron un urocultivo positivo, en 431 de estos se aisló E. coli, 54 fueron positivos para BLEE y 29 correspondieron a CTX-M-15. La mayoría de los aislamientos de E. coli productor de BLEE fueron sensibles a ertapenem, fosfomicina y amikacina. La ITU complicada se asoció fuertemente con infecciones por E. coli productor de BLEE (OR = 3,89; IC 95%: 1,10–13,89; p = 0,03). E. coli productor de CTX-M-15 mostró 10 electroferotipos diferentes; de estos, el 65% correspondieron al ST131. La mayoría de estos aislamientos tuvieron 8 de los 9 factores de virulencia analizados. Discusión E. coli portador del gen blaCTX-M-15 asociado al ST131 sigue siendo frecuente en Colombia. La presencia de ITU-IC complicada aumenta el riesgo de tener E. coli productor de BLEE, lo cual debe tenerse en cuenta para ofrecer

  4. Structural basis of jasmonate-amido synthetase FIN219 in complex with glutathione S-transferase FIP1 during the JA signal regulation

    PubMed Central

    Chen, Chun-Yen; Ho, Sih-Syun; Kuo, Tzu-Yen; Cheng, Yi-Sheng

    2017-01-01

    Far-red (FR) light-coupled jasmonate (JA) signaling is necessary for plant defense and development. FR insensitive 219 (FIN219) is a member of the Gretchen Hagen 3 (GH3) family of proteins in Arabidopsis and belongs to the adenylate-forming family of enzymes. It directly controls biosynthesis of jasmonoyl-isoleucine in JA-mediated defense responses and interacts with FIN219-interacting protein 1 (FIP1) under FR light conditions. FIN219 and FIP1 are involved in FR light signaling and are regulators of the interplay between light and JA signaling. However, how their interactions affect plant physiological functions remains unclear. Here, we demonstrate the crystal structures of FIN219–FIP1 while binding with substrates at atomic resolution. Our results show an unexpected FIN219 conformation and demonstrate various differences between this protein and other members of the GH3 family. We show that the rotated C-terminal domain of FIN219 alters ATP binding and the core structure of the active site. We further demonstrate that this unique FIN219–FIP1 structure is crucial for increasing FIN219 activity and determines the priority of substrate binding. We suggest that the increased FIN219 activity resulting from the complex form, a conformation for domain switching, allows FIN219 to switch to its high-affinity mode and thereby enhances JA signaling under continuous FR light conditions. PMID:28223489

  5. Reductive C(sp(2))-N Elimination from Isolated Pd(IV) Amido Aryl Complexes Prepared Using H2O2 as Oxidant.

    PubMed

    Abada, Elikplim; Zavalij, Peter Y; Vedernikov, Andrei N

    2017-01-18

    Di-2-pyridyl ketone (dpk)-supported amidoarylpallada(II)cycles derived from various 2-(N-R-amino)biphenyls (R = H, Me, CF3CO, MeSO2, CF3SO2) react with hydrogen peroxide in MeOH, THF, MeCN or AcOH to form the corresponding C-N coupled products, N-R-substituted carbazoles, in 82-98% yield. For R = MeSO2 and CF3SO2, the corresponding reaction intermediates, amidoaryl Pd(IV) complexes were isolated and characterized by single crystal X-ray diffraction and/or NMR spectroscopy. For the first time, the C(sp(2))-N reductive elimination from isolated amidoaryl Pd(IV) complexes has been studied in detail.

  6. Amido-based potassium-alkaline earth metallates--synthesis and structures of heterobimetallic complexes of heavy s-block elements.

    PubMed

    Glock, Carsten; Görls, Helmar; Westerhausen, Matthias

    2011-08-28

    The metathesis reaction of potassium N-isopropylanilide with alkaline earth metal diiodides of calcium, strontium and barium in a molar ratio of 4:1 yields the corresponding alkaline earth metalates of the type [(THF)(n)K(μ-NPhiPr)(2)Ae(μ-NPhiPr)(2)K(THF)(n)] (1: Ae = Ca, n = 2). Stabilization and crystallization of such derivatives succeeds after exchange of the THF ligands by multidentate amino bases such as tetramethylethylenediamine (TMEDA) or pentamethyldiethylenetriamine (PMDETA). The influence of the size and hardness of the alkaline earth metal center on the molecular structures is studied with [(L)K(μ-NPhiPr)(2)Ae(μ-NPhiPr)(2)K(L)] (2: Ae = Ca, L = TMEDA; 3: Ae = Sr, L = TMEDA; 4: Ae = Sr, L = PMDETA; and 5: Ae = Ba, L = PMDETA). The molecular structures are dominated by (attractive and repulsive) electrostatic and steric factors leading to a shortening of the non-bonding AeK distances from calcium to barium.

  7. How do the full-generation poly(amido)amine (PAMAM) dendrimers activate blood platelets? Platelet membrane zeta potential and other membrane-associated phenomena.

    PubMed

    Watala, Cezary; Karolczak, Kamil; Kassassir, Hassan; Siewiera, Karolina; Maczynska, Katarzyna; Pieniazek, Anna; Labieniec-Watala, Magdalena

    2016-03-16

    We explored the hypothesis that zeta potential altered by polycations affects blood platelet activation and reactivity, the phenomena associated with membrane lipid fluidity and platelet mitochondrial bioenergetics. PAMAM dendrimers generation- and dose-dependently enhanced zeta potential of platelets (from -10.7 mV to -4.3 mV). Increased expressions of activation markers, P-selectin and the active complex αIIbβ3, as well as significantly enhanced fibrinogen binding occurred upon the in vitro incubation of blood platelets in the presence of PAMAMs G3 and G4 (resp. 62.1% and 69.4% vs. 1.4% and 2.7% in control for P-selectin, P<0.0001). PAMAM dendrimers increased fluidity of platelet membrane lipid bilayer, while they did not affect platelet mitochondria respiration. Increased platelet activation and their responses to agonists in vitro were statistically associated with the revealed alterations in zeta potential. Our results support the hypothesis that polycation-mediated "neutralized" zeta potential may underlie the activating effects of PAMAMs on blood platelets.

  8. Transcript profiles of auxin efflux carrier and IAA-amido synthetase genes suggest the role of auxin on apple (Malus x domestica) fruit maturation patterns

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Plant growth regulators are known to regulate fruit development at various stages including flowering, fruit growth, maturation and ripening. Recent transcriptome studies indicated that auxin might play an essential role in regulating apple fruit maturation and ripening beside the well-defined role...

  9. Crystal structure of 4-(3-carb-oxy-pro-pan-amido)-2-hy-droxy-benzoic acid mono-hydrate.

    PubMed

    Tahir, Muhammad Nawaz; Ahmed, Muhammad Naeem; Butt, Arshad Farooq; Shad, Hazoor Ahmad

    2014-12-01

    In the title hydrate, C11H11NO6·H2O, the organic mol-ecule is approximately planar (r.m.s. deviation for the non-H atoms = 0.129 Å) and an intra-molecular O-H⋯O hydrogen bond closes an S(6) ring. In the crystal, the benzoic acid group participates in an O-H⋯O hydrogen bond to the water mol-ecule and accepts a similar bond from another water mol-ecule. The other -CO2H group forms a carb-oxy-lic acid inversion dimer, thereby forming an R 2 (2)(8) loop. These bonds, along with N-H⋯O and C-H⋯O inter-actions, generate a three-dimensional network.

  10. Potentiometric and Blood Plasma Simulation Studies of Nickel(II) Complexes of Poly(amino)amido Pentadentate Ligands: Computer Aided Metal-Based Drug Design.

    PubMed

    Odisitse, Sebusi; Jackson, Graham E

    2014-01-01

    The thermodynamic equilibria of nickel(II) with N,N'-di(aminoethylene)-2,6-pyridinedicarbonylamine (L1), Bis-(N,N-dimethylethyl)-2,6-pyridinedicarboxamide (L2), and N,N'-bis[2(2-pyridyl)-methyl]pyridine-2,6-dicarboxamide (L3) have been studied at 25°C and an ionic strength of 0.15 mol dm(-3) by glass electrode potentiometry. The protonation and formation constants added to blood plasma model predict that Cu(II) competes effectively against Ni(II), Zn(II), and Ca(II) for these ligands in vivo.

  11. Concepciones y concepciones alternativas de estudiantes universitarios/as de biologia y futuros maestros/as de Ciencia de escuela secundaria sobre la teoria de evolucion biologica por seleccion natural

    NASA Astrophysics Data System (ADS)

    Morales Ramos, Egda M.

    La teoria de evolucion biologica (TEB) por seleccion natural es uno de los conceptos unificadores mas importantes del curriculo de Biologia. En Puerto Rico se han hecho pocas investigaciones que abunden sobre las concepciones y concepciones alternativas (CA) que tienen los estudiantes universitarios/as de Biologia y los maestros/as de Ciencia del nivel secundario sobre esta teoria. La politica publica educativa actual establece mediante documentos normativos como los Estandares de contenido y Expectativas de grado del Programa de Ciencias [Puerto Rico Core Standards] la ensenanza de esta teoria. Sin embargo, no se encontraron preguntas sobre la seleccion natural en los ejercicios de practica provistos por el Departamento de Educacion para las pruebas estandarizadas lo cual puede influir para que no se ensene adecuadamente. Las preguntas de investigacion fueron 1. ¿Cuales son las concepciones y concepciones alternativas de estudiantes universitarios/as y de los futuros maestros y maestras de Ciencia sobre la TEB? 2. ¿Cuales conceptos que seleccionan los estudiantes universitarios/as y los futuros maestros y maestras de Ciencia sobre la TEB coinciden con lo aceptado como valido por la comunidad cientifica? y 3. ¿Como comparan las respuestas de la prueba original. v. Entendiendo el cambio biologico que mide concepciones y CA sobre la TEB por seleccion natural, con las de la traducida al idioma espanol? Se utilizo el metodo cuantitativo con un diseno de investigacion transversal por encuesta. La tecnica principal para recopilar los datos fue una prueba con doce items, que formo parte de un instrumento para el cual se recopilaron diversas fuentes de evidencia acerca de su validez. Las muestras estuvieron formadas por 69 estudiantes de Ciencias Naturales y por 16 estudiantes futuros maestros y maestras del nivel secundario de la UPR-RP. Se utilizaron estadisticas descriptivas, analisis de Ji cuadrado y se calcularon los coeficientes alfa de Cronbach y de Spearman

  12. Relación masa-radio para estrellas enanas blancas y la interpretación de recientes mediciones hechas por Hipparcos

    NASA Astrophysics Data System (ADS)

    Panei, J. A.; Althaus, L. G.; Benvenuto, O. G.

    Recientes mediciones de la masa y el radio hechas por Hipparcos de las estrellas enanas blancas 40 Eri B y Procyon B (Shipman, H. & Provencal, J. - ApJ. 1998, 494, 759), sugieren un núcleo compuesto de hierro para dichas estrellas, en lugar de carbono y oxígeno como predice la teoría standard de evolución estelar. Para interpretar estas observaciones, presentamos aquí, relaciones masa-radio para configuraciones degeneradas a temperatura finita para distintas composiciones químicas centrales. Para tal fin hemos calculado secuencias evolutivas de enanas blancas utilizando el código de evolución estelar, desarrollado en el Observatorio de La Plata. Dicho código resuelve las ecuaciones de estructura y evolución estelar mediante la técnica de relajación de Henyey, y esta basado en una descripción física muy detallada y actualizada.

  13. Bifurcación de las soluciones de vientos impulsados por radiación en estrellas Be: formación de líneas

    NASA Astrophysics Data System (ADS)

    Curé, M.; Rial, D.; Cidale, L.; Venero, R.

    Se ha estudiado la topología de la ecuación hidrodinámica no-lineal que describe el perfil de velocidades de vientos impulsados por radiación en estrellas tempranas. Al aplicar este modelo a estrellas Be se encuentra que existen dos tipos De soluciones: la estándar, que describe el viento polar, y una nueva, que describe un viento más denso y lento y que explicaría el disco que se encuentra alrededor de estos objetos. Existe una región de transición en donde ambas soluciones coexisten (bifurcación}). Ambas soluciones satisfacen en esta región las mismas condiciones de borde. Para estas dos soluciones se han obtenido los perfiles de líneas de hidrógeno del visible y del IR, resolviendo el transporte de radiación en el ``comoving frame". Para la solución estándar, se obtienen perfiles con componentes en emisión, mientras que para la nueva solución se obtienen perfiles en absorción. Se comparan cualitativamente los resultados con las observaciones.

  14. Weight of ABCB1 and POR genes on oral tacrolimus exposure in CYP3A5 nonexpressor pediatric patients with stable kidney transplant.

    PubMed

    Almeida-Paulo, G N; Dapía García, I; Lubomirov, R; Borobia, A M; Alonso-Sánchez, N L; Espinosa, L; Carcas-Sansuán, A J

    2017-01-17

    Tacrolimus (TAC) is highly effective for the prevention of acute organ rejection. However, its clinical use may be challenging due to its large interindividual pharmacokinetic variability, which can be partially explained by genetic variations in TAC-metabolizing enzymes and transporters. The aim of this study was to evaluate the influence of genetic and clinical factors on TAC pharmacokinetic variability in 21 stable pediatric renal transplant patients. This study was nested in a previous Prograf to Advagraf conversion clinical trial. CYP3A5, ABCB1 and two POR genotypes were assessed by real-time PCR. The impact on TAC pharmacokinetics of individual genetic variants on CYP3A5 nonexpressors was evaluated by genetic score. Explicative models for TAC AUC0-24h, Cmax and Cmin after Advagraf were developed by linear regression. The built genetic scores explain 13.7 and 26.5% of the total AUC0-24h and Cmin total variability, respectively. Patients genetic information should be considered to monitorizate and predict TAC exposure.The Pharmacogenomics Journal advance online publication, 17 January 2017; doi:10.1038/tpj.2016.93.

  15. IgE Reactivity of Blue Swimmer Crab (Portunus pelagicus) Tropomyosin, Por p 1, and Other Allergens; Cross-Reactivity with Black Tiger Prawn and Effects of Heating

    PubMed Central

    Varese, Nirupama; Zubrinich, Celia; Lopata, Andreas L.; O'Hehir, Robyn E.; Rolland, Jennifer M.

    2013-01-01

    Shellfish allergy is a major cause of food-induced anaphylaxis, but the allergens are not well characterized. This study examined the effects of heating on blue swimmer crab (Portunus pelagicus) allergens in comparison with those of black tiger prawn (Penaeus monodon) by testing reactivity with shellfish-allergic subjects' serum IgE. Cooked extracts of both species showed markedly increased IgE reactivity by ELISA and immunoblotting, and clinical relevance of IgE reactivity was confirmed by basophil activation tests. Inhibition IgE ELISA and immunoblotting demonstrated cross-reactivity between the crab and prawn extracts, predominantly due to tropomyosin, but crab-specific IgE-reactivity was also observed. The major blue swimmer crab allergen tropomyosin, Por p 1, was cloned and sequenced, showing strong homology with tropomyosin of other crustacean species but also sequence variation within known and predicted linear IgE epitopes. These findings will advance more reliable diagnosis and management of potentially severe food allergy due to crustaceans. PMID:23840718

  16. Fuentes de variabilidad en el diagnóstico de gastritis atrófica multifocal asociada con la infección por Helicobacter pylori1

    PubMed Central

    Bravo, Luis Eduardo; Bravo, Juan Carlos; Realpe, José Luis; Zarama, Guillermo; Piazuelo, MarÍa Blanca; Correa, Pelayo

    2014-01-01

    RESUMEN Introducción El mapeo de las diferentes regiones del estómago y el número de fragmentos de mucosa gástrica disponibles para evaluación histopatológica son fuentes importantes de variación en el momento de clasificar y hacer la gradación de la gastritis crónica. Objetivos Estimar la sensibilidad del número de fragmentos de mucosa gástrica necesarios para establecer los diagnósticos de gastritis atrófica con metaplasia intestinal (MI), displasia y estado de infección por Helicobacter pylori. Además evaluar la variabilidad intra-observador en la clasificación de estas lesiones precursoras del cáncer gástrico. Materiales y métodos En una cohorte de 6 años de seguimiento se evaluaron 1,958 procedimientos de endoscopia realizados por dos gastroenterólogos. En cada procedimiento y de cada participante se obtuvieron 5 biopsias de mucosa gástrica que representaban antro, incisura angularis y cuerpo. Un único patólogo hizo la interpretación histológica de las 5 biopsias y proporcionó un diagnóstico definitivo global que se utilizó como patrón de referencia. Cada fragmento de mucosa gástrica examinado condujo a un diagnóstico individual para cada biopsia que se comparó con el patrón de referencia. La variabilidad intra-observador se evaluó en 127 personas que corresponden a una muestra aleatoria de 20% del total de endoscopias hechas a los 72 meses de seguimiento. Resultados La sensibilidad del diagnóstico de MI y displasia gástrica aumentó de manera significativa con el número de fragmentos de mucosa gástrica evaluados El sitio anatómico de mayor sensibilidad para el diagnóstico de MI y displasia fue la incisura angularis. Para descubrir H. pylori se logró alta sensibilidad con el estudio de un solo fragmento de mucosa gástrica (95.9%) y fue independiente del sitio de obtención de la biopsia. El acuerdo intra-observador para el diagnóstico de gastritis crónica fue 86.1% con valor kappa de 0.79 IC 95% (0.76-0.85). Las

  17. A UV-vis study of the effects of alcohols on formation and stability of Mn(por)(O)(OAc) complexes.

    PubMed

    Mohajer, Daryoush; Jahanbani, Maryam

    2012-06-01

    Interactions of three different (acetato) (tetraarylporphyrinato) manganese (III) Mn(III)(por) with tetra-n-butylammonium hydrogen monopersulfate (n-Bu(4)NHSO(5)), in the presence of excess tetra-n-butylammonium acetate (n-Bu(4)NOAc) and in the absence or presence of various alcohols (alcohols=CH(3)OH, C(2)H(5)OH, i-C(3)H(7)OH, t-C(4)H(9)OH) in CH(2)Cl(2), were monitored by their UV-vis spectral changes, under identical conditions, at room temperature. (Acetato) (tetrakispentafluorophenylporphyrinato) manganese (III) Mn(III)(tpfpp)(OAc) and (acetato) (tetramesitylporphyrinato) manganese (III) Mn(III)(tmp)(OAc) produced their corresponding high valent Mn(tpfpp)(O)(OAc) and Mn(tmp)(O)(OAc) both in the absence or presence of alcohols. Whereas, (acetato) (tetraphenylporphyrinato) manganese (III) Mn(III)(tpp)(OAc) only generated Mn(tpp)(O)(OAc) in the presence of less bulky alcohols. In the absence of alcohols or in the presence of t-C(4)H(9)OH, the UV-vis spectra displayed a very weak sign of formation of Mn(tpp)(O)(OAc) complex. It was observed that alcohols generally increased the rate of formation of Mn-oxo species in accordance with their acidity or hydrogen bonding strength, and enhanced the stability of Mn-oxo complexes, as their size increases. Attempts are made to explain these effects. A mechanistic scheme is also suggested for the decomposition of HSO(5)(-) to O(2) and HSO(4)(-), through the formation and dimerization of Mn-oxo species.

  18. A UV-vis study of the effects of alcohols on formation and stability of Mn(por)(O)(OAc) complexes

    NASA Astrophysics Data System (ADS)

    Mohajer, Daryoush; Jahanbani, Maryam

    2012-06-01

    Interactions of three different (acetato) (tetraarylporphyrinato) manganese (III) MnIII(por) with tetra-n-butylammonium hydrogen monopersulfate (n-Bu4NHSO5), in the presence of excess tetra-n-butylammonium acetate (n-Bu4NOAc) and in the absence or presence of various alcohols (alcohols = CH3OH, C2H5OH, i-C3H7OH, t-C4H9OH) in CH2Cl2, were monitored by their UV-vis spectral changes, under identical conditions, at room temperature. (Acetato) (tetrakispentafluorophenylporphyrinato) manganese (III) MnIII(tpfpp)(OAc) and (acetato) (tetramesitylporphyrinato) manganese (III) MnIII(tmp)(OAc) produced their corresponding high valent Mn(tpfpp)(O)(OAc) and Mn(tmp)(O)(OAc) both in the absence or presence of alcohols. Whereas, (acetato) (tetraphenylporphyrinato) manganese (III) MnIII(tpp)(OAc) only generated Mn(tpp)(O)(OAc) in the presence of less bulky alcohols. In the absence of alcohols or in the presence of t-C4H9OH, the UV-vis spectra displayed a very weak sign of formation of Mn(tpp)(O)(OAc) complex. It was observed that alcohols generally increased the rate of formation of Mn-oxo species in accordance with their acidity or hydrogen bonding strength, and enhanced the stability of Mn-oxo complexes, as their size increases. Attempts are made to explain these effects. A mechanistic scheme is also suggested for the decomposition of HSO5- to O2 and HSO4-, through the formation and dimerization of Mn-oxo species.

  19. Estudio teórico de la desorción de Na y K de SiO2 estimulada por la acción de fotones o electrones

    NASA Astrophysics Data System (ADS)

    Domínguez Ariza, D.; López, N.; Illas, F.; Pacchioni, G.; Madey, T. E.

    Se ha estudiado el mecanismo de generación de sodio y potasio atómico a partir de muestras de SiO2 utilizando cálculos basados tanto en la teoría del funcional de la densidad como en métodos post-Hartree Fock, así como en el método de cluster para modelar el sólido. Como consecuencia del estudio se han propuesto distintos caminos posibles para la desorción, estimulada por la acción de fotones o electrones, de sodio y potasio desde el óxido de silicio, proporcionando por lo tanto una explicación a la atmósfera tenue de sodio y potasio de La Luna.

  20. Long-term RNA persistence of porcine rubulavirus (PorPV-LPMV) after an outbreak of a natural infection: the detection of viral mRNA in sentinel pigs suggests viral transmission.

    PubMed

    Cuevas-Romero, S; Hernández-Baumgarten, E; Kennedy, S; Hernández-Jáuregui, P; Berg, M; Moreno-López, J

    2014-08-08

    The persistence of porcine rubulavirus (PorPV-LPMV) in five pigs that had survived an outbreak of a natural infection was determined. After the resolution of the outbreak, each animal was housed in an isolation pen together with one sentinel pig. Approximately every 2 months thereafter one group of animals was euthanized and tissue samples taken for virological and serological analysis. Infectious virus was not isolated from any samples; antibodies to PorPV-LPMV were detected in convalescent pigs by virus neutralisation test and blocking ELISA but not in sentinel pigs. PorPV-LPMV mRNA of the nucleoprotein (NP) and phosphoprotein (P) genes was detected by a nested polymerase chain reaction (nPCR) in samples of trigeminal and optic nerves, cervical spinal cord, tonsils, salivary gland, lung and pancreas from convalescent pigs. mRNA was also detected in the midbrain, corpus callosum, or olfactory bulb in four out of five pigs by nRT-PCR, this result was confirmed by the sequencing of a 260bp PCR product of P gene region. The highest average viral copies/μg of total RNA occurred in the olfactory bulb and pancreas tissues of convalescent pigs and midbrain, tonsil and pancreas of sentinel pigs housed with the convalescent pigs. Satellitosis and gliosis of the midbrain, olfactory bulb, corpus callosum, medulla oblongata or choroid plexus were microscopically observed in four convalescent pigs. The control pig remained negative in all tests. The results indicate that PorPV-LPMV mRNA persists and induces a durable humoral immune response in pigs that have recovered from a natural infection. After a possible reactivation of the virus, it was transmitted to sentinel pigs in contact with the convalescent pigs.

  1. Comparación de resultados del método de clasificación de órbitas por análisis de frecuencias con el método de exponentes de Lyapunov

    NASA Astrophysics Data System (ADS)

    Carpintero, D. D.; Muzzio, J. C.; Wachlin, F. C.

    Hemos realizado extensas comparaciones del método de análisis de frecuencias con el de exponentes de Lyapunov. El primero resulta claramente superior por las siguientes razones: 1) permite distinguir distintos tipos de órbitas y no sólo si son regulares o caóticas 2) es mucho más veloz requiriendo mucho menos tiempo de cómputo. La concordancia de resultados es, en general, buena y se discuten algunas discrepancias.

  2. La inserción en el mercado laboral de los inmigrantes latinos en España y en los Estados Unidos: Diferencias por país de origen y estatus legal

    PubMed Central

    Connor, Phillip; Massey, Douglas

    2013-01-01

    Resumen Este artículo compara los resultados económicos entre los inmigrantes latinoamericanos en España y Estados Unidos. Detectamos un efecto de selección por el que la mayoría de los inmigrantes latinoamericanos en España proceden de Sudamérica de un entorno de clases medias, mientras la mayoría de los inmigrantes que van a los Estados Unidos son centroamericanos de clase baja. Este efecto de selección explica las diferencias transnacionales en la probabilidad de empleo, logro ocupacional y salarios obtenidos. A pesar de las diferencias en los orígenes y las características de los latinoamericanos en ambos países, los factores demográficos, humanos y de capital social parecen operar de forma similar en ambos países; y cuando los modelos se estiman separadamente por estatus legal, descubrimos que los efectos se acentúan más entre los inmigrantes irregulares cuando se los compara con los regulares, especialmente en Estados Unidos. PMID:24532857

  3. Aquisição fonológica do português brasileiro por crianças ouvintes bilíngues bimodais e surdas usuárias de implante coclear

    PubMed Central

    Cruz, Carina Rebello; Finger, Ingrid

    2014-01-01

    Resumo O presente estudo investiga a aquisição fonológica do Português Brasileiro (PB) por 24 crianças ouvintes bilíngues bimodais, com acesso irrestrito à Língua Brasileira de Sinais (Libras), e por 6 crianças surdas que utilizam implante coclear (IC), com acesso restrito ou irrestrito à Libras. Para a avaliação do sistema fonológico das crianças em PB, foi utilizada a Parte A, Prova de Nomeação, do ABFW – Teste de Linguagem Infantil (ANDRADE et al. 2004). Os resultados revelaram que as crianças ouvintes bilíngues bimodais e a criança surda usuária de IC com acesso irrestrito à Libras apresentaram processo de aquisição fonológica esperada (normal) para a sua faixa etária. Considera-se que a aquisição precoce e o acesso irrestrito à Libras podem ter sido determinantes para o desempenho dessas crianças no teste oral utilizado. PMID:25506105

  4. The Understanding of Astronomy Concepts by Students from Basic Education of a Public School. (Spanish Title: El Entendimiento de Conceptos de Aastronmía Por Los Alumnos de Educación Básica en Una Escuela Pública.) O Entendimento de Conceitos de Astronomia Por Alunos da Educação Básica: O Caso de Uma Escola Pública Brasileira

    NASA Astrophysics Data System (ADS)

    Iria Machado, Daniel; dos Santos, Carlos

    2011-07-01

    We present the results obtained in a research on the comprehension of basic astronomical concepts, in which 561 students from fifth grade middle school to third grade high school of a public school of the city of Foz do Iguaçu (Brazil) took part. A test with 20 multiple-choice questions was applied to indentify the most common conceptions expressed by the students. This test was elaborated based on the literature about misconceptions and covered the following topics: the day-night cycle; the time zones; the seasons of the year; the phases of the Moon; the movement of the Moon; the apparent movement of the Sun in the celestial sphere; the eclipses; the dimensions and distances in the Universe; the brightness of the stars and its observation from Earth. Though a small progress was verified in the proportion of scientifically acceptable answers when comparing the eighth grade of middle school to the fifth, and the third grade of high school to the first, there was an overall predominance of alternative conceptions regarding most of the explored subjects, which persisted up to the last year of secondary school. The comparison to data found in this research made in other socio-cultural contexts revealed, in many aspects, similar notions and difficulties revealed by the students. Se presentan los resultados de una investigación sobre la comprensión de conceptos astronómicos básicos, en la cual participaron 561 estudiantes que cursaban entre el quinto grado de la enseñanza primaria y el tercer año de la enseñanza secundaria de una escuela pública de la ciudad de Foz do Iguaçu (Brasil). Se utilizó un test de 20 preguntas de opción múltiple para identificar las concepciones más comunes expresadas por los estudiantes. Este instrumento de recolección de datos se desarrolló en base a la literatura sobre las concepciones alternativas y trató los siguientes temas: el ciclo día-noche, los husos horarios, las estaciones del año, las fases de la Luna, el

  5. One-step purification and porin transport activity of the major outer membrane proteins P2 from Haemophilus influenzae, FomA from Fusobacterium nucleatum and PorB from Neisseria meningitidis.

    PubMed

    Kattner, Christof; Pfennig, Sabrina; Massari, Paola; Tanabe, Mikio

    2015-03-01

    Bacterial porins are major outer membrane proteins that function as essential solute transporters between the bacteria and the extracellular environment. Structural features of porins are also recognized by eukaryotic cell receptors involved in innate and adaptive immunity. To better investigate the function of porins, proper refolding is necessary following purification from inclusion bodies [1, 2]. Using a single-step size exclusion chromatographic method, we have purified three major porins from pathogenic bacteria, the OmpP2 (P2) from Haemophilus influenzae, FomA from Fusobacterium nucleatum and PorB from Neisseria meningitidis, at high yield and report their unique solute transport activity with size exclusion limit. Furthermore, we have optimized their purification method and achieved improvement of their thermostability for facilitating functional and structural analyses.

  6. Crystal structure of bis­{4-bromo-2-[(carb­amim­id­amido­imino)­meth­yl]phenolato-κ3 N,N′,O}cobalt(III) nitrate di­methyl­formamide monosolvate

    PubMed Central

    Buvaylo, Elena A.; Kasyanova, Katerina A.; Vassilyeva, Olga Yu.; Skelton, Brian W.

    2016-01-01

    The title compound, [Co(C8H8BrN4O)2]NO3·C3H7NO, is formed of discrete [CoL 2]+ cations, nitrate anions and di­methyl­formamide (DMF) mol­ecules of crystallization. The cation has no crystallographically imposed symmetry. The ligand mol­ecules are deprotonated at the phenol O atom and octa­hedrally coordinate the CoIII atoms through the azomethine N and phenolate O atoms in a mer configuration. The deprotonated ligand mol­ecules adopt an almost planar conformation. In the crystal lattice, the cations are arranged in layers in the ab plane divided by the nitrate anions and solvent mol­ecules. No π–π stacking is observed. All of the amine H atoms are involved in hydrogen bonding to nitrate, DMF or ligand O atoms or to one of the Br atoms, forming two-dimensional networks parallel to (100). PMID:27555929

  7. Crystal structure of bis-{4-bromo-2-[(carb-amim-id-amido-imino)-meth-yl]phenolato-κ(3) N,N',O}cobalt(III) nitrate di-methyl-formamide monosolvate.

    PubMed

    Buvaylo, Elena A; Kasyanova, Katerina A; Vassilyeva, Olga Yu; Skelton, Brian W

    2016-07-01

    The title compound, [Co(C8H8BrN4O)2]NO3·C3H7NO, is formed of discrete [CoL 2](+) cations, nitrate anions and di-methyl-formamide (DMF) mol-ecules of crystallization. The cation has no crystallographically imposed symmetry. The ligand mol-ecules are deprotonated at the phenol O atom and octa-hedrally coordinate the Co(III) atoms through the azomethine N and phenolate O atoms in a mer configuration. The deprotonated ligand mol-ecules adopt an almost planar conformation. In the crystal lattice, the cations are arranged in layers in the ab plane divided by the nitrate anions and solvent mol-ecules. No π-π stacking is observed. All of the amine H atoms are involved in hydrogen bonding to nitrate, DMF or ligand O atoms or to one of the Br atoms, forming two-dimensional networks parallel to (100).

  8. Design, synthesis, and biological evaluation of 4-(5-dimethylamino-naphthalene-1-sulfon-amido)-3-(4-iodophenyl)butanoic acid as a novel molecular probe for apoptosis imaging

    SciTech Connect

    Zeng, Wenbin; Miao, Weimin; Le Puil, Michael; Shi, Guangqing; Biggerstaff, John; Kabalka, George W.; Townsend, David

    2010-07-30

    Research highlights: {yields} Annexin V is the gold standard probe for imaging apoptosis. {yields} Unfavorable profiles of Annexin V make it difficult to apply in the clinic. {yields} A novel small-molecular probe DNSBA was designed as an alternative to Annexin V. {yields} DNSBA specifically and selectively detect apoptotic cancer cells at all stages. {yields} DNSBA is a potential SPECT and PET agent when labeled with radioiodine. -- Abstract: Apoptosis (programmed cell death) plays a crucial role in the pathogenesis of many disorders, thus the detection of apoptotic cells can provide the physician with important information to further therapeutic strategies and would substantially advance patient care. A small molecule, 4-(5-dimethylamino-naphthalene-1-sulfonamido)-3-(4-iodo-phenyl)butanoic acid (DNSBA), was designed as a novel probe for imaging apoptosis and synthesized with good yield. The biological characterization demonstrated that DNSBA can be used to specifically and selectively detect apoptotic cancer cells at all stages. DNSBA is also designed as a potential SPECT and PET probe when labeled with radioiodine (I-123, -124, and -131).

  9. Crystal structures of μ-oxalato-bis­[azido­(hista­mine)­copper(II)] and μ-oxalato-bis­[(dicyan­amido)(hista­mine)­copper(II)

    PubMed Central

    Liu, Chen; Abboud, Khalil A.

    2015-01-01

    The title compounds, μ-oxalato-κ4 O 1,O 2:O 1′,O 2′-bis­[[4-(2-amino­eth­yl)-1H-imid­azole-κ2 N 3,N 4](azido-κN 1)copper(II)], [Cu2(C2O4)(N3)2(C5H9N3)2], (I), and μ-ox­al­ato-κ4 O 1,O 2:O 1′,O 2′-bis­[[4-(2-amino­eth­yl)-1H-imidazole-κ2 N 3,N 4](dicyanamido-κN 1)copper(II)], [Cu2(C2O4)(C2N3)2(C5H9N3)2], (II), are two oxalate-bridged dinuclear copper complexes. Each CuII ion adopts a five-coordinate square-pyramidal coordination sphere where the basal N2O2 plane is formed by two O atoms of the oxalate ligand and two N atoms of a bidentate chelating histamine mol­ecule. The apical coordination site in compound (I) is occupied by a monodentate azide anion through one of its terminal N atoms. The apical coordination site in compound (II) is occupied by a monodentate dicyanamide anion through one of its terminal N atoms. The mol­ecules in both structures are centrosymmetric. In the crystals of compounds (I) and (II), the dinuclear complexes are linked through N—H⋯X and C—H⋯X (X = N, O) hydrogen bonds where the donors are provided by the histamine ligand and the acceptor atoms are provided by the azide, dicyanamide, and oxalate ligands. In compound (I), the coordinatively unsaturated copper ions inter­act with the histamine ligand via a C—H⋯Cu inter­action. The coordinatively unsaturated copper ions in compound (II) inter­act via a weak N⋯Cu inter­action with the dicyanamide ligand of a neighboring mol­ecule. The side chain of the histamine ligand is disordered over three sets of sites in (II). PMID:26594515

  10. Chlamydia trachomatis clinical isolates identified as tetracycline resistant do not exhibit resistance in vitro: whole-genome sequencing reveals a mutation in porB but no evidence for tetracycline resistance genes.

    PubMed

    O'Neill, C E; Seth-Smith, H M B; Van Der Pol, B; Harris, S R; Thomson, N R; Cutcliffe, L T; Clarke, I N

    2013-04-01

    Chlamydia trachomatis is the most common bacterial sexually transmitted infection worldwide and the leading cause of preventable blindness in developing countries. Tetracycline is commonly the drug of choice for treating C. trachomatis infections, but cases of antibiotic resistance in clinical isolates have previously been reported. Here, we used antibiotic resistance assays and whole-genome sequencing to interrogate the hypothesis that two clinical isolates (IU824 and IU888) have acquired mechanisms of antibiotic resistance. Immunofluorescence staining was used to identify C. trachomatis inclusions in cell cultures grown in the presence of tetracycline; however, only antibiotic-free control cultures yielded the strong fluorescence associated with the presence of chlamydial inclusions. Infectivity was lost upon passage of harvested cultures grown in the presence of tetracycline into antibiotic-free medium, so we conclude that these isolates were phenotypically sensitive to tetracycline. Comparisons of the genome and plasmid sequences for the two isolates with tetracycline-sensitive strains did not identify regions of low sequence identity that could accommodate horizontally acquired resistance genes, and the tetracycline binding region of the 16S rRNA gene was identical to that of the sensitive control strains. The porB gene of strain IU824, however, was found to contain a premature stop codon not previously identified, which is noteworthy but unlikely to be related to tetracycline resistance. In conclusion, we found no evidence of tetracycline resistance in the two strains investigated, and it seems most likely that the small, aberrant inclusions previously identified resulted from the high chlamydial load used in the original antibiotic resistance assays.

  11. Characterization of invasive Neisseria meningitidis from Atlantic Canada, 2009 to 2013: With special reference to the nonpolysaccharide vaccine targets (PorA, factor H binding protein, Neisseria heparin-binding antigen and Neisseria adhesin A)

    PubMed Central

    Tsang, Raymond SW; Law, Dennis KS; Gad, Rita R; Mailman, Tim; German, Gregory; Needle, Robert

    2015-01-01

    BACKGROUND: Serogroup B Neisseria meningitidis (MenB) has always been a major cause of invasive meningococcal disease (IMD) in Canada. With the successful implementation of a meningitis C conjugate vaccine, the majority of IMD in Canada is now caused by MenB. OBJECTIVE: To investigate IMD case isolates in Atlantic Canada from 2009 to 2013. Data were analyzed to determine the potential coverage of the newly licensed MenB vaccine. METHODS: Serogroup, serotype and serosubtype antigens were determined from IMD case isolates. Clonal analysis was performed using multilocus sequence typing. The protein-based vaccine antigen genes were sequenced and the predicted peptides were investigated. RESULTS: The majority of the IMD isolates were MenB (82.5%, 33 of 40) and, in particular, sequence type (ST)-154 B:4:P1.4 was responsible for 47.5% (19 of 40) of all IMD case isolates in Atlantic Canada. Isolates of this clone expressed the PorA antigen P1.4 and possessed the nhba genes encoding for Neisseria heparin-binding antigen peptide 2, which together matched exactly with two of the four components of the new four-component meningococcal B vaccine. Nineteen MenB isolates had two antigenic matches, another five MenB and one meningitis Y isolate had one antigenic match. This provided 75.8% (25 of 33) potential coverage for MenB, or a 62.5% (25 of 40) overall potential coverage for IMD. CONCLUSION: From 2009 to 2013, IMD in Atlantic Canada was mainly caused by MenB and, in particular, the B:4:P1.4 ST-154 clone, which accounted for 47.5% of all IMD case isolates. The new four-component meningococcal B vaccine appeared to offer adequate coverage against MenB in Atlantic Canada. PMID:26744586

  12. Eficacia de la detección sistemática de la gripe en las fronteras en los viajeros que llegan por vía aérea*

    PubMed Central

    Priest, Patricia C.; Jennings, Lance C.; Duncan, Alasdair R.; Brunton, Cheryl R.; Baker, Michael G.

    2015-01-01

    Objetivos. Se midieron los síntomas y la prevalencia de la gripe (también llamada influenza), así como la eficacia del mecanismo de detección sistemática basado en los síntomas y la temperatura para diagnosticar la gripe en viajeros internacionales que llegaban por vía aérea. Métodos. El presente estudio transversal recopiló datos de viajeros que llegaron al aeropuerto internacional de Christchurch (Nueva Zelandia) en el invierno del 2008 mediante un cuestionario de salud, medición de la temperatura y toma de muestras de las vías respiratorias. Resultados. De los viajeros, 15 976 (68%) entregaron los formularios completos. De ellos, 17% notificaron al menos un síntoma de gripe; los síntomas más comunes fueron rinorrea o congestión nasal (10%) y tos (8%). Se tomaron muestras de las vías respiratorias de 3 769 viajeros. La prevalencia estimada de la gripe fue de 1,1% (4% en las personas sintomáticas, 0,2% en las asintomáticas). La sensibilidad de los criterios de detección varió de 84% para “cualquier síntoma” a 3% para la fiebre de 37,8 °C o mayor. El valor predictivo positivo fue bajo para todos los criterios. Conclusiones. El método de detección sistemática en las fronteras mediante la autonotificación de síntomas y la toma de la temperatura presenta limitaciones para impedir que una gripe pandémica entre en un país. Basarse en criterios como “cualquier síntoma” o la tos haría que se investigara a varias personas no infectadas, mientras que algunas personas infectadas pasarían inadvertidas. Si se usaran criterios más específicos como la fiebre, la mayoría de las personas infectadas entrarían en el país a pesar del mecanismo de detección.

  13. Meio- and Macrofaunal Communities in Artificial Water-Filled Tree Holes: Effects of Seasonality, Physical and Chemical Parameters, and Availability of Food Resources

    PubMed Central

    Ptatscheck, Christoph; Traunspurger, Walter

    2015-01-01

    Objectives In this study we investigated the dynamics of meiofaunal and macrofaunal communities in artificial water-filled tree holes. The abundances and, for the first time, biomasses and secondary production rates of these communities were examined. The experimental set-up consisted of 300 brown plastic cups placed in temperate mixed forests and sampled five times over a period of 16 months to determine the impact of (i) seasonal events, (ii) physicochemical parameters, and (iii) food resources on the tree hole metazoans. Outcomes Metazoan organisms, especially the meiofauna (rotifers and nematodes) occupied nearly all of the cups (> 99%) throughout the year. Between 55% and 99% of the metazoan community was represented by rotifers (max. 557,000 individuals 100 cm-2) and nematodes (max. 58,000 individuals 100 cm-2). Diptera taxa, particularly Dasyhelea sp. (max. 256 individuals 100 cm-2) dominated the macrofaunal community. Macrofauna accounted for the majority of the metazoan biomass, with a mean dry weight of 5,800 μg 100 cm-2 and an annual production rate of 20,400 μg C 100 cm-2, whereas for meiofauna mean biomass and annual production were 100 μg 100 cm-2 and 5,300 μg C 100 cm-2, respectively. The macrofaunal taxa tended to show more fluctuating population dynamic while the meiofaunal dynamic was rather low with partly asynchronous development. Seasonality (average temperature and rain intervals) had a significant impact on both meiofauna and macrofauna. Furthermore, bottom-up control (chlorophyll-a and organic carbon), mainly attributable to algae, was a significant factor that shaped the metazoan communities. In contrast, physicochemical water parameters had no evident influence. 23.7% of organism density distribution was explained by redundancy analysis (RDA) indicating a high dynamic and asynchrony of the systems. PMID:26284811

  14. Characterisation of the Adhesive Proteins of a Major Fouling Organism, the Barnacle. Part 4

    DTIC Science & Technology

    1994-03-25

    cCGDeimino-cCGoxo- (--Citrulline) N,5-Deamidino- (=Ornithine) L- Aspartic acid N-Acetyl- I -Amido- 3-Hydroxy- 04-Methyl- L-Asparagine N4-Glycosyl- Iso- (=1...Amido- aspartic acid ) L-Cysteine 2-Dehydro-3-demnercapto- (=didehydroalanine) S-Calactosyl- S-Clucosyl- S-(y-Glutamyl)- S-(l-Glycero)- S-Mercapto- Seleno

  15. [Anxiety in clinical settings: constructing a scale for medical students].

    PubMed

    Rodrigues, Joana Ramos; Castelo-Branco, Miguel; Pereira, Henrique; Afonso, Rosa Marina

    2014-01-01

    IntroduçÉo: A Escala de Ansiedade em Meio Clínico foi construída para avaliar o nível de ansiedade dos estudantes de Medicina quando expostos ao meio clínico e identificar quais as situações mais propensas a desencadear maior nível de ansiedade nesse contexto.Material e Métodos: Este instrumento é constituído por doze itens e foi construído tendo por base a revisÉo da literatura sobre a temática da ansiedade em meio clínico e os dados provenientes de um focus group realizado com estudantes entre o 1'º e o 5'º ano do curso de Medicina da Universidade da Beira Interior (n = 10). As suas propriedades psicométricas foram testadas mediante um estudo com 557 alunos do curso de Medicina de quatro universidades portuguesas, entre o 1'º e o 6'º ano.Resultados: A validaçÉo da Escala de Ansiedade em Meio Clínico contemplou a análise de três par'metros principais: sensibilidade, fiabilidade e análise da estrutura fatorial, sendo que a última resultou na obtençÉo de quatro factores: 'Incómodo perante procedimentos invasivos', 'Ansiedade face ao doente', 'Ansiedade face ao desempenho' e 'Ansiedade face à dimensÉo humana' com 70,6% da vari'ncia explicada.DiscussÉo: A Escala de Ansiedade em Meio Clínico total demonstra uma boa coerência interna (Alpha de Cronbach = 0,84) e boa capacidade de discriminaçÉo de sujeitos, apresentando-se, assim, como instrumento consistente e fiável para a avaliaçÉo de ansiedade nos estudantes de Medicina quando expostos ao meio clínico.ConclusÉo: A Escala de Ansiedade em Meio Clínico permite avaliar a ansiedade nos estudantes de Medicina quando expostos ao meio clínico e poderá vir a ser útil na delineaçÉo de estratégias de ensino para a preparaçÉo dos futuros médicos.

  16. Por los Ninos (For the Children): Education of Undocumented Children.

    ERIC Educational Resources Information Center

    Gonzalez, Elena R.; Team, Linda B.

    Published as a special project of Texas IMPACT and the Texas Conference of Churches, this booklet outlines legal aspects of the education of undocumented children, lists moral and practical reasons for educating them, provides reasons for changing the Texas law which prohibits use of state funds for education of children who are not legally…

  17. La busqueda textual por computadora (Textual Search by Computer)

    ERIC Educational Resources Information Center

    Davison, Ned J.

    1977-01-01

    Describes the use of the computer program EDIT for textual searches to locate a certain programmed word or word root. In the examples explained here, the vocabulary search is performed on poetry and allows examination of the metaphorical and conceptual poetic atmosphere achieved through word use. (Text is in Spanish.) (CHK)

  18. Decade of Venezuela’s President Hugo Chavez, Por Ahora

    DTIC Science & Technology

    2009-04-01

    controversial expansion of control was seen with Venezuela’s state-owned oil company Petroleos de Venezuela S.A. ( PDVSA ), which, to this day has been...grew in response corruption reports related to the siphoning off money from PDVSA . In 2002, pro-Hugo Chavez groups, ‘Chavistas,’ engaged in...protest.16 Within a few days, the counter-coup facilitated Chavez’s return to power but problems remained. PDVSA witnessed a devastating strike

  19. 2-({[(Pyridin-1-ium-2-ylmeth­yl)carbamo­yl]form­amido}­meth­yl)pyridin-1-ium bis­(3,5-di­carb­oxy­benzoate): crystal structure and Hirshfeld surface analysis

    PubMed Central

    Jotani, Mukesh M.; Syed, Sabrina; Halim, Siti Nadiah Abdul; Tiekink, Edward R. T.

    2016-01-01

    The asymmetric unit of the title salt, C14H16N4O2 2+·2C9H5O6 −, comprises half a dication, being located about a centre of inversion, and one anion, in a general position. The central C4N2O2 group of atoms in the dication are almost planar (r.m.s. deviation = 0.009 Å), and the carbonyl groups lie in an anti disposition to enable the formation of intra­molecular amide-N—H⋯O(carbon­yl) hydrogen bonds. To a first approximation, the pyridinium and amide N atoms lie to the same side of the mol­ecule [Npy—C—C—Namide torsion angle = 34.8 (2)°], and the anti pyridinium rings are approximately perpendicular to the central part of the mol­ecule [dihedral angle = 68.21 (8)°]. In the anion, one carboxyl­ate group is almost coplanar with the ring to which it is connected [Cben—Cben—Cq—O torsion angle = 2.0 (3)°], whereas the other carboxyl­ate and carb­oxy­lic acid groups are twisted out of the plane [torsion angles = 16.4 (3) and 15.3 (3)°, respectively]. In the crystal, anions assemble into layers parallel to (10-4) via hy­droxy-O—H⋯O(carbon­yl) and charge-assisted hy­droxy-O—H⋯O(carboxyl­ate) hydrogen bonds. The dications are linked into supra­molecular tapes by amide-N—H⋯O(amide) hydrogen bonds, and thread through the voids in the anionic layers, being connected by charge-assisted pyridinium-N—O(carboxyl­ate) hydrogen bonds, so that a three-dimensional architecture ensues. An analysis of the Hirshfeld surface points to the importance of O—H⋯O hydrogen bonding in the crystal structure. PMID:26958398

  20. Crystal structure of the inverse crown ether tetra­kis­[μ2-bis­(tri­methyl­sil­yl)amido]-μ4-oxido-dicobalt(II)disodium, [Co2Na2{μ2-N(SiMe3)2}4](μ4-O)

    PubMed Central

    Hansen, Christopher B.; Filatov, Alexander S.; Hillhouse, Gregory L.

    2016-01-01

    The title compound, [Co2Na2{μ2-N(SiMe3)2}4](μ4-O), (I), represents a new entry in the class of inverse crown ethers. In the mol­ecule, each Co atom is formally in the oxidation state +II. The structure contains one half of a unique mol­ecule per asymmetric unit with the central μ4-oxido ligand residing on an inversion center, leading to a planar coordination to the Na and Co atoms. In the crystal, bulky tri­methyl­silyl substituents prevent additional inter­actions with cobalt. However, weak inter­molecular Na⋯H3C—Si inter­actions form an infinite chain along [010]. The structure is isotypic with its Mg, Mn and Zn analogues. PMID:27308041

  1. Amidoselenation and Amidotelluration of Alkenes using Oxygen as Terminal Oxidant.

    PubMed

    Sun, Kai; Wang, Xin; Zhang, Chong; Zhang, Saifei; Chen, Yao; Jiao, Hezhen; Du, Weimin

    2017-03-16

    A protocol has been established for oxygen-mediated amidoselenation and amidotelluration of alkenes under mild conditions. This method provides a simple route to a series of structurally diverse β-amido selenides and β-amido tellurides in moderate to high yields. The wide substrate scope, good functional group tolerance, ease of large-scale preparation and potential for product derivatization make this reaction attractive for the synthesis of nitrogen-, selenium- and tellurium-containing molecules.

  2. Síndrome del Outlet Torácico: ¿Una Patología Siempre Quirúrgica? Análisis de una Serie de 31 Cirugías Realizadas por Vía Supraclavicular Serie clínica

    PubMed Central

    Socolovsky, Mariano; Di Masi, Gilda; Binaghi, Daniela; Campero, Álvaro; Páez, Miguel Domínguez; Dubrovsky, Alberto

    2014-01-01

    Introducción: El síndrome de outlet torácico es una compresión del plexo braquial que suscita polémica. Se clasifica en Outlet Torácico Verdadero o neurogénico (OTV) y Outlet Torácico Disputado o no neurogénico (OTD). El primero presenta síntomas motores en la mano, mientras que el segundo sólo síntomas sensitivos en el miembro superior. El objetivo de este trabajo es analizar los resultados obtenidos en una serie de 31 cirugías. Métodos: Se analizaron las cirugías de nervios efectuadas entre 2003-2012, tomando los diagnósticos de outlet torácico cuyo período de seguimiento post-operatorio mínimo fuera de 6 meses. Se buscaron los siguientes datos: edad, sexo, presencia de síntomas sensitivos y/o motores, clasificación, resultado de los estudios neurofisiológicos y de imágenes, resultado de la cirugía, complicaciones post-operatorias y recidivas. Resultados: Se incluyeron 31 cirugías realizadas en 30 pacientes, 9 OTV (8 mujeres) de 24.3 años, y 21 con OTD (18 mujeres) de 37.4 años de edad en promedio. Un 90% presentaron alteraciones neurofisiológicas preoperatorias, y 66,6% imagenológicas. En el intraoperatorio, el 100% de los OTV presentó una alteración anatómica relacionada con la sintomatología, hecho observado sólo en el 36.7% de los OTD operados. El 87,5% de los OTV mejoraron sensitivamente, mientras que 77,7% mejoraron la atrofia. Por el contrario, 45.4% de los OTD mejoraron permanentemente, 36.3% no tuvieron cambios, 13.6% mejoraron transitoriamente y 4.5% (un caso) empeoró. Las complicaciones post-operatorias fueron más frecuentes aunque transitorias en el grupo de OTV (3 casos sobre 9 operados, 33.3%) que en los OTD (3 casos sobre 22, un 13.6%). Conclusión: El OTV suele mayormente mejorar luego de la cirugía, igual que el OTD aunque en una proporción mucho menor. Estos hallazgos coinciden con otros reportes recientes de esta patología. PMID:25165614

  3. A Comparison Between PSRK and GERG-2004 Equation of State for Simulation of Non-Isothermal Compressible Natural Gases Mixed with Hydrogen in Pipelines / Porównanie równań stanu opracowanych według metody PSRK oraz GERG-2004 wykorzystanych do symulacji zachowania ściśliwych mieszanin gazu ziemnego i wodoru w rurociągach, w warunkach przepływów nie-izotermicznych

    NASA Astrophysics Data System (ADS)

    Uilhoorn, Frits E.

    2013-06-01

    In this work, the GERG-2004 equation of state based on a multi-fluid approximation explicit in the reduced Helmholtz energy is compared with the predictive Soave-Redlich-Kwong group contribution method. In the analysis, both equations of state are compared by simulating a non-isothermal transient flow of natural gas and mixed hydrogen-natural gas in pipelines. Besides the flow conditions also linepack-energy and energy consumption of the compressor station are computed. The gas flow is described by a set of partial differential equations resulting from the conservation of mass, momentum and energy. A pipeline section of the Yamal-Europe gas pipeline on Polish territory has been selected for the case study. W artykule dokonano porównania wyników uzyskanych przy wykorzystaniu równania stanu GERG- 2004 opartego na jawnym przybliżeniu wyników dla wielu cieczy w oparciu o zredukowaną energię Helmhotza oraz wyników uzyskanych w oparciu o metodę Soave-Redlich Kwonga. Obydwa równania stanu porównano poprzez przeprowadzenie symulacji stanów przejściowych przepływów gazu ziemnego oraz mieszanin gazu ziemnego i wodoru w rurociągach w warunkach przepływów nie-izotermicznych. Oprócz warunków przepływu, określono energię w napełnionym układzie oraz zużycie energii przez stację kompresora. Przepływ gazu opisano zbiorem równań różniczkowych cząstkowych, wyprowadzonych w oparciu o prawa zachowania masy, pędu i energii. Jako studium przypadku wybrano fragment rurociągu jamalskiego (Yamal- Europa) przebiegającego przez terytorium Polski.

  4. [The occurrence of Biomphalaria straminea (Pulmonata: Planorbidae) on an aquaculture farm of IBAMA in Uberlândia, MG. Instituto Brasileiro do Meio Ambiente a dos Recursos Naturais Renováveis].

    PubMed

    Silveira, E de P; Marçal Júnior, O; Machado, M I

    1997-01-01

    This work evaluates the occurrence of freshwater snails in the IBAMA's fish breeding station in Uberlândia, Minas Gerais State. We verified the presence of Biomphalaria straminea in 39.5% of all breeding tanks. None of the snails were infected by Schistosoma mansoni, but further investigation should be done in the area.

  5. An Iron(II) Ylide Complex as a Masked Open-Shell Iron Alkylidene Species in Its Alkylidene-Transfer Reactions with Alkenes.

    PubMed

    Liu, Jian; Hu, Lianrui; Wang, Lei; Chen, Hui; Deng, Liang

    2017-03-15

    Transition-metal alkylidenes are important reactive organometallic intermediates, and our current knowledge on them has been mainly restricted to those with closed-shell electronic configurations. In this study, we present an exploration on open-shell iron alkylidenes with a weak-field tripodal amido-phosphine-amido ligand. We found that a high-spin (amido-phosphine-amido)iron(II) complex can react with (p-tolyl)2CN2 to afford a high-spin (amido-ylide-amido)iron(II) complex, 2, which could transfer its alkylidene moiety to a variety of alkenes, either the electron-rich or electron-deficient ones, to form cyclopropane derivatives. The reaction of 2 with cis-β-deuterio-styrene gave deuterated cyclopropane derivatives with partial loss of the stereochemical integrity with respect to the cis-styrene. Kinetic study on the cyclopropanation reaction of 2 with 4-fluoro-styrene disclosed the activation parameters of ΔH(⧧) = 23 ± 1 kcal/mol and ΔS(⧧) = -20 ± 3 cal/mol/K, which are comparable to those of the cyclopropanation reactions involving transition-metal alkylidenes. However, the cyclopropanation of para-substituted styrenes by 2 shows a nonlinear Hammett plot of log(kX/kH) vs σp. By introduction of a radical parameter, a linear plot of log(kX/kH) vs 0.59σp + 0.55σc(•) was obtained, which suggests the "nucleophilic" radical nature of the transition state of the cyclopropanation step. In corroboration with the experimental observations, density functional theory calculation on the reaction of 2 with styrene suggests the involvement of an open-shell (amido-phosphine-amido)iron alkylidene intermediate that is higher in energy than its (amido-ylide-amido)iron(II) precursor and an "outer-sphere" radical-type mechanism for the cyclopropanation step. The negative charge distribution on the alkylidene carbon atoms of the open-shell states (S = 2 and 1) explains the high activity of the cyclopropanation reaction toward electron-deficient alkenes. The study

  6. Rational design of catalysts for asymmetric diamination reaction using transition state modeling.

    PubMed

    Jindal, Garima; Sunoj, Raghavan B

    2014-05-07

    The stereoselective synthesis of 1,2-diamines has remained a formidable challenge. A recent palladium-catalyzed asymmetric diamination of conjugated double bonds using di-tert-butyldiaziridinone appears promising. The axially chiral binol phosphoramidite ligands are successful in offering high enantioselectivity. The density functional theory investigations revealed that the energies of the stereocontrolling transition states for the C-N bond formation depend on a number of weak non-covalent interactions such as C-H···π, C-H···O and anagostic interactions. We envisaged that the modulation in these interactions in the transition states, through subtle changes in chiral phosphoramidite substituents, could be exploited toward steering the stereoselectivity. The effect of systematic modifications on both 3,3' positions of the binol as well as on the amido nitrogen on the stereochemical outcome is predicted. It is identified that high enantioselectivity requires a balance between the nature of the substituents on binol and amido groups. The reduced size of the amido substituents demands increased bulk on the binol whereas lowering the size on the binol demands increased bulk on the amido for higher stereoselectivity. The substituent at the α-position of the amido group is found to be vital and appears to be a hot spot for modifications. These insights derived from studies on the stereocontrolling transition states could help improve the catalytic efficacies in palladium-catalyzed asymmetric diamination reactions.

  7. Square-planar ruthenium(II) complexes: control of spin state by pincer ligand functionalization.

    PubMed

    Askevold, Bjorn; Khusniyarov, Marat M; Kroener, Wolfgang; Gieb, Klaus; Müller, Paul; Herdtweck, Eberhardt; Heinemann, Frank W; Diefenbach, Martin; Holthausen, Max C; Vieru, Veacheslav; Chibotaru, Liviu F; Schneider, Sven

    2015-01-07

    Functionalization of the PNP pincer ligand backbone allows for a comparison of the dialkyl amido, vinyl alkyl amido, and divinyl amido ruthenium(II) pincer complex series [RuCl{N(CH2 CH2 PtBu2 )2 }], [RuCl{N(CHCHPtBu2 )(CH2 CH2 PtBu2 )}], and [RuCl{N(CHCHPtBu2 )2 }], in which the ruthenium(II) ions are in the extremely rare square-planar coordination geometry. Whereas the dialkylamido complex adopts an electronic singlet (S=0) ground state and energetically low-lying triplet (S=1) state, the vinyl alkyl amido and the divinyl amido complexes exhibit unusual triplet (S=1) ground states as confirmed by experimental and computational examination. However, essentially non-magnetic ground states arise for the two intermediate-spin complexes owing to unusually large zero-field splitting (D>+200 cm(-1) ). The change in ground state electronic configuration is attributed to tailored pincer ligand-to-metal π-donation within the PNP ligand series.

  8. See the World on the Internet: Tips for Parents of Young Readers--and "Surfers" = Vea el mundo por Internet: Ideas por padres de jovenes lectores y exploradores.

    ERIC Educational Resources Information Center

    Moss, Jeanette

    Regardless of whether a parent has Internet access at home, it is essential that parents learn with their children and be aware of where their travels on the Internet are taking them. Many libraries have Internet workshops for parents or children or both. In the excitement of looking at sites, children may not even realize they are reading. Many…

  9. Chemical enhancement of fingermark in blood on thermal paper.

    PubMed

    Hong, Sungwook; Seo, Jin Yi

    2015-12-01

    Chemical enhancement methods for fingermark in blood deposited on the surface of a thermal paper substrate were examined. The blood-sensitive reagents compared were LCV (leuco crystal violet), Amido black and Hungarian red. Fingermark in blood on the surface of thermal paper can be fixed with 2% 5-sulfosalicylic acid solution. LCV was found as an inadequate blood staining reagent because of bubbling, diffusion, and blurring on the surface of thermal paper. Hungarian red was also an inadequate blood staining reagent because excess Hungarian red on the surface of thermal paper was not washed away in the de-staining procedure. Amido black was the best staining reagent among three staining reagents compared. The maximum dilution ratio visible to the naked eye after Amido black staining was 1 in 80 for the thermally sensitive surface and 1 in 20 for the thermally non-sensitive surface.

  10. Ensenando El Espanol por Medio de Accion (Teaching Spanish through Action).

    ERIC Educational Resources Information Center

    Segal, Bertha

    A teaching guide containing 102 elementary to intermediate level Spanish lessons is presented. The lessons are based on the Total Physical Response technique of second language teaching. They follow the stages of first language acquisition: listening, speaking, and reading. Each of the ten units contains a list of new vocabulary words, individual…

  11. Master equipment list 500 CFM portable exhauster POR-005 skid C

    SciTech Connect

    KRISKOVICH, J.R.

    1999-07-08

    The Master Equipment List (MEL) lists all the major components of the 500 cfm exhauster PORO5. The purpose of this Master Equipment List is to provide basic information and references to other documents for the listed components.

  12. Teaching Probability for Conceptual Change (La Ensenanza de la Probabilidad por Cambio Conceptual).

    ERIC Educational Resources Information Center

    Castro, Cesar Saenz

    1998-01-01

    Presents a theoretical proposal of a methodology for the teaching of probability theory. Discusses the importance of the epistemological approach of Lakatos and the perspective of the conceptual change. Discusses research using a proposed didactic method with Spanish high school students (N=6). Concludes that significant differences on all…

  13. Producao d Dijatos por Dupla Troca de Pomeron Exclusiva no Experimento D0

    SciTech Connect

    Murilo Santana Rangel

    2008-01-01

    The first search for exclusive diffractive dijet production with invariant mass ≳ 100 GeV in Run II of the Fermilab Tevatron Collider is performed. The set of data used is the Run IIa, corresponding to an integrated luminosity of 30 pb-1 of p$\\bar{p}$ collisions at √s = 1.96 TeV taken with the D0 detector. At 95% CL, an upper limit for the ratio between the number of diffractive exclusive events and the number of non diffractive events is set to be 7.5 x 10-6, excluding two of the three models proposed to explain this production.

  14. Abuso sexual por parte de los empleados del colegio (Sexual Misconduct by School Employees). ERIC Digest.

    ERIC Educational Resources Information Center

    Goorian, Brad

    This digest in Spanish defines sexual misconduct and offers guidelines that school boards and administrators can initiate to protect students from unwanted sexual behavior. The law recognizes two types of sexual misconduct: quid pro quo, when a school employee grants a student a favor in exchange for sexual gratification, and hostile environment,…

  15. El Titulo IX y La Discriminacion por Sexo (Title IX and Sex Discrimination).

    ERIC Educational Resources Information Center

    Office for Civil Rights (ED), Washington, DC.

    Title IX of the Education Amendments of 1972 protects people from discrimination based on sex in education programs or activities that receive Federal financial assistance. This brochure outlines the responsibilities of education programs and activities covered by Title IX, the responsibilities of the Office for Civil Rights (OCR) in enforcing…

  16. Renovando la Esperanza por una Educacion sin Exclusiones (Rekindling the Hope for an Education without Exclusion).

    ERIC Educational Resources Information Center

    Revista Interamericana de Educacion de Adultos, 2001

    2001-01-01

    Articles in this issue, written in Spanish, focus on the following: current status and outlook of youth and adult education; opening statement of the 50th anniversary commemoration; regional framework for the education of youth and adults in Latin America and the Caribbean; interculturalism and the education of youth and adults; participation of…

  17. Pulsaciones excitadas por la quema de hidrógeno en enanas blancas

    NASA Astrophysics Data System (ADS)

    Camisassa, M. E.; Córsico, A. H.; Althaus, L. G.

    2016-08-01

    Recent works show that low-mass white dwarfs derived from low-metallicity progenitors, in the absence of third dredge-up episodes during the asymptotic giant branch, are born with a hydrogen envelope thick enough to make stable hydrogen shell burning the most important energy source even at low luminosities. This extra source of energy delays the cooling times of these white dwarfs. Furthermore, in this type of stars some pulsational -modes could be excited by the epsilon mechanism due to the hydrogen shell burning. Motivated by these results, we decided to explore the pulsational properties of this type of stars, aimed at constraining hydrogen shell burning and the occurrence of third dredge-up during the AGB evolution of the progenitor stars. For this purpose, we have constructed nonadiabatic pulsation models of white dwarfs from low-metallicity progenitors with . Our calculations show that some modes are excited due to hydrogen shell burning.

  18. Microbicidas Metodo de Prevencion en VIH/SIDA Controlado por Mujeres.

    PubMed

    Ruiz, Cindy; Torres, Viviana; Cianelli, Rosina; Ferrer, Lilian

    2009-03-01

    HIV/AIDS continues to expand throughout the world, and in recent times has had a severe impact on the number of women living with HIV. Access to methods of prevention for HIV/AIDS around the world is limited and for many women may not be feasible. Examples of such methods are sexual abstinence, which though recognized as an effective method of prevention is difficult for many women to achieve. Mutual fidelity is another option, but many women cannot control the sexual behavior of their partners. Finally, the male condom continues to be an available method of HIV prevention for sexually active people. However, in many places, gender inequality, social norms, and economic disparities severely limit women's capacity to negotiate the use of a condom with their partner. For this reason, an urgent need exists to develop a product for the prevention of HIV/AIDS that can be handled by women. Microbicides, products that can reduce HIV risk when applied intravaginally, hold promise for stopping the advance of HIV/AIDS, especially when considering that women can make their own decisions about whether to use them when other methods of prevention are not available. The objective of the current literature review was to understand the scientific advances related to microbicides in the prevention of HIV/AIDS in women through the analysis of available literature in this area. Interest in this topic emerged from the need to contribute to women's health and HIV/AIDS prevention. To achieve this review's objective, a search was carried out in multiple databases, including OVID, PUBMED, PROQUEST, and CINAHL, as well as published materials from organizations related to this area such as UNAIDS and CONASIDA, and literature available from the Internet. Upon completion of the literature review, it was concluded that microbicides are an effective method for preventing HIV/AIDS for women as well as their partners. Although they have a high level of acceptance among the female population, the majority of microbicides are still in clinical studies, requiring further evaluation for their safe use in humans. There are 3 microbicides in the final phases of clinical studies that will soon be available on the market. One of these was found to be 60% effective in protecting against the transmission of HIV and was used by women in 50% of their sexual activity, which resulted in avoiding approximately 2.5 million new HIV infections in men, women, and children over a 3-year period.

  19. Home before You Know It = De regres en casa en un dos por tres.

    ERIC Educational Resources Information Center

    Vida Health Communications, Inc., Cambridge, MA.

    The arrival of a newborn requires a great deal of adjustment. Intended for new and expectant parents, this booklet and companion video provide practical advice and hands-on demonstrations of the essentials of mother and baby care, from birth to the first visit to the pediatrician. The first part of the booklet, which comes in both English- and…

  20. El Libro de la Escritura por Pinguino Tinto (The Writing Book, by Inky Penguin).

    ERIC Educational Resources Information Center

    Padgett, Ron

    Presented completely in Spanish and intended for elementary level students, this book offers 12 writing ideas and several suggestions on how students can make a book using their writing. Each writing idea is presented with a brief description (addressed to the student), several examples of student writing, and a blank page on which to write.…

  1. Looking for a Job: Step by Step = Buscando Trabajo: Paso por Paso.

    ERIC Educational Resources Information Center

    Edwards, Patricia

    This bilingual document provides guidelines and learning activities to assist migrant workers in looking for a job. The document covers the following areas: (1) a checklist providing an overview of job search skills; (2) developing a fact sheet of personal information; (3) listing good work qualities; (4) identifying references and securing…

  2. Evolución de una protuberancia observada por el HASTA

    NASA Astrophysics Data System (ADS)

    Luoni, M. L.; Francile, C.

    Prominence eruptions are one of the most spectacular manifestations of solar activity; in addition to flares and coronal mass ejections. Both filaments and prominences are chromospheric material suspended in the corona by the magnetic field. Hence their importance as tracers of field ejections. Some parts of their magnetic structure are not well understood; especially with regard to the loss of stability. On 06 December 2010 the H-Alpha Telescope for Argentina (HASTA) observed a prominence in the eastern solar limb including when part of it was ejected. In this paper the evolution of the filament is analyzed; its structure before and after the eruption; determining parameters that characterize it from HASTA data. FULL TEXT IN SPANISH

  3. Microbicidas Metodo de Prevencion en VIH/SIDA Controlado por Mujeres

    PubMed Central

    Ruiz, Cindy; Torres, Viviana; Cianelli, Rosina; Ferrer, Lilian

    2016-01-01

    HIV/AIDS continues to expand throughout the world, and in recent times has had a severe impact on the number of women living with HIV. Access to methods of prevention for HIV/AIDS around the world is limited and for many women may not be feasible. Examples of such methods are sexual abstinence, which though recognized as an effective method of prevention is difficult for many women to achieve. Mutual fidelity is another option, but many women cannot control the sexual behavior of their partners. Finally, the male condom continues to be an available method of HIV prevention for sexually active people. However, in many places, gender inequality, social norms, and economic disparities severely limit women's capacity to negotiate the use of a condom with their partner. For this reason, an urgent need exists to develop a product for the prevention of HIV/AIDS that can be handled by women. Microbicides, products that can reduce HIV risk when applied intravaginally, hold promise for stopping the advance of HIV/AIDS, especially when considering that women can make their own decisions about whether to use them when other methods of prevention are not available. The objective of the current literature review was to understand the scientific advances related to microbicides in the prevention of HIV/AIDS in women through the analysis of available literature in this area. Interest in this topic emerged from the need to contribute to women's health and HIV/AIDS prevention. To achieve this review's objective, a search was carried out in multiple databases, including OVID, PUBMED, PROQUEST, and CINAHL, as well as published materials from organizations related to this area such as UNAIDS and CONASIDA, and literature available from the Internet. Upon completion of the literature review, it was concluded that microbicides are an effective method for preventing HIV/AIDS for women as well as their partners. Although they have a high level of acceptance among the female population, the majority of microbicides are still in clinical studies, requiring further evaluation for their safe use in humans. There are 3 microbicides in the final phases of clinical studies that will soon be available on the market. One of these was found to be 60% effective in protecting against the transmission of HIV and was used by women in 50% of their sexual activity, which resulted in avoiding approximately 2.5 million new HIV infections in men, women, and children over a 3-year period. PMID:28111528

  4. Enfermedad diarreica aguda por Escherichia coli patógenas en Colombia

    PubMed Central

    Gómez-Duarte, Oscar G.

    2014-01-01

    Resumen Las cepas de E. coli patógenas intestinales son causas importantes de la enfermedad diarreica aguda (EDA) en niños menores de 5 años en América Latina, África y Asia y están asociadas a alta mortalidad en niños en las comunidades más pobres de África y el Sudeste Asiático. Estudios sobre el papel de las E. coli patógenas intestinales en la EDA infantil en Colombia y otros países de América Latina son limitados debido a la carencia de ensayos para detección de estos patógenos en los laboratorios clínicos de centros de salud. Estudios recientes han reportado la detección de E. coli patógenas intestinales en Colombia, siendo la E. coli enterotoxigénica la cepa más frecuentemente asociada a diarrea en niños menores de 5 años. Otros patógenos detectados en estos pacientes incluyen las E. coli enteroagregativa, enteropatógena, productora de toxina Shiga, y de adherencia difusa. Con base en estudios que reportan la presencia de E. coli productora de toxina Shiga y E. coli enteroagregativa en carnes y vegetales en supermercados, se cree que productos alimentarios contaminados contribuyen a la transmisión de estos patógenos y a la infección del huésped susceptible. Más estudios son necesarios para evaluar los mecanismos de transmisión, el impacto en la epidemiologia de la EDA, y las pautas de manejo y prevención de estos patógenos que afectan la población pediátrica en Colombia. PMID:25491457

  5. PREJUICIO Y DISTANCIA SOCIAL HACIA PERSONAS HOMOSEXUALES POR PARTE DE JÓVENES UNIVERSITARIOS

    PubMed Central

    Fernández Rodríguez, María del C.; Squiabro, José Calderón

    2014-01-01

    Se realizó un estudio descriptivo transversal con el propósito de explorar actitudes de rechazo y distancia social hacia las personas gays y lesbianas (GL) en 565 universitarios. Se utilizó una escala para medir Prejuicio y otra escala para medir Distancia Social. Los participantes reflejaron niveles moderados de prejuicio y distancia social (DS) hacia las personas gays y lesbianas. Los varones (M=104.5, DT= 27.47) mostraron significativamente más prejuicio que las mujeres (M=98.8, DT= 23.41). Los hombres (M=22.7, DT= 7.00) mostraron significativamente mayor DS que las mujeres (M=21.1, DT= 5.41). Las personas que asisten con regularidad a la iglesia mostraron más prejuicio y DS que los que no asisten. Se analiza importancia de incluir el tema de la diversidad sexual a través del currículo para desmontar prejuicios hacia la comunidad homosexual. PMID:25606066

  6. The Escuela Moderna Movement of Francisco Ferrer: "Por la Verdad y la Justicia."

    ERIC Educational Resources Information Center

    Fidler, Geoffrey C.

    1985-01-01

    The educational theory and practice of the Escuela Modern (Modern School) movement of the Spanish educator Francisco Ferrer, born in 1850, are discussed. Two fundamental tendencies of the movement are child-centered education and education in didactic terms. (RM)

  7. Luchando por una educacion: A Qualitative Understanding of Undocumented Latina/o College Student Motivation

    ERIC Educational Resources Information Center

    Navarro, Elvia Lorena

    2013-01-01

    The current qualitative study explored the factors and resources that motivate undocumented Latino/a college students to persist in higher education. Through the data obtained from the four qualitative open-ended survey questions, a content analysis revealed specific codes, themes, and subthemes addressing the factors and resources that motivate…

  8. Language and La Academia, If English Works, Por Que Se Emplea Espanol?

    ERIC Educational Resources Information Center

    Jonz, Jon G.

    1978-01-01

    The dynamics of Mexican American nationalism reflected in the publications of the Academia de la Nueva Raza and in a 1971 work by Ricardo Sanchez are examined in this article. The connection between language and ideology is discussed in the context of Chicano nationalist writing. (GC)

  9. Phantom of RAMSES (POR): A new Milgromian dynamicsN-body code

    NASA Astrophysics Data System (ADS)

    Lüghausen, Fabian; Famaey, Benoit; Kroupa, Pavel

    2015-02-01

    Since its first formulation in 1983, Milgromian dynamics (MOND) has been very successful in predicting the gravitational potential of galaxies from the distribution of baryons alone, including general scaling relations and detailed rotation curves of large statistical samples of individual galaxies covering a large range of masses and sizes. Most predictions however rely on static models, and only a handful of N-body codes have been developed over the years to investigate the consequences of the Milgromian framework for the dynamics of complex evolving dynamical systems. In this work, we present a new Milgromian N-body code, which is a customized version of the RAMSES code (Teyssier 2002) and thus comes with all its features: it includes particles and gas dynamics, and importantly allows for high spatial resolution of complex systems due to the adaptive mesh refinement (AMR) technique. It further allows the direct comparison between Milgromian simulations and standard Newtonian simulations with dark matter particles. We provide basic tests of this customized code and demonstrate its performance by presenting N-body computations of dark-matter-free spherical equilibrium models as well as dark-matter-free disk galaxies in Milgromian dynamics.

  10. The PorGrow project: overall cross-national results, comparisons and implications.

    PubMed

    Millstone, E; Lobstein, T

    2007-05-01

    European policymakers need more information on policy responses to obesity that stakeholders judge effective and acceptable. The Policy Options for Responding to the Growing Challenge of Obesity Research Project gathered such intelligence by interviewing key stakeholder groups in nine countries. Interviews used an innovative multi-criteria mapping (MCM) methodology that gathers quantitative and qualitative information on the stakeholders' perceptions and judgements. Aggregating across all participants, a comprehensive portfolio of policy measures, integrated into a coherent programme, would be well-supported by broad coalitions of stakeholders. Those portfolios should include measures (i) to provide improved educations in schools and to the general adult population; (ii) measures to improve access to and incentives for physical activity; (iii) measures to improve information about both foods and physical activity and (iv) changes to the supply of and demand for foodstuffs. There was little support for fiscal measures and technological 'fixes'; they were judged ineffective and unacceptable. Significant differences were found across European regions, and across different stakeholder perspectives, but not across genders. There is a strong case for improved monitoring of body mass index levels, dietary habits and physical activity. An MCM study can effectively cover several countries, rather than being confined to just one, and generate both national and cross-national policy analyses and proposals.

  11. Perfis de temperatura eletrônica em regiões HII

    NASA Astrophysics Data System (ADS)

    Copetti, M. V. F.

    2003-08-01

    As flutuações de temperatura eletrônica em regiões HII, inicialmente propostas para explicar as discrepâncias entre os valores de temperatura obtidos por diferentes métodos, têm sido apontadas como a causa mais provável das enormes diferenças encontradas entre as abundâncias químicas medidas através de linhas excitadas colisionalmente e de linhas de recombinação. Recentemente têm sido reportadas tentativas de detecção e quantificação diretas das flutuações de temperatura eletrônica através de medidas ponto a ponto, obtidas por meio de espectroscopia de fenda longa, das razões de linhas [OIII]l4263/l5007 e [NII]l5755/l6584, principais sensores de temperatura. Neste trabalho, utilizamos o código numérico de fotoionização Cloudy para avaliar a confiabilidade desse procedimento. Concluímos que, para valores de densidade eletrônica e de temperatura efetiva da estrela ionizante típicos das regiões HII, os perfis superficiais de temperatura obtidos via medidas do sensor [OIII]l4263/l5007 são bons traçadores dos gradientes internos de temperatura eletrônica. Já os perfis de temperatura eletrônica medidos por meio da razão [NII]l5755/l6584 não reproduzem os gradientes verdadeiros de temperatura.

  12. Adsorption of an anionic azo dye by cross-linked chitosan/bentonite composite.

    PubMed

    Liu, Qian; Yang, Bingchao; Zhang, Lujie; Huang, Ruihua

    2015-01-01

    In this study, cross-linked chitosan (CCS)/bentonite (BT) composite was prepared by the intercalation of chitosan in bentonite and the cross-linking reaction between chitosan and glutaraldehyde. CCS/BT composite was characterized by using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD) and thermal gravimetric analyses (TGA). Their adsorption characteristics were assessed by using an azo dye (Amido Black 10B) as a model adsorbate. The adsorption of Amido Black 10B onto the CCS/BT composite was found to be optimal at pH 2. The adsorption isotherm was well described by the Langmuir model and the maximum adsorption capacity was 323.6 mg/g at 293K and pH 2. Amido Black 10B adsorption kinetics followed a pseudo-second-order kinetic model. The calculated thermodynamic parameters showed that the adsorption of Amido Black 10B by CCS/BT composite was spontaneous and endothermic in nature.

  13. Acylsilanes in Iridium-Catalyzed Directed Amidation Reactions and Formation of Heterocycles via Siloxycarbenes.

    PubMed

    Becker, Peter; Pirwerdjan, Ramona; Bolm, Carsten

    2015-12-14

    Exposing ortho-amido aroylsilanes to visible light or heat leads to cyclization reactions that provide N-heterocyclic compounds via siloxycarbenes as key intermediates. The previously unreported starting materials have been prepared by directed amidations of aromatic acylsilanes in the presence of an iridium catalyst followed by N-alkylation.

  14. Synthesis of Antidotes for Organophosphorus Acetylcholinesterase Inhibitors

    DTIC Science & Technology

    1991-08-30

    etal.ɟ> These compounds are imidazolium salts with one relatively complex nitrogen substituent and amido or methyl substituents at C-2. 11 TABLE...pyridinium p-toluenesulfonate (4.0 g, 10 mmol) and nicotinic acid hydrazide (1.52 g, 11 mmol) was refluxed in absolute ethanol (105 mL) for 2 h. The

  15. Zinc-Catalyzed Highly Isoselective Ring Opening Polymerization of rac-Lactide

    PubMed Central

    2015-01-01

    A family of chiral zinc amido-oxazolinate complexes are shown to be highly active and isoselective initiators for the ring-opening polymerization (ROP) of rac-lactide, yielding isotactic stereoblock polylactides (PLA) with Pm up to 0.91. This represents the highest isoselectivity observed with zinc-based catalysts for ROP of rac-lactide. PMID:25068079

  16. RHEOLOGY OF CONCENTRATED SOLUTIONS OF HYPERBRANCHED POLYESTERS

    EPA Science Inventory

    The solution rheology of different generations of hyperbranched polyesters in N-methyl-2- pyrrolidinone (NMP) solvent was examined in this study. The solutions exhibited Newtonian behavior over a wide range of polyester concentrations. Also, the relative viscosities of poly(amido...

  17. Contagem de fontes de radio na direção de aglomerados ricos de galaxias

    NASA Astrophysics Data System (ADS)

    Andreazza, C. M.; Andernach, H.

    A contagem de fontes de rádio, na direção de aglomerados ricos de galáxias, deve fornecer uma distribuçãto acima da média do campo devido aos efeitos do meio. No entanto, a distribução de radiofontes de alguns aglomerados, investigada por vários autores no passado, mostrou, em alguns casos, uma deficência de fontes fracas. Neste trabalho, analisamos os levantamentos em 2.7 GHz (Reuter e Andernach 1990, 1990A&AS...82..279R; Loiseau et al. 1988, 1988A&AS...75...67L) e o catálogo 6CII em 151 MHz (Hales et al. 1988, 1988MNRAS.234..919H). Nosso estudio da distribução de radiofontes, na direção de aglomerados ricos de galáxias, nestas duas frequências, mostra um excesso de fontes fortes somente nas regiões centrais dos aglomerados. Este resultado pode ser explicado devido à evidência de confinamento das radiofontes pelo gás, do meio intra-aglomerado, e devido aos processos de colisão, coalescência e canibalismo de galáxias.

  18. Simulação de ejeções de massa coronal

    NASA Astrophysics Data System (ADS)

    Corsini, M. A.; Silva, A. V. R.

    2003-08-01

    Ejeções de massa coronal (EMC) são bolhas gigantes de gás permeadas por campos magnéticos que são ejetadas do Sol durante um período de várias horas. Caso estas ejeções atinjam a Terra, geralmente, causam uma série de distúrbios às comunicações de longa distância e navegação, além de danos a satélites e transformadores. Portanto, é desejável que sejamos capazes de prever quando estas ejeções atingirão a Terra. Para tanto, é necessário um bom entendimento dos mecanismos causadores das ejeções e, principalmente, de como se dá a propagação das EMC e sua interação com o vento solar que permeia o meio interplanetário. Nesse sentido foi desenvolvido um programa computacional para resolver as equações MHD (Magneto-Hidro-Dinâmica) que regem a evolução das EMC. Primeiramente foram estabelecidas as condições necessárias para descrever o vento solar, no estado estacionário, que permeia todo o meio interplanetário. Num primeiro momento, resolveu-se o sistema de equações para o caso do vento isotérmico, conhecida como a solução de Parker, a fim de testarmos o modelo. Então, foi considerado o caso do vento solar com temperatura variável no meio interplanetário. Este resultado foi utilizado como a base de nosso sistema em seu instante inicial. Posteriormente foram feitas as considerações necessárias para descrever a propagação da Ejeção de Massa Coronal. As EMC foram simuladas como um aumento de densidade e temperatura local na coroa solar. A órbita e a posição da Terra foram incluídas no sistema. Os dados gerados possibilitaram uma análise da evolução da EMC pelo meio interplanetário até encontrar-se com a Terra. Os perfis de densidade e temperatura a 1 Unidade Astronômica são comparados com os dados de satélites reportados na literatura.

  19. Bis­{(E)-3-[2-(hy­droxy­imino)­propan­amido]-2,2-dimethyl­propan-1-aminium} bis[μ-(E)-N-(3-amino-2,2-dimethyl­prop­yl)-2-(hy­droxy­imino)­propanamido­(2−)]bis­{[(E)-N-(3-amino-2,2-dimethyl­prop­yl)-2-(hy­droxy­imino)­propanamide]­copper(II)} bis­((E)-{3-[2-(hy­droxy­imino)­propanamido]-2,2-dimethyl­prop­yl}carbamate) acetonitrile disolvate

    PubMed Central

    Buvailo, Andrii I.; Pavlishchuk, Anna V.; Penkova, Larysa V.; Kotova, Natalia V.; Haukka, Matti

    2012-01-01

    The reaction between copper(II) nitrate and (E)-N-(3-amino-2,2-dimethyl­prop­yl)-2-(hy­droxy­imino)­propanamide led to the formation of the dinuclear centrosymmetric copper(II) title complex, (C8H18N3O2)2[Cu2(C8H15N3O2)2(C8H17N3O2)2](C9H16N3O4)2·2CH3CN, in which an inversion center is located at the midpoint of the Cu2 unit in the center of the neutral [Cu2(C8H15N3O2)2(C8H17N3O2)2] complex fragment. The Cu2+ ions are connected by two N—O bridging groups [Cu⋯Cu separation = 4.0608 (5) Å] while the CuII ions are five-coordinated in a square-pyramidal N4O coordination environment. The complex mol­ecule co-crystallizes with two mol­ecules of acetonitrile, two mol­ecules of the protonated ligand (E)-3-[2-(hy­droxy­imino)­propanamido]-2,2-dimethyl­propan-1-aminium and two negatively charged (E)-{3-[2-(hy­droxy­imino)­propanamido]-2,2-dimethyl­prop­yl}carbamate anions, which were probably formed as a result of condensation between (E)-N-(3-amino-2,2-dimethyl­prop­yl)-2-(hy­droxy­imino)­propanamide and hydro­gencarbonate anions. In the crystal, the complex fragment [Cu2(C8H15N3O2)2(C8H17N3O2)2] and the ion pair C8H18N3O2 +.C9H16N3O4 − are connected via an extended system of hydrogen bonds. PMID:23468704

  20. Melhoramentos no código Wilson-Devinney para binárias eclipsantes

    NASA Astrophysics Data System (ADS)

    Vieira, L. A.; Vaz, L. P. R.

    2003-08-01

    A análise de curvas de luz e velocidades radiais de sistemas binários eclipsantes pode ser feita por meio de vários modelos. Um desses é o Modelo Wilson-Devinney (WD). Ao longo dos anos, esse modelo sofreu várias alterações em seus códigos principais, com a finalidade de torná-lo mais consistente tanto fíisica como numericamente. O Modelo WD tem sido melhorado de várias maneiras em seus dois códigos: um para a predição das curvas de luz teórica e de velocidade radiais e outra para as soluções destas curvas. Teoricamente, na física do modelo, nós introduzimos a possibilidade de levar em conta os efeitos do movimento apsidal. Numericamente, nós introduzimos a possibilidade de usar o Método SIMPLEX no procedimento da solução, como uma alternativa para o já implementado Método de Mínimos Quadrados (Least Squares Method). Estas modificações, juntamente com outras já introduzidas pelo nosso grupo anteriormente, tornam o código mais eficiente na solução das curvas de luz e de velocidade radiais de binárias eclipsantes. Como o modelo tem sido usado para analisar sistemas com componentes pré-sequência principal (TY CrA, Casey et al. 1998, Vaz et al. 1998), SM 790, Stassun et al. 2003), este melhoramento beneficiará estes casos também. Apresentamos os resultados obtidos com a modificação do código WD por meio do uso de dados da estrela GL Carinae, comprovando, (1) que os parâmetros orbitais calculados por nós são coerentes com os obtidos anteriormente na literatura (Giménez & Clausen, 1986) e com os obtidos por Faria (1987), e (2) que a implementação do Método SIMPLEX torna o código mais lento mas completamente consistente internamente e evita os problemas gerados pelo uso do Método de Mínimos Quadrados, tais como imprecisão no cálculo das derivadas parciais e convergência para mínimos locais.

  1. Que hay de nuevo acerca de la inmersion? Un Breve Recorrido por sus Fundamentos y por las Investigaciones Actuales (What's New in Immersion? A Brief Overview of Its Bases and Present-Day Research).

    ERIC Educational Resources Information Center

    Sierra, Josu

    This discussion briefly surveys the development of the immersion method of second language teaching, outlining the central program strategies and characteristics using Curtain's and Pesola's descriptions. An overview of recent research focuses on error correction and feedback studies as an example of pedagogical-methodological evolution in this…

  2. Padres Trabajando por la Paz: a randomized trial of a parent education intervention to prevent violence among middle school children.

    PubMed

    Murray, N G; Kelder, S H; Parcel, G S; Frankowski, R; Orpinas, P

    1999-06-01

    This paper reports the results of a randomized trial to test the effectiveness of a theoretically derived intervention designed to increase parental monitoring among Hispanic parents of middle school students. Role model story newsletters developed through the process of Intervention Mapping were mailed to half of a subsample of parents whose children participated in Students for Peace, a comprehensive violence prevention program. The results indicated that parents in the experimental condition (N = 38) who had lower social norms for monitoring at baseline reported higher norms after the intervention than the parents in the control condition (N = 39) (P = 0.009). Children of parents in the experimental group reported slightly higher levels of monitoring at follow-up across baseline values, whereas control children who reported moderate to high levels of monitoring at pre-test reported lower levels at follow-up (P = 0.04). These newsletters are a population-based strategy for intervention with parents that show some promise for comprehensive school-based interventions for youth.

  3. Distribución superficial de impactos en Iapetus originada por el remanente de una colisión

    NASA Astrophysics Data System (ADS)

    Zoppetti, F. A.; Leiva, A. M.; Briozzo, C. B.

    2015-08-01

    By means of Circular Restricted Three Body Problem Saturn--Iapetus, we analize potential impact distributions on the surface of Iapetus, originated from considering a low-energy population generated as remnants of a collisional event occurred in the past on the surface of this satellite. The results are analized in order to offer a new approach to explain the origin of the albedo dichotomy observed on Iapetus.

  4. Os Atores da Mobilizacao por Creches e Pre-Escolas Comunitarias (Mobilizing Agents for Nurseries and Infant Schools).

    ERIC Educational Resources Information Center

    Filgueiras, Cristina Almeida Cunha

    1995-01-01

    Discusses the role of community nurseries and preschools, within the context of Brazilian popular movements and social policy of the last 15 years. States that the experiences of these organizations reveal great complexity in terms of social, political, and pedagogic mobilization. Concludes that for all involved there are several levels of…

  5. Reconnaissance evaluation of Honduran geothermal sites. Una evaluacion por medio de reconocimiento de seis areas geotermicas en Honduras

    SciTech Connect

    Eppler, D.; Fakundiny, R.; Ritchie, A.

    1986-12-01

    Six geothermal spring sites were selected on the basis of preliminary investigations conducted in Honduras over the last decade and were evaluated in terms of their development potential. Of the six, the Platanares and San Ignacio sites have high base temperatures and high surface fluid discharge rates and appear to have the best potential for further development as sources of electrical power. A third site, Azacualpa, has a high enough base temperature and discharge rate to be considered as a back-up, but the logistical problems involved in geophysical surveys make it less attractive than the two primary sites. Of the remaining three sites, Pavana may be a source of direct-use heat for local agricultural processing. Sambo Creek and El Olivar have either severe logistical problems that would impede further investigation and development or base temperatures and flow rates that are too low to warrant detailed investigation at this time.

  6. La trama celeste: por qué educar en astronomía. Una oportunidad de aprendizajes múltiples

    NASA Astrophysics Data System (ADS)

    García, B.

    2016-08-01

    Astronomy education at all levels has been an issue addressed by the International Astronomical Union as part of its 2010--2020 plan. The content on astronomical topics are in the curriculum at primary and secondary levels worldwide. Being a cross-discipline, astronomy is also a science that allows to introduce students to the study of the nature in a non-confrontational way: no one is indifferent to their concepts and discoveries. The International Astronomical Union, through its Commission on Education and Development of Astronomy, has implemented, sponsored and carried out over the past five years two special programs, one about didactics of astronomy for teachers of middle level and another one for the transmission of astronomical topics for the disabled. In this presentation, achievements and impact of these programs are shared.

  7. Como ayudar a los padres a prevenir el envenenamiento por plomo (Helping Parents Prevent Lead Poisoning). ERIC Digest.

    ERIC Educational Resources Information Center

    Binns, Helen J.; Ricks, Omar Benton

    Children are at greater risk than adults for lead poisoning because children absorb lead more readily than adults, and a small amount of lead in children's bodies can do a great deal of harm. This Spanish-language Digest summarizes some of the causes and effects of childhood lead poisoning and suggests some lead poisoning prevention strategies…

  8. Relationship between hepatic phenotype and changes in gene expression in cytochrome P450 reductase (POR) null mice

    PubMed Central

    Wang, Xiu Jun; Chamberlain, Mark; Vassieva, Olga; Henderson, Colin J.; Wolf, C. Roland

    2005-01-01

    Cytochrome P450 reductase is the unique electron donor for microsomal cytochrome P450s; these enzymes play a major role in the metabolism of endogenous and xenobiotic compounds. In mice with a liver-specific deletion of cytochrome P450 reductase, hepatic cytochrome P450 activity is ablated, with consequent changes in bile acid and lipid homoeostasis. In order to gain insights into the metabolic changes resulting from this phenotype, we have analysed changes in hepatic mRNA expression using microarray analysis and real-time PCR. In parallel with the perturbations in bile acid levels, changes in the expression of key enzymes involved in cholesterol and lipid homoeostasis were observed in hepatic cytochrome P450 reductase null mice. This was characterized by a reduced expression of Cyp7b1, and elevation of Cyp7a1 and Cyp8b1 expression. The levels of mRNAs for other cytochrome P450 genes, including Cyp2b10, Cyp2c29, Cyp3a11 and Cyp3a16, were increased, demonstrating that endogenous factors play a role in regulating the expression of these proteins and that the increases are due, at least in part, to altered levels of transcripts. In addition, levels of mRNAs encoding genes involved in glycolysis and lipid transport were also increased; the latter may provide an explanation for the increased hepatic lipid content observed in the hepatic null mice. Serum testosterone and oestradiol levels were lowered, accompanied by significantly decreased expression of Hsd3b2 (3β-hydroxy-Δ5-steroid dehydrogenase-2), Hsd3b5 (3β-hydroxy-Δ5-steroid dehydrogenase-5) and Hsd11b1 (11β-hydroxysteroid dehydrogenase type 1), key enzymes in steroid hormone metabolism. These microarray data provide important insights into the control of metabolic pathways by the cytochrome system. PMID:15717863

  9. Perfiles de densidad de galaxias 3-D y segregación por tipo espectral en grupos de galaxias

    NASA Astrophysics Data System (ADS)

    Díaz, E.; Zandivarez, A.; Merchán, M. E.; Muriel, H.

    We have analysed the distribution of galaxies in groups identified in the largest redshift surveys available: the final release of the 2dF Galaxy Our work comprises the study of the galaxy density profiles and the fraction of galaxies per spectral type as a function of the group-centric distance. We have calculated the projected galaxy density profiles of groups using composite samples in order to increase the statistical significance of the results and we infer the 3-D galaxy density profiles using a deprojection method similar to the developed by Allen & Fabian. Special cares have been taken in order to avoid possible biases in the group identification and the construction of the projected galaxy density profile estimator due to the irregular sky coverage of the 2dF Galaxy Redshift Survey. We have adopted a generalized King profile to fit the obtained projected density profiles and use them to construct mock clusters and obtain the 3-D density profiles per spectral type. From the 3-D galaxy density profile we have estimated the 3-D fraction of galaxies per spectral type. Comparing with the fraction of galaxies computed using the projected profiles we observe a similar behavior of the galaxy spectral type segregation as the obtained by Domínguez et al. for groups in the early data release of the 2dF Galaxy Redshift Survey. As expected, the trends obtained for the 3-D galaxy fractions show steeper slopes.

  10. Monitoreo óptico de eta-Carina durante el pasaje por el periastro en 2014.6

    NASA Astrophysics Data System (ADS)

    Fernández-Lajús, E.; Salerno, N. E.; Scalia, M. C.; Ramos, X. S.; Giudici, F. N.; Gamen, R. C.

    2015-08-01

    We present the H light curves resulting from the 2013 and 2014 observing seasons of Car as well as its spectral evolution, including the latest ``event'' occurred in mid-2014. The direct CCD observations were made with the telescope ``VS Niemela'' the Observatory of La Plata, and spectroscopic observations were made with the telescope ``J. Sahade'' of Casleo, Argentina.

  11. Evaluacion de que consister y por que se lleva acabo? (Evaluation: What Does it Consist of, and for What Purpose?).

    ERIC Educational Resources Information Center

    Austin Independent School District, TX. Office of Research and Evaluation.

    A guide is presented for the evaluation of the bilingual programs in the Austin, Texas, Independent School District. The reasons for an evaluation and a definition of program objectives and evaluation instruments are given. The program components, objectives and evaluation instruments for each grade level (K-4) are listed. The components involved…

  12. En otras palabras: Perfeccionamiento del espanol por medio de la traduccion (In Other Words: Perfecting Spanish Language Skills through Translation).

    ERIC Educational Resources Information Center

    Lunn, Patricia V.; Lunsford, Ernest J.

    This publication, written primarily in Spanish, is an activity book designed to teach Spanish through translation based on the theory that, in order to produce an acceptable translation, students must focus their attention on lexical and grammatical detail. The book combines incisive grammar explanations, relevant lexical information, and a wide…

  13. Theophylline-7-acetic acid derivatives with amino acids as anti-tuberculosis agents.

    PubMed

    Voynikov, Yulian; Valcheva, Violeta; Momekov, Georgi; Peikov, Plamen; Stavrakov, Georgi

    2014-07-15

    A series of amides were synthesized by condensation of theophylline-7-acetic acid and eight commercially available amino acid methyl ester hydrochlorides. Consecutive hydrolysis of six of the amido-esters resulted in the formation of corresponding amido-acids. The newly synthesized compounds were evaluated for their in vitro activity against Mycobacterium tuberculosis H37Rv. The activity varied depending on the amino acid fragments and in seven cases exerted excellent values with MICs 0.46-0.26 μM. Assessment of the cytotoxicity revealed that the compounds were not cytotoxic against the human embryonal kidney cell line HEK-293T. The theophylline-7-acetamides containing amino acid moieties appear to be promising lead compounds for the development of antimycobacterial agents.

  14. [Studies on normal and mildewy Auricularia auricular by Fourier transform infrared spectroscopy].

    PubMed

    Shi, You-ming; Liu, Gang; Sun, Yan-lin; Wei, Sheng-xian; Yan, Cui-qiong

    2011-03-01

    In order to verify the capability of Fourier transform infrared spectroscopy in food safety, Fourier transform infrared spectroscopy (FTIR) was used to obtain the spectra of normal and mildewy auricularia auricula, The result showed the frequency of hydroxyl and aliphatic absorption band in their spectra had evident differentia, with the dispersion being 23.31 and 13.41 cm(-1) respectively. The curve-fitting analysis was used for the fold peaks of hydroxyl and amido, and it presented that the content of hydroxyl and amido had evident change. The substances in the auricularia auricula generated chemical change, and Fourier transform infrared spectroscopy could show the differentia easily. The results show that Fourier transform infrared spectroscopy can provide valuable information about the auricularia auricula. It could be used as a reference method for identification of the normal and mildewy auricularia auricula.

  15. Diamino-diamido tetrathiafulvalene for the sensing of anions and cations: a view in electrochemistry and structure.

    PubMed

    Shi, Zheng; Lu, Zhe-Jun; Zhu, Qin-Yu; Huo, Li-Bin; Han, Qiong-Hua; Bian, Guo-Qing; Dai, Jie

    2011-03-31

    A new cation- and anion-sensitive system based on a TTF derivative with a diamino-diamido moiety (H(2)L) has been studied. The results of cyclic voltammetry indicated that the redox potentials of the protonated H(2)L (H(4)L(2+)) selectively respond to later transition metal cations and some oxo anions. Solid-state structures of the cation-anion compounds formed by H(4)L(2+) and oxo anions were characterized crystallographically, which is helpful to understand the matter of the sensitivity for the anion. There are two types of hydrogen bonds in these compounds, one is with an amino group and the other is with an amido group. The shift of the redox potential is obviously related to formation of hydrogen bonding with the amido group. The packing structures of these cation-anion compounds are arranged to layered sandwiched structures assembled by an oxo-anion layer and two TTF layers through hydrogen bonding.

  16. Group A rotavirus gastroenteritis: post-vaccine era, genotypes and zoonotic transmission.

    PubMed

    Luchs, Adriana; Timenetsky, Maria do Carmo Sampaio Tavares

    2016-01-01

    ABSTRACTThis article provides a review of immunity, diagnosis, and clinical aspects of rotavirus disease. It also informs about the changes in epidemiology of diarrheal disease and genetic diversity of circulating group A rotavirus strains following the introduction of vaccines. Group A rotavirus is the major pathogen causing gastroenteritis in animals. Its segmented RNA genome can lead to the emergence of new or unusual strains in human populations via interspecies transmission and/or reassortment events.RESUMOEste artigo fornece uma revisão sobre imunidade, diagnóstico e aspectos clínicos da doença causada por rotavírus. Também aponta as principais mudanças no perfil epidemiológico da doença diarreica e na diversidade genética das cepas circulantes de rotavírus do grupo A, após a introdução vacinal. O rotavírus do grupo A é o principal patógeno associado à gastroenterite em animais. Seu genoma RNA segmentado pode levar ao surgimento de cepas novas ou incomuns na população humana, por meio de transmissão entre espécies e eventos de rearranjo.

  17. 77 FR 45600 - Certain New Chemicals; Receipt and Status Information

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-01

    ... cooling water. (1:1), polymer with sodium phosphinate (1:1), hydrolyzed. P-12-0376...... 05/29/2012 08/26.../2012 3M Company (G) Curative... (G) Amido amine polyether polymer. P-12-0382...... 06/05/2012 09/02...)-, homopolymer, 2- propylheptyl ester, isomerized. P-12-0396...... 06/11/2012 09/08/2012 CBI (S) Polymer for...

  18. N′-(Di-2-pyridylmethyl­ene)benzo­hydrazide

    PubMed Central

    Warad, Ismail; Al-Nuri, Mohammed; Al-Resayes, Saud; Al-Farhan, Khalid; Ghazzali, Mohamed

    2009-01-01

    In the title Schiff base, C18H14N4O, the amido –NH– unit is connected to one of the two pyridyl N atoms at an N(—H)⋯N distance of 2.624 (2) Å. The mol­ecular packing features an inter­molecular C—H⋯N R 2 2(6) hydrogen-bonding ring motif. PMID:21582871

  19. Indium-Catalyzed Amide Allylation of N-Carbonyl Imides: Formation of Azaspiro-γ-lactones via Ring Opening-Reclosure.

    PubMed

    Sengoku, Tetsuya; Murata, Yusuke; Aso, Yuwa; Kawakami, Ai; Inuzuka, Toshiyasu; Sakamoto, Masami; Takahashi, Masaki; Yoda, Hidemi

    2015-12-04

    A novel and facile synthesis of azaspiro-γ-lactones with a methylene-lactam framework from N-carbonyl imides is described. Mechanistic investigations provide evidence for a two-step reaction process involving ZnCl(2)-promoted addition of β-amido allylindium species followed by an unexpectedly molecular-sieves-mediated ring opening-reclosure concomitantly with the loss of an N-carbonyl unit.

  20. Synthesis of cis-octahydroindoles via intramolecular 1,3-dipolar cycloaddition of 2-acyl-5-aminooxazolium salts.

    PubMed

    Basch, Corey H; Brinck, Jameson A; Ramos, Joaquin E; Habay, Stephen A; Yap, Glenn P A

    2012-11-16

    A concise method for the diastereoselective synthesis of octahydroindoles is presented. The products contain 2-amido and 7-hydroxyl substituents. A series of 2-acyl-5-aminooxazoles were prepared in one step. Upon methylation of the oxazole nitrogen atom, the substrates underwent rapid intramolecular 1,3-dipolar cycloaddition with a tethered alkene and, after reduction with excess hydride, produced octahydroindoles with excellent diastereoselectivity. The method allows for the installation of α-quaternary stereogenic carbon atoms.

  1. Chelate electronic properties control the redox behaviour and superoxide reactivity of seven-coordinate manganese(II) complexes.

    PubMed

    Liu, Gao-Feng; Dürr, Katharina; Puchta, Ralph; Heinemann, Frank W; van Eldik, Rudi; Ivanović-Burmazović, Ivana

    2009-08-28

    We have synthesized and characterized two Mn(II) seven-coordinate complexes with N5 pentadentate ligands, which contain hydrazone and hydrazide groups respectively. We have shown that insertion of hydrazido (amido) groups into the ligand sphere increases the negative charge of the chelate, without changing a donor atom set and coordination geometry, and radically modulate a redox activity of seven-coordinate manganese complexes, which is important for the function of manganese as a superoxide dismutase catalytic center.

  2. FTIR characterization of heparinizable polymer-coated materials for application in biomedicine

    NASA Astrophysics Data System (ADS)

    Barbucci, Rolando; Magnani, Agnese

    1992-03-01

    Fourier Transform Attenuated Total Reflection Infrared Spectroscopy (ATR/FTIR) was used for surface characterization of some commercial materials used in the biomedical field [polyurethane (PU), plasticized polyvinylchloride (PVC), glass, polytetrafluoroethylene (Goretex) and polyethyleneterephthalate (Dacron)] coated with a well-characterized heparin-complexing biomaterial (PUPA) based on polyurethane and poly(amido-amine) components. In particular, difference spectroscopy was used to analyze the coating-substrate interaction to which the material stability is related, and the heparin-material surface binding.

  3. Corrosion-resistant metal surfaces

    DOEpatents

    Sugama, Toshifumi

    2009-03-24

    The present invention relates to metal surfaces having thereon an ultrathin (e.g., less than ten nanometer thickness) corrosion-resistant film, thereby rendering the metal surfaces corrosion-resistant. The corrosion-resistant film includes an at least partially crosslinked amido-functionalized silanol component in combination with rare-earth metal oxide nanoparticles. The invention also relates to methods for producing such corrosion-resistant films.

  4. Variable coordination of amine functionalised N-heterocyclic carbene ligands to Ru, Rh and Ir: C-H and N-H activation and catalytic transfer hydrogenation.

    PubMed

    Cross, Warren B; Daly, Christopher G; Boutadla, Youcef; Singh, Kuldip

    2011-10-14

    Chelating amine and amido complexes of late transition metals are highly valuable bifunctional catalysts in organic synthesis, but complexes of bidentate amine-NHC and amido-NHC ligands are scarce. Hence, we report the reactions of a secondary-amine functionalised imidazolium salt 2a and a primary-amine functionalised imidazolium salt 2b with [(p-cymene)RuCl(2)](2) and [Cp*MCl(2)](2) (M = Rh, Ir). Treating 2a with [Cp*MCl(2)](2) and NaOAc gave the cyclometallated compounds Cp*M(C,C)I (M = Rh, 3; M = Ir, 4), resulting from aromatic C-H activation. In contrast, treating 2b with [(p-cymene)RuCl(2)](2), Ag(2)O and KI gave the amine-NHC complex [(p-cymene)Ru(C,NH(2))I]I (5). The reaction of 2b with [Cp*MCl(2)](2) (M = Rh, Ir), NaO(t)Bu and KI gave the amine-NHC complex [Cp*Rh(NH(2))I]I (6) or the amido-NHC complex Cp*Ir(C,NH)I (7); both protonation states of the Ir complex could be accessed: treating 7 with trifluoroacetic acid gave the amine-NHC complex [Cp*Ir(C,NH(2))I][CF(3)CO(2)] (8). These are the first primary amine- or amido-NHC complexes of Rh and Ir. Solid-state structures of the complexes 3-8 have been determined by single crystal X-ray diffraction. Complexes 5, 6 and 7 are pre-catalysts for the catalytic transfer hydrogenation of acetophenone to 1-phenylethanol, with ruthenium complex 5 demonstrating especially high reactivity.

  5. Mitigation of cardiovascular toxicity in a series of CSF-1R inhibitors, and the identification of AZD7507.

    PubMed

    Scott, David A; Dakin, Les A; Daly, Kevin; Del Valle, David J; Diebold, R Bruce; Drew, Lisa; Ezhuthachan, Jayachandran; Gero, Thomas W; Ogoe, Claude A; Omer, Charles A; Redmond, Sean P; Repik, Galina; Thakur, Kumar; Ye, Qing; Zheng, Xiaolan

    2013-08-15

    The potent and selective 3-amido-4-anilinoquinoline CSF-1R inhibitor AZ683 suffered from cardiovascular liabilities, which were linked to the off-target activities of the compound and ion channel activity in particular. Less basic and less lipophilic examples from both the quinoline and cinnoline series demonstrated cleaner secondary pharmacology profiles. Cinnoline 31 retained the required potency and oral PK profile, and was progressed through the safety screening cascade to be nominated into development as AZD7507.

  6. A joint experimental/theoretical investigation of the MMA polymerization initiated by yttrium phenoxyamine complexes.

    PubMed

    Fang, Jian; Tschan, Mathieu J-L; Brulé, E; Robert, Carine; Thomas, Christophe M; Maron, Laurent

    2013-07-07

    A joint experimental/theoretical study has been carried out on the putative MMA polymerization catalyzed by an yttrium isopropyloxide complex. Despite its high activity in lactone polymerization, this catalyst is found to be unreactive on methyl methacrylate (MMA) polymerization. This surprising result is rationalized using a computational approach at the DFT level. Indeed, the endothermicity of the initiation step explains this lack of reactivity. The theoretical proposal of yttrium amido complexes as catalysts allows overcoming this initiation problem.

  7. A general and efficient approach to aryl thiols: CuI-catalyzed coupling of aryl iodides with sulfur and subsequent reduction.

    PubMed

    Jiang, Yongwen; Qin, Yuxia; Xie, Siwei; Zhang, Xiaojing; Dong, Jinhua; Ma, Dawei

    2009-11-19

    A CuI-catalyzed coupling reaction of aryl iodides and sulfur powder takes place in the presence of K(2)CO(3) at 90 degrees C. The coupling mixture is directly treated with NaBH(4) or triphenylphosphine to afford aryl thiols in good to excellent yields. A wide range of substituted aryl thiols that bear methoxy, hydroxyl, carboxylate, amido, keto, bromo, and fluoro groups can be assembled through this procedure.

  8. Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6‐Diisopropyl‐N‐(trimethylsilyl)anilino Ligand

    PubMed Central

    Fuentes, M. Ángeles; Zabala, Andoni; Kennedy, Alan R.

    2016-01-01

    Abstract Bulky amido ligands are precious in s‐block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n‐butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe3)(Dipp)]− (Dipp=2,6‐iPr2‐C6H3). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s‐block metal amides. Solvation by N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (PMDETA) or N,N,N′,N′‐tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi‐solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe3)(Dipp)}2(μ‐nBu)]∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies. PMID:27573676

  9. Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilino Ligand.

    PubMed

    Fuentes, M Ángeles; Zabala, Andoni; Kennedy, Alan R; Mulvey, Robert E

    2016-10-10

    Bulky amido ligands are precious in s-block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n-butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe3 )(Dipp)](-) (Dipp=2,6-iPr2 -C6 H3 ). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s-block metal amides. Solvation by N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) or N,N,N',N'-tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi-solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe3 )(Dipp)}2 (μ-nBu)]∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies.

  10. Intramolecular cycloaddition reactions of furo[3,4-b]indoles for alkaloid synthesis.

    PubMed

    Padwa, Albert; Zou, Yan; Cheng, Bo; Li, Hao; Downer-Riley, Nadale; Straub, Christopher S

    2014-04-04

    Model studies dealing with the Cu(II)- or Rh(II)-catalyzed carbenoid cyclization/cycloaddition cascade of several α-diazo indolo amido esters have been carried out as an approach to the alkaloid scandine. The Cu(II)-catalyzed reaction of an α-diazo indolo diester that contains a tethered oxa-pentenyl side chain was found to give rise to a reactive benzo[c]furan which undergoes a subsequent [4 + 2]-cycloaddition across the tethered π-bond. The reaction proceeds by the initial generation of a copper carbenoid intermediate which cyclizes onto the adjacent carbonyl group to give a reactive benzo[c]furan which in certain cases can be isolated. Disappointingly, the analogous reaction with the related amido indolo ester failed to take place, even when the tethered π-bond contained an electron-withdrawing carbomethoxy group. It would seem that the geometric requirements for the intramolecular cycloaddition of the furo[3,4-b]indole system with the tethered π-bond imposes distinct restrictions upon the bond angles of the reacting centers to prevent the cycloaddition reaction from occurring. However, the incorporation of another carbonyl group on the nitrogen atom of the tethered alkenyl diazo amido indolo ester seemingly provides better orbital overlap between the reacting π-systems and allows the desired cycloaddition reaction to occur.

  11. Low-density lipoprotein oxidation and its prevention by amidothionophosphate antioxidants.

    PubMed

    Tirosh, O; Katzhendler, J; Barenholz, Y; Kohen, R

    1999-01-01

    Amidothionophosphates (AMTPs) are a novel group of antioxidants that are lacking in pro-oxidant activity. In this paper, we compare two different amidothionophosphates: 2-hydroxy-ethyl amido, diethyl thionophosphate (AMTP-B), which contains a single primary amido group, and N,N',N-tripropylamidothionophosphate (AMTP-3A), which contains three primary amido groups. The lipoprotein/medium partition coefficients of AMTP-3A and AMTP-B are 74 and 38, respectively. Both protected isolated human low density lipoprotein (LDL) against oxidative damage induced by copper sulfate. Oxidative damage to polyunsaturated acyl chains was determined by gas chromatography (GC), and oxidation kinetics were monitored by following the accumulation of conjugated dienes spectrophotometrically at 234 nm. The AMTP antioxidants significantly protected the LDL against Cu2+-induced oxidation. However, if the LDLs were already partially oxidized, protection against oxidation by the AMTPs was reduced. AMTP-3A was more effective in protecting LDL than was AMTP-B. The difference in antioxidant activity was attributed to the 15-fold higher reactivity of AMTP-3A toward peroxides. Oxidizability of plasma lipoproteins from guinea pigs injected with AMTPs was strongly reduced.

  12. A teoria da percolação aplicada às galáxias aneladas peculiares

    NASA Astrophysics Data System (ADS)

    Poppe, P. C. R.; Martin, V. A. F.; de Medeiros, N. G. F.; Faúndez-Abans, M.; Oliveira-Abans, M.

    2003-08-01

    Formulado no final da década de 50, o modelo de percolação concentra-se em descrever o meio poroso, que será visto neste trabalho como uma rede de canais aleatórios, por onde escoa um fluido determinístico. Se o número de canais for suficientemente grande, então eles estarão ligados e o meio se tornará permeável à passagem do fluido. Neste caso, dizemos que houve a percolação do fluido. Reformulando o modelo acima, podemos escrever um código particularmente adaptado para simulações em Galáxias, onde iremos supor que os canais formam um reticulado, e que cada sítio da rede representa um poro que será interpretado como uma região ativa de formação estelar. Para cada elo teremos um pequeno canal ligando dois sítios vizinhos, que poderá, após um tempo "t", induzir ou não a formação de uma região ativa no poro vizinho. Para simular a passagem desta região ativa através dos poros, diremos que um elo está aberto com probabilidade p e fechado com probabilidade 1-p. Dessa forma, passamos a imaginar configurações de elos abertos e fechados, onde cada configuração ocorre com uma certa probabilidade, dada por p|A|(1-p)|F|, onde |A| é o número de elos abertos e |F| o número de elos fechados da configuração. A expressão anterior só tem importância física se |A| e |F| forem ambos finitos, pois, caso contrário, a probabilidade de ocorrência de uma dada configuração será sempre nula. Neste trabalho, foram considerados dados cinemáticos publicados na literatura bem como aqueles obtidos pelos autores a partir de observações fotométricas realizadas no Observatório de Las Campanãs, em 1994, para a Galáxia Anelada Peculiar HRG 03401. Mostraremos que para certos valores de p, situados entre 0,5 e 0,6, os clusters assim formados irão simular, de maneira coerente, o referido objeto.

  13. The effects of the porous buffer layer and doping with dysprosium on internal stresses in the GaInP:Dy/por-GaAs/GaAs(100) heterostructures

    SciTech Connect

    Seredin, P. V.; Gordienko, N. N.; Glotov, A. V.; Zhurbina, I. A.; Domashevskaya, E. P.; Arsent'ev, I. N. Shishkov, M. V.

    2009-08-15

    In structures with a porous buffer layer, residual internal stresses caused by a mismatch between the crystal-lattice parameters of the epitaxial GaInP alloy and the GaAs substrate are redistributed to the porous layer that acts as a buffer and is conducive to disappearance of internal stresses. Doping of the epitaxial layer with dysprosium exerts a similar effect on the internal stresses in the film-substrate structure.

  14. Communicating with Mexican Americans: Por Su Buena Salud = Communicando Con Mexico Americanos: For Their Good Health. Proceedings of the Conference (Houston, TX, September 13-14, 1979).

    ERIC Educational Resources Information Center

    Moore, Thomas J., Ed.; And Others

    The conference focused on the role of the Mexican American's cultural language, tradition, life style, health practices, and media utilization in the design of effective health education and information programs. Representing various local, state, and national health, education, and media organizations, the 108 participants attended sessions on…

  15. Unanswered Questions in Colombia's Foreign Language Education Policy (Preguntas por responder en la política educativa de lenguas extranjeras en Colombia)

    ERIC Educational Resources Information Center

    Bonilla Carvajal, Camilo Andrés; Tejada-Sánchez, Isabel

    2016-01-01

    Following the trend of much of the Western, non-English speaking world, Colombia has tirelessly strived for spreading English education in an effort to augment economic benefits. This paper aims at providing a critical account of foreign language education policy in Colombia, with special attention to English. It outlines the impact of its…

  16. Ameiridae Boeck and Argestidae Por revisited, with establishment of Parameiropsidae, a new family of Harpacticoida (Crustacea, Copepoda) from deep-sea sediments

    NASA Astrophysics Data System (ADS)

    Corgosinho, P. H. C.; Martínez Arbizu, P.

    2010-09-01

    Four new species of Parameiropsis are described from Angola and Guinea Basins and the Arctic Laptev Sea. The male of Parameiropsis poseidonicus sp. n. differs from that of P. neptuni sp. n. and P. senckenbergi sp. n. in antennule segmentation, length of the proximal aesthetasc, length of the outermost seta of the antennary endopod, degree of reduction of the mouthparts, relative length of the inner spine of the basis of thoracopod 1, shape of the furca and body length. The female of P. amphitriteae sp. n. differs from previously described females of other species in the smaller exopod and endpod of thoracopod 1, reduced armature of thoracopods 1-6, length of the outer setae of exopods and endopods of thoracopods 2-4, and mandible exopod weakly developed and fused to the basis. Parameiropsis is redefined by the following autapomorphies: presence of aesthetasc on 3rd segment of female antennule; antenna strong, with endopod curved upwardly, and shape of the outermost (strongly ornamented) spine; triangular labrum; elongated corpus mandibularis, gnathobasis very long; basis of mandibular palp unarmed; elongated maxillule, with long and flexible setae on praecoxal arthrite; basis of the maxilla with strongly modified claw. To discuss the phylogenetic position of Parameiropsis, we revaluated the subfamilies of Ameiridae (viz. Ameirinae and Stenocopiinae) and the family Argestidae. Anoplosomella and Malacopsyllus revealed to be not closely related to Ameiridae and are transferred to Argestidae, sharing with other members of this family the morphology of the mandible gnathobasis, armature of maxilla and armature and length of the first segment of the antennule. Argestoides prehensilis does not show any of the characters that we consider autapomorphic for Argestidae. Instead, it shows many characters in common with several Ameiridae species. Parameiropsis does not have any character that could justify its inclusion within Ameiridae or even within Podogennonta. It also cannot be included satisfactorily within Argestidae nor Exanechentera. Therefore, we here propose a new family for Parameiropsis, with unclear relationships within Harpacticoida. After these taxonomic rearrangements, Ameiridae and Argestidae are considered monophyletic based on certain maxilla characters that we consider autapomorphic for each group. A key to the identification of the known species of Parameiropsis is added at the end.

  17. Diseño, Construcción Y Desarrollo De Un Sistema Limitado Por Difracción Para Telescopios Terrestres: Fastcam

    NASA Astrophysics Data System (ADS)

    Lopez Lopez, Roberto

    2013-02-01

    This work describes the concept, design, development, evolution and application of the FastCam instrument. FastCam is an image photometer for astronomy with image capture in a high-frequency range and diraction limited, in order to apply the Lucky Imaging technique to medium- and large-sized ( 1.5 to 4 m) telescopes. The Lucky Imaging technique allows, for ground-based telescopes, to achieve the resolution limit for astronomical images under suitable conditions. This work describes the atmospheric problems and the active and adaptive optics techniques to solve them, as well as the Lucky Imaging fundamentals. A description of the considerations to the project development and design parameters is performed. Then, the optical design and dierent adaptations to several telescopes will be revised. In a next step, some of the scientic results obtained thanks to this project are shown, both in position astronomy and complex structures in globular cluster and binary systems. Dierent designs arising from the basic idea and the instruments now in development that are expanding the system's capabilities and the technique are explained. Some other possible applications to other elds in which the image sharpness is necessary despite uctuations or instabilities of the observing system will be also pointed out: ophthalmology, video-control, etc.

  18. Un Programa de Espanol para Colegio Universitario: Esfuerzos por Lograr una Mejor Articulacion (A Spanish Program for Colleges and Universities: Efforts to Improve Articulation).

    ERIC Educational Resources Information Center

    Latoja, Luis E.

    1996-01-01

    Describes a three-year plan for colleges and universities in which the Spanish program attempts to increase its course offerings and improve articulation within the institution. The program is designed to put into practice the goals of a regional collaborative project on articulation of which the university is an integral part. (six references)…

  19. "¿Por qué leemos esto en la clase de español?": The Politics of Teaching Literature in Spanglish

    ERIC Educational Resources Information Center

    Postma, Regan L.

    2013-01-01

    This article discusses what is at stake in teaching works written in "Spanglish" in Spanish departments and what teaching such works might mean for students and the scholarly community at large. This article primarily comes out of the author's experiences teaching "Spanglish" works in Spanish courses at a major research…

  20. Library Safari: Tips for Parents of Young Readers and Explorers = De safari por la biblioteca: Consejos para padres de lectores y exploradores jovenes.

    ERIC Educational Resources Information Center

    Clements, Aedin

    Visiting the library is a great way for parents to encourage their child's imagination and learning. It gives parents the opportunity to model good reading behavior and to show their child that they value books and reading. No matter how young the child is, a trip to the library can be an enjoyable outing for parents and their children. Most…

  1. Study of morphological characteristic of por-Si formed using metal-assisted chemical etching by BET-method and fractal geometry

    NASA Astrophysics Data System (ADS)

    Boyko, Anton N.; Pyatilova, Olga V.; Kalmykov, Rustam M.; Gaev, Dahir S.; Timoshenkov, Sergei P.; Gavrilov, Sergei A.

    2016-12-01

    Study of new materials and composites based on porous silicon is of great interest for electronics and microelectronics industry. Functional characteristics of structured layers are closely associated with their morphology properties and treatment conditions correspondently. In this work a porous silicon layers formed by metal-assisted chemical etching (MACE) with the use of gas adsorption-desorption method, scanning electron microscopy (SEM) and fractal geometry have been examined. Specific surface area given by multi-point BET method was about of 7 m2/g and 13 m2/g for n-Si and p-Si specimens correspondently. Surface fractal dimension Ds was estimated for p-type mesoporous silicon from BET results using Neimark's thermodynamic approach, the value is Ds=2.86. "Slit islands" Mandelbrot's algorithm was applied for analysis of SEM images and calculations of surface fractal dimension Ds, computation gives Ds = 2.52 for n-Si sample and Ds = 2.84 for p-Si sample. The study testified the fractal nature of porous layers formed by MACE and exhibits correlation between different methods of fractal dimension estimation. The results can be applied for improvement of methods of structured solids characterization.

  2. Realidades Suburbanas: Latinos en el Condado de Dakota. Una Investigacion Dirigida por HACER = Suburban Realities: Latinos in Dakota County. A Study Conducted by HACER.

    ERIC Educational Resources Information Center

    HACER: Hispanic Advocacy and Community Empowerment through Research, Minneapolis, MN.

    A research project was conducted between April and December of 1998 to learn about the experiences of the sizable numbers of Latinos who live in Dakota County (Minnesota). This diverse group was studied through examining existing demographic information, conducting interviews with 45 Latino and Anglo individuals, and conducting several focus…

  3. Efectos de Campos Magnéticos en las Tasas de Consumo de Madera por Coptotermes formosanus, la Termita Subterránea de Formosa.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sixty groups of 500 workers and 50 soldiers of Coptotermes formosanus were maintained in costume designed containers and fed with a piece of red oak wood (Quercus rubra). Twenty of these groups were exposed to permanent magnets with a flux of 800 G. Another 20 groups were exposed to a permanent mag...

  4. Comparacion de modelos de Educacion Sexual en el conocimiento y cambio de actitudes en practicas sexuales por alumnos de nivel superior en la region de Caguas, Puerto Rico

    NASA Astrophysics Data System (ADS)

    Juan, Vallejo Ramos L.

    In opposition to the Sexual Education Traditional Model (SETM) that is used in the state schools of Puerto Rico, the Health Beliefs Model (HBM) appears. It facilitates a curricular design that improves the ability of the students to respond to the group pressure by means of attitudes that stimulate sexual conducts of smaller risk of propagation of the Sexually Transmitted Diseases (STD). In addition, it provides activities to increase the self-esteem, the communication and the decision making. This investigation had the intention to compare the SETM and the HBM in the increase of knowledge and change of attitudes of high risk of propagation of the STD using a validated questionnaire (Agency of the United States for the International-USAID Development), named "Endesa 2007" and, adapted to Puerto Rico by the Dra.Marta Collazo to a sample of students between the 17 and 19 years of 2 state schools of San Lorenzo, as a pretest, and, selected by convenience. Then, a 10 hours training was administered to half of the students using the SETM to STD and condom use lessons. The other half of the students received additional lessons using the HBM. Finally, both groups took the questionnaire again as a posttest. The sample of students, in average, did not reach the knowledge and basic levels of attitudes towards the STD in the pretest. This reflected 2 possible implications on the SETM. In first place, that the way in which the STD is implemented as part of the Sexual Education curriculum is inefficient. Secondly, the possibility that the acquired information or attitudes does not have permanence. Culminated the questionnaire, the HBM increase the knowledge of the STD in 0.41 points (average) over the SETM. There was not a significant difference between both models, in attitudes, implying that both models are equally effective. The findings suggests that the HBM is more effective increasing the knowledge on the STD, but equally effective than the SETM in attitude change for the Puerto Rican youth.

  5. The HoMBReS and HoMBReS Por un Cambio Interventions to Reduce HIV Disparities Among Immigrant Hispanic/Latino Men.

    PubMed

    Rhodes, Scott D; Leichliter, Jami S; Sun, Christina J; Bloom, Fred R

    2016-02-12

    Hispanics/Latinos in the United States are affected disproportionately by human immunodeficiency virus (HIV) infection, acquired immunodeficiency syndrome (AIDS), and other sexually transmitted diseases (STDs); however, few effective evidence-based prevention interventions for this population exist. This report describes the Hombres Manteniendo Bienestar y Relaciones Saludables (Men Maintaining Wellbeing and Healthy Relationships) (HoMBReS) intervention, which was developed by a community-based, participatory research partnership in North Carolina and initially implemented during 2005-2009. HoMBReS is an example of an effective intervention that uses lay health advisors (known as Navegantes [navigators]) in the context of existing social networks (i.e., recreational soccer teams) to promote consistent condom use and HIV and STD testing among Hispanic/Latino men. In 2012, HoMBReS was classified as a best-evidence community-level HIV prevention intervention (CDC. Compendium of evidence-based behavioral interventions and best practices for HIV prevention. Atlanta, GA: US Department of Health and Human Services, CDC; 2015). The intervention has been implemented elsewhere, enhanced, and further evaluated in longitudinal intervention and implementation studies. HoMBReS has been adapted for other populations, including men who have sex with men and transgender persons. Additional evaluation has found that Navegantes continue in their roles as health advisors, opinion leaders, and community advocates after study support ends. Hispanic/Latino men's social networks can be leveraged to promote sexual health within the community by decreasing HIV risk behaviors among Hispanics/Latinos in the United States.

  6. The HoMBReS and HoMBReS Por un Cambio Interventions to Reduce HIV Disparities Among Immigrant Hispanic/Latino Men

    PubMed Central

    Rhodes, Scott D.; Leichliter, Jami S.; Sun, Christina J.; Bloom, Fred R.

    2016-01-01

    Summary Hispanics/Latinos in the United States are affected disproportionately by human immunodeficiency virus (HIV) infection, acquired immunodeficiency syndrome (AIDS), and other sexually transmitted diseases (STDs); however, few effective evidence-based prevention interventions for this population exist. This report describes the Hombres Manteniendo Bienestar y Relaciones Saludables (Men Maintaining Wellbeing and Healthy Relationships) (HoMBReS) intervention, which was developed by a community-based, participatory research partnership in North Carolina and initially implemented during 2005–2009. HoMBReS is an example of an effective intervention that uses lay health advisors (known as Navegantes [navigators]) in the context of existing social networks (i.e., recreational soccer teams) to promote consistent condom use and HIV and STD testing among Hispanic/Latino men. In 2012, HoMBReS was classified as a best-evidence community-level HIV prevention intervention (CDC. Compendium of evidence-based behavioral interventions and best practices for HIV prevention. Atlanta, GA: US Department of Health and Human Services, CDC; 2015). The intervention has been implemented elsewhere, enhanced, and further evaluated in longitudinal intervention and implementation studies. HoMBReS has been adapted for other populations, including men who have sex with men and transgender persons. Additional evaluation has found that Navegantes continue in their roles as health advisors, opinion leaders, and community advocates after study support ends. Hispanic/Latino men’s social networks can be leveraged to promote sexual health within the community by decreasing HIV risk behaviors among Hispanics/Latinos in the United States. PMID:26916740

  7. "Pig in a poke (gato por liebre)": the "mota" (Calophysus macropterus) fishery, molecular evidence of commercialization in Colombia and toxicological analyses.

    PubMed

    Salinas, Cristian; Cubillos, Juan Camilo; Gómez, Rigoberto; Trujillo, Fernando; Caballero, Susana

    2014-06-01

    Overfishing has affected the population abundance trends of many commercial fish species. In the Amazon, the fishery of a catfish commonly known as "mota" or "piracatinga" (Calophysus macropterus) has become an important economic activity in the region as this species has replaced a number of other overexploited great catfish species in the markets. Due to this high exploitation, ways in which to increase captures have been identified. One strategy is to use decomposing animal carcasses as bait. Such strategy has increased the hunting pressure on endangered species such as caimans and river dolphins. We investigated which catfish species are currently commercialized in Colombian fish markets using DNA barcoding, and measured mercury concentration in the tissues of fish molecularly identified as C. macropterus. We collected 86 fish samples in markets of four Colombian cities. Sixty-eight of these were identified molecularly as C.macropterus. The mercury concentration of 29 such samples was analyzed. Samples presented total Hg concentrations higher than the limit for human consumption established by the WHO (0.5 μg/g). These results are worrisome and suggest that (1) C. macropterus is a widely used fish species for human consumption in Colombia and (2) C. macropterus has high concentrations of total Hg, making its consumption a public health risk. Results presented here suggest that C. macropterus has replaced capaz in most Colombian markets. This fishery threatens wild species of river dolphins and caimans, and is also a public health risk given the high mercury levels we found in a subsample of these fishes.

  8. Comparacion de Modelos de Educacion Sexual en El Conocimiento y Cambio de Actitudes en Practicas Sexuales por Alumnos de Nivel Superior en La Region De Caguas, Puerto Rico

    ERIC Educational Resources Information Center

    Juan, Vallejo Ramos L.

    2012-01-01

    In opposition to the Sexual Education Traditional Model (SETM) that is used in the state schools of Puerto Rico, the Health Beliefs Model (HBM) appears. It facilitates a curricular design that improves the ability of the students to respond to the group pressure by means of attitudes that stimulate sexual conducts of smaller risk of propagation of…

  9. (2,3,7,8,12,13,17,18-Octa­ethyl­por­phin­ato)(trifluoro­methane­sulfonato)iron(III)

    PubMed Central

    Xu, Nan; Powell, Douglas R.; Richter-Addo, George B.

    2008-01-01

    The title compound, [Fe(CF3O3S)(C36H44N4)], is an iron(III) porphyrin complex with the trifluoro­methane­sulfonate anion as an axial ligand. The Fe atom is displaced by 0.219 (2) Å toward the trifluoro­methane­sulfonate anion from the 24-atom mean plane of the porphyrin, resulting in a distorted FeN4O square-based pyramidal geometry. One ethyl­ene group is disordered over two orientations in a 0.502 (6):0.498 (6) ratio. PMID:21580825

  10. The Department of Defense’s Transition of Program of Record (POR) Systems from Internet Protocol Version Four (IPv4) to Internet Protocol Version Six (IPv6)

    DTIC Science & Technology

    2006-12-01

    Protocol IA Information Assurance IANA Internet Assigned Numbers Authority ICANN Internet Corporation for Assigned Names and Numbers ICE... ICANN ) is responsible for the global coordination of the Internet’s system of unique identifiers. Unique identifies include domain names like .org...or .museum, and country codes such as .UK .IE. Any new RIR shall, on recognition by ICANN receive an IPv6 allocation from the IANA. A RIR is

  11. Datação do disco galáctico pela nucleocosmocronologia do [Th/Eu

    NASA Astrophysics Data System (ADS)

    del Peloso, E. F.; da Silva, L.; Arany-Prado, L. I.

    2003-08-01

    A nucleocosmocronologia emprega abundâncias de nuclídeos radioativos na datação de escalas de tempo astrofísicas. O 232Th é um nuclídeo radioativo com meia-vida de 14 Gano, enquanto que os dois isótopos mais abundantes do Eu são estáveis. O decaimento radioativo do Th modifica as razões de abundâncias [Th/Eu], fornecendo assim um meio de sondar a escala de formação das populações estelares. O objetivo deste trabalho é averiguar a possibilidade de estimar uma idade para o disco Galáctico através da nucleocosmocronologia do [Th/Eu] e investigar o nível de incerteza associado a esta estimativa. Para tanto, foi selecionada uma amostra de 20 estrelas anãs ou subgigantes de tipos espectrais F5 a G9, com -1,00 £ [Fe/H] £ +0,30 e idade(Gano) £ 13. As abundâncias de Th e Eu foram obtidas por síntese espectral das linhas localizadas em 4019,1 Å e 4129,7 Å, respectivamente. Uma comparação destas abundâncias com outros resultados da literatura demonstra que nossos valores apresentam dispersão 2 a 3 vezes menor que qualquer trabalho anterior. Os parâmetros atmosféricos e abundâncias dos elementos que contaminam as regiões espectrais destas linhas foram determinados por nós, de maneira totalmente autoconsistente, através de análise espectral detalhada diferencial em relação ao Sol. As idades estelares individuais foram determinadas através de curvas isócronas teóricas no diagrama HR. Foi realizada, então, uma análise cronológica dos gráficos [Th/Eu] vs. [Fe/H] e [Th/Eu] vs. idade. Os dados estelares foram comparados a curvas calculadas para 3 idades do disco Galáctico - 9, 12, 15 Gano - e foi estudada a sensibilidade à idade assumida no cálculo do ajuste destas curvas aos dados. Estas curvas foram calculadas com base num modelo analítico de evolução química da Galáxia que leva em consideração a formação de refugos, que são compostos pelos remanescentes da evolução estelar, pelos resíduos da formação de estrelas de

  12. Discos de acresção em sistemas Be-X

    NASA Astrophysics Data System (ADS)

    Lopes de Oliveira, R.; Janot-Pacheco, E.

    2003-08-01

    Alguns fenômenos de outbursts em Be-X sugerem a existência, mesmo que temporária, de um disco de acresção quando da passagem do objeto compacto pelo periastro orbital. Neste trabalho avaliamos a possibilidade de formação do disco de acresção em sistemas Be+estrela de neutrons e Be+anã branca, e a influência da excentricidade orbital na ocorrência deste fenômeno. Utilizamos a expressão analítica para o momento angular específico da matéria constituinte de um meio em expansão lenta, como é o caso do disco circunstelar das estrelas Be, proposta por Wang(1981), sob a condição básica de que o raio de circularização deva ser maior do que o raio de Alfvén. Concluímos que existe um limite para o período orbital do sistema acima do qual não é possível a formação do disco de acresção, e que este valor aumenta para sistemas com excentricidade orbital maior.

  13. Laryngeal complications by orotracheal intubation: Literature review.

    PubMed

    Mota, Luiz Alberto Alves; de Cavalho, Glauber Barbosa; Brito, Valeska Almeida

    2012-04-01

    Introdução: As lesões causadas pela intubação orotraqueal são comuns no nosso meio e amplamente relatadas pela literatura. Geralmente são causadas por acidentes na colocação do tubo ou consequência de sua permanência nas vias aéreas do paciente. Há diversos tipos de lesões laríngeas, causadas por múltiplos mecanismos.Objetivo: Verificar, na literatura, as principais causas de complicações laríngeas pós-intubação orotraqueal e seus mecanismos de lesão.Revisão de Literatura: As bases de dados pesquisadas foram LILACS, BIREME e SCIELO. Foram utilizados artigos, livros e teses, delimitando-se o período entre 1953 a 2009. As palavras-chaves utilizadas para a busca dos artigos foram: complicações, lesões, laringe, intubação, entubação, endotraqueal, orotraqueal, granulomas, estenose. Foram selecionadas 59 referências. Os critérios de inclusão utilizados para a escolha dos artigos foram os que mostraram os diversos tipos de lesões ocasionadas pela intubação orotraqueal e suas fisiopatologias.Considerações Finais: Esta revisão de literatura foi motivada pela observação na prática clínica de um grande número de sequelas laríngeas em pacientes submetidos à intubação orotraqueal. Diante disto é importante o conhecimento, pelos profissionais da área de saúde, dos tipos de complicações e de suas causas, com o intuito de evitá-las, adotando medidas de prevenção dessas lesões.

  14. Investigação dos perfís temporais de alta resolução de explosões solares tipo-III decimétricas

    NASA Astrophysics Data System (ADS)

    Cecatto, J. R.; Fernandes, F. C. R.; Sawant, H. S.; Madsen, F. R. H.

    2003-08-01

    Explosões solares tipo-III indicam a presença de feixes de elétrons acelerados durante "flares" solares. Sua investigação fornece informações tanto sobre os processos de aceleração de partículas quanto das características do agente causador e do local de aceleração. Explosões tipo-III decimétricas são geradas por feixes de elétrons viajando através de arcos magnéticos densos da baixa coroa solar. Os perfís temporais destes fenômenos, quando tomados com alta resolução, informam sobre os mecanismos de aceleração de partículas do feixe e o meio de transporte da energia liberada a partir da região de aceleração. Usando o Brazilian Solar Spectroscope (BSS), em operação no INPE, foram registradas dezenas de explosões tipo-III decimétricas, dentro da faixa de 2050-2250 MHz com alta resolução temporal (20 ms), em 13 de setembro de 2001, entre 13:00 e 16:10 UT. Foram selecionadas 10 explosões isoladas para uma investigação estatística detalhada de seus perfís temporais, em todos os cerca de 50 canais de freqüência. Os resultados indicam que cerca de 70% dos perfís temporais são complexos tanto durante a subida quanto descida. Os 30% restantes indicam que os perfís da subida podem ser bem representados, na maioria dos casos, por um processo não-linear e uma parcela significativa por processos lineares. Os perfís temporais da descida são dominados por um decaimento não-linear. Neste trabalho, será efetuada uma análise dos perfís temporais, tanto durante a subida quanto descida do fluxo, para as explosões selecionadas, em termos dos prováveis mecanismos de aceleração e relaxamento. 2

  15. Precessão do jato de 3C120: simulações hidrodinâmicas 3D

    NASA Astrophysics Data System (ADS)

    Caproni, A.; de Gouveia dal Pino, E. M.; Abraham, Z.; Raga, A. C.

    2003-08-01

    Observações com técnicas de interferometria com longa linha de base têm mostrado a existência de um jato relativístico com componentes superluminais na região central de 3C 120. Estas componentes são ejetadas em distintas direções no plano do céu e com diferentes velocidades aparentes. Estas características foram interpretadas em trabalhos anteriores como efeitos da precessão do jato relativístico. Neste trabalho, realizamos simulações tri-dimensionais do jato de 3C 120 utilizando os parâmetros de precessão determinados em trabalhos anteriores e variando as características iniciais do jato e meio ambiente, tais como densidade numérica e temperatura. Todas as simulações foram feitas com o código hidrodinâmico YGUAZÚ-A, assumindo-se um jato adiabático descrito por uma equação de estado relativística. Pelo fato de estarmos utilizando um código hidrodinâmico, nós assumimos que a intensidade do campo magnético e a distribuição de partículas, necessários para se calcular a emissão sincrotron, são proporcionais à pressão hidrodinâmica. Comparação entre dois cenários distintos, nos quais o material do jato é ejetado com velocidade constante (jato contínuo) e com velocidade modulada por um padrão sinusoidal no tempo (jato intermitente), é apresentada e discutida. Para jatos que apresentam fenômenos de precessão e intermitência, com amplitude de variação na velocidade de injeção maior que dez por cento da velocidade média de injeção, a hipótese balística, controlada pela intermitencia, é mais provável. Por outro lado, para jatos com precessão mas sem intermitência (ou com amplitude de variabilidade em velocidade mais baixa que no caso anterior), o efeito da precessão na morfologia do jato não é desprezível. Portanto, de um modo geral, ambos efeitos (precessão e movimentos balísticos) devem estar concorrendo para afetar a morfologia dos jatos superluminais.

  16. Exploring the recovery and detection of messenger RNA and DNA from enhanced fingermarks in blood.

    PubMed

    Fox, A; Gittos, M; Harbison, S A; Fleming, R; Wivell, R

    2014-05-01

    Often in the examination of bloodstained fingermarks discussion occurs around whether to prioritise the fingerprint evidence or focus on the biological evidence. Collecting a sample for genetic profiling may result in the loss of ridge detail that could have been used for fingerprint comparison. Fingermark enhancement and recovery methods along with sample collection methods could also compromise downstream genetic analysis. Previous forensic casework has highlighted circumstances where, after enhancement had been performed, it would have been extremely valuable to both identify the body fluid and generate a DNA profile from the same sample. We enhanced depletion series of fingermarks made in blood, using single treatments consisting of aqueous amido black, methanol-based amido black, acid yellow and leucocrystal violet, and exposure to long wave UV light. We then extracted the DNA and RNA for profiling, to assess the recovery and detection of genetic material from the enhanced fingermarks. We have shown that genetic profiling of bloodstained fingermarks can be successful after chemical enhancement; however it may still be necessary to prioritise evidence types in certain circumstances. From our results it appears that even with visible bloodstained fingermarks, leucocrystal violet can reduce the effectiveness of subsequent messenger RNA profiling. Aqueous amido black and acid yellow also have adverse effects on messenger RNA profiling of depleted fingermarks with low levels of cellular material. These results help with forensic decision-making by expanding knowledge of the extent of the detrimental effects of blood-enhancement reagents on both DNA profiling and body fluid identification using messenger RNA profiling.

  17. Organogels based on J- and H-type aggregates of amphiphilic perylenetetracarboxylic diimides.

    PubMed

    Wu, Haixia; Xue, Lin; Shi, Yan; Chen, Yanli; Li, Xiyou

    2011-03-15

    Three new perylenetetracarboxylic diimide (PDI) compounds substituted with hydrophobic and/or hydrophilic groups at the two imide nitrogen positions, namely N,N'-di[N-(4-aminophenyl)-3,4,5-tris(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)benzamide]-1,7-di(4-tert-butylphenoxy)perylene-3,4;9,10-tetracarboxylic diimide (1), N,N'-di[N-amido-3,4,5-tris(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)benzamide]-1,7-di(4-tert-butylphenoxy)perylene-3,4;9,10-tetracarboxylic diimide (2), and N-amido-3,4,5-tris(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)benzamide-N'-amido-3,4,5-tris(dodecyloxy)benzamide-1,7-di(4-tert-butylphenoxy)perylene-3,4;9,10-tetracarboxylate diimide (3), have been designed and prepared. The gelating abilities of them in different solvents have been investigated, and the results indicated that compounds 1 and 3 can form fluorescent gels whereas compound 2 cannot. The properties of the gels of compounds 1 and 3 have been investigated by UV-vis absorption and emission spectra. The results indicate that the gel of compound 1 is composed of H-aggregates, whereas the gel of compound 3 is composed of J-aggregates. The reversible transformation between gel and solution states induced by temperature change is observed. The structure of dried gel has been investigated by X-ray diffraction (XRD) experiments, and the morphology has been measured by atomic force microscopy (AFM). This research revealed successfully the crucial roles of amphiphilic properties and the side-chain conformations in controlling the gelating properties of PDI molecules. This information may be useful for the design of novel organogels based on perylenetetracarboxylic diimides.

  18. Enzyme action in the regulation of plant hormone responses.

    PubMed

    Westfall, Corey S; Muehler, Ashley M; Jez, Joseph M

    2013-07-05

    Plants synthesize a chemically diverse range of hormones that regulate growth, development, and responses to environmental stresses. The major classes of plant hormones are specialized metabolites with exquisitely tailored perception and signaling systems, but equally important are the enzymes that control the dose and exposure to the bioactive forms of these molecules. Here, we review new insights into the role of enzyme families, including the SABATH methyltransferases, the methylesterases, the GH3 acyl acid-amido synthetases, and the hormone peptidyl hydrolases, in controlling the biosynthesis and modifications of plant hormones and how these enzymes contribute to the network of chemical signals responsible for plant growth, development, and environmental adaptation.

  19. Suicide Inhibitors of Reverse Transcriptase in the Therapy of AIDS and Other Retroviruses

    DTIC Science & Technology

    1989-07-01

    Acquired Immun Deficiency Syndrome (AIDS) (7-8). The most recent evaluation of the AIDS epidemic in the U.S. (4) indicates that the currer total of...are shown below. One of the first, [N-(L-3-tran carboxyxiran-2-carbonyl)-L-leucyl]-amido (4-guanido) butane was isolated from Asperg /II japonicus and...risk of acquired immune deficiency syndrome (AIDS). Science. 2.4: 497- 500 (1983). 9. Kopkrowski H., De Freitas E.C., Harper M.E., Woliheim S.M

  20. Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution. 2: Polycondensations

    NASA Technical Reports Server (NTRS)

    Kolb, Vera; Orgel, Leslie E.

    1995-01-01

    We have prepared a (P-32)-labeled oligonucleotide probe carrying a ureido (-NH-CO-NH2) function at its 3'-terminus. This labeled oligomer was used to study polycondensations of urea and formaldehyde and of various phenols and formaldehyde in aqueous solution. The formation of formaldehyde copolymers attached to the amido-function of the probe was monitored by gel electrophoresis. Our results are generally in agreement with those obtained using conventional techniques. Our method is suitable for monitoring potentially prebiotic polycondensation reactions involving formaldehyde.

  1. Homolytic N–H Activation of Ammonia: Hydrogen Transfer of Parent Iridium Ammine, Amide, Imide, and Nitride Species

    PubMed Central

    2015-01-01

    The redox series [Irn(NHx)(PNP)] (n = II–IV, x = 3–0; PNP = N(CHCHPtBu2)2) was examined with respect to electron, proton, and hydrogen atom transfer steps. The experimental and computational results suggest that the IrIII imido species [Ir(NH)(PNP)] is not stable but undergoes disproportionation to the respective IrII amido and IrIV nitrido species. N–H bond strengths are estimated upon reaction with hydrogen atom transfer reagents to rationalize this observation and are used to discuss the reactivity of these compounds toward E–H bond activation. PMID:26192601

  2. A Nanocrystal-based Ratiometric pH Sensor for Natural pH Ranges.

    PubMed

    Somers, Rebecca C; Lanning, Ryan M; Snee, Preston T; Greytak, Andrew B; Jain, Rakesh K; Bawendi, Moungi G; Nocera, Daniel G

    A ratiometric fluorescent pH sensor based on CdSe/CdZnS nanocrystal quantum dots (NCs) has been designed for biological pH ranges. The construct is formed from the conjugation of a pH dye (SNARF) to NCs coated with a poly(amido amine) (PAMAM) dendrimer. The sensor exhibits a well-resolved ratio response at pH values between 6 and 8 under linear or two-photon excitation, and in the presence of a 4% bovine serum albumin (BSA) solution.

  3. Microwave-Assisted Synthesis of 2-Aryl-2-oxazolines, 5,6-Dihydro-4H-1,3-oxazines, and 4,5,6,7-Tetrahydro-1,3-oxazepines.

    PubMed

    Mollo, María C; Orelli, Liliana R

    2016-12-02

    The first general procedure for the synthesis of 5- to 7-membered cyclic iminoethers by microwave-assisted cyclization of ω-amido alcohols promoted by polyphosphoric acid (PPA) esters is presented. 2-Aryl-2-oxazolines and 5,6-dihydro-4H-1,3-oxazines were efficiently prepared using ethyl polyphosphate/CHCl3. Trimethylsilyl polyphosphate in solvent-free conditions allowed for the synthesis of hitherto-unreported 4,5,6,7-tetrahydro-1,3-oxazepines. The method involves good to excellent yields and short reaction times.The reaction mechanism and the role of PPA esters were investigated in a chiral substrate.

  4. Chemical rate model for the surface pyrolysis of tetrakis(dimethylamido)titanium to form titanium nitride films

    NASA Astrophysics Data System (ADS)

    Toprac, Anthony J.; Iacoponi, John A.; Littau, Karl A.

    1998-09-01

    A chemical kinetic rate model for the deposition of titanium nitride films from the surface reaction of tetrakis(dimethyl-amido)titanium (TDMAT) was developed. Without ammonia addition, TDMAT forms a titanium nitride film by pyrolyzing on the hot substrate surface. Experimental data from the applied materials 5000 deposition tool was modeled using a CSTR formulation. With the parameters of the surface reaction model regressed to fit portions of the experimental results, reasonably accurate model predictions over the entire domain of experimental data were obtained.

  5. Gas-Phase Intramolecular Cyclization of Argentinated N-Allylbenzamides

    NASA Astrophysics Data System (ADS)

    Sun, Hezhi; Chai, Yunfeng; Jin, Zhe; Sun, Cuirong; Pan, Yuanjiang

    2015-05-01

    The fragmentations of argentinated N-allylbenzamides have been exhaustively studied through collision-induced dissociation and through deuterium labeling. The intriguing elimination of AgOH is certified as the consequence of intramolecular cyclization between terminal olefin and carbonyl carbon following proton transfer to carbonyl oxygen, rather than simple enolization of amide. Linear free energy correlations and density functional theory (DFT) calculations were performed to understand the competitive relationship between AgOH loss and AgH loss, which results from the 1,2-elimination of α-hydrogen (to the amido nitrogen) with the silver.

  6. Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution: II. Polycondensations

    NASA Technical Reports Server (NTRS)

    Kolb, V.; Orgel, L. E.

    1995-01-01

    We have prepared a [32P]-labeled oligonucleotide probe carrying a ureido (-NH-CO-NH2) function at its 3'-terminus. This labeled oligomer was used to study polycondensations of urea and formaldehyde and of various phenols and formaldehyde in aqueous solution. The formation of formaldehyde copolymers attached to the amido-function of the probe was monitored by gel electrophoresis. Our results are generally in agreement with those obtained using conventional techniques. Our method is suitable for monitoring potentially prebiotic polycondensation reactions involving formaldehyde.

  7. Polyamine sensitization in offshore workers handling drilling muds.

    PubMed

    Ormerod, A D; Wakeel, R A; Mann, T A; Main, R A; Aldridge, R D

    1989-11-01

    Oil-based mud, a complex mixture containing amines in emulsifiers, is used in offshore drilling operations. It is a skin irritant that occasionally gives rise to allergic contact sensitivity. In patch testing patients with allergy to drilling mud, we have identified polyamine (diethylenetriamine and triethylenetetramine) sensitivity in 5 patients. All 5 patients were also allergic to emulsifiers. These emulsifiers are cross-linked fatty acid amido-amines, in which unreacted amine groups are thought to cross-sensitize with these constituent polyamines. Cross-reactivity between ethylenediamine, diethylenetetramine and triethylenetetramine was found in 9 subjects.

  8. Palladium(II)-catalyzed ortho-C-H arylation/alkylation of N-benzoyl α-amino ester derivatives.

    PubMed

    Misal Castro, Luis C; Chatani, Naoto

    2014-04-14

    The palladium-catalyzed arylation/alkylation of ortho-C-H bonds in N-benzoyl α-amino ester derivatives is described. In such a system both the NH-amido and the CO2R groups in the α-amino ester moieties play a role in successful C-H activation/C-C bond formation using iodoaryl coupling partners. A wide variety of functional groups and electron-rich/deficient iodoarenes are tolerated. The yields obtained range from 20 to 95%.

  9. A Nanocrystal-based Ratiometric pH Sensor for Natural pH Ranges

    PubMed Central

    Somers, Rebecca C.; Lanning, Ryan M.; Snee, Preston T.; Greytak, Andrew B.; Jain, Rakesh K.

    2014-01-01

    Summary A ratiometric fluorescent pH sensor based on CdSe/CdZnS nanocrystal quantum dots (NCs) has been designed for biological pH ranges. The construct is formed from the conjugation of a pH dye (SNARF) to NCs coated with a poly(amido amine) (PAMAM) dendrimer. The sensor exhibits a well–resolved ratio response at pH values between 6 and 8 under linear or two–photon excitation, and in the presence of a 4% bovine serum albumin (BSA) solution. PMID:26413260

  10. Hyperbranched chelating polymers for the polymer-assisted ultrafiltration of boric acid

    SciTech Connect

    Smith, B.M.; Todd, P.; Bowman, C.N.

    1999-07-01

    Two hyperbranched chelating polymers, glucoheptonamide derivatives of dendrimetric poly(amido amine) and poly(ethylene imine), were employed in polymer-assisted ultrafiltration and concentration of boron from aqueous feed streams. For feeds containing approximately 1 mM B (10 ppm), volume reduction factors of 20 were observed in cyclic adsorption-desorption. The concentrations of both polymers declined due to permeation through an ultrafiltration membrane with pore sizes which should have retained them. Acid-catalyzed hydrolysis of the amide linkages between the polymer backbone and the chelating side groups is implicated in this loss of polymer mass and effectiveness.

  11. Mechanism of the alternating copolymerization of epoxides and CO2 using beta-diiminate zinc catalysts: evidence for a bimetallic epoxide enchainment.

    PubMed

    Moore, David R; Cheng, Ming; Lobkovsky, Emil B; Coates, Geoffrey W

    2003-10-01

    A series of zinc beta-diiminate (BDI) complexes and their solid-state structures, solution dynamics, and copolymerization behavior with CO(2) and cyclohexene oxide (CHO) are reported. Stoichiometric reactions of the copolymerization initiation steps show that zinc alkoxide and bis(trimethylsilyl)amido complexes insert CO(2), whereas zinc acetates react with CHO. [(BDI-2)ZnOMe](2) [(BDI-2) = 2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene] and (BDI-1)ZnO(i)Pr [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene] react with CO(2) to form [(BDI-2)Zn(mu-OMe)(mu,eta(2)-O(2)COMe)Zn(BDI-2)] and [(BDI-1)Zn(mu,eta(2)-O(2)CO(i)Pr)](2), respectively. (BDI-2)ZnN(SiMe(3))(2) inserts CO(2) and eliminates trimethylsilyl isocyanate to give [(BDI-2)Zn(mu-OSiMe(3))](2). [(BDI-7)Zn(mu-OAc)](2) [(BDI-7) = 3-cyano-2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene] reacts with 1.0 equiv of CHO to yield [(BDI-7)Zn(mu,eta(2)-OAc)(mu,eta(1)-OCyOAc)Zn(BDI-7)]. Under typical polymerization conditions, rate studies on the copolymerization exhibit no dependence in [CO(2)], a first-order dependence in [CHO], and orders in [Zn](tot) ranging from 1.0 to 1.8 for [(BDI)ZnOAc] complexes. The copolymerizations of CHO (1.98 M in toluene) and 300 psi CO(2) at 50 degrees C using [(BDI-1)ZnOAc] and [(BDI-2)ZnOAc] show orders in [Zn](tot) of 1.73 +/- 0.06 and 1.02 +/- 0.03, respectively. We propose that two zinc complexes are involved in the transition state of the epoxide ring-opening event.

  12. Gold-Catalyzed β-Regioselective Formal [3 + 2] Cycloaddition of Ynamides with Pyrido[1,2-b]indazoles: Reaction Development and Mechanistic Insights.

    PubMed

    Yu, Yinghua; Chen, Gui; Zhu, Lei; Liao, Yun; Wu, Yufeng; Huang, Xueliang

    2016-09-16

    Here, we report an unprecedented gold(I)-induced β-site regioselective formal [3 + 2] cycloaddition of ynamides with pyrido[1,2-b]indazoles, giving 3-amido-7-(pyrid-2'-yl)indoles in good to excellent yields. A complex of gold(I) catalyst with ynamide was isolated and characterized by X-ray diffraction analysis for the first time. Mechanistic investigations suggest the reaction pathway involves a gold-stabilized carbocation intermediate, which in turn participated in sequential C-H bond functionalization of the ortho-position of the phenyl ring.

  13. Abundâncias de oxigênio e enxofre nas estrelas de tipo solar da vizinhança solar

    NASA Astrophysics Data System (ADS)

    Requeijo, F.; Porto de Mello, G. F.

    2003-08-01

    Alguns resultados sugerem que o Sol seja 58% mais abundante em oxigênio que o meio interestelar local. Esta anomalia parece estender-se para o carbono e o criptônio. Entre as possíveis explicações deste fenômeno estão: uma supernova de tipo II que tenha enriquecido a nebulosa protosolar, tornando-a superabundante em oxigênio; um episódio de infall de material pobre em metais sobre o disco Galático, diluindo o meio interestelar local ou uma migração dinâmica do Sol de uma órbita mais interna da Galáxia para sua posição atual. A escolha entre estes cenários exige o conhecimento preciso da abundância solar em relação às anãs G da vizinhança. Neste contexto, o oxigênio e enxofre, são elementos-chave por serem ambos produzidos pelas supernovas de tipo II, devendo portanto possuir o mesmo padrão de abundância. Este projeto visa esclarecer qual a posição do Sol na distribuição local de abundâncias de enxofre e oxigênio para uma amostra de estrelas de tipo solar com idades e metalicidades bem conhecidas. Para tal, analisamos espectros de alta resolução e alta relação sinal-ruído nas regiões espectrais de ll 6300, 7774 (O) e l8695 (S). Para o enxofre encontramos que o Sol parece ser uma estrela típica dentre as da vizinhança, e que este elemento não mostra a sobreabundância para baixas metalicidades, já bem estabelecida para o oxigênio. Discutimos as abundâncias do enxofre no contexto da Evolução Química da Galáxia. Apresentamos resultados preliminares muito precisos para a linha proibida do oxigênio l6300 e comparamos estes com os obtidos para o tripleto em l7774. Quantificamos os efeitos não-ETL presentes no tripleto em função dos parâmetros atmosféricos estelares.

  14. Identification, Expression and IAA-Amide Synthetase Activity Analysis of Gretchen Hagen 3 in Papaya Fruit (Carica papaya L.) during Postharvest Process

    PubMed Central

    Liu, Kaidong; Wang, Jinxiang; Li, Haili; Zhong, Jundi; Feng, Shaoxian; Pan, Yaoliang; Yuan, Changchun

    2016-01-01

    Auxin plays essential roles in plant development. Gretchen Hagen 3 (GH3) genes belong to a major auxin response gene family and GH3 proteins conjugate a range of acylsubstrates to alter the levels of hormones. Currently, the role of GH3 genes in postharvest physiological regulation of ripening and softening processes in papaya fruit is unclear. In this study, we identified seven CpGH3 genes in a papaya genome database. The CpGH3.1a, CpGH3.1b, CpGH3.5, CpGH3.6, and CpGH3.9 proteins were identified as indole-3-acetic acid (IAA)-specific amido synthetases. We analyzed the changes in IAA-amido synthetase activity using aspartate as a substrate for conjugation and found a large increase (over 5-fold) during the postharvest stages. Ascorbic acid (AsA) application can extend the shelf life of papaya fruit. Our data showed that AsA treatment regulates postharvest fruit maturation processes by promoting endogenous IAA levels. Our findings demonstrate the important role of GH3 genes in the regulation of auxin-associated postharvest physiology in papaya. PMID:27812360

  15. Understanding the bonding nature of uranyl ion and functionalized graphene: a theoretical study.

    PubMed

    Wu, Qun-Yan; Lan, Jian-Hui; Wang, Cong-Zhi; Xiao, Cheng-Liang; Zhao, Yu-Liang; Wei, Yue-Zhou; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-03-20

    Studying the bonding nature of uranyl ion and graphene oxide (GO) is very important for understanding the mechanism of the removal of uranium from radioactive wastewater with GO-based materials. We have optimized 22 complexes between uranyl ion and GO applying density functional theory (DFT) combined with quasi-relativistic small-core pseudopotentials. The studied oxygen-containing functional groups include hydroxyl, carboxyl, amido, and dimethylformamide. It is observed that the distances between uranium atoms and oxygen atoms of GO (U-OG) are shorter in the anionic GO complexes (uranyl/GO(-/2-)) compared to the neutral GO ones (uranyl/GO). The formation of hydrogen bonds in the uranyl/GO(-/2-) complexes can enhance the binding ability of anionic GO toward uranyl ions. Furthermore, the thermodynamic calculations show that the changes of the Gibbs free energies in solution are relatively more negative for complexation reactions concerning the hydroxyl and carboxyl functionalized anionic GO complexes. Therefore, both the geometries and thermodynamic energies indicate that the binding abilities of uranyl ions toward GO modified by hydroxyl and carboxyl groups are much stronger compared to those by amido and dimethylformamide groups. This study can provide insights for designing new nanomaterials that can efficiently remove radionuclides from radioactive wastewater.

  16. Liquid chromatography tandem mass spectrometry analysis of photodegradation of a diazo compound: a mechanistic study.

    PubMed

    Meetani, M A; Hisaindee, S M; Abdullah, F; Ashraf, S S; Rauf, M A

    2010-06-01

    The photolytic degradation of the diazo dye, Amido Black, using UV/H(2)O(2) has been carried out experimentally and parameters for most efficient dye degradation have been determined. The degradation of the dye was followed by UV-Vis spectroscopy, HPLC, and LC-MS and is proposed to be initiated by ()OH radicals formed by the photolysis of H(2)O(2). A detailed study was also carried out using LC-MS and LC-MS/MS to determine the degradation pathway of the dye as well as to identify some of the intermediate products formed. Our results suggest that Amido Black degradation occurs preferentially by ()OH radical attack at the more electron rich diazo functionality of the molecule. Furthermore, evidence is presented that subsequent steps in this diazo dye degradation pathway include radical denitration, radical desulfonation and radical diazotization. This report is one of the very few studies that have proposed possible mechanistic pathways for the degradation pathways of a diazo compound.

  17. A unique geometry of the active site of angiotensin-converting enzyme consistent with structure-activity studies

    NASA Astrophysics Data System (ADS)

    Mayer, Dorica; Naylor, Christopher B.; Motoc, Ioan; Marshall, Garland R.

    1987-04-01

    Previous structure-activity studies of captopril and related active angiotensin-converting enzyme (ACE) inhibitors have led to the conclusion that the basic structural requirements for inhibition of ACE involve (a) a terminal carboxyl group; (b) an amido carbonyl group; and (c) different types of effective zinc (Zn) ligand functional groups. Such structural requirements common to a set of compounds acting at the same receptor have been used to define a pharmacophoric pattern of atoms or groups of atoms mutually oriented in space that is necessary for ACE inhibition from a stereochemical point of view. A unique pharmacophore model (within the resolution of approximately 0.15 Å) was observed using a method for systematic search of the conformational hyperspace available to the 28 structurally different molecules under study. The method does not assume a common molecular framework, and, therefore, allows comparison of different compounds that is independent of their absolute orientation. Consequently, by placing the carboxyl binding group, the binding site for amido carbonyl, and the Zn atom site in positions determined by ideal binding geometry with the inhibitors' functional groups, it was possible to clearly specify a geometry for the active site of ACE.

  18. Development of group IV molecular catalysts for high temperature ethylene-α-olefin copolymerization reactions.

    PubMed

    Klosin, Jerzy; Fontaine, Philip P; Figueroa, Ruth

    2015-07-21

    This Account describes our research related to the development of molecular catalysts for solution phase olefin polymerization. Specifically, a series of constrained geometry and nonmetallocene (imino-amido-type) complexes were developed for high temperature olefin polymerization reactions. We have discovered many highly active catalysts that are capable of operating at temperatures above 120 °C and producing copolymers with a useful range of molecular weights (from medium to ultrahigh depending on precatalyst identity and polymerization conditions) and α-olefin incorporation capability. Constrained geometry catalysts (CGCs) exhibit very high activities and are capable of producing a variety of copolymers including ethylene-propylene and ethylene-1-octene copolymers at high reactor temperatures. Importantly, CGCs have much higher reactivity toward α-olefins than classical Ziegler-Natta catalysts, thus allowing for the production of copolymers with any desired level of comonomer. In search of catalysts with improved performance, we discovered 3-amino-substituted indenyl-based CGCs that exhibit the highest activity and produce copolymers with the highest molecular weight within this family of catalysts. Phenanthrenyl-based CGCs were found to be outstanding catalysts for the effective production of high styrene content ethylene-styrene copolymers under industrially relevant conditions. In contrast to CGC ligands, imino-amido-type ligands are bidentate and monoionic, leading to the use of trialkyl group IV precatalysts. The thermal instability of imino-amido complexes was addressed by the development of imino-enamido and amidoquinoline complexes, which are not only thermally very robust, but also produce copolymers with higher molecular weights, and exhibit improved α-olefin incorporation. Imido-amido and imino-enamido catalysts undergo facile chain transfer reactions with metal alkyls, as evidenced by a sharp decrease in polymer molecular weight when the

  19. Expectation as a factor of influence on the success of use of hearing aids in elderly individuals.

    PubMed

    Schuster, Larissa Cristina; Costa, Maristela Julio; Menegotto, Isabela Hoffmeister

    2012-04-01

    Introdução: Próteses auditivas destacam-se em função das tecnologias que as tornam cada vez menores, mais potentes e eficientes. O marketing pode gerar expectativas irreais quanto aos resultados com o uso de amplificação, principalmente em indivíduos inexperientes.Objetivo: Verificar a relação entre expectativas e sucesso do processo de seleção e adaptação de próteses auditivas em idosos.Método: Estudo clínico e experimental, 16 indivíduos idosos, inexperientes com o uso de amplificação, foram avaliados 15 dias antes e após a seleção e adaptação de próteses auditivas. Utilizou-se “Questionário para avaliação das expectativas do indivíduo adulto/idoso, novo usuário de próteses auditivas”, Hearing Handicap Inventory for the Elderly/Screening Version, para avaliação da percepção da restrição de participação e o Questionário Internacional - Aparelho de Amplificação Sonora Individual (QI-AASI), para verificar o benefício subjetivo com o uso das próteses auditivas. Determinou-se o Índice Percentual de Reconhecimento de Sentenças no Silêncio (IPRSS), por meio do teste Listas de Sentenças em Português para verificar o benefício objetivo da adaptação. Os dados foram analisados por meio de teste não-paramétrico, com nível de significância de 5%.Resultados: Toda a amostra apresentou expectativas positivas. Subjetivamente verificou-se benefício pela diminuição da percepção da restrição de participação e pela avaliação positiva da adaptação, evidenciada pelo QI-AASI. Objetivamente a melhora do IPRSS com o uso de próteses auditivas também evidenciou beneficio.Conclusão: a expectativa quanto aos resultados com o uso de amplificação, foi fator de influência negativa no sucesso do processo de seleção e adaptação de próteses auditivas, no âmbito subjetivo.

  20. The history of the parathyroid surgery.

    PubMed

    Toneto, Marcelo Garcia; Prill, Shandi; Debon, Leticia Manoel; Furlan, Fernando Zucuni; Steffen, Nedio

    2016-01-01

    The authors conducted a review of the major aspects of progression of knowledge about the surgical treatment of hyperparathyroidism. Through literature review, we analyzed articles on the history of the evolution of anatomical, physiological, pathological and surgical knowledge of the parathyroid glands. Because of their unique anatomical features, the parathyroid glands were the last of the endocrine glands to be discovered, which greatly hindered proper treatment until the first decades of the twentieth century. Technological developments in the last 30 years greatly facilitated the location of the glands and hyperparathyroidism surgery. However, an experienced and dedicated surgeon is still essential to the excellence of treatment. RESUMO Os autores fizeram uma revisão dos principais aspectos históricos da progressão do conhecimento sobre o tratamento cirúrgico do hiperparatireoidismo. Por meio de revisão bibliográfica, foram analisados artigos selecionados sobre a história da evolução do conhecimento anatômico, fisiológico, patológico e cirúrgico das glândulas paratireoides. Devido às suas características anatômicas peculiares, as paratireoides foram as últimas das glândulas endócrinas a serem descobertas, o que dificultou sobremaneira seu tratamento adequado até as primeiras décadas do Século XX. A evolução tecnológica ocorrida nos últimos 30 anos facilitou sobremaneira a localização das glândulas e a cirurgia do hiperparatireoidismo. Contudo, um cirurgião experiente e dedicado ao tratamento dessa enfermidade ainda é fundamental para a excelência do tratamento.

  1. Incorporando a variabilidade no processo de identificação do modelo de máximo global no Grade of Membership (GoM): considerações metodológicas

    PubMed Central

    Guedes, Gilvan Ramalho; Siviero, Pamila Cristina Lima; Caetano, André Junqueira; Machado, Carla Jorge; Brondízio, Eduardo

    2012-01-01

    A disponibilidade de bases de dados cada vez mais complexas e multidimensionais é um dos principais motivadores para o aumento do número de estudos que utilizam análises multivariadas baseadas em lógica de conjuntos nebulosos. Apesar da disseminação do método Grade of Membership nos trabalhos empíricos brasileiros da área de ciências sociais e saúde, questões relativas à identificabilidade e estabilidade dos parâmetros finais estimados pelo programa GoM 3.4 não foram suficientemente aprofundadas. Dada a relevância de se obterem parâmetros únicos e estáveis, Guedes et al. (2010) propuseram um procedimento empírico para localizar um modelo de máximo global (MG) com parâmetros estáveis. Entretanto, seu localizador de MG não incorpora qualquer medida de variabilidade. Neste artigo, tal limitação é contornada por meio da utilização de uma estatística de ponderação – Máximo Global Ponderado (MGP) – semelhante ao coeficiente de variação. Esse indicador busca não penalizar de forma desproporcional situações nas quais os desvios médios, apesar de diferentes de zero, são muito pequenos. Apresentam-se evidências de que o localizador MGP reduz a distância do modelo identificado à real estrutura latente dos dados em análise, quando comparados ao modelo identificado pelo localizador não ponderado, MG. PMID:23293402

  2. Foreign body ingestion: rare cause of cervical abscess.

    PubMed

    Costa, Liliana; Larangeiro, João; Pinto Moura, Carla; Santos, Margarida

    2014-01-01

    IntroduçÉo: A ingestÉo de corpo estranho é um motivo frequente de recurso à urgência hospitalar. As complicações graves, embora raras, incluem perfuraçÉo faringo-esofágica, fistula aorto-esofágica e infecçÉo cervical profunda.Material e Métodos: Foram analisados, retrospectivamente, os casos de ingestÉo de corpo estranho com internamento num hospital terciário, entre 1989 e 2011. Seleccionaram-se os casos complicados por abcesso cervical profundo, descrevendo-se a semiótica, resultados de meios complementares de diagnóstico, terapêutica efectuada e evoluçÉo clínica.Resultados: Dos 1679 casos, 319 referentes a crianças e 1360 a adultos, reportam-se dois casos (0,12%): uma criança, 13 meses, com abcesso retrofaríngeo após ingestÉo de osso de frango e um adulto, 41 anos, com abcesso parafaríngeo após ingestÉo de espinha de peixe. As complicações manifestaram-se quatro e três dias após remoçÉo do corpo estranho, respectivamente. Em ambos foram efectuadas Tomografias Computorizadas cervicais com contraste e drenagem cirúrgica dos abcessos; a criança foi ainda submetida a esofagoscopia rígida para remoçÉo de corpo estranho residual e encerramento da perfuraçÉo esofágica associada.DiscussÉo: Os abcessos cervicais sÉo uma complicaçÉo possível da ingestÉo de corpo estranho e constituem um desafio diagnóstico, principalmente em idade pediátrica. A manipulaçÉo esofágica prévia por fibroscopia poderá ser considerada um factor de risco. A imagiologia (Tomografia Computorizada cervical com contraste ou Resson'ncia Magnética Cervical) foi essencial para o diagnóstico e o planeamento cirúrgico.ConclusÉo: Embora raros, perante a história recente de ingestÉo/remoçÉo de corpo estranho esofágico e a presença de sintomas compatíveis, os abcessos cervicais devem ser tidos em consideraçÉo, dado o potencial de morbilidade e mortalidade na ausência de uma abordagem terapêutica adequada.

  3. Abundância química de simbióticas na direção do bojo galáctico

    NASA Astrophysics Data System (ADS)

    Luna, G. J. M.; Costa, R. D. D.

    2003-08-01

    O estudo da distribuição de metalicidades de gigantes K no Bojo indica um largo intervalo com valores entre 0.1 a 10 vezes o valor solar. As razões elementais Ca/Fe, Si/Fe, Mg/Fe são típicas de estrelas do halo, apontando para um processo rápido de enriquecimento, via estrelas masssivas (SN's tipo II). No entanto, este cenário não combina com os resultados derivados de nebulosas planetárias do bojo tais como os de Ratag et al. (1992, A&A,255,270), Cuisinier et al.(2000, A&A,353, 543), Escudero e Costa (2001, A&A,380, 300),que obtêm abundâncias análogas às do disco. Neste cenário, o estudo de estrelas simbióticas possibilita uma abordagem particularmente apropriada para o problema das abundâncias químicas de estrelas de massa intermediária em estágios avançados da evoluçao estelar. Apresentamos aqui os resultados da determinacão das abundâncias do grupo do CNO numa extensa amostra de simbióticas do bojo. Aliás, com a disponibilidade de espectros no visível determinamos também abundâncias de Ar, Ne, S e He, fundamentais para analisar os processos de enriquecimento químico ocorridos ao longo da evolução estelar, bem como a evolução química do meio interestelar. Com os espectros UV do satelite IUE obtivemos abundâncias de C, necessárias no estudo da evolução dos sistemas. As relaçoes C/N-O/N mostram que o material nebular é produto do vento da componente gigante e não dos eventos de nova que às vezes acontecem nestes sistemas, como foi mostrado por Nussbaumer et al (1988,A&A,198,179). As abundâncias de Ar, S, Ne e O são compativeis com resultados de fontes no disco e bojo, seguindo o gradiente proposto por muitos autores na literatura a partir de diferentes objetos como cefeidas, nebulosas planetárias e anãs G. (CAPES,FAPESP,CNPq)

  4. Abundâncias em estrelas de Bário

    NASA Astrophysics Data System (ADS)

    Allen, D. M.

    2003-08-01

    Estrelas de Bário apresentam linhas intensas de elementos produzidos pelo processos (ex: Ba, Y, Sr, Zr) e bandas intensas de CN, C2 e CH. A hipótese mais aceita sobre a origem deste grupo peculiar é a de que essas estrelas façam parte de sistemas binários, tendo recebido material enriquecido em elementos pesados da companheira mais evoluída. Apresentamos neste trabalho uma análise detalhada de uma amostra de estrelas desta classe, incluindo determinação de parâmetros atmosféricos e cálculo de abundâncias. As temperaturas efetivas foram determinadas a partir de dados fotométricos obtidos com o Fotrap instalado no telescópio Zeiss do LNA (Laboratório Nacional de Astrofísica) (B-V, V-I, R-I, V-R), e coletados na literatura nos catálogos Hipparcos (B-V), 2MASS (Two Micron All Sky Survey) (V-K) e The General Catalogue Photometric Data (sistema Geneva). Obtivemos uma faixa de temperaturas de 4400 £ Tef £ 6500. As metalicidades foram determinadas a partir de linhas de Fe I e Fe II, estando os resultados no intervalo -1 £ [Fe/H] £ +0.1. O log g foi determinado pelo equilíbrio de ionização e pela relação com a magnitude bolométrica, a temperatura e a massa, sendo os resultados na faixa 1.5 £ log g £ 4.5. As distâncias utilizadas foram determinadas com o auxílio das paralaxes Hipparcos, e as massas determinadas por modelos de isócronas. Os espectros utilizados foram obtidos com o espectrógrafo FEROS no Telescópio de 1,5m do ESO (European Southern Observatory). As abundâncias foram calculadas por meio de síntese espectral de linhas individuais incluindo elementos alfa, pico do Fe, s e r. Encontramos um excesso de elementos pesados em relação ao Fe, como esperado para estrelas de Bário.

  5. Estimativa de imagens solares soho através de redes neurais artificiais

    NASA Astrophysics Data System (ADS)

    Andrade, M. C.; Fernandes, F. C. R.; Cecatto, J. R.; Rios Neto, A.; Rosa, R. R.; Sawant, H. S.

    2003-08-01

    A Rede Neural Artificial (RNA), no âmbito da teoria computacional, constitui uma teoria emergente que, por possuir habilidade em aprender a partir de dados de entrada, encontra diferentes aplicações em diferentes áreas. Um exemplo é a utilização de RNA na caracterização de padrões associados à dinâmica de processos espaço-temporais relacionados a fenômenos físicos não-lineares. Para obter informações sobre o comportamento destes fenômenos físicos utiliza-se, em diversos casos, seqüências de imagens digitalizadas, onde a caracterização de alguns fenômenos espaço-temporais é o procedimento mais viável para descrever a dinâmica das regiões ativas do Sol. Com base em imagens observadas por telescópios a bordo de satélites, estudos de previsão de eventos solares podem ser programados, permitindo prever possíveis efeitos posteriores nas regiões mais próximas da Terra (tempestades geomagnéticas e irregularidades ionosféricas). Neste trabalho avaliamos o desempenho da RNA para estimar padrões espaço-temporais, ou seja, imagens solares em ultravioleta, obtidas através do telescópio a bordo do satélite SOHO. Os resultados mostraram que as RNA conseguem generalizar os padrões de maneira satisfatória sem perder de forma significativa os principais aspectos da configuração global da atmosfera solar, comprovando a eficácia da RNA como ferramenta para esse tipo de aplicação. Portanto, este trabalho comprova a viabilidade de uso desta ferramenta em projetos voltados ao estudo do comportamento solar, em trabalhos do grupo de Física do Meio Interplanetário (FMI) na DAS e em programas desenvolvidos pelo Núcleo de Simulação e Análise de Sistemas Complexos (NUSASC) do Laboratório Associado de Computação e Matemática Aplicada (LAC) do INPE.

  6. Detecção inesperada de efeitos de lentes fracas em grupos de galáxias pouco luminosos em raios-X

    NASA Astrophysics Data System (ADS)

    Carrasco, R.; Mendes de Oliveira, C.; Sodrã©, L., Jr.; Lima Neto, G. B.; Cypriano, E. S.; Lengruber, L. L.; Cuevas, H.; Ramirez, A.

    2003-08-01

    Obtivemos, como parte do programa de verificação científica do GMOS Sul, imagens profundas de três grupos de galáxias: G97 e G102 (z~0,4) e G124 (z = 0,17). Esses alvos foram selecionados a partir do catálogo de fontes extensas de Vikhlinin (1998), por terem luminosidades em raios X menores que 3´1043 ergs s-1, valor cerca de uma ou duas ordens de grandeza inferior ao de aglomerados de galáxias. O objetivo primário dessas observações é o estudo da evolução de galáxias em grupos. Grupos são ambientes menos densos que aglomerados, contêm a grande maioria das galáxias do Universo mas que, até o momento, foram estudados detalhadamente apenas no Universo local (z~0). Com esses dados efetuamos uma análise estatística da distorção na forma das galáxias de fundo (lentes gravitacionais fracas) como forma de inferir o conteúdo e a distribuição de massa nesses grupos apesar de que, em princípio, esse efeito não deveria ser detectado uma vez que os critérios de seleção adotados previlegiam sistemas de baixa massa. De fato, para G124 obtivemos apenas um limite superior para sua massa que é compatível com sua luminosidade em raios X. De modo contrário e surpreendente, os objetos G102 e G097, aparentam ter massas que resultariam em dispersões de velocidade maiores que 1000 km s-1, muito maiores do que se espera para grupos de galáxias. Com efeito, para G097 obtivemos, a partir de dados do satélite XMM, uma estimativa para a temperatura do gás intragrupo de kT = 2,6 keV, que é tipica de sistemas com dispersões de velocidade de ~ 600 km s-1, bem característica de grupos. Essas contradições aparentes entre lentes fracas e raios X podem ser explicadas de dois modos: i) a massa obtida por lentes estaria sobreestimada devido à superposição de estruturas massivas ao longo da linha de visada ou ii) a temperatura do gás do meio intra-grupo reflete o potencial gravitacional de estruturas menores que estariam se fundindo para formar uma

  7. From health plan companies to international insurance companies: changes in the accumulation regime and repercussions on the healthcare system in Brazil.

    PubMed

    Bahia, Ligia; Scheffer, Mario; Tavares, Leandro Reis; Braga, Iale Falleiros

    2016-11-03

    The concentration and internationalization of health plan companies in Brazil gave them a clearly financial face. Based on the need to understand the health care industry's capital accumulation patterns, the current study examines health plan companies' expansion strategies through the classification of their supply and demand characteristics by recent historical periods and an analysis of recent shareholding trends in one of the leading corporations in the Brazilian health care industry. The 1960s to 2000s witnessed changes in the scale of demands for health plans and adherence by companies to long-term accumulation strategies. Beginning in the early 21st century, changes in the shareholding structures of the largest Brazilian company, consistent with the financialization of its accumulation regime, resulted in the rapid multiplication of its capital. Deepening segmentation of the health care system in a context marked by the downturn in the national economy challenges the preservation of public subsidies for private health plans. Resumo: A concentração e internacionalização de empresas de planos de saúde no Brasil conferiram-lhes feição financeira. Considerando a necessidade de compreender os padrões de acumulação desse setor, o trabalho examina estratégias de expansão das empresas de planos de saúde por meio da periodização de atributos da oferta e demanda e exame da trajetória patrimonial recente de um dos grandes grupos do setor. Entre os anos 1960 e 2000, ocorreram alterações na escala das demandas por planos de saúde e adesão das empresas a estratégias de acumulação de longo prazo. A partir do século XXI, as alterações nas estruturas societárias da maior empresa brasileira, compatíveis com o regime de acumulação financeirizada, resultaram na multiplicação de seu capital em um curto intervalo de tempo. O aprofundamento da segmentação do sistema de saúde, em um contexto marcado pela desaceleração da economia, questiona a

  8. TECNOLOGÍAS DE INFORMACIÓN Y COMUNICACIÓN PARA LA PREVENCIÓN Y CONTROL DE LA INFECCIÓN POR EL VIH Y OTRAS ITS*

    PubMed Central

    Curioso, Walter H.; Blas, Magaly M.; Kurth, Ann E.; Klausner, Jeffrey D.

    2010-01-01

    Avances tecnológicos innovadores como Internet, computadoras personales de bolsillo, teléfonos celulares y otros equipos son un arsenal en crecimiento en el esfuerzo de impedir y controlar el VIH y otras infecciones de transmisión sexual (ITS). A pesar que existe una diversidad de tecnologías de información y comunicación en diferentes etapas de desarrollo para la prevención del VIH e ITS, la investigación en esta área se encuentra aún en crecimiento, y el impacto en la incidencia de enfermedad, las evaluaciones con diseños rigurosos y los estudios económicos todavía son muy limitados. Sin embargo, algunas de estas evidencias son prometedoras y poseen un gran potencial para su uso en nuestro medio. En este artículo hemos realizado una revisión sistemática de la literatura relacionada con el uso de la tecnología aplicada a la prevención y control del VIH e ITS. De ser usada apropiadamente, esta tecnología podría mejorar la vigilancia del VIH y otras ITS, diagnóstico, notificación de parejas, prevención, manejo clínico, y capacitación de profesionales de la salud. PMID:26339254

  9. About to Graduate from High School? Consider Career Education Opportunities. EdSource Student/Parent Guide = Estas por graduarte de la escuela preparatoria? Considera oportunidades para seguir tu educacion de carrera. EdSource guia de estudiantes y padres

    ERIC Educational Resources Information Center

    EdSource, 2006

    2006-01-01

    Getting a sound education is important to a student's ability to make a good living in a field they will enjoy. For many students graduating from high school, that includes high quality career technical (or vocational) education tailored to a specific job. In California, such programs are available in a wide range of fields, from healthcare to the…

  10. VISIÓN GENERAL DE LA EVALUACIÓN DEL RIESGO EN SALUD INFANTIL EMPLEANDO UN ENFOQUE POR ETAPAS DE DESARROLLO (American translation is: Overview of a Life Stage Approach to Children's Health Risk Assessment)

    EPA Science Inventory

    Discussing the challenges associated with estimating and interpreting toxicant exposures and health risks from biomonitoring data. This extended abstract was translated in Spanish and published in Acta Toxicologica Argentina.

  11. Ingestion Reiterada de Cuerpos Extranos. Forma Inusual de Presentacion del Sindrome de Munchausen por Poderes (Reiterated Ingestion of Foreign Bodies. Unusual Form of Presentation of Munchausen Syndrome by Proxy).

    ERIC Educational Resources Information Center

    Terreros, I. Gomez de; And Others

    1996-01-01

    An unusual case of Munchausen syndrome by proxy is reported. A mother with a psychiatric record of behavior disorders and family dysfunction perpetrated the ingestion of foreign bodies (for example, earrings, a screw, sewing needles) on a 10-month-old infant with a history of prematurity, repeated visits to emergency rooms, and nonjustified…

  12. Vistazos Intimos De Puebla; Una Compilacion De Informes Individuales Preparados Por Los Participantes Del Instituto De Verano (NDEA) (Close-ups on Puebla; A Compilation of Individual Reports Prepared by the Participants of the NDEA Summer Institute).

    ERIC Educational Resources Information Center

    Wichita State Univ., KS.

    The individual and committee reports on the sociology of Puebla, Mexico, which are collected here, were written by participants in an NDEA Summer Institute program of the University of Wichita, Kansas. The underlying motives of the program, described in the preface, were to provide participants with real language experience and a chance to…

  13. Guiandose por la Intrincada Senda de la Educacion Especial: Una Guia para Padres y Maestros. Tercera Edicion. (Negotiating the Special Education Maze: A Guide for Parents & Teachers. Third Edition).

    ERIC Educational Resources Information Center

    Anderson, Winifred; Chitwood, Stephen; Hayden, Deidre

    Designed to assist Spanish-speaking parents and teachers in understanding special education procedures, this book describes the process for obtaining school services for children with disabilities. An introduction reviews six major provisions of the Individuals with Disabilities Education Act (IDEA) that relate to children's rights to a free,…

  14. Fields without Borders: An Anthology of Documentary Writing and Photography by Student Action with Farmworkers' Interns = Campos sin Fronteras: Una Antologia de Obras Escritas y Fotografia por Estudiantes Internos de Accion Estudiantil con Trabajadores Agricolas.

    ERIC Educational Resources Information Center

    Manly, Libby, Ed.; Okie, Alejandra, Ed.; Wiggins, Melinda, Ed.

    In this booklet, essays and poems, presented both in English and in Spanish, portray the feelings, conditions, and economic plight of migrant and seasonal farmworkers in North and South Carolina, often in their own words. A preface describes Student Action with Farmworkers summer internships in which college students spend 10 weeks working with…

  15. The Latinas' Guide to the Information Superhighway: A Bilingual Guide for Latinas by Latinas = Guia para Mujeres Latinas sobre la Supercarretera de la Informacion: Una Guia Bilingue para Latinas por medio de Latinas.

    ERIC Educational Resources Information Center

    MANA, A National Latina Organization, Washington, DC.

    This guide to the Internet is designed to give Latinas basic information on computers and the information superhighway. Written in both Spanish and English, the guide begins by defining the Internet and making some suggestions about acquiring access to a computer. Among the topics discussed are how to choose an Internet service provider, how to…

  16. John Tracy Clinic: Programa de Ensenanza por Correspondencia para Los Padres de Ninos Sordo-Ciegos de Edad Preescolar (John Tracy Clinic Correspondence Learning Program for Parents of Preschool Deaf-Blind Children).

    ERIC Educational Resources Information Center

    Thielman, Virginia B.; And Others

    Written in Spanish, the document contains a correspondence learning program for parents of deaf blind preschoolers. An introductory section gives preliminary instructions, an introduction to sign language, and a list of resources for deaf blind children. Twelve lessons follow with information on: the parent's role in teaching the child, visual…

  17. Engaging Foreign Language Learners in a Web 2.0-Mediated Collaborative Learning Process (Inclusión de estudiantes de lenguas extranjeras en procesos colaborativos de aprendizaje mediados por la web 2.0)

    ERIC Educational Resources Information Center

    Cote Parra, Gabriel Eduardo

    2015-01-01

    The purpose of this action research was to explore the types of interactions that foreign language learners experience while using a wiki as a supporting tool for a face-to-face research course. This design allowed me to play a dual role: first, I studied my own classroom setting and students. Second, I implemented a pedagogical intervention based…

  18. Dermatitis causada por Hylesia metabus (Lepidoptera: Hemileucidae) en la región costera del Estado del Delta del Amacuro, Venezuela [Dermatitis caused by Hylesia metabus (Lepidoptera: Hemileucidae) in the costal region of the state of Delta Amacuro, Venezuela].

    PubMed

    Rodríguez-Acosta, A; Rubiano, H; Reyes, M; Fernández, C T

    1998-01-01

    2 cases of acute dermatitis caused by butterfly Hylesia metabus in an area that so far has not been considered as endemic for this species were presented. The dermatitis observed in these individuals may be described as very circumscribed, pruriginous, erythematous generalized protruding papules that may be compared with urticaria, and with a variable degree oedema. Monomorphic eruption consisting in small hard papules crowned by a little vesicle was also present. The lesions of these 2 patients evolved with intensely pruriginous papules for a week and after that they healed without dermatological sequelae.

  19. Less and Less for More and More. Economic Organization Booklet 1. Teacher's Edition=Menos y menos por mas y mas. Organizacion economica libro 1. Manual para El Maestro.

    ERIC Educational Resources Information Center

    California State Univ., Los Angeles. National Dissemination and Assessment Center.

    The booklet is part of a grade 10-12 social studies series produced for bilingual education. The series consists of six major thematic modules, with four to five booklets in each. The interdisciplinary modules are based on major ideas and are designed to help students understand some major human problems and make sound, responsive decisions to…

  20. Por Que Mami No Puede Cambiar una Goma? Tercer Modulo de una Serie para Maestros de Escuela Elemental. (Why Can't Mommy Change a Flat Tire? Third Module of a Series for Elementary School Teachers).

    ERIC Educational Resources Information Center

    Molina, Carmen Eneida, Ed.; And Others

    This guide for teachers, in English and Spanish, examines the role parents play in the socialization of sex roles. A pre-test and post test are included to measure the user's awareness of sexual stereotyping. Five object lessons cover the following topics: (1) stereotypes which exist prior to a baby's birth; (2) behavioral standards on which…

  1. Proyecto de Ley por el Cual se Dicta el Estatuto General de Educacion y Pliego de Modificaciones Propuesto (Bill Establishing a General Statute for Education and Explanation of Proposed Modifications).

    ERIC Educational Resources Information Center

    Suarez Villa, Diego

    This document contains the 1971 Colombian education bill and suggested bill modifications. The bill states educational objectives and establishes the structure of the national education system, the organization for educational administration, financing procedures, regulations for educational personnel, and the means for implementing the…

  2. Por Que Rosa No Es Valiente? Cuarto Modulo de una Serie para Maestros de Escuela Elemental (Why Isn't Rosie Brave? Fourth Module of a Series for Elementary School Teachers).

    ERIC Educational Resources Information Center

    Molina, Carmen Eneida, Ed.; And Others

    This guide in English and Spanish provides teachers with methods for identifying textbook bias and stereotyping. A pre-test and post-test designed to measure awareness of textbook stereotypes are included. Four object lessons discuss the function of repetition, cumulative effect, omission, and distortion in reinforcing stereotypes, especially…

  3. Viajando por la Carretera de la Educacion Especial: Una Guia para los Padres para Tener un Viaje Feliz y Seguro (Traveling the Special Education Highway: A Parent's Guide to a Safe and Happy Journey).

    ERIC Educational Resources Information Center

    Santa Maria, Karen

    Designed for Spanish-speaking parents, this brochure, written in Spanish, uses a car-trip analogy to describe special education services for students with disabilities. It addresses: (1) child find; (2) initial evaluation and eligibility determination; (3) categories of students who receive special education services and related services; (4)…

  4. Association between Obstructive Sleep Apnea and Myocardial Infarction: A Systematic Review.

    PubMed

    Porto, Fernanda; Sakamoto, Yuri Saho; Salles, Cristina

    2017-03-30

    Obstructive sleep apnea (OSA) has been associated to cardiovascular risk factors. However, the association between OSA and cardiovascular disease is still controversial. The objective of the present study was to verify the association between OSA and myocardial infarction (MI). This is a systematic review of the literature performed through electronic data sources MEDLINE/PubMed, PubMed Central, Web of Science and BVS -Biblioteca Virtual em Saúde (Virtual Health Library). The descriptors used were: 'obstructive sleep apnea' AND 'polysomnography' AND 'myocardial infarction' AND 'adults NOT 'treatment.' The present work analysed three prospective studies, selected from 142 articles. The studies followed a total sample of 5,067 OSA patients, mostly composed by male participants. All patients underwent night polysomnography, and all studies found an association between OSA and fatal and non-fatal cardiovascular outcomes. Thus, we were able to observe that 644 (12.7%) of the 5,067 patients suffered MI or stroke, or required a revascularization procedure, and 25.6% of these cardiovascular events were fatal. MI was responsible for 29.5% of all 644 analysed outcomes. There is an association between OSA and MI, in male patients, and apnea and hypopnea index (AHI) are the most reliable markers. Resumo A apneia obstrutiva do sono (AOS) tem sido associada a fatores de risco cardiovascular, porém a relação entre a AOS e doença cardiovascular ainda é controversa. O objetivo do presente estudo foi verificar a associação entre AOS e infarto do miocárdio (IM). Revisão sistemática de literatura por meio das fontes de dados eletrônicas MEDLINE/PubMed, PubMed Central, Web of Science e Biblioteca Virtual em Saúde (BVS). Os descritores utilizados foram: "obstructive sleep apnea" AND "polysomnography" AND "myocardial infarction" AND "adults" NOT "treatment".O presente trabalho analisou três estudos prospectivos, selecionados dentre 142 artigos encontrados. Os estudos

  5. Oncology Referral Concerning Paediatric Neurosurgery? Analysis of the Situation between 2008-2013 in the North of Portugal.

    PubMed

    Batista, Ana; Nogueira-Silva, Luís; Vaz, Rui; Oliveira, Joana

    2016-01-01

    Introdução: Os tumores primários do sistema nervoso central representam o segundo grupo de neoplasias mais frequente e são a principal causa de morte devido a tumores sólidos em crianças. O nosso estudo teve como objetivos realizar a mais atualizada análise epidemiológica desta doença no norte de Portugal e avaliar o possível benefício da centralização de cuidados. Material e Métodos: Este estudo de base populacional incluiu todos os tumores primários do sistema nervoso central diagnosticados e histologicamente confirmados em indivíduos menores de 18 anos de idade, que residem no norte do país, desde Janeiro 2008 até Dezembro 2013. Os dados foram obtidos por meio da avaliação dos processos clínicos dos doentes. Nós descrevemos as características das crianças e dos seus tumores e analisámos os quocientes doente: neurocirurgião pediátrico e tipo histológico de tumor: neurocirurgião pediátrico e as taxas de sobrevivência, mortalidade, complicações e recidiva. Resultados: Foram registados 147 casos. A média de idade ao diagnóstico foi de 8,0 ± 5,2 anos. Os astrocitomas foram o tipo histológico mais frequentemente encontrado (34%). O tipo histológico foi a única variável com influência estatisticamente significativa na mortalidade (p = 0,001). As sobrevivências a um, três e cinco anos relativas ao período entre 2008 - 2013 foram estatisticamente superiores às do intervalo entre 2005 - 2007. Os astrocitomas apresentam a mais alta taxa de sobrevivência, sendo estatisticamente diferente dos outros tipos de tumor (p = 0,015). Estimámos uma média de 12,25 casos tratados anualmente por neurocirurgião pediátrico no nosso hospital. Discussão: Os nossos resultados são, globalmente, consistentes com os encontrados na literatura mundial, mas registrámos taxas de sobrevivência mais altas. O número de casos tratados por neurocirurgião pediátrico está de acordo com o recomendado. Conclusão: Demonstrámos que houve melhoria

  6. Structural Basis for Prereceptor Modulation of Plant Hormones by GH3 Proteins

    SciTech Connect

    Westfall, Corey S.; Zubieta, Chloe; Herrmann, Jonathan; Kapp, Ulrike; Nanao, Max H.; Jez, Joseph M.

    2013-04-08

    Acyl acid amido synthetases of the GH3 family act as critical prereceptor modulators of plant hormone action; however, the molecular basis for their hormone selectivity is unclear. Here, we report the crystal structures of benzoate-specific Arabidopsis thaliana AtGH3.12/PBS3 and jasmonic acid-specific AtGH3.11/JAR1. These structures, combined with biochemical analysis, define features for the conjugation of amino acids to diverse acyl acid substrates and highlight the importance of conformational changes in the carboxyl-terminal domain for catalysis. We also identify residues forming the acyl acid binding site across the GH3 family and residues critical for amino acid recognition. Our results demonstrate how a highly adaptable three-dimensional scaffold is used for the evolution of promiscuous activity across an enzyme family for modulation of plant signaling molecules.

  7. Photocatalytic activity of Cr-doped TiO2 nanoparticles deposited on porous multicrystalline silicon films

    PubMed Central

    2014-01-01

    This work deals with the deposition of Cr-doped TiO2 thin films on porous silicon (PS) prepared from electrochemical anodization of multicrystalline (mc-Si) Si wafers. The effect of Cr doping on the properties of the TiO2-Cr/PS/Si samples has been investigated by means of X-ray diffraction (XRD), atomic force microcopy (AFM), photoluminescence, lifetime, and laser beam-induced current (LBIC) measurements. The photocatalytic activity is carried out on TiO2-Cr/PS/Si samples. It was found that the TiO2-Cr/PS/mc-Si type structure degrades an organic pollutant (amido black) under ultraviolet (UV) light. A noticeable degradation of the pollutant is obtained for a Cr doping of 2 at. %. This result is discussed in light of LBIC and photoluminescence measurements. PMID:25313302

  8. Low dimensional magnetic solids and single crystal elpasolites: Need for improved crystal growing techniques

    NASA Technical Reports Server (NTRS)

    Good, M. L.; Watkins, S.; Schwartz, R. W.

    1979-01-01

    The need for extensive crystal growing experiments to develop techniques for preparing crystals suitable for magnetic anisotropy measurements and detailed X-ray and neutron diffraction studies is rationalized on the basis of the unique magnetic properties of the materials and their hydrogen bonded structures which have many features in common with metalloenzyme and metalloprotein active sites. Single crystals of the single and mixed lanthanide species are prepared by the Bridgeman technique of gradient solidification of molten samples. The effects of crystal imperfections on the optical properties of these materials are an important part of the projected research. A series of a-amido acid complexes of first row transition metals were prepared which crystallize as infinite linear chains and exhibit low dimensional magnetic ordering (one or two) at temperature below 40 K.

  9. An alignment independent 3D QSAR study of the antiproliferative activity of 1,2,4,5-tetraoxanes.

    PubMed

    Cvijetić, Ilija N; Zizak, Zeljko P; Stanojković, Tatjana P; Juranić, Zorica D; Terzić, Natasa; Opsenica, Igor M; Opsenica, Dejan M; Juranić, Ivan O; Drakulić, Branko J

    2010-10-01

    An alignment-free 3D QSAR study on antiproliferative activity of the thirty-three 1,2,4,5-tetraoxane derivatives toward two human dedifferentiated cell lines was reported. GRIND methodology, where descriptors are derived from GRID molecular interaction fields (MIF), were used. It was found that pharmacophoric pattern attributed to the most potent derivatives include amido NH of the primary or secondary amide, and the acetoxy fragments at positions 7 and 12 of steroid core which are, along with the tetraoxane ring, common for all studied compounds. Independently, simple multiple regression model obtained by using the whole-molecular properties, confirmed that the hydrophobicity and the H-bond donor properties are the main parameters influencing potency of compounds toward human cervix carcinoma (HeLa) and human malignant melanoma (FemX) cell lines. Corollary, similar structural motifs are found to be important for the potency toward both examined cell lines.

  10. Homogeneous and Supported Niobium Catalysts as Lewis Acid and Radical Catalysts

    SciTech Connect

    Wayne Tikkanen

    2006-12-31

    The synthesis of tetrachlorotetraphenylcyclopentadienyl group 5 metal complexes has been accomplished through two routes, one a salt metathesis with lithiumtetraphenylcyclopentadiende and the other, reaction with trimethyltintetraphenylcyclopentadiene. The reactants and products have been characterized by {sup 1}H and {sup 13}C({sup 1}H) NMR spectroscopy. The niobium complex promotes the silylcyanation of butyraldehyde. The grafting of metal complexes to silica gel surfaces has been accomplished using tetrakisdimethylamidozirconium as the metal precursor. The most homogeneous binding as determined by CP-MAS {sup 13}C NMR and infrared spectroscopy was obtained with drying at 500 C at 3 mtorr vacuum. The remaining amido groups can be replaced by reaction with alcohols to generate surface bound metal alkoxides. These bound catalysts promote silylcyanation of aryl aldehydes and can be reused three times with no loss of activity.

  11. Cationic Group-IV pincer-type complexes for polymerization and hydroamination catalysis.

    PubMed

    Luconi, Lapo; Klosin, Jerzy; Smith, Austin J; Germain, Stéphane; Schulz, Emmanuelle; Hannedouche, Jérôme; Giambastiani, Giuliano

    2014-03-21

    Neutral Zr(IV) and Hf(IV) dimethyl complexes stabilized by unsymmetrical dianionic {N,C,N'} pincer ligands have been prepared from their corresponding bis-amido complexes upon treatment with AlMe₃. Their structure consists of a central ó-bonded aryl donor group (C) capable of forming robust M-C bonds with the metal center, enforced by the synergic effect of both the coordination of peripheral donor groups (N) and the chelating rigid structure of the {N,C,N} ligand framework. Such a combination translates into systems having a unique balance between stability and reactivity. These Zr(IV) and Hf(IV) dimethyl complexes were converted in situ into cationic species [M(IV){N⁻,C⁻,N}Me][B(C₆F₅)₄] which are active catalysts for the room temperature (r.t.) intramolecular hydroamination/cyclization of primary and secondary aminoalkenes as well as for the high temperature ethylene-1-octene copolymerizations.

  12. Synthesis of 17beta-N-substituted 19-Nor-10-azasteroids as inhibitors of human 5alpha-reductases I and II.

    PubMed

    Scarpi, Dina; Occhiato, Ernesto G; Danza, Giovanna; Serio, Mario; Guarna, Antonio

    2002-11-01

    The synthesis of 17beta-[N-(phenyl)methyl/phenyl-amido] substituted 10-azasteroids has been accomplished by either the TiCl4- or TMSOTf-catalysed reaction of carbamates 11 and 12 with Danishefsky's diene. The reaction provided 5alpha-H isomers 3a-5a and 5beta-H isomers 3b-5b depending on the reaction conditions. Both epimers of each compound were tested against human 5alpha-reductase types I and II. Unexpectedly, 5beta-H compounds were found more active than their 5alpha-H counterparts, the best inhibitors being 3b (IC50=279 and 2000 nM toward isoenzyme I and II, respectively) and 5b (IC50=913 and 247 nM toward isoenzymes I and II, respectively).

  13. Magnetic properties of copper(II) complexes containing peptides. Crystal structure of [Cu(phe-leu)

    NASA Astrophysics Data System (ADS)

    Sanchiz, J.; Kremer, C.; Torre, M. H.; Facchin, G.; Kremer, E.; Castellano, E. E.; Ellena, J.

    2006-09-01

    A novel copper(II) complex containing the peptide phe-leu has been prepared and characterized. The crystal structure of [Cu(phe-leu)] ( 1) was determined by X-ray diffraction. The presence of carboxylate and amido bridges allows the formation of an extended 2D arrangement. This structure is similar to those found in [Cu(gly-val)] · 1/2H 2O ( 2), [Cu(val-gly)] ( 3), [Cu(val-phe)] ( 4), and [Cu(phe-phe)] ( 5). The magnetic properties of compounds 1- 5 were studied and analyzed comparatively. The experimental data show that the magnetic interactions are mainly transmitted through μ 2-COO - bridges, being ferromagnetic for 1 and 3, and antiferromagnetic for 2, 4 and 5.

  14. A technique for collection of exudate from pea seedlings

    NASA Technical Reports Server (NTRS)

    Hanson, S. D.; Cohen, J. D.; Bandurski, R. S. (Principal Investigator)

    1985-01-01

    Ethylenediaminetetraacetic acid (EDTA), at concentrations higher than 1.0 millimolar, is phytotoxic to etiolated seedlings of Pisum sativum. Substantial vascular exudation from pea epicotyls could be obtained without tissue damage at 0.5 millimolar EDTA if the solution was buffered at pH 7.5 with sodium N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid. Treated seedlings exuded 950 micrograms (leucine equivalents) of ninhydrin-positive material per day and 870 micrograms (glucose equivalents) of anthrone-positive material per day. Amino acid analysis showed the exudate to have glutamine as the major amido nitrogen containing compound and sucrose was shown to be the major sugar. Radiolabeled tryptophan and sucrose applied to cotyledons were transferred through the epicotyl and into the collection medium. The pH profile for exudation shows half maximal exudation at pH 7.2, indicating the promotion of exudation by EDTA is probably not due simply to Ca2+ chelation.

  15. Photodynamic therapy application of PAMAM-porphyrin molecule on stomach cancer cells

    NASA Astrophysics Data System (ADS)

    Kiris, Tugba; Burgucu, Mehmet Necmi; Sagir, Tugba; Senel, Mehmet; Isik, Sevim; Bölük-basi Ates, Gamze; Tabakoglu, Hasim Ozgur

    2015-03-01

    In this study, effect of a novel LED-based light source developed for 96-well-plates cell culture applications, was tried on AGS stomach cancer cell line, in combination with Poly(amido amine) (PAMAM) modified - porhyrin molecule. For each 4 generation of modified PpIX molecule 5 different concentrations tried. According to results PAMAM molecule doesnt have any photosensitizer property also didn't show any toxic effect even if higher concentrations. Morphology and real time monitoring analysis results hold up each other and confirmed that, PpIX molecules with and without modificated high concentrations (>100μM) caused cell death via toxicicity this reason optimal concentration for PAMAM modified PpIX should be between 25 - 50 μm concentration .

  16. In situ product removal of ketoses by immobilized 3-amino phenyl boronic acid: effect of immobilization method on pH profile.

    PubMed

    Dukler, A; Freeman, A

    2001-10-05

    The use of polymeric derivatives of phenylboronic acid (PBA) as an effective means for specific in situ product removal of ketoses from aldose-containing reaction mixtures, strongly depends on the retention of selective binding of ketoses exhibited by soluble PBA and 3-amino PBA, by their polymeric, water insoluble analogs. In this communication we demonstrate that immobilization chemistry has a strong effect on ketose preferred binding by polymeric PBA derivatives. Our results indicate that for the preparation of an effective and more specific adsorbent, 3-amino PBA should be coupled to the polymeric carrier via alkylamino chemistry and not via the commonly employed amido derivative. Immobilized alkylamino-PBA exhibited selective fructose and xylulose binding throughout glucose and xylose isomerization processes at the pH range of 7.0-8.0.

  17. New substituted amides and hydrazides of pectic acid

    SciTech Connect

    Lapenko, V.L.; Potapova, L.B.; Slivkin, A.I.; Razumnaya, Z.A.

    1988-05-10

    Structural variants of pectin amides and hydrazides are of practical value as flocculants in water treatment. The purpose of this work was to further investigate the synthesis of substituted amides and hydrazides of pectic acid and to study their activity as flocculants. They used pectin, methylation products of pectin, pectic acid, and methyl pectates. The synthesized analogs of pectinic materials containing nitrogen are essentially copolymers of hydrazido (amido) and carboxyl (methoxyl) derivatives of D-galacturonic acid. The flocculant activity of the new polymers was monitored with simulated drainage water containing kaolin or abrasive powder (for glass manufacture) in the presence of polyvalent metal ions. The use of the new ampholytic flocculants in the purification of water from suspended impurities permits a high degree of clarification with a sharp decrease in reagent consumption.

  18. Design, synthesis, and evaluation of caffeic acid amides as synergists to sensitize fluconazole-resistant Candida albicans to fluconazole.

    PubMed

    Dai, Li; Zang, Chengxu; Tian, Shujuan; Liu, Wei; Tan, Shanlun; Cai, Zhan; Ni, Tingjunhong; An, Maomao; Li, Ran; Gao, Yue; Zhang, Dazhi; Jiang, Yuanying

    2015-01-01

    A series of caffeic acid amides were designed, synthesized, and their synergistic activity with fluconazole against fluconazole-resistant Candida albicans was evaluated in vitro. The title caffeic acid amides 3-30 except 26 exhibited potent activity, and the subsequent SAR study was conducted. Compound 3, 5, 21, and 34c, at a concentration of 1.0 μg/ml, decreased the MIC₈₀ of fluconazole from 128.0 μg/ml to 1.0-0.5 μg/ml against the fluconazole-resistant C. albicans. This result suggests that the caffeic acid amides, as synergists, can sensitize drug-resistant fungi to fluconazole. The SAR study indicated that the dihydroxyl groups and the amido groups linking to phenyl or heterocyclic rings are the important pharmacophores of the caffeic acid amides.

  19. The inhibitory effect of some amphoteric surfactants on the irritation potential of alkylsulphates.

    PubMed

    Domínguez, J G; Balaguer, F; Parra, J L; Pelejero, C M

    1981-04-01

    Synopsis The physico-chemical and biological properties of an amphoteric/anionic system and its behaviour against a proteinic support have been thoroughly investigated. A considerable inhibition of adsorption of SLS (sodium lauryl sulphate) on human callus caused by the presence of definite amounts of AABet (alkyl-amido-betaines) in the treatment bath is observed. These physico-chemical results are in agreement with those obtained by some in vivo biological tests. A mechanism of the process via the formation of mixed micelles is postulated emphasizing the stability of such systems as a function of pH, the influence of the chain length of the amphoteric surfactant and the molar relative ratio SLS/AABet. Consequently, our work offers the possibility of a wide applicability of the synergic mixtures of both types of surfactants to inhibit considerably skin irritation of cosmetic finished products.

  20. Structure of an Amino Acid-Decorated Exopolysaccharide Secreted by a Vibrio alginolyticus Strain

    PubMed Central

    Drouillard, Sophie; Jeacomine, Isabelle; Buon, Laurine; Boisset, Claire; Courtois, Anthony; Thollas, Bertrand; Morvan, Pierre-Yves; Vallée, Romuald; Helbert, William

    2015-01-01

    Vibrio alginolyticus (CNCM I-4994) secretes an exopolysaccharide that can be used as an ingredient in cosmetic applications. The structure was resolved using chromatography and one- and two-dimensional NMR spectroscopy experiments. The results show that the carbohydrate backbone is made of two residues: d-galacturonic acid and N-acetyl-d-glucosamine (GlcNac), which together constitute a tetrasaccharide repetition unit: [→3)-α-d-GalA-(1→4)-α-d-GalA-(1→3)-α-d-GalA-(1→3)-β-GlcNAc(1→]. Two amino acids, alanine and serine, are linked to GalA residues via amido linkages. The position and the distribution of the amino acids were characterized by two-dimensional NMR spectroscopy. To our knowledge, this is the first description of a structure for a marine exopolysaccharide decorated with an amino acid. PMID:26528992

  1. Homogeneous models for mechanisms of surface reactions: Propylene ammoxidation

    SciTech Connect

    Chan, D.M.T.; Nugent, W.A.; Fultz, W.C.; Rose, D.C.; Tulip, T.H.

    1987-04-01

    The proposed active sites on the catalyst surface in heterogeneous propylene ammoxidation have been successfully modelled by structurally characterized pinacolato W(VI) tert-butylimido complexes. These compounds exist as an equilibrating mixture of amine-bis(imido) and imido-bis(amido) complexes, the position of this equilibrium is dependent on the electronic nature of the glycolate ligand. Both of the C-N bond-forming reactions proposed in recent studies by Grasselli et al. (1) have been reproduced using discrete Group VI d{sup 0} organoimido complexes under mild conditions suitable for detailed mechanistic studies. These reactions are: (1) oxidative trapping of radicals at molybdenum imido sites, and (2) migration of the allyl group from oxygen to an imido nitrogen atom.

  2. 7-(2,2-Dimethylpropanamido)-2-methyl-1,8-naphthyridin-1-ium chloride monohydrate

    PubMed Central

    Fun, Hoong-Kun; Kia, Reza; Das, Nirmal Kumar; Sen, Debabrata; Goswami, Shyamaprosad

    2009-01-01

    The asymmetric unit of the title compound, C14H18N3O+·Cl−·H2O, comprises a substituted amido–naphthyridine cation, a chloride anion and a water mol­ecule of crystallization. Intra­molecular C—H⋯O hydrogen bonds generate six-membered rings, producing an S(6) ring motif. The amido group is twisted from the naphthyridine ring, making a dihedral angle of 17.65 (7)°. The crystal structure is stabilized by inter­molecular N—H⋯O, N—H⋯Cl, O—H⋯Cl (× 2), and C—H⋯O (× 2) hydrogen bonds. These inter­actions linked neighbouring mol­ecules into chains along the a and b axes of the crystal, thus forming mol­ecular sheets parallel to the (001) plane. PMID:21581941

  3. Toward multifunctional "clickable" diamond nanoparticles.

    PubMed

    Khanal, Manakamana; Turcheniuk, Volodymyr; Barras, Alexandre; Rosay, Elodie; Bande, Omprakash; Siriwardena, Aloysius; Zaitsev, Vladimir; Pan, Guo-Hui; Boukherroub, Rabah; Szunerits, Sabine

    2015-04-07

    Nanodiamonds (NDs) are among the most promising new carbon based materials for biomedical applications, and the simultaneous integration of various functions onto NDs is an urgent necessity. A multifunctional nanodiamond based formulation is proposed here. Our strategy relies on orthogonal surface modification using different dopamine anchors. NDs simultaneously functionalized with triethylene glycol (EG) and azide (-N3) functions were fabricated through a stoichiometrically controlled integration of the dopamine ligands onto the surface of hydroxylated NDs. The presence of EG functionalities rendered NDs soluble in water and biological media, while the -N3 group allowed postsynthetic modification of the NDs using "click" chemistry. As a proof of principle, alkynyl terminated di(amido amine) ligands were linked to these ND particles.

  4. Transcriptional responses of human aortic endothelial cells to nanoconstructs used in biomedical applications

    PubMed Central

    Moos, Philip J.; Honeggar, Matthew; Malugin, Alexander; Herd, Heather; Thiagarajan, Giridhar; Ghandehari, Hamidreza

    2013-01-01

    Understanding the potential toxicities of manufactured nanoconstructs used for drug delivery and biomedical applications may help improve their safety. We sought to determine if surface modified silica nanoparticles and poly(amido amine) dendrimers elicit genotoxic responses on vascular endothelial cells. The nanoconstructs utilized in this study had distinct geometry (spheres vs. worms) and surface charge, which were used to evaluate the contributions of these parameters to any potential adverse effects of these materials. Time-dependent cytotoxicity was found for surfaced-functionalized but geometrically distinct silica materials while amine-terminated dendrimers displayed time-independent cytotoxicity and carboxylated dendrimers were nontoxic in our assays. Transcriptomic evaluation of HAEC responses indicated time-dependent gene induction following silica exposure, consisting of cell cycle gene repression and pro-inflammatory gene induction. However, the dendrimers did not induce genomic toxicity, despite displaying general cytotoxicity. PMID:23806026

  5. Carbamo­yl(di­amino­methyl­idene)aza­nium 3-nitro-5-oxo-4,5-di­hydro-1H-1,2,4-triazol-4-ide

    PubMed Central

    Huang, Xin-Ping; Wang, Bo-Zhou; Li, Dong-Ping; Ng, Seik Weng

    2013-01-01

    In the anion of the title salt, C2H7N4O+·C2HN4O3 −, the negative charge resides formally on the N3 atom of the triazole ring. In the crystal, the N3 and exocyclic O atoms are hydrogen-bond acceptors with respect to the formally double-bond iminium and amido N atoms of the cation. The cation and anion are almost planar (r.m.s. deviations = 0.012 and 0.051 Å, respectively), but they are slightly bent with respect to each other [dihedral angle = 12.6 (1)°]. In the crystal, adjacent anions and cations are linked by extensive N—H⋯N and N—H⋯O hydrogen bonds, generating a ribbon running along the b-axis direction. PMID:24046649

  6. Synthesis of fluorescent dipeptidomimetics and their ribosomal incorporation into green fluorescent protein.

    PubMed

    Chowdhury, Sandipan Roy; Maini, Rumit; Dedkova, Larisa M; Hecht, Sidney M

    2015-11-01

    The synthesis and incorporation into position 66 of green fluorescent protein (GFP) by in vitro protein translation of novel oxazole and thiazole based dipeptidomimetics are described. The compounds may be regarded as GFP chromophore analogues, and are strongly fluorescent. An α-amido-β-ketoester intermediate was obtained via bisacylation of a protected glycine. The intermediate underwent dehydrative cyclization to afford the 1,3-oxazole and was treated with Lawesson's reagent to furnish the 1,3-thiazole. When these fluorophores were introduced into position 66 of GFP in place of Tyr66, the resulting GFP analogues exhibited fluorescence emission several-fold greater than wild-type GFP; the emission was also shifted to shorter wavelength. It may be noted that compared to the typical fluorophores formed in the natural and modified fluorescent proteins, the oxazole and thiazole fluorophores are completely stable and do not require activation by posttranslational modification to exhibit fluorescence.

  7. Photocatalytic activity of Cr-doped TiO2 nanoparticles deposited on porous multicrystalline silicon films.

    PubMed

    Hajjaji, Anouar; Trabelsi, Khaled; Atyaoui, Atef; Gaidi, Mounir; Bousselmi, Latifa; Bessais, Brahim; El Khakani, My Ali

    2014-01-01

    This work deals with the deposition of Cr-doped TiO2 thin films on porous silicon (PS) prepared from electrochemical anodization of multicrystalline (mc-Si) Si wafers. The effect of Cr doping on the properties of the TiO2-Cr/PS/Si samples has been investigated by means of X-ray diffraction (XRD), atomic force microcopy (AFM), photoluminescence, lifetime, and laser beam-induced current (LBIC) measurements. The photocatalytic activity is carried out on TiO2-Cr/PS/Si samples. It was found that the TiO2-Cr/PS/mc-Si type structure degrades an organic pollutant (amido black) under ultraviolet (UV) light. A noticeable degradation of the pollutant is obtained for a Cr doping of 2 at. %. This result is discussed in light of LBIC and photoluminescence measurements.

  8. Oxygen reduction reaction catalyzed by cobalt(III) complexes of macrocyclic ligands supported on multiwalled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Nasini, Udaya B.; Gartia, Yashraj; Ramidi, Punnamchandar; Kazi, Abul; Shaikh, Ali U.; Ghosh, Anindya

    2013-04-01

    A class of amido-macrocyclic cobalt(III) complexes along with multiwalled carbon nanotubes have been studied for electro-catalytic activity to reduce oxygen. These complexes are efficient for oxygen reduction reaction (ORR) in wide range of pH conditions by following ideal fuel cell reduction mechanism. Depending on the stability of complexes in different pH, electrochemical studies were performed to predict the reduction mechanism. Rotating disk electrode and rotating ring-disk electrode studies show that these complexes reduce oxygen via four electron reduction process in mild acidic pH and two step two electron reduction processes in basic conditions, with negligible amount of hydrogen peroxide generation.

  9. [The mechanism of action of cannabis and cannabinoids].

    PubMed

    Scholten, W K

    2006-01-21

    The effect ofcannabis can be explained on the basis of the function of the cannabinoid receptor system, which consists of CB receptors (CB1, CB2), endoligands to activate these receptors and an enzyme--fatty acid amidohydrolase--to metabolize the endoligands. The endoligands of the cannabinoid receptor system are arachidonic acid-like substances, and are called endocannabinoids. Indications exist that the body also contains arachidonic acid-like substances that inhibit fatty acid amido hydrolase. Various cannabinoids have diverse effects on the receptors, functioning as agonists, antagonists or partial antagonists, as well as affecting the vanilloid receptor. Many known effects ofcannabis can be explained on the basis of this mechanism of action as can the use ofcannabis in various conditions including multiple sclerosis, Parkinson's disease, glaucoma, nausea, vomiting and rheumatoid arthritis.

  10. Comparison of the solid-phase fragment condensation and phase-change approaches in the synthesis of salmon I calcitonin.

    PubMed

    Gatos, D; Tzavara, C

    2001-02-01

    Salmon I calcitonin was synthesized using both phase-change and conventional solid-phase fragment condensation (SPFC) approaches, utilizing the Rink amide linker (Fmoc-amido-2,4-dimethoxybenzyl-4-phenoxyacetic acid) combined with 2-chlorotrityl resin and the Fmoc/tBu(Trt)-based protection scheme. Phase-change synthesis, performed by the selective detachment of the fully protected C-terminal 22-mer peptide-linker from the resin and subsequent condensation in solution with the N-terminal 1-10 fragment, gave a product of slightly less purity (85 vs. 92%) than the corresponding synthesis on the solid-phase. In both cases salmon I calcitonin was easily obtained in high purity.

  11. Structure of an Amino Acid-Decorated Exopolysaccharide Secreted by a Vibrio alginolyticus Strain.

    PubMed

    Drouillard, Sophie; Jeacomine, Isabelle; Buon, Laurine; Boisset, Claire; Courtois, Anthony; Thollas, Bertrand; Morvan, Pierre-Yves; Vallée, Romuald; Helbert, William

    2015-10-30

    Vibrio alginolyticus (CNCM I-4994) secretes an exopolysaccharide that can be used as an ingredient in cosmetic applications. The structure was resolved using chromatography and one- and two-dimensional NMR spectroscopy experiments. The results show that the carbohydrate backbone is made of two residues: d-galacturonic acid and N-acetyl-d-glucosamine (GlcNac), which together constitute a tetrasaccharide repetition unit: [→3)-α-d-GalA-(1→4)-α-d-GalA-(1→3)-α-d-GalA-(1→3)-β-GlcNAc(1→]. Two amino acids, alanine and serine, are linked to GalA residues via amido linkages. The position and the distribution of the amino acids were characterized by two-dimensional NMR spectroscopy. To our knowledge, this is the first description of a structure for a marine exopolysaccharide decorated with an amino acid.

  12. Regioselective Synthesis of Quinazolinone-/Phenanthridine-Fused Heteropolycycles by Pd-Catalyzed Direct Intramolecular Aerobic Oxidative C-H Amination from Aromatic Strained Amides.

    PubMed

    Banerji, Biswadip; Bera, Suvankar; Chatterjee, Satadru; Killi, Sunil Kumar; Adhikary, Saswati

    2016-03-01

    A new route for the expedient synthesis of specific regioisomer of quinazolinone- and phenanthridine-fused heterocycles through a palladium-catalyzed regioselective intramolecular oxidative C-H amination from cyclic strained amides of aromatic amido-amidine systems (quinazolinones) has been developed. The amine functionalization of an aromatic C-H bond from a strained amide nitrogen involved in aromaticity has been a challenging work so far. The fusion of two heterocyclic cores, quinazolinone and phenanthridine, can occur in two different ways (linear and angular), but under the conditions reported here, only linear type isomer is exclusively produced. This approach provides a variety of substituted quinazolinone- and phenanthridine-fused derivatives in moderate to excellent yields. Moreover, such fused molecules show excellent fluorescent properties and have great potential to be a new type of fluorophores for the use in medicinal and material science.

  13. Access to enantioenriched alpha-amino esters via rhodium-catalyzed 1,4-addition/enantioselective protonation.

    PubMed

    Navarre, Laure; Martinez, Rémi; Genet, Jean-Pierre; Darses, Sylvain

    2008-05-14

    Conjugate addition of potassium trifluoro(organo)borates 2 to dehydroalanine derivatives 1, mediated by a chiral rhodium catalyst and in situ enantioselective protonation, afforded straightforward access to a variety of protected alpha-amino esters 3 with high yields and enantiomeric excesses up to 95%. Among the tested chiral ligands and proton sources, Binap, in combination with guaiacol (2-methoxyphenol), an inexpensive and nontoxic phenol, afforded the highest asymmetric inductions. Organostannanes have also shown to participate in this reaction. By a fine-tuning of the ester moiety, and using Difluorophos as chiral ligand, increased levels of enantioselectivity, generally close to 95%, were achieved. Deuterium labeling experiments revealed, and DFT calculation supported, an unusual mechanism involving a hydride transfer from the amido substituent to the alpha carbon explaining the high levels of enantioselectivity attained in controlling this alpha chiral center.

  14. Possibility of Solid-State Graft Copolymerization on Poly(ethylene terephthalate) Films by Plasma Irradiation and Effects of Surface Modification

    NASA Astrophysics Data System (ADS)

    Narushima, Kazuo; Matsuda, Noriko; Mizutani, Chie; Yamashita, Nanami; Inagaki, Norihiro; Iio, Kokoro; Isono, Yoshihiro; Islam, Mohammed Rafiqul

    2007-07-01

    A solid-state graft copolymerization for poly(ethylene terephthalate) (PET) films was proposed for a new surface modification technique. The functional groups included in graft monomers can be introduced on a PET surface. Allylbiguanide hydrochloric acid salt (ABG), N-methylol acrylamide (NM-AAm), and N-isopropyl acrylamide (NIP-AAm) were used as graft monomers. This technique led to a large change in the N/C atomic ratio on the PET film surfaces, which shows that nitrogen functional groups were introduced on PET surfaces. On the grafted PET films, a new N 1s spectrum appeared. This N 1s spectrum contained two components, namely, amino and amido groups, which suggests that the two groups were introduced onto the PET surfaces. In particular, isopropyl groups were introduced on the PET surface in the case of NIP-AAm. The formation of these functional groups demonstrated changes in the surface properties of PET, such as improved wettability.

  15. Synthesis, characterization and biological activity of Rhein-cyclodextrin conjugate

    NASA Astrophysics Data System (ADS)

    Liu, Manshuo; Lv, Pin; Liao, Rongqiang; Zhao, Yulin; Yang, Bo

    2017-01-01

    Cyclodextrin conjugate complexation is a useful method to enhance the solubility and absorption of poorly soluble drugs. A series of new Rhein-β-cyclodextrin conjugates (Rh-CD conjugates) have been synthesized and examined. Rhein is covalently linked with the β-CD by amido linkage in a 1:1 molar ratio. The conjugates were characterized by 1H NMR, 13C NMR, HRMS, powder X-ray diffraction (powder XRD) as well as thermogravimetric analysis (TGA). The results reveal that incorporation of β-CD could improve the aqueous solubility of Rhein and the cytotoxicity against hepatocellular carcinoma (HepG2) cell line as well as antibacterial activity against three organisms. The improved biological activity and the satisfactory water solubility of the conjugates will be potentially useful for developing novel drug-cyclodextrin conjugates, such as herbal medicine.

  16. Detection of Proteins on Blot Membranes.

    PubMed

    Goldman, Aaron; Harper, Sandra; Speicher, David W

    2016-11-01

    Staining of blot membranes enables the visualization of bound proteins. Proteins are usually transferred to blot membranes by electroblotting, by direct spotting of protein solutions, or by contact blots. Staining allows the efficiency of transfer to the membrane to be monitored. This unit describes protocols for staining proteins after electroblotting from polyacrylamide gels to blot membranes such as polyvinylidene difluoride (PVDF), nitrocellulose, or nylon membranes. The same methods can be used if proteins are directly spotted, either manually or using robotics. Protocols are included for seven general protein stains (amido black, Coomassie blue, Ponceau S, colloidal gold, colloidal silver, India ink, and MemCode) and three fluorescent protein stains (fluorescamine, IAEDANS, and SYPRO Ruby). Also included is an in-depth discussion of the different blot membrane types and the compatibility of different protein stains with downstream applications, such as immunoblotting or N-terminal Edman sequencing. © 2016 by John Wiley & Sons, Inc.

  17. Bisorption of chromium(VI) from aqueous solutions by Sargassum thunbergii Kuntze

    PubMed Central

    Wang, Yun; Li, Yingxia; Zhao, Feng Juan

    2014-01-01

    The potential to remove Cr(VI) from aqueous solutions through biosorption using dried Sargassum thunbergii Kuntze was investigated with respect to initial pH, amount of biosorbent, initial Cr(VI) concentrations and temperature. Cr(VI) removal efficiency was influenced significantly by the variation of pH, and the optimum pH was about 2.0. Moreover, the biosorption kinetics followed the pseudo-second-order model. The adsorption equilibrium was well described by the Langmuir and Freundlich isotherm models. The maximum adsorption capacity was 1.855 mmol/g at 318 K and pH 2.0. The adsorption processes were endothermic and the biosorption heat was 15.8 kJ/mol. Furthermore, the Fourier transform infrared spectroscopy suggested that amido-, hydroxyl-, C = O and C—O groups were involved in the biosorption of Cr(VI) onto S. thunbergii. PMID:26019511

  18. Aryl Amination using Ligand-Free Ni(II) Salts and Photoredox Catalysis

    PubMed Central

    Corcoran, Emily B.; Pirnot, Michael T.; Lin, Shishi; Dreher, Spencer D.; DiRocco, Daniel A.; Davies, Ian W.; Buchwald, Stephen L.; MacMillan, David W. C.

    2016-01-01

    Over the past two decades, there have been major developments in transition metal-catalyzed aminations of aryl halides to form anilines, a common structure found in drug agents, natural product isolates, and fine chemicals. Many of these approaches have enabled highly efficient and selective coupling through the design of specialized ligands, which facilitate reductive elimination from a destabilized metal center. We postulated that a general and complementary method for C–N bond formation could be developed through the destabilization of a metal amido complex via photoredox catalysis, thus providing an alternative approach to the use of structurally complex ligand systems. Herein, we report the development of a distinct mechanistic paradigm for aryl amination using ligand-free nickel(II) salts, in which facile reductive elimination from the nickel metal center is induced via a photoredox-catalyzed electron-transfer event. PMID:27338703

  19. Decolorization of synthetic dyes by solid state cultures of Lentinula (Lentinus) edodes producing manganese peroxidase as the main ligninolytic enzyme.

    PubMed

    Boer, Cinthia Gandolfi; Obici, Larissa; de Souza, Cristina Giatti Marques; Peralta, Rosane M

    2004-09-01

    The ability of the white-rot fungus Lentinula (Lentinus) edodes to decolorize several synthetic dyes was investigated using solid state cultures with corn cob as substrate. Cultures, containing amido black, congo red, trypan blue, methyl green, remazol brilliant blue R, methyl violet, ethyl violet and Poly R478 at 200 ppm, were completely decolorized after 18 days of incubation. Partial decolorization was observed in the cultures containing 200 ppm of brilliant cresyl blue and methylene blue. High manganese peroxidase activity (2600 U/g substrate), but very low lignin peroxidase (<10 U/g substrate) and laccase (<16 U/g substrate) activities were detected in the cultures. In vitro, the dye decolorization was markedly decreased by the absence of manganic ions and H2O2. These data suggest that manganese peroxidase appear to be the main responsible for the capability of L. edodes to decolorize synthetic dyes.

  20. Education Through Aerospace Components. (Spanish Title: Educación Através de Elementos Aeroespaciales.) Educação Através de Elementos Aeroespaciais

    NASA Astrophysics Data System (ADS)

    Barbosa Loureda, Oswaldo; Sobral de Araújo, Jéssyca B.

    2008-12-01

    tal, dispõe-se de diversos métodos e meios que vêm implantar idéias em prol do avanço do povo brasileiro nos aspectos pedagógicos, psicológicos e culturais. Alfabetizar é um ato que exige muito cuidado e responsabilidade; o comportamento e desempenho de um indivíduo na sociedade é resultado da maneira com que ele foi instruído. Contudo, a área de exatas exige especial atenção, pois os conhecimentos adquiridos são imprescindíveis para o desenvolvimento pessoal do individuo, assim como para o futuro tecnológico do País. Como meio alternativo ou complementar de ensino é sugerido o uso de elementos aeroespaciais, devido ao fato de comportar uma vasta quantidade e qualidade de disciplinas envolvidas respectivamente com competências de grande importância para sua vida profissional futura. Uma nova Corrida acontece, porém dessa vez a meta não é a Lua e sim o conhecimento.

  1. 30 years later: Social Representations about AIDS and sexual practices of rural towns residents.

    PubMed

    Furtado, Francisca Marina de Souza Freire; Santos, José Anderson Galdino; Loredanna, Stedile; Araújo, Eunice; Saldanha, Ana Alayde Werba; Silva, Josevânia da

    2016-06-01

    no estado da Paraíba/Brasil. Os dados foram coletados por um meio de um questionário e o teste de associação livre de palavras. Os resultados mostraram baixa preocupação com doença, percepção de invulnerabilidade à contaminação pelo HIV e o não uso do preservativo nas relações sexuais, sendo a confiança no parceiro o principal motivo relacionado. Também mostraram perdurar representações de natureza pejorativa e estereotipada, revelando que ainda perduram, no meio rural, crenças e representações referentes ao início da epidemia. A partir de tais achados, é possível apontar deficiências em termos de cuidados oferecidos pelos serviços de saúde nestas localidades, o que pode resultar em maiores vulnerabilidades dessa população ao adoecimento, havendo assim a necessidade da intensificação de campanhas de informação e intervenção.

  2. Quantum Chemical Studies of the Substituent Effect on the Reaction of Carbonyl Oxime with Amine.

    PubMed

    Kaya, Yunus

    2016-07-21

    The reaction of the two different substitue carbonyl oximes (isonitrosoacetylnaphthaline, inanH and nitro-isonitrosoacetophenone, ninapH) with two different amines (1-phenylethanol amine, pea, and ethanol amine, ea) was carried out and characterized by elemental analyses, IR, and (1)H and (13)C NMR spectroscopic methods. As a result of these experimental studies, two different levels for all reactions were determined: (I) formation of imine oxime and (II) rearrangement of imine oxime or formation of amido alcohol. After a mechanism was suggested for all of these reactions, the reaction mechanism of carbonyl oxime with amine was first studied by means of the B3LYP/6-311G(d,p) method. Because of the deficiency of density functional theory (DFT) on dispersion effects, the wB97X-D/6-311G(d,p) method, which includes dispersion correction, was used to obtain the reaction heat and free energy barriers to explain why the formation (imine oxime) and unexpected rearrangement products (amido alcohol) occurred or did not occur. The statistical thermodynamic method was used to obtain the changes in thermodynamic properties of the studied molecules between 100 and 500 K. From a kinetic viewpoint, the slowest step of the reactions is the IN1-TS2-IN2 step, which determines the steps of the reaction kinetics. In addition, spectroscopic properties such as vibrational and NMR chemical shifts were studied for all of the molecules. The frontier molecular orbitals (FMOs), highest occupied molecular orbitals (HOMOs), and lowest unoccupied molecular orbitals (LUMOs) were monitored for all of the molecules.

  3. Structural Characterization of a Specific Glycopeptidolipid Containing a Novel N-Acyl-Deoxy Sugar from Mycobacterium intracellulare Serotype 7 and Genetic Analysis of Its Glycosylation Pathway▿ †

    PubMed Central

    Fujiwara, Nagatoshi; Nakata, Noboru; Maeda, Shinji; Naka, Takashi; Doe, Matsumi; Yano, Ikuya; Kobayashi, Kazuo

    2007-01-01

    The nontuberculous Mycobacterium avium-Mycobacterium intracellulare complex (MAC) is distributed ubiquitously in the environment and is an important cause of respiratory and lymphatic disease in humans and animals. These species produce polar glycopeptidolipids (GPLs), and of particular interest is their serotype-specific antigenicity. Structurally, GPLs contain an N-acylated tetrapeptide-amino alcohol core that is glycosylated at the C terminal with 3,4-di-O-methyl rhamnose and at the d-allo-threonine with a 6-deoxy-talose. This serotype nonspecific GPL is found in all MAC species. The serotype-specific GPLs are further glycosylated with a variable haptenic oligosaccharide at 6-deoxy-talose. At present, 31 distinct serotype-specific GPLs have been identified on the basis of oligosaccharide composition, and the complete structures of 14 serotype-specific GPLs have been defined. It is considered that the modification of the GPL structure plays an important role in bacterial physiology, pathogenesis, and host immune responses. In this study, we defined the complete structure of a novel serotype 7 GPL that has a unique terminal amido sugar. The main molecular mass is 1,874, and attached to the tetrapeptide-amino alcohol core is the serotype 7-specific oligosaccharide unit of 4-2′-hydroxypropanoyl-amido-4,6-dideoxy-2-O-methyl-β-hexose-(1→3)-α-l-rhamnose-(1→3)-α-l-rhamnose-(1→3)-α-l-rhamnose-(1→2)-α-l-6-deoxy-talose. Moreover, we isolated and characterized the serotype 7-specific gene cluster involved in glycosylation of the oligosaccharide. Nine open reading frames (ORFs) were observed in the cluster. Based on the sequence homology, the ORFs are thought to participate in the biosynthesis of the serotype 7 GPL. PMID:17122347

  4. Redox regulation of protein tyrosine phosphatase 1B (PTP1B): Importance of steric and electronic effects on the unusual cyclization of the sulfenic acid intermediate to a sulfenyl amide

    NASA Astrophysics Data System (ADS)

    Sarma, Bani Kanta

    2013-09-01

    The redox regulation of protein tyrosine phosphatase 1B (PTP1B) via the unusual transformation of its sulfenic acid (PTP1B-SOH) to a cyclic sulfenyl amide intermediate is studied by using small molecule chemical models. These studies suggest that the sulfenic acids derived from the H2O2-mediated reactions o-amido thiophenols do not efficiently cyclize to sulfenyl amides and the sulfenic acids produced in situ can be trapped by using methyl iodide. Theoretical calculations suggest that the most stable conformer of such sulfenic acids are stabilized by nO → σ*S-OH orbital interactions, which force the -OH group to adopt a position trans to the S⋯O interaction, leading to an almost linear arrangement of the O⋯S-O moiety and this may be the reason for the slow cyclization of such sulfenic acids to their corresponding sulfenyl amides. On the other hand, additional substituents at the 6-position of o-amido phenylsulfenic acids that can induce steric environment and alter the electronic properties around the sulfenic acid moiety by S⋯N or S⋯O nonbonded interactions destabilize the sulfenic acids by inducing strain in the molecule. This may lead to efficient the cyclization of such sulfenic acids. This model study suggests that the amino acid residues in the close proximity of the sulfenic acid moiety in PTP1B may play an important role in the cyclization of PTP1B-SOH to produce the corresponding sulfenyl amide.

  5. Rare earth complexes of phenoxy-thioether ligands: synthesis and reactivity in the ring opening polymerization of cyclic esters.

    PubMed

    Mazzeo, Mina; Tramontano, Roberta; Lamberti, Marina; Pilone, Alessia; Milione, Stefano; Pellecchia, Claudio

    2013-07-07

    The potential of the phenoxy-thioether moieties as ancillary ligands in the coordination chemistry of group 3 metals was explored. The amine elimination reactions between yttrium and scandium amido precursors {M [N(SiHMe2)2]3 (THF)n} with the proligands {4,6-tBu2-OC6H2-2-CH2S(2-R-C6H4)}H [R = H (L1-H), CH3 (L2-H), Br (L3-H), CF3 (L4-H)], bearing different substituents at the ortho position of the thiophenol aryl ring, were studied. The outcome of aminolysis reactions gave different results depending on the structure of the proligand and the reaction conditions. Heteroleptic scandium and yttrium amido complexes with general formula {(L)2M [N(SiHMe2)2] (THF)n} were prevailingly obtained from phenoxy-thioether proligands L1-H and L4-H. In contrast, homoleptic yttrium complexes bearing three phenoxy-thioether ligands were favored with L2-H and L3-H. The activities of all the synthesized complexes toward the ring-opening polymerization of ε-caprolactone and L- and rac-lactide were investigated, also in combination with an alcohol as an external chain transfer agent. Polyesters with controlled molecular parameters (Mn, end groups) and low polydispersities were obtained. The monoinsertion adduct, produced by the reaction of {(L1)2ScN(SiHMe2)2} and 1 equiv. of ε-caprolactone, was isolated proving that a coordination-insertion mechanism of ring-opening polymerization was operative. In the polymerization of rac-lactide, yttrium complexes exerted a high degree of stereocontrol producing heterotactic polylactides (P(r) up to 0.91).

  6. Carbohydrate protease conjugates: Stabilized proteases for peptide synthesis

    SciTech Connect

    Wartchow, C.A.; Wang, Peng; Bednarski, M.D.; Callstrom, M.R. |

    1995-12-31

    The synthesis of oligopeptides using stable carbohydrate protease conjugates (CPCs) was examined in acetonitrile solvent systems. CPC[{alpha}-chymotrypsin] was used for the preparation of peptides containing histidine, phenylalanine, tryptophan in the P{sub 1} position in 60-93% yield. The CPC[{alpha}-chymotrypsin]-catalyzed synthesis of octamer Z-Gly-Gly-Phe-Gly-Gly-Phe-Gly-Gly-OEt from Z-Gly-Gly-Phe-Gly-Gly-Phe-OMe was achieved in 71% yield demonstrating that synthesis peptides containing both hydrophylic and hydrophobic amino acids. The P{sub 2} specificity of papain for aromatic residues was utilized for the 2 + 3 coupling of Z-Tyr-Gly-OMe to H{sub 2}N-Gly-Phe-Leu-OH to generate the leucine enkephalin derivative in 79% yield. Although papain is nonspecific for the hydrolysis of N-benzyloxycarbonyl amino acid methyl esters in aqueous solution, the rates of synthesis for these derivitives with nucleophile leucine tert-butyl ester differed by nearly 2 orders of magnitude. CPC[thermolysin] was used to prepare the aspartame precursor Z-Asp-Phe-OMe in 90% yield. The increased stability of CPCs prepared from periodate-modified poly(2-methacryl- amido-2-deoxy-D-glucose), poly(2-methacrylamido-2-deoxy-D-galactose), and poly(5-methacryl-amido-5-deoxy-D-ribose), carbohydrate materials designed to increase the aldehyde concentration in aqueous solution, suggests that the stability of CPCs is directly related to the aldehyde concentration of the carbohydrate material. Periodate oxidation of poly(2-methacrylamido-2-deoxy-D-glucose) followed by covalent attachment to {alpha}-chymotrypsin gave a CPC with catalytic activity in potassium phosphate buffer at 90{degrees}C for 2 h. 1 fig., 1 tab., 40 refs.

  7. [Attenuated total reflection-fourier transform infrared spectroscopic study of dried shark fin products].

    PubMed

    Han, Wan-qing; Luo, Hai-ying; Xian, Yan-ping; Luo, Dong-hui; Mu, Torng-na; Guo, Xin-dong

    2015-02-01

    Sixty-four pieces of shark fin dried products (including real, fake and artificial shark fin products) and real products coated with gelatin were rapidly and nondestructively analyzed by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR). The characteristic of IR spectrograms among the above four kinds of samples were systematically studied and comparied, the results showed that the spectrograms of the same kind of samples were repeatable, and different kinds of shark fin products presented significant differences in the spectrograms, which mainly manifested as the specific absorption peaks of amido bonds in protein (1650, 1544 cm(-1)) and skeletal vibration in polysaccharide (1050 cm(-1)). The spectrograms of real shark fins were characterized by the strong absorption peaks of protein characteristic amide I and II absorbent (1650, 1544 cm(-1)) and relatively weak C--O--C vibration absorbent (1050 cm(-1)) owing to the high content of protein and relatively low level of polysaccharide. For fake shark fin products that were molded form by mixing together with the offcut of shark, collagen and other substances, the introduction of non-protein materials leaded to the weaker amido bonds absorbent than real products along with a 30 cm(-1) blue shift of amide I absorbent. Opposite to the real sample, the relatively strong absorption peak of polysaccharide (approximately 1047 cm(-1)) and barely existed amide absorbent were the key features of the spectrogram of artificial samples, which was synthersized by polysaccharide like sodium alginate. Real samples coated with gelatin, the peak strength of protein and polysaccharide were decreased simultaneously when the data collection was taken at the surface of sample, while the spectrogram presented no significant difference to real samples when the data was collected in the section. The results above indicated that by analyzing the characteristic of IR spectrograms and the value range of Apro

  8. N-ammonia assimilation, 2-oxoglutarate transport, and glutamate export in spinach chloroplasts in the presence of dicarboxylates in the light.

    PubMed

    Woo, K C; Boyle, F A; Flugge, I U; Heldt, H W

    1987-11-01

    The direct incorporation of (15)NH(4)Cl into amino acids in illuminated spinach (Spinacia oleracea L.) chloroplasts in the presence of 2-oxoglutarate plus malate was determined. The amido-N of glutamine was the most highly labeled N-atom during (15)NH(4) assimilation in the presence of malate. In 4 minutes the (15)N-label of the amido-N of glutamine was 37% enriched. In contrast, values obtained for both the N-atom of glutamate and the amino-N of glutamine were only about 20% while that of the N-atom of aspartate was only 3%. The addition of malate during the assimilation of (15)NH(4)Cl and Na(15)NO(2) greatly increased the (15)N-label into glutamine but did not qualitatively change the order of the incorporation of (15)N-label into all the amino acids examined. This evidence indicates the direct involvement of the glutamine synthetase/glutamate synthase pathway for ammonia and nitrite assimilation in isolated chloroplasts. The addition of malate or succinate during ammonia assimilation also led to more than 3-fold increase in [(14)C]2-oxoglutarate transport into the chloroplast as well as an increase in the export of [(14)C]glutamate out of the chloroplast. Little [(14)C]glutamine was detected in the medium of the chloroplast preparations. The stimulation of (15)N-incorporation and [(14)C]glutamate export by malate could be directly attributed to the increase in 2-oxoglutarate transport activity (via the 2-oxoglutarate translocator) observed in the presence of exogenous malate.

  9. /sup 15/N-Ammonia assimilation, 2-oxoglutarate transport, and glutamate export in spinach chloroplasts in the presence of dicarboxylates in the light

    SciTech Connect

    Woo, K.C.; Boyle, F.A.; Flugge, I.U.; Heldt, H.W.

    1987-11-01

    The direct incorporation of /sup 15/NH/sub 4/Cl into amino acids in illuminated spinach (Spinacia oleracea L.) chloroplasts in the presence of 2-oxoglutarate plus malate was determined. The amido-N of glutamine was the most highly labeled N-atom during /sup 15/NH/sub 4/ assimilation in the presence of malate. In 4 minutes the /sup 15/N-label of the amido-N of glutamine was 37% enriched. In contrast, values obtained for both the N-atom of glutamate and the amino-N of glutamine were only about 20% while that of the N-atom of aspartate was only 3%. The addition of malate during the assimilation of /sup 15/NH/sub 4/Cl and Na/sup 15/NO/sub 2/ greatly increased the /sup 15/N-label into glutamine but did not qualitatively change the order of the incorporation of /sup 15/N-label into all the amino acids examined. This evidence indicates the direct involvement of the glutamine synthetase/glutamate synthase pathway for ammonia and nitrite assimilation in isolated chloroplasts. The addition of malate or succinate during ammonia assimilation also led to more than 3-fold increase in (/sup 14/C)2-oxoglutarate transport into the chloroplast as well as an increase in the export of (/sup 14/C)glutamate out of the chloroplast. Little (/sup 14/C)glutamine was detected in the medium of the chloroplast preparations. The stimulation of /sup 15/N-incorporation and (/sup 14/C)glutamate export by malate could be directly attributed to the increase in 2-oxoglutarate transport activity (via the 2-oxoglutarate translocator) observed in the presence of exogenous malate.

  10. In vivo and in vitro anti-inflammatory and anti-nociceptive effects of the methanol extract of Inonotus obliquus.

    PubMed

    Park, Young-Mi; Won, Jong-Heon; Kim, Yang-Hee; Choi, Jong-Won; Park, Hee-Juhn; Lee, Kyung-Tae

    2005-10-03

    The mushroom Inonotus obliquus (Fr.) Pilát (Hymenochaetaceae), has been traditionally used for the treatment of gastrointestinal cancer, cardiovascular disease and diabetes in Russia, Poland and most of Baltic countries. This study was designed to investigate the anti-inflammatory and anti-nociceptive effects of the methanol extract from Inonotus obliquus (MEIO) in vivo and in vitro. MEIO (100 or 200 mg/(kgday), p.o.) reduced acute paw edema induced by carrageenin in rats, and showed analgesic activity, as determined by an acetic acid-induced abdominal constriction test and a hot plate test in mice. To reveal the mechanism of the anti-inflammatory effect of MEIO, we examined its effect on lipopolysaccharide (LPS)-induced responses in a murine macrophage cell line RAW 264.7. MEIO was found to significantly inhibit the productions of nitric oxide (NO), prostaglandin E2 (PGE2) and tumor necrosis factor-alpha (TNF-alpha) in LPS-stimulated RAW 264.7 macrophages. Consistent with these observations, MEIO potently inhibited the protein and mRNA expressions of inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2). Furthermore, MEIO inhibited the LPS-induced DNA binding activity of nuclear factor-kappaB (NF-kappaB), and this was associated with the prevention of inhibitor kappaB degradation and a reduction in nuclear p65 protein levels. Taken together, our data indicate that the anti-inflammatory and anti-nociceptive properties of MEIO may be due to the inhibition of iNOS and COX-2 expression via the down-regulation of NF-kappaB binding activity.

  11. [Burnout in Portuguese Healthcare Professionals: An Analysis at the National Level].

    PubMed

    Marôco, João; Marôco, Ana Lúcia; Leite, Ema; Bastos, Cristina; Vazão, Maria José; Campos, Juliana

    2016-01-01

    Introdução: O burnout é uma síndrome psicológica, caracterizada por elevada exaustão emocional, elevada despersonalização e baixa realização profissional, que conduz à erosão dos valores pessoais, profissionais e de saúde. Este estudo reporta a prevalência do burnout em profissionais de saúde Portugueses. Material e Métodos: Os níveis de burnout foram estimados pelo Maslach Burnout Inventory - Human Services Survey numa escala ordinal de zero (nunca) a seis (sempre) pontos. A amostra foi constituída por 1 262 enfermeiros e 466 médicos com médias de idade de 36,8 anos (DP = 12,2) e 38,7 (DP = 11,0), respetivamente. Os participantes foram provenientes de todos os distritos nacionais (35% Lisboa; 18% Porto; 6% Aveiro, 6% Setúbal, 5% Coimbra; 5% regiões autónomas), com atuação em meio hospitalar (54%), centros de saúde (Unidade de Saúde Familiar - 30%; Unidades de Cuidados de Saúde Primários - 8%) e outras instituições públicas/privadas (8%). Resultados: A análise dos níveis de burnout revelou que ambas as categorias profissionais apresentaram níveis moderados a elevados de burnout (M = 3,0; DP = 1,7) não sendo significativas as diferenças entre as duas profissões. Vila Real (M = 3,8; SD = 1,7) e a Madeira (M = 2,5; DP = 1,5) são as regiões onde os níveis de burnout são mais e menos elevados, respetivamente. Os níveisde burnout não diferiram significativamente entre Hospitais, Unidades de Cuidados de Saúde Personalizados e Unidades de Saúde Familiares. Os profissionais com maior tempo na função são menos acometidos por burnout (r = -0,15) não ocorrendo associação significativa com a duração da jornada de trabalho (r = 0,04). A má qualidade das condições de trabalho foi o melhor preditor do burnout (r = -0,35). Discussão: A ocorrência da síndrome de burnout em profissionais de saúde portugueses é frequente, estando associada à percepção de más condições de trabalho e à menor duração do tempo de servi

  12. Fotometria diferencial de estrelas T Tauri

    NASA Astrophysics Data System (ADS)

    Pereira, P. C. R.; Santos-Júnior, J. M.; Cruz, W. S.

    2003-08-01

    Neste trabalho apresentamos os resultados preliminares de um monitoramento de estrelas jovens, que pretende ser de longa duração. As estrelas estão em sua maioria localizadas no complexo Lupus-Scorpius. Nosso objetivo principal é o estudo da variabilidade em escalas de tempo de minutos até vários dias para estrelas cujos períodos não estão determinados ou apresentam discrepâncias entre diferentes publicações. A técnica utilizada foi a fotometria diferencial, com exposições de 60s e 90s, com as câmaras CCD SBIG ST7E e ST8E acopladas aos telescópios Schmidt-Cassegrain LX200 (10 e 12 polegadas), instalados na Fundação Planetário da Cidade do Rio de Janeiro. Os primeiros resultados indicam que a técnica é bastante sólida com relação à instabilidade na transparência do céu, mesmo com o uso de telescópios de pequeno porte. Objetos de magnitude 14, no telescópio de 10 polegadas, apresentam dispersões na diferença de magnitudes das comparações, em torno de 0,008mag nas exposições de 60s. Note-se, ainda, que a dispersão pode ser melhorada utilizando-se a técnica de soma de imagens. Destacamos AK Sco, GW Lup, GQ Lup e TW Hya. AK Sco é uma binária que, apesar de ter a sua órbita e período cobertos espectroscopicamente (13,6dias), nunca teve seus eclipses estudados por meio de fotometria. GW Lup não tem período determinado na literatura. Temos acompanhado este objeto há alguns anos, e sugestões de períodos entre 5 e 6 dias têm sido encontradas. O objeto que mereceu maior atenção foi TW Hya por apresentar vários trabalhos fotométricos e espectroscópicos com resultados discrepantes quanto ao período rotacional, que varia de 1,8 a 4,4 dias (Rucinsky & Krautter 1983, A&A 121, 217; Herbst & Koret 1988, AJ 96, 1949; Mekkaden 1988, A&A 340, 135; Batalha et al. 2002, ApJ 580, 343). Dedicamos 13 noites para essa estrela, totalizando cerca de 2.000 pontos na curva de luz. Nossos dados indicam a presença de uma modulação com dois

  13. Observações espectroscópicas da candidata a pós-AGB IRAS 19386+0155

    NASA Astrophysics Data System (ADS)

    Lorenz-Martins, S.; Pereira, C. B.

    2003-08-01

    Nesse trabalho apresentamos a análise fotosférica da estrela candidata a pós-AGB IRAS 19386+0155. Com os dados obtidos no espectrógrafo FEROS foram determinados os parâmetros atmosféricos e abundâncias fotosféricas utilizando o código MOOG. A análise do espectro mostrou que IRAS 19386+0155 possui os seguintes parâmetros atmosféricos : Teff = 6800K, log g = 1.4, [M/H] = -1.5 e Vt = 8.4 km/s. O padrão de abundância obtido para os elementos mais leves (Carbono, Nitrogênio e Oxigênio) e elementos a (Magnésio, Silício e Cálcio) foi inferior ao solar (log C = 7.74, log N = 7.28, Log O = 8.43, log Mg = 7.14, log Si = 7.54 e log Ca = 5.91). Uma inspeção visual do espectro ISO deste objeto revela a presença de poeira fria na forma de silicatos cristalinos. Embora as bandas mais marcantes de silicatos amorfos (em 10 mm e 18mm) não sejam observadas, a emissão em 21 mm, presente em algumas pós-AGBs também não está presente. O espectro ISO parece revelar um meio rico em oxigênio, mas a forma da distribuição de energia no infravermelho não obedece ao padrão apresentado por outras pós-AGBs. Nossos resultados nos levam a sugerir que IRAS 19386+0155 talvez faça parte de um sistema binário, uma vez que outras pós-AGBs que são membros de sistemas binários apresentam padrão de abundância semelhante.

  14. Advances in lung ultrasound.

    PubMed

    Francisco, Miguel José; Rahal, Antonio; Vieira, Fabio Augusto Cardillo; Silva, Paulo Savoia Dias da; Funari, Marcelo Buarque de Gusmão

    2016-01-01

    Ultrasound examination of the chest has advanced in recent decades. This imaging modality is currently used to diagnose several pathological conditions and provides qualitative and quantitative information. Acoustic barriers represented by the aerated lungs and the bony framework of the chest generate well-described sonographic artifacts that can be used as diagnostic aids. The normal pleural line and A, B, C, E and Z lines (also known as false B lines) are artifacts with specific characteristics. Lung consolidation and pneumothorax sonographic patterns are also well established. Some scanning protocols have been used in patient management. The Blue, FALLS and C.A.U.S.E. protocols are examples of algorithms using artifact combinations to achieve accurate diagnoses. Combined chest ultrasonography and radiography are often sufficient to diagnose and manage lung and chest wall conditions. Chest ultrasonography is a highly valuable diagnostic tool for radiologists, emergency and intensive care physicians. RESUMO O exame ultrassonográfico do tórax avançou nas últimas décadas, sendo utilizado para o diagnóstico de inúmeras condições patológicas, e fornecendo informações qualitativas e quantitativas. Os pulmões aerados e o arcabouço ósseo do tórax representam barreira sonora para o estudo ultrassonográfico, gerando artefatos que, bem conhecidos, são utilizados como ferramentas diagnósticas. Eco pleural normal, linhas A, linhas B, linhas C, linhas E e Z (conhecidas como falsas linhas B) são artefatos com características peculiares. Os padrões de consolidação e de pneumotórax também são bem estabelecidos. Alguns protocolos têm sido utilizados no manuseio dos pacientes: Blue Protocol, Protocolo FALLS e Protocolo C.A.U.S.E são exemplos de três propostas que, por meio da associação entre os artefatos, permitem sugerir diagnósticos precisos. A ultrassonografia de tórax, aliada à radiografia de tórax, muitas vezes é suficiente para o diagn

  15. Innovation and communicative action: health management networks and technologies.

    PubMed

    Rivera, Francisco Javier Uribe; Artmann, Elizabeth

    2016-11-03

    avaliação da atratividade das atividades e que ajudem a antecipar formas de inovação por meio de uma análise prospectiva sistemática podem potencializar o processo de geração da inovação como produto de redes.

  16. Changing dietary habits among Akwen Xerente.

    PubMed

    Rocha, Tatiana Evangelista da Silva; Silva, Reijane Pinheiro da; Nascimento, Maira Messias do

    2016-06-01

    The research aimed to identify the current feed of Xerente people in Indian villages Porteira and Funil in the city of Tocantinia / TO. It was used a qualitative ethnographic approach. Conducted from September 2013 to August 2014. The data were presented in a diary, through participant observation of food practices with the guidance of a script. A process of dietary change that permeates the culture of this people is taking place. Factors such as the deficit in the planting gardens, the recent arrival of energy, and therefore the technology has allowed access to processed foods. But some families still maintain the farming of cassava, yam, and beans. The main animals that are hunted in the village are peccary, deer and armadillo. It was possible to point which foods are inserted in the Xerente feed and factors related to this situation. A pesquisa objetivou identificar a alimentação atual do povo Xerente, nas aldeias indígenas Porteira e Funil, no município de Tocantínia / TO. Utilizou-se uma abordagem etnográfica qualitativa. Realizada entre setembro de 2013 a agosto de 2014. Os dados foram descritos através de um diário de campo, por meio da observação das práticas alimentares com a orientação de um roteiro. Está ocorrendo um processo de mudança alimentar na cultura deste povo. Fatores como o déficit no plantio das roças, a chegada da energia, e consequentemente a tecnologia, permitiu o acesso a alimentos industrializados. Mas algumas famílias ainda mantem o cultivo de mandioca, inhame, feijão andu. Os principais animais que são caçados na aldeia são caititu, veado e tatu. Foi possível encontrar a presença de alimentos industrializados inseridos na alimentação do Xerente e isso tem provocado alterações nos hábitos desse povo.

  17. Física e Arte nas Estações do Ano

    NASA Astrophysics Data System (ADS)

    Pessôa Queiroz, Glória; da Conceição Barbosa Lima, Maria; Navarro Vasconcellos das Mercês, Maria

    2004-12-01

    The paper deals with the subject of the Four Seasons, exploring elements of Science and the Art in order to motivate students or public of museums of science and technology to understand it from their current cultural experiences and of old times. Physics joins to Astronomy to explain the phenomenon, while the use of Music and Painting make possible the immersion in the subject in way to many trips to the imagination capable to awake emotions.A proposal didactic is presented and justified for some consensus of the research in the area of teaching-learning of science, since that related to the persistent alternative conceptions concerning the causes of the changes observed at the different times of the year until the qualitative modelling of phenomena that appeals three-dimensional pedagogical models. Such proposal was developed in the activity named " Hiper interesting Talk: The Four Seasons, Science and Art" in the first Sunday of August/2003 in the Museum of Astronomy, MAST. O artigo trata do tema das Estações do Ano, explorando elementos da Ciência e da Arte como forma de motivar estudantes ou público de museus de ciência e tecnologia a compreendê-lo a partir de vivências culturais atuais e de outras épocas. A Física se junta à Astronomia para explicar o fenômeno, enquanto a Música e a Pintura possibilitam a imersão no tema em meio a muitas viagens à imaginação capazes de despertar emoções.Uma proposta didática é apresentada e justificada por consensos das muitas pesquisas na área de ensino-aprendizagem de ciências, desde os que se referem às persistentes concepções alternativas acerca das causas das mudanças observadas nas diferentes épocas do ano até à modelagem qualitativa de fenômenos que recorre a modelos pedagógicos tridimensionais. Tal proposta foi desenvolvida na atividade "Bate papo Hiperinteressante: As Quatro Estações, Ciência e Arte" realizada no primeiro domingo do mês de agosto de 2003 no Museu de Astronomia.

  18. Multifrequency tympanometry in infants.

    PubMed

    de Moraes, Tamyne Ferreira Duarte; Macedo, Camila de Cássia; Feniman, Mariza Ribeiro

    2012-04-01

    Introdução: O uso de uma única frequência na timpanometria não é sensível na detecção de todos os casos de alteração na orelha média, dificultando o diagnóstico preciso.Objetivo: Caracterização das medidas de imitância acústica de lactentes utilizando três tipos de sonda. Estudo prospectivo.Método: Foram avaliados 54 lactentes, com idade entre zero e três meses. Os critérios de inclusão foram ausência de infecções de vias aéreas, presença de emissões otoacústicas evocadas transientes, ausência de indicadores de risco para perda auditiva. Foi realizada entrevista audiológica, inspeção visual do meato acústico externo e medidas de imitância acústica nas frequências de 226Hz, 678Hz e 1000Hz. Foram coletados os registros timpanométricos de efeito de oclusão, curva e pressão de pico timpanométrico, volume equivalente do meato acústico externo e pico compensado da admitância acústica estática.Resultados: Os resultados indicaram presença de efeito de oclusão (2,88% em 226Hz, 4,81% em 678Hz e 3,85% em 1000Hz); predomínio de curva em pico único (65,35% em 226Hz, 81,82% em 678Hz e 77,00% em 1000Hz); pressão de pico variando de -150 a 180daPa; aumento do volume equivalente do meato acústico externo com aumento da frequência da sonda (0,64ml em 226Hz, 1,63mmho em 678Hz e 2,59mmho em 1000Hz); aumento do pico compensado da admitância acústica estática (0,51ml em 226Hz, 0,55mmho em 678Hz e 1,20mmho em 1000Hz). Foram classificados como normais 93,06% dos timpanogramas com 226Hz, 80,81% em 678Hz e 82,00% em 1000Hz.Conclusão: Por meio destas avaliações e resultados foi possível caracterizar as medidas de imitância acústica dos lactentes.

  19. Adult Acne: Prevalence and Portrayal in Primary Healthcare Patients, in the Greater Porto Area, Portugal.

    PubMed

    Semedo, Diogo; Ladeiro, Filipa; Ruivo, Mariana; D'Oliveira, Carlos; De Sousa, Filipa; Gayo, Mariana; Lima, Clara; Magalhães, Frederico; Brandão, Rui; Branco, Maria; Da Silva, Isabel; Batista, Joana; Amado, João; Massa, António; Neves-Amado, João

    2016-09-01

    Introdução: A acne, apesar de caraterística no adolescente, afeta frequentemente o adulto. Em Portugal, não são conhecidos estudos sobre a prevalência da acne no adulto, nomeadamente observada nos grandes centros populacionais. Os objetivos deste estudo foram estimar a prevalência da acne nos utentes dos serviços de cuidados de saúde primários, as suas características, incluindo fatores de risco para início e/ou agravamento, além de coletar informação relacionada com a automedicação e/ou tratamento prescrito. Material e Métodos: Aplicação de questionário e exame físico a amostra composta por adultos entre os 20 - 60 anos de idade que visitaram, em dias aleatórios, cinco centros de saúde da área do Grande Porto. Resultados: Dos 1 055 adultos avaliados, a prevalência estimada de acne foi de 61,5%. Apenas 36,8% dos portadores estavam cientes da sua condição e somente 25% afirmou ter procurado tratamento. Mais de metade dos fumadores (62,3%) apresentavam acne. A zona mais afetada foi a região malar, diferindo da forma adolescente da doença. Discussão: A prevalência encontrada de acne foi mais elevada do que em outros estudos. A acne aparentou estar relacionada com a ingestão calórica aumentada, tabagismo, consumo de leite gordo ou meio gordo, hirsutismo, alopécia e seborreia. Conclusão: No contexto dos cuidados de saúde primários, mais de metade dos adultos eram portadores de acne. Estes números demonstram o quão importante pode ser a prevenção e intervenção pelos profissionais dos cuidados de saúde primários, tanto para a redução de eventuais factores de risco como para a intervenção terapêutica e consequências psicossociais relacionadas com a acne. Palavras-chave: Acne Vulgaris/epidemiologia; Adulto; Cuidados de Saúde Primários; Portugal; Prevalência.

  20. Análise sobre o Conhecimento de um Grupo de Alunos do Ensino Médio da Rede Estadual de São Paulo sobre Termos e Fenômenos Astronômicos do Cotidiano

    NASA Astrophysics Data System (ADS)

    de Oliveira, E. F.; Voelzke, M. R.; Amaral, L. H.

    2007-08-01

    Embora os Parâmetros Curriculares Nacionais do Ensino Médio (PCN-EM) e as orientações complementares a esses Parâmetros (PCN+) apontem a importância de uma abordagem significativa de conceitos relacionados à astronomia nas aulas de Física, muitos estudantes terminam o Ensino Médio (EM) sem compreender a razão de certos acontecimentos de origem celeste, ainda que estes façam parte de seu cotidiano. Este trabalho tem por objetivo analisar os conhecimentos básicos em astronomia dos alunos de EM da escola estadual Batista Renzi, bem como investigar os meios através dos quais estes conhecimentos foram adquiridos. Para tanto foi elaborado um questionário de múltipla escolha aplicado a 310 alunos distribuídos entre as três séries do EM dos períodos matutino e noturno. Dessa forma, observou-se que apenas 34,5% relacionaram as estações do ano à inclinação do eixo de rotação da Terra, 21,3% indicaram a influência gravitacional da Lua e do Sol como responsáveis pelo fenômeno das marés, 24,5% indicaram corretamente quais são os objetos celestes mais próximos da Terra, 36,1% identificaram ano-luz como uma medida de distância e 34,2% reconheceram uma estrela cadente como meteoro. Em contrapartida, 67,1% compreendiam a sucessão entre dia e noite, 73,9% identificaram o Sol como estrela e 52,3% relacionaram o Big Bang à origem do Universo. Além disso, foram comparadas as respostas de alunos de diferentes séries e períodos, observando-se, dentre outras coisas, que os estudantes do terceiro ano apresentam um percentual de acertos semelhante ao dos alunos do primeiro, caracterizando que a abordagem de tópicos relacionados à astronomia no EM não tem contribuído para uma maior compreensão dos fenômenos e conceitos.

  1. Quality of Recovery after Anesthesia: Validation of the Portuguese Version of the 'Quality of Recovery 15' Questionnaire.

    PubMed

    Sá, Ana Carolina; Sousa, Gabriela; Santos, Alice; Santos, Cristina; Abelha, Fernando José

    2015-01-01

    Introdução: O questionário "Quality of Recovery 15" tem sido utilizado para o estudo da qualidade de recuperação após anestesia. O objetivo deste estudo foi validar a versão Portuguesa do questionário "Quality of Recovery 15". Material e Métodos: Após aprovação pela Comissão de ética institucional, foi realizado um estudo de coorte prospectivo em doentes submetidos a cirurgia eletiva de junho a agosto de 2013. A versão portuguesa do "Quality of Recovery 15" foi aplicada antes da cirurgia (T0) e 24 h após a cirurgia (T1) em 170 doentes. Os doentes incapazes de dar consentimento informado ou com comprometimento cognitivo foram excluídos. Má qualidade de recuperação foi definida para pontuações de "Quality of Recovery 15" em T1 inferiores à média das pontuações de "Quality of Recovery 15" menos 1 desvio padrão. Confiabilidade e discordãncia entre observadores foram avaliadas por meio da correlação intraclasse. Testes não-paramétricos foram utilizados para comparações. Resultados: Observou-se uma correlação negativa entre pontuações de "Quality of Recovery 15" e tempo de internamento na Unidade Pós-Anestésica (p = -0,264, p = 0,004) e tempo de internamento hospitalar (p = -0,274, p = 0,004). Trinta e dois doentes (19%) tiveram má qualidade de recuperação. Os doentes com má qualidade de recuperação tinham mais frequentemente diabetes mellitus e hipertensão arterial e estavam medicados com antidepressivos com mais frequência. Os doentes com má qualidade de recuperação foram mais frequentemente submetidos a anestesia combinada e menos frequente a anestesia geral e locorregional (p = 0,008). O questionário teve boa consistência interna; a confiabilidade do teste-reteste foi boa. Discussão: A versão portuguesa do "Quality of Recovery 15" mostrou boa correlação com a versão original. Conclusão: Este questionário parece ser uma avaliação precisa e confiável para a qualidade de recuperação.

  2. Uma Visão do Universo Segundo um Grupo de Alunos do Ensino Médio de São Paulo

    NASA Astrophysics Data System (ADS)

    Elias, D. S.; Araújo, M.; Amaral, L. H.; Voelzke, M. R.; Araújo, M.

    2005-08-01

    A astronomia, embora seja uma ciência popular, com inúmeras descobertas de interesse público, ainda é apresentada desconsiderando-se os aspectos históricos e científicos relacionados ao seu desenvolvimento, sendo geralmente veiculada nos meios de comunicação de maneira pouco esclarecedora e não raro com imprecisões. Neste trabalho analisou-se a concepção de um grupo de estudantes de Ensino Médio sobre conceitos de astronomia, visando identificar sua visão de mundo a respeito do Universo, envolvendo idéias sobre espaço e tempo. Para issso, foi aplicado um questionário em três escolas da grande São Paulo em um espaço amostral de 270 alunos. Constatou-se que, embora o ensino de astronomia esteja previsto nos PCNEM, os resultados obtidos na pesquisa mostram que há grande deficiência no conhecimento dos temas investigados. Nesse sentido, verificou-se que apenas 20% dos alunos eram capazes de relacionar a sucessão das semanas com as fases da lua, enquanto 28% associaram as estações do ano à inclinação do eixo de rotação da Terra. Por outro lado, somente 23% dos alunos tinham noções das distâncias entre os objetos celestes próximos da Terra e 56% conseguiram relacionar o Big Bang com a origem do Universo. Finalmente, constatou-se que 37% reconheciam o ano-luz como uma unidade de distância e 60% reconheciam o Sol como sendo uma estrela. Apesar de 60% dos alunos indicarem que a escola é a principal fonte para aquisição dos conhecimentos de astronomia, conclui-se que seus conceitos nessa área ainda são inadequados, havendo necessidade de ampliação e aprimoramento da abordagem desses conteúdos nos ambientes escolares.

  3. Cosmoeducação: uma proposta para o ensino de astronomia

    NASA Astrophysics Data System (ADS)

    Medeiros, L. A. L.; Jafelice, L. C.

    2003-08-01

    Entende-se por cosmoeducação o desenvolvimento vivencial da unidade homem-cosmo. Este conceito é norteado pela psicologia transpessoal, que estuda o ser humano em sua totalidade, onde suas relações ecológicas e cósmicas são de grande importância. Constata-se uma necessidade latente no ser humano moderno em resgatar uma relação holística com o Universo. Neste trabalho exploramos meios de cultivar a consciência de que o ser humano constitui parte integrante do cosmo e se relaciona com este com o objetivo de promover em si uma percepção ambiental mais ampla. Nossa hipótese de trabalho inicial foi que o ensino de conteúdos básicos em astronomia realizado através de uma abordagem holística, que incorpore práticas vivenciais correlacionadas àqueles conteúdos, pode despertar no indivíduo sua identidade cósmica. O método que utilizamos é o fenomenológico e o universo desta pesquisa é um grupo de estudantes da disciplina de Astronomia (Curso de Licenciatura em Geografia/UFRN), onde realizamos observação participante, entrevistas, depoimentos e as práticas vivenciais mencionadas. Neste caso estamos desenvolvendo e adaptando exercícios de algumas técnicas terapêuticas de psicologia transpessoal, que um de nós (LALM) tem aplicado no contexto clínico, para trabalhar aspectos cognitivos envolvidos naquele processo de conscientização cósmica. Resultados parciais claramente referendam a hipótese inicial. Um resultado a destacar é fruto de uma dinâmica de representação corporal interiorizada do eclipse lunar, envolvendo um pequeno grupo daqueles estudantes, na qual conteúdos míticos afloraram de maneira espontânea e contundente para todos, sugerindo ressonância, ou pelo menos isomorfismo, entre o macro e o microcosmo. Este e outros resultados são discutidos em detalhe neste trabalho. (PPGECNM/UFRN; PRONEX/FINEP; NUPA/USP; Temáticos/FAPESP).

  4. [Atypical femoral fractures and bisphosphonates treatment: is it a risk factor?].

    PubMed

    Geada, Nuno; Mafra, Inês; Barroso, Rogério; Franco, José

    2014-01-01

    IntroduçÉo: Os bifosfonatos têm eficácia comprovada na prevençÉo das fracturas osteoporóticas. Contudo, têm sido descritas fracturas femorais atípicas associadas à toma prolongada de bifosfonatos com um padrÉo radiológico bem definido. Os objectivos no nosso estudo foram caracterizar os doentes de idade ≥ 65 anos com fracturas femorais (subtrocantéricas/diafisárias) consideradas típicas e atípicas e avaliar a relaçÉo entre a ocorrência das fracturas atípicas e o uso de bifosfonatos.Material e Métodos: Realizámos um estudo caso-controlo com os doentes admitidos no nosso Hospital por fractura subtrocantérica ou diafisária do fémur, num período de cinco anos e meio. Após aplicaçÉo dos critérios de exclusÉo, as 92 fracturas (91 doentes) foram classificadas como atípicas ou típicas. A determinaçÉo do tratamento prévio com bifosfonatos foi obtida através do historial clínico dos doentes.Resultados: Foram encontradas 11 fracturas atípicas (10 doentes) e 81 fracturas típicas (81 doentes). A idade mediana entre os dois grupos foi estatisticamente diferente (72 anos - atípicas vs 80 anos - típicas, p < 0,01). A razÉo do uso de bifosfonatos foi de 0,60 nas fracturas atípicas e de 0,01 nas típicas, traduzindo um odds ratio de 101,1 (p < 0,01).DiscussÉo: Na generalidade, os nossos resultados sÉo apoiados e estÉo de acordo com os estudos publicados referentes à ocorrência de fracturas femorais atípicas associadas à toma de bifosfonatos.ConclusÉo: Apesar do pequeno número de casos foi possível demonstrar a relaçÉo, estatisticamente, significativa entre as fracturas femorais atípicas e a toma de bifosfonatos. De notar que estas fracturas atípicas ocorreram em doentes, significativamente, mais jovens do que os doentes com fracturas típicas.

  5. Evolution of the Astronomy Concepts Along Basic Education Cycle. (Breton Title: Evolução dos Conceitos de Astronomia no Decorrer da Educação Básica.) La Evolución de los Conceptos de Astronomía Durante la Educación Básica

    NASA Astrophysics Data System (ADS)

    Darroz, Luiz Marcelo; da Rosa, Cleci Werner; Becker da Rosa, Álvaro; Samudio Pèrez, Carlos Ariel

    2014-07-01

    learning of astronomy in basic education. Embora a astronomia seja considerada uma das ciências mais antigas da humanidade e ainda que a compreensão de seus conceitos tenha trazido enormes avanços para a Ciência e, consequentemente, para a sociedade, observa-se que uma parcela significativa de pessoas encontra-se à margem desses conhecimentos. De acordo com os Parâmetros Curriculares Nacionais para a Educação Básica, cabe à escola a difusão dos conceitos cientificamente corretos, entre eles os relacionados à área de astronomia. Pertinente a essa questão, apresenta-se uma pesquisa realizada com 140 estudantes do nono ano do ensino fundamental e com 120 estudantes da terceira série do ensino médio de quatro escolas da região de Passo Fundo/RS. Buscou-se averiguar, por meio de um questionário composto de questões abertas e de múltipla escolha, o conhecimento desse grupo de estudantes acerca de termos e fenômenos astronômicos básicos e, também, verificar se o índice de acertos cresce à medida que eles avançam nas diferentes e gradativas séries dos ensinos fundamental e médio. De modo geral, os resultados apresentados demonstram que o ensino de astronomia na educação básica enfrenta deficiências. Das 20 questões investigadas, em 17 os índices de acertos são semelhantes nas respostas dadas por estudantes de nível fundamental e médio, revelando que muitas concepções equivocadas permanecem ao longo da educação básica. Isso evidencia que tais temas não são - ou são pouco - abordados durante esses dois níveis de escolarização. Assim, conclui-se que a discussão dos conceitos relacionados com a astronomia deve receber maior ênfase na abordagem dos diferentes conteúdos, sendo necessária uma ação nacional em prol do seu ensino. Acredita-se que essa ação nacional deve estar apoiada em um pilar triplo de atores coletivos: comunidade científica, comunidade astronômica semiprofissional e comunidade escolar. Por fim, esse pilar seria

  6. Forms of Appropriation of Tools for the Astronomy Education in Continuous Training of Teachers. (Spanish Title: Formas de Apropriación de Herramientas Para la Enseñanza de la Astronomía en la Formación Docente Continua.) Formas de Apropriação de Instrumentos Para o Ensino de Astronomia na Formação Continuada de Professores

    NASA Astrophysics Data System (ADS)

    Marques Soares, Leonardo; Sousa Nascimento, Silvania

    2012-07-01

    siete relatos. O objetivo principal desse artigo é apresentar algumas reflexões sobre a maneira como um grupo de professores se apropriaram dos instrumentos do KIT PARA O ENSINO DE ASTRONOMIA (KITPEA). Os sujeitos dessa pesquisa participaram do curso de especialização em ensino de astronomia oferecido pelo Projeto de Formação Continuada (Foco) no Centro de Ensino de Ciências e Matemática (CECIMIG) da Faculdade de Educação da Universidade Federal de Minas Gerais (FaE/UFMG). Coletamos as informações por meio de um questionário e de uma entrevista, aplicados a esses professores. Estruturamos a análise dessas informações com a ajuda da Teoria da Atividade e da Teoria da Ação Mediada. Interpretamos as falas dos professores usando como dispositivo analítico os elementos constituintes do sistema de atividade e os conceitos de apropriação e domínio. Dentre os 11 sujeitos que participaram da pesquisa, foi possível identificar a apropriação dos instrumentos em 7 narrativas.

  7. Qual o Papel da Escola e da Mídia na Obtenção dos Conhecimentos Astronômicos?

    NASA Astrophysics Data System (ADS)

    da Cunha, W. S.; Voelzke, M. R.; Amaral, L. H.

    2007-08-01

    É amplamente reconhecido que as pessoas em geral têm grande fascínio e interesse pela Astronomia. Por outro lado, o conteúdo dessa área incluído no ensino formal está longe de ser abrangente e suficiente para suprir a demanda. Esse interesse permite aperfeiçoar a divulgação e o ensino não formal de Astronomia através da mídia aliando a adequação do conteúdo à expectativa das pessoas. A reforma do Currículo Básico da Escola Pública da maioria dos Estados brasileiros tem introduzido Astronomia desde a pré-escola até o Ensino Médio. Num estudo realizado com 1180 alunos do Ensino Médio de seis escolas estaduais, revelou-se através da aplicação de um formulário contendo questões que abordavam conhecimentos básicos em Astronomia, como foram adquiridos tais conhecimentos e à infra-estrutura da escola. Para 66,1% dos entrevistados o professor já fez alguma apresentação a respeito de Astronomia. O presente estudo revelou também que 54,4% dos alunos entrevistados adquiriram seus conhecimentos astronômicos na escola, 18,4% através da televisão e 27,1% afirmaram que seus conhecimentos foram obtidos através de outros tipos de mídia (internet, livros didáticos, filmes e revistas). Embora o estudo revele claramente que há certo equilíbrio no meio em que os alunos obtiveram seus conhecimentos astronômicos, a mídia busca não somente sua difusão, mas a disponibilização desse conhecimento de maneira correta, que às vezes, não é atingido, apresentando conceitos sem fundamentação e incorretos. Por outro lado, no dia-a-dia escolar, é comum encontrar professores que vêm para as aulas com concepções prévias, que podem diferir substancialmente das idéias a serem ensinadas, dificultando o aprendizado de futuros conceitos científicos. Uma avaliação criteriosa, avaliando as dificuldades dos professores em determinar o sentido correto dos conceitos e observando a metodologia que utilizam no ensino, poderá proporcionar uma melhor

  8. Fingerprint enhancement revisited and the effects of blood enhancement chemicals on subsequent profiler Plus fluorescent short tandem repeat DNA analysis of fresh and aged bloody fingerprints.

    PubMed

    Frégeau, C J; Germain, O; Fourney, R M

    2000-03-01

    This study was aimed at determining the effect of seven blood enhancement reagents on the subsequent Profiler Plus fluorescent STR DNA analysis of fresh or aged bloody fingerprints deposited on various porous and nonporous surfaces. Amido Black, Crowle's Double Stain. 1,8-diazafluoren-9-one (DFO), Hungarian Red, leucomalachite green, luminol and ninhydrin were tested on linoleum, glass, metal, wood (pine, painted white), clothing (85% polyester/15% cotton, 65% polyester/35% cotton, and blue denim) and paper (Scott 2-ply and Xerox-grade). Preliminary experiments were designed to determine the optimal blood dilutions to use to ensure a DNA typing result following chemical enhancement. A 1:200 blood dilution deposited on linoleum and enhanced with Crowle's Double Stain generated enough DNA for one to two rounds of Profiler Plus PCR amplification. A comparative study of the DNA yields before and after treatment indicated that the quantity of DNA recovered from bloody fingerprints following enhancement was reduced by a factor of 2 to 12. Such a reduction in the DNA yields could potentially compromise DNA typing analysis in the case of small stains. The blood enhancement chemicals selected were also evaluated for their capability to reveal bloodmarks on the various porous and nonporous surfaces chosen in this study. Luminol. Amido Black and Crowle's Double Stain showed the highest sensitivity of all seven chemicals tested and revealed highly diluted (1:200) bloody fingerprints. Both luminol and Amido Black produced excellent results on both porous and nonporous surfaces, but Crowle's Double Stain failed to produce any results on porous substrates. Hungarian Red, DFO, leucomalachite green and ninhydrin showed lower sensitivities. Enhancement of bloodmarks using any of the chemicals selected, and short-term exposure to these same chemicals (i.e., less than 54 days), had no adverse effects on the PCR amplification of the nine STR systems surveyed (D3S 1358, HumvWA, Hum

  9. Mild Wind Series, Minute Steak Event

    DTIC Science & Technology

    1992-11-20

    AD-A286 599 _C *POR-6546’ IWT-65461 MILD WIND SERIES MINUTE STEAK EVENT PROJECT OFFICERS REPORT TECHNICAL DIRECTORS SUMMARY REPORT flELECTL...POR-6546 (2) POR-2039 (2) POR-6300 (2) POR-2725 (2) POR-6337 (2) POR-3000 (2) WT-561 (2) WT-601 (2) POR-6546 (WT-6546) MILD WIND SERIES MINUTE STEAK ...PAGE IS INTENTIONALLY LEFT BLANK. r lit ! ABSTRACT MINUTE STEAK was a Department of Defense Vertical Line of Sight (LOS) undergound It was detonated

  10. CO2-switchable fluorescence of a dendritic polymer and its applications

    NASA Astrophysics Data System (ADS)

    Gao, Chunmei; Lü, Shaoyu; Liu, Mingzhu; Wu, Can; Xiong, Yun

    2015-12-01

    The synthesis and properties of CO2 responsive and fluorescent dendritic polymers, poly(amido amine)/Pluronic F127 (PAMAM/F127), are reported in this paper. The morphologies and sizes of PAMAM/F127 dendritic polymers were investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM). PAMAM/F127 dendritic polymers showed unimolecular micelle morphologies at low concentrations, and changed to multimolecular micelles at higher concentrations. Additionally, fluorescence spectra and confocal laser scanning microscopy images showed that PAMAM/F127 dendritic polymers exhibited a fluorescent enhancement response to the presence of CO2. Apart from that, the release behavior of PAMAM/F127 gels under simulated body fluids was investigated by choosing curcumin as the hydrophobic drug. The results indicated that PAMAM/F127 dendritic polymers can be used to improve the solubility of curcumin, and the drug released faster in the presence of CO2. Such CO2 responsive fluorescent dendritic polymers are potentially applicable in cellular imaging or drug controlled release.The synthesis and properties of CO2 responsive and fluorescent dendritic polymers, poly(amido amine)/Pluronic F127 (PAMAM/F127), are reported in this paper. The morphologies and sizes of PAMAM/F127 dendritic polymers were investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM). PAMAM/F127 dendritic polymers showed unimolecular micelle morphologies at low concentrations, and changed to multimolecular micelles at higher concentrations. Additionally, fluorescence spectra and confocal laser scanning microscopy images showed that PAMAM/F127 dendritic polymers exhibited a fluorescent enhancement response to the presence of CO2. Apart from that, the release behavior of PAMAM/F127 gels under simulated body fluids was investigated by choosing curcumin as the hydrophobic drug. The results indicated that PAMAM/F127 dendritic polymers can be used to improve the

  11. Synthesis, pharmacological assessment, molecular modeling and in silico studies of fused tricyclic coumarin derivatives as a new family of multifunctional anti-Alzheimer agents.

    PubMed

    Shaik, Jeelan Basha; Palaka, Bhagath Kumar; Penumala, Mohan; Kotapati, Kasi Viswanath; Devineni, Subba Rao; Eadlapalli, Siddhartha; Darla, M Manidhar; Ampasala, Dinakara Rao; Vadde, Ramakrishna; Amooru, G Damu

    2016-01-01

    A series of fused tricyclic coumarin derivatives bearing iminopyran ring connected to various amido moieties were developed as potential multifunctional anti-Alzheimer agents for their cholinesterase inhibitory and radical scavenging activities. In vitro studies revealed that most of these compounds exhibited high inhibitory activity on acetylcholinesterase (AChE), with IC50 values ranging from 0.003 to 0.357 μM which is 2-220 folds more potent than the positive control, galantamine. Their inhibition selectivity against AChE over butyrylcholinesterase (BuChE) has increased about 194 fold compared with galantamine. The developed compounds also showed potent ABTS radical scavenging activity (IC50 7.98-15.99 μM). Specifically, the most potent AChE inhibitor 6n (IC50 0.003 ± 0.0007 μM) has an excellent antioxidant profile as determined by the ABTS method (IC50 7.98 ± 0.77 μM). Moreover, cell viability studies in SK N SH cells showed that the compounds 6m-q have significant neuroprotective effects against H2O2-induced cell death, and are not neurotoxic at all concentrations except 6n and 6q. The kinetic analysis of compound 6n proved that it is a mixed-type inhibitor for EeAChE (Ki1 0.0103 μM and Ki2 0.0193 μM). Accordingly, the molecular modeling study demonstrated that 6m-q with substituted benzyl amido moiety possessed an optimal docking pose with interactions at catalytic active site (CAS) and peripheral anionic site (PAS) of AChE simultaneously and thereby they might prevent aggregation of Aβ induced by AChE. Furthermore, in silico ADMET prediction studies indicated that these compounds satisfied all the characteristics of CNS acting drugs. Most active inhibitor 6n is permeable to BBB as determined in the in vivo brain AChE activity. To sum up, the multipotent therapuetic profile of these novel tricyclic coumarins makes them promising leads for developing anti-Alzheimer agents.

  12. Catalytic addition of amine N-H bonds to carbodiimides by half-sandwich rare-earth metal complexes: efficient synthesis of substituted guanidines through amine protonolysis of rare-earth metal guanidinates.

    PubMed

    Zhang, Wen-Xiong; Nishiura, Masayoshi; Hou, Zhaomin

    2007-01-01

    Reaction of [Ln(CH(2)SiMe(3))(3)(thf)(2)] (Ln=Y, Yb, and Lu) with one equivalent of Me(2)Si(C(5)Me(4)H)NHR' (R'=Ph, 2,4,6-Me(3)C(6)H(2), tBu) affords straightforwardly the corresponding half-sandwich rare-earth metal alkyl complexes [{Me(2)Si(C(5)Me(4))(NR')}Ln(CH(2)SiMe(3))(thf)(n)] (1: Ln = Y, R' = Ph, n=2; 2: Ln = Y, R' = C(6)H(2)Me(3)-2,4,6, n=1; 3: Ln = Y, R' = tBu, n=1; 4: Ln = Yb, R' = Ph, n=2; 5: Ln = Lu, R' = Ph, n=2) in high yields. These complexes, especially the yttrium complexes 1-3, serve as excellent catalyst precursors for the catalytic addition of various primary and secondary amines to carbodiimides, efficiently yielding a series of guanidine derivatives with a wide range of substituents on the nitrogen atoms. Functional groups such as C[triple chemical bond]N, C[triple chemical bond]CH, and aromatic C--X (X: F, Cl, Br, I) bonds can survive the catalytic reaction conditions. A primary amino group can be distinguished from a secondary one by the catalyst system, and therefore, the reaction of 1,2,3,4-tetrahydro-5-aminoisoquinoline with iPrN==C==NiPr can be achieved stepwise first at the primary amino group to selectively give the monoguanidine 38, and then at the cyclic secondary amino unit to give the biguanidine 39. Some key reaction intermediates or true catalyst species, such as the amido complexes [{Me(2)Si(C(5)Me(4))(NPh)}Y(NEt(2))(thf)(2)] (40) and [{Me(2)Si(C(5)Me(4))(NPh)}Y(NHC(6)H(4)Br-4)(thf)(2)] (42), and the guanidinate complexes [{Me(2)Si(C(5)Me(4))(NPh)}Y{iPrNC(NEt(2))(NiPr)}(thf)] (41) and [{Me(2)Si(C(5)Me(4))(NPh)}Y{iPrN}C(NC(6)H(4)Br-4)(NHiPr)}(thf)] (44) have been isolated and structurally characterized. Reactivity studies on these complexes suggest that the present catalytic formation of a guanidine compound proceeds mechanistically through nucleophilic addition of an amido species, formed by acid-base reaction between a rare-earth metal alkyl bond and an amine N--H bond, to a carbodiimide, followed by amine protonolysis of the

  13. Synthesis and reactivity of rare earth metal alkyl complexes stabilized by anilido phosphinimine and amino phosphine ligands.

    PubMed

    Liu, Bo; Cui, Dongmei; Ma, Jia; Chen, Xuesi; Jing, Xiabin

    2007-01-01

    Anilido phosphinimino ancillary ligand H(2)L(1) reacted with one equivalent of rare earth metal trialkyl [Ln{CH(2)Si(CH(3))(3)}(3)(thf)(2)] (Ln=Y, Lu) to afford rare earth metal monoalkyl complexes [L(1)LnCH(2)Si(CH(3))(3)(THF)] (1 a: Ln=Y; 1 b: Ln=Lu). In this process, deprotonation of H(2)L(1) by one metal alkyl species was followed by intramolecular C--H activation of the phenyl group of the phosphine moiety to generate dianionic species L(1) with release of two equivalnts of tetramethylsilane. Ligand L(1) coordinates to Ln(3+) ions in a rare C,N,N tridentate mode. Complex l a reacted readily with two equivalents of 2,6-diisopropylaniline to give the corresponding bis-amido complex [(HL(1))LnY(NHC(6)H(3)iPr(2)-2,6)(2)] (2) selectively, that is, the C--H activation of the phenyl group is reversible. When 1 a was exposed to moisture, the hydrolyzed dimeric complex [{(HL(1))Y(OH)}(2)](OH)(2) (3) was isolated. Treatment of [Ln{CH(2)Si(CH(3))(3)}(3)(thf)(2)] with amino phosphine ligands HL(2-R) gave stable rare earth metal bis-alkyl complexes [(L(2-R))Ln{CH(2)Si(CH(3))(3)}(2)(thf)] (4 a: Ln=Y, R=Me; 4 b: Ln=Lu, R=Me; 4 c: Ln=Y, R=iPr; 4 d: Ln=Y, R=iPr) in high yields. No proton abstraction from the ligand was observed. Amination of 4 a and 4 c with 2,6-diisopropylaniline afforded the bis-amido counterparts [(L(2-R))Y(NHC(6)H(3)iPr(2)-2,6)(2)(thf)] (5 a: R=Me; 5 b: R=iPr). Complexes 1 a,b and 4 a-d initiated the ring-opening polymerization of d,l-lactide with high activity to give atactic polylactides.

  14. Trinuclear alkyl hydrido rare-earth complexes supported by amidopyridinato ligands: synthesis, structures, C-Si bond activation and catalytic activity in ethylene polymerization.

    PubMed

    Lyubov, Dmitry M; Cherkasov, Anton V; Fukin, Georgy K; Ketkov, Sergey Yu; Shavyrin, Andrey S; Trifonov, Alexander A

    2014-10-14

    The reaction of Ap(9Me)Lu(CH2SiMe3)2(thf) (Ap(9Me) = (2,4,6-trimethylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amido ligand) with two molar equivalents of PhSiH3 affords a trinuclear alkyl-hydrido cluster [(Ap(9Me)Lu)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2]. The analogous reactions with Ap(9Me)Ln(CH2SiMe3)2(thf) (Ln = Y, Yb) are more complex and result in the formation of mixtures of two types of trinuclear alkyl-hydrido complexes [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] and [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiH2Ph)(thf)2] differing in the alkyl group. The DFT calculations of [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] (Ap* = (2,6-diisopropylphenyl)[6-(2,4,6-triisopropylphenyl)pyridine-2-yl]amido ligand) confirm localization of the HOMO on the Ap*-Y(1A)-CH2SiMe3 fragment, thus explaining its enhanced reactivity. Analysis of the electron density distribution reveals the Y-H and H-H bonding interactions in the (Y)3(μ(2)-H)3(μ(3)-H)2 moiety. The NMR studies of diamagnetic complexes [(Ap(9Me)Lu)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] and [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] demonstrated that the trinuclear cores are retained in the solution and revealed exchange between μ(3)- and μ(2)-bridging hydrido ligands. Complexes [(Ap*Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2], the cationic yttrium hydrido cluster [(Ap*Y)3(μ(2)-H)3(μ(3)-H)2(thf)3](+)[B(C6F5)4](-) as well as [(Ap(9Me)Ln)3(μ(2)-H)3(μ(3)-H)2(CH2SiMe3)(thf)2] proved to be active in catalysis of ethylene polymerization under mild conditions.

  15. Stable divalent germanium, tin and lead amino(ether)-phenolate monomeric complexes: structural features, inclusion heterobimetallic complexes, and ROP catalysis.

    PubMed

    Wang, Lingfang; Roşca, Sorin-Claudiu; Poirier, Valentin; Sinbandhit, Sourisak; Dorcet, Vincent; Roisnel, Thierry; Carpentier, Jean-François; Sarazin, Yann

    2014-03-21

    Stable germanium(II) and lead(II) amido complexes {LO(i)}M(N(SiMe3)2) (M = Ge(II), Pb(II)) bearing amino(ether)phenolate ligands are readily available using the proteo-ligands {LO(i)}H of general formula 2-CH2NR2-4,6-tBu2-C6H2OH (i = 1, NR2 = N((CH2)2OCH3)2; i = 2, NR2 = NEt2; i = 3, NR2 = aza-15-crown-5) and M(N(SiMe3)2)2 precursors. The molecular structures of these germylenes and plumbylenes, as well as those of {LO(3)}GeCl, {LO(3)}SnCl and of the congeneric {LO(4)}Sn(II)(N(SiMe3)2) where NR2 = aza-12-crown-4, have been determined crystallographically. All complexes are monomeric, with 3-coordinate metal centres. The phenolate systematically acts as a N^O(phenolate) bidentate ligand, with no interactions between the metal and the O(side-arm) atoms in these cases (for {LO(1)}(-), {LO(3)}(-) and {LO(4)}(-)) where they could potentially arise. For each family, the lone pair of electrons essentially features ns(2) character, and there is little, if any, hybridization of the valence orbitals. Heterobimetallic complexes {LO(3)}M(N(SiMe3)2)·LiOTf, where the Li(+) cation sits inside the tethered crown-ether, were prepared by reaction of {LO(3)}M(N(SiMe3)2) and LiOTf (M = Ge(II), Sn(II)). The inclusion of Li(+) (featuring a close contact with the triflate anion) in the macrocycle bears no influence on the coordination sphere of the divalent tetrel element. In association with iPrOH, the amido germylenes, stannylenes and plumbylenes catalyse the controlled polymerisation of L- and racemic lactide. The activity increases linearly according to Ge(II) ≪ Sn(II) ≪ Pb(II). The simple germylenes generate very sluggish catalysts, but the activity is significantly boosted if the heterobimetallic complex {LO(3)}Ge(N(SiMe3)2)·LiOTf is used instead. On the other hand, with 10-25 equiv. of iPrOH, the plumbylenes afford highly active binary catalysts, converting 1000 or 5000 equiv. of monomer at 60 °C within 3 or 45 min, respectively, in a controlled fashion.

  16. Spectroscopic and thermal degradation behavior of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes with thiopental sodium anesthesia drug

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.

    2013-04-01

    A new series of Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complexes have been synthesized with thiopental sodium anesthesia drug. The elemental analyses of the complexes are confined to stoichiometry of the formulas [M(TPL)3]ṡnH2O (M = Cr(III) or Fe(III); n = 6 or 5), [M(TPL)2(H2O)2]ṡnH2O (M = Mn(II), Co(II) or Ni(II); n = 0 or 4), and [M(TPL)2] (M = Cu(II) or Zn(II); n = 2 or 0) respectively, where TPL is thiopental chelating agent. Structures have been discussed and suggested upon elemental analyses, infrared, Raman, electronic, electron spin resonance, 1H NMR spectral data and magnetic studies. The X-ray powder diffraction (XRD) was performed of metal complexes. The XRD patterns indicate crystalline nature for the complexes. The measured low molar conductance values in dimethylsulfoxide indicate that the complexes are non-electrolyte nature. Spectroscopic discussion refer that coordination take place through three types: Cdbnd N (pyrimidine moiety) nitrogen and C2sbnd S (2-thiolate group) for Cr(III), Mn(II) and Fe(III), C6dbnd O (amido group) oxygen and C2sbnd S (2-thiolate group) for Co(II) and Ni(II), and Cu(II) and Zn(II) ions coordinated via Cdbnd N (pyrimidine moiety) nitrogen, C2dbnd S (2-thiolate group) and C6dbnd O (amido group) oxygen, respectively. The thermal behavior (TG/DTG/DTA) of the complexes was studied and kinetic parameters were determined by Horowitz-Metzger and Coats-Redfern methods. The thiopental and its complexes have been screened for their antimicrobial (G+ and G-) bacteria (Escherichia coli, Staphylococcus aureus, Bacillus subtilis and Pseudomonas aeruginosa) and fungi (Aspergillus flavus and Candida albicans) activities by minimum inhibitory concentration (MIC) method.

  17. Peroxidase-like oxidative activity of a manganese-coordinated histidyl bolaamphiphile self-assembly

    NASA Astrophysics Data System (ADS)

    Kim, Min-Chul; Lee, Sang-Yup

    2015-10-01

    A peroxidase-like catalyst was constructed through the self-assembly of histidyl bolaamphiphiles coordinated to Mn2+ ions. The prepared catalyst exhibited oxidation activity for the organic substrate o-phenylenediamine (OPD) in the presence of hydrogen peroxide (H2O2). The histidyl bolaamphiphiles of bis(N-alpha-amido-histidine)-1,7-heptane dicarboxylates self-assembled to make spherical structures in an aqueous solution. Subsequent association of Mn2+ ions with the histidyl imidazoles in the self-assembly produced catalytic active sites. The optimal Mn2+ ion concentration was determined and coordination of the Mn2+ ion with multiple histidine imidazoles was investigated using spectroscopy analysis. The activation energy of the produced catalysts was 55.0 kJ mol-1, which was comparable to other peroxidase-mimetic catalysts. A detailed kinetics study revealed that the prepared catalyst followed a ping-pong mechanism and that the turnover reaction was promoted by increasing the substrate concentration. Finally, application of the prepared catalyst for glucose detection was demonstrated through cascade enzyme catalysis. This study demonstrated a facile way to prepare an enzyme-mimetic catalyst through the self-assembly of an amphiphilic molecule containing amino acid segments.A peroxidase-like catalyst was constructed through the self-assembly of histidyl bolaamphiphiles coordinated to Mn2+ ions. The prepared catalyst exhibited oxidation activity for the organic substrate o-phenylenediamine (OPD) in the presence of hydrogen peroxide (H2O2). The histidyl bolaamphiphiles of bis(N-alpha-amido-histidine)-1,7-heptane dicarboxylates self-assembled to make spherical structures in an aqueous solution. Subsequent association of Mn2+ ions with the histidyl imidazoles in the self-assembly produced catalytic active sites. The optimal Mn2+ ion concentration was determined and coordination of the Mn2+ ion with multiple histidine imidazoles was investigated using spectroscopy

  18. Small molecule activation by POC(sp3)OP-nickel complexes.

    PubMed

    Hao, Jingjun; Vabre, Boris; Mougang-Soumé, Berline; Zargarian, Davit

    2014-09-22

    This contribution describes the reactivities of CO2 , CO, O2 , and ArNC with the pincer-type complexes [(κ(P) ,κ(C) ,κ(P') -POC sp 3OP)NiX] (POC sp 3OP=(R2 POCH2 )2 CH; R=iPr; X=OSiMe3 , NArH; Ar=2,6-iPr2 C6 H3 ). Reaction of the amido derivative with CO2 and CO leads to a simple insertion into the NiN bond to give stable carbamate and carbamoyl derivatives, respectively, the pincer ligand backbone remaining intact in both cases. In contrast, the analogous reactions with the siloxide derivative produced kinetically labile insertion products that either revert to the starting material (in the case of CO2 ) or react further to give the mixed-valent, dinickel species [(POC sp 3OP)Ni(II) {μ,κ(O) ,κ(P) ,κ(P') -OCOCH(CH2 CH2 OPR2 )2 }Ni(0) (CO)2 ]. The zero-valent center in the latter compound is ligated by a new ligand arising from transformation of the POC sp 3OP ligand backbone. The carbonylation and carboxylation of the siloxido derivative also produced minor quantities of a side-product identified as the trinickel species, [{(η(3) -allyl)Ni(μ(O) ,κ(P) -R2 PO)2 }2 Ni], arising from total dismantling of the POC sp 3OP ligand. Similar reactivities were observed with isonitrile, ArNC: reaction with the siloxido derivative resulted in a complex sequence of steps involving initial insertion, a 1,3-hydrogen shift, and an Arbuzov rearrangement to give [Ni(CNAr)4 ] and a methacrylamide based on fragments of the POC sp 3OP ligand. Oxygenation of the amido and siloxido derivatives led to the phosphinate derivative, [(POC sp 3OP)Ni(OP(O)R2 )], arising from oxidative transformation of the original ligand frame; the reaction with the Ni-NHAr derivative also gave ArHNP(O)R2 through a complex NP bond-forming reaction.

  19. In Vitro Increase in Chloroquine Accumulation Induced by Dihydroethano- and Ethenoanthracene Derivatives in Plasmodium falciparum-Parasitized Erythrocytes

    PubMed Central

    Pradines, Bruno; Alibert, Sandrine; Houdoin, Carole; Santelli-Rouvier, Christiane; Mosnier, Joel; Fusai, Thierry; Rogier, Christophe; Barbe, Jacques; Parzy, Daniel

    2002-01-01

    The effects of a series of dihydroethano- and ethenoanthracene derivatives on chloroquine (CQ) accumulation in CQ-susceptible strain 3D7 and CQ-resistant clone W2 were assessed. The levels of CQ accumulation increased little or none in CQ-susceptible strain 3D7 and generally increased markedly in CQ-resistant strain W2. At 10 μM, 28 compounds yielded cellular accumulation ratios (CARs) greater than that observed with CQ alone in W2. At 10 μM, in strain W2, 21 of 31 compounds had CQ CARs two or more times higher than that of CQ alone, 15 of 31 compounds had CQ CARs three or more times higher than that of CQ alone, 13 of 31 compounds had CQ CARs four or more times higher than that of CQ alone, and 9 of 31 compounds had CQ CARs five or more times higher than that of CQ alone. At 1 μM, 17 of 31 compounds had CQ CARs two or more times higher than that of CQ alone, 12 of 31 compounds had CQ CARs three or more times higher than that of CQ alone, 6 of 31 compounds had CQ CARs four or more times higher than that of CQ alone, and 3 of 31 compounds had CQ CARs five or more times higher than that of CQ alone. At 1 μM, 17 of 31 compounds were more potent inducers of CQ accumulation than verapamil and 12 of 31 compounds were more potent inducers of CQ accumulation than promethazine. The nature of the basic group seems to be associated with increases in the levels of CQ accumulation. At 1 and 10 μM, 10 of 14 and 13 of 14 compounds with amino group (amines and diamines), respectively, had CARs ≥3, while at 1 and 10 μM, only 1 of the 13 derivatives with amido groups had CARs ≥3. Among 12 of the 31 compounds which were more active inducers of CQ accumulation than promethazine at 1 μM, 10 had amino groups and 1 had an amido group. PMID:12069956

  20. Bispecific Antibody Conjugated Manganese-Based Magnetic Engineered Iron Oxide for Imaging of HER2/neu- and EGFR-Expressing Tumors.

    PubMed

    Wu, Shou-Cheng; Chen, Yu-Jen; Wang, Hsiang-Ching; Chou, Min-Yuan; Chang, Teng-Yuan; Yuan, Shyng-Shiou; Chen, Chiao-Yun; Hou, Ming-Feng; Hsu, John Tsu-An; Wang, Yun-Ming

    2016-01-01

    The overexpression of HER2/neu and EGFR receptors plays important roles in tumorigenesis and tumor progression. Targeting these two receptors simultaneously can have a more widespread application in early diagnosis of cancers. In this study, a new multifunctional nanoparticles (MnMEIO-CyTE777-(Bis)-mPEG NPs) comprising a manganese-doped iron oxide nanoparticle core (MnMEIO), a silane-amino functionalized poly(ethylene glycol) copolymer shell, a near infrared fluorescence dye (CyTE777), and a covalently conjugated anti-HER2/neu and anti-EGFR receptors bispecific antibody (Bis) were successfully developed. In vitro T2-weighted MR imaging studies in SKBR-3 and A431 tumor cells incubated with MnMEIO-CyTE777-(Bis)-mPEG NPs showed - 94.8 ± 3.8 and - 84.1 ± 2.8% negative contrast enhancement, respectively. Pharmacokinetics study showed that MnMEIO-CyTE777-(Bis)-mPEG NPs were eliminated from serum with the half-life of 21.3 mins. In vivo MR imaging showed that MnMEIO-CyTE777-(Bis)-mPEG NPs could specifically and effectively target to HER2/neu- and EGFR-expressing tumors in mice; the relative contrast enhancements were 11.8 (at 2 hrs post-injection) and 61.5 (at 24 hrs post-injection) fold higher in SKBR-3 tumors as compared to Colo-205 tumors. T2-weighted MR and optical imaging studies revealed that the new contrast agent (MnMEIO-CyTE777-(Bis)-mPEG NPs) could specifically and effectively target to HER2/neu- and/or EGFR-expressing tumors. Our results demonstrate that MnMEIO-CyTE777-(Bis)-mPEG NPs are able to recognize the tumors expressing both HER2/neu and/or EGFR, and may provide a novel molecular imaging tool for early diagnosis of cancers expressing HER2/neu and/or EGFR.

  1. Por que no dejar a los estudiantes con habilidad superior comenzar la escuela en enero? Estudio de la Compactaction del Curriculum. Monografia Investigativa 94401 (Why Not Let High Ability Students Start School in January? The Curriculum Compacting Study. Research Monograph 94401).

    ERIC Educational Resources Information Center

    Reis, Sally M.; And Others

    This report presents an executive summary, in Spanish, of a study which examined the effects of curriculum compacting, a curriculum modification technique for gifted and talented students. The study involved approximately 436 elementary teachers and 783 students in 27 school districts throughout the United States. The study was designed to…

  2. Selection and processing of the spatial enhanced multispectral Landsat TM images - comparison between the results from merged and source data. (Polish Title: Selekcja i przetwarzanie wzmocnionych przestrzennie obrazów wielospektralnych Landsat TM - porównanie wyników opartych o dane scalone i dane zródłowe)

    NASA Astrophysics Data System (ADS)

    Pirowski, T.; Szczaciuk, G.

    2013-12-01

    The paper presents results of merging lower-resolution spectral data (Landsat, 30m) with panchromatic images of higher spatial resolution (IRS 5.8m). During the first stage of the research, thirty methods of merging satellite data (including their variants) have been tested. The first assessment was based on statistical measures covering spectral distortion and spatial enhancement of pansharpened images. The second assessment was based on the color composite factors essential for photo interpretation. Comparing both obtained ranks of methods revealed substantial differences in their assessed spectral distortion. On the other hand, there appeared similarities in the obtained values for the spatial enhancement of pansharpened images. The reasons of such discrepancies were defined. The research allowed appointing the HPF (High Pass Filter) and LCM (Local Correlation Modeling) methods as the best according to the tested factors. In the second part of the research, the applicability of the selected methods was tested. Information content of color composites was analyzed as well as tresholding and band ratioing. In the tests there were used images fused through five merging methods: HPF, LCM, IHS (Intensity, Hue, Saturation), PCA (Principal Components Analysis) and WMK (based on band ratioing and having specific photo interpretation features). The findings of the research suggest that none of the merging algorithms provide universal solution. Depending on the data processing technique used, the best results are based on images obtained from various integration methods. It means that the method ranks do not correspond with method applicability. Methods appointed as the best ones obtain poor results in some tests and methods which came low in the rank received high rank in some tests. If this conclusion becomes confirmed, it might be necessary to revise the assessment methods of merged images.

  3. Comparison of point clouds derived from aerial image matching with data from airborne laser scanning. (Polish Title: Porównanie wóaściwości chmury punktów wygenerowanej metodą dopasowania obrazów zdjęć lotniczych z danymi z lotniczego skanowania)

    NASA Astrophysics Data System (ADS)

    Dominik, W.

    2014-12-01

    The aim of this study was to investigate the properties of point clouds derived from aerial image matching and to compare them with point clouds from airborne laser scanning. A set of aerial images acquired in years 2010-2013 over the city of Elblag were used for the analysis. Images were acquired with the use of three digital cameras: DMC II 230, DMC I and DigiCAM60 with a GSD varying from 4.5 cm to 15 cm. Eight sets of images that were used in the study were acquired at different stages of the growing season - from March to December. Two LiDAR point clouds were used for the comparison - one with a density of 1.3 p/m2 and a second with a density of 10 p/m2. Based on the input images point clouds were created with the use of the semi-global matching method. The properties of the obtained point clouds were analyzed in three ways: - by the comparison of the vertical accuracy of point clouds with reference to a terrain profile surveyed on bare ground with GPS-RTK method - by visual assessment of point cloud profiles generated both from SGM and LiDAR point clouds - by visual assessment of a digital surface model generated from a SGM point cloud with reference to a digital surface model generated from a LiDAR point cloud. The conducted studies allowed a number of observations about the quality of SGM point clouds to be formulated with respect to different factors. The main factors having influence on the quality of SGM point clouds are GSD and base/height ratio. The essential problem related to SGM point clouds are areas covered with vegetation where SGM point clouds are visibly worse in terms of both accuracy and the representation of terrain surface. It is difficult to expect that in these areas SGM point clouds could replace LiDAR point clouds. This leads to a general conclusion that SGM point clouds are less reliable, more unpredictable and are dependent on more factors than LiDAR point clouds. Nevertheless, SGM point clouds generated with appropriate parameters can have better accuracy than LiDAR point clouds and present more detailed information about the terrain surface.

  4. The Impact of Regional Differences on Elementary School Teachers' Attitudes towards Their Students' Use of Code Switching in a South Texas School District (El impacto de las diferencias regionales en las actitudes de docentes de primaria respecto a la alternancia de códigos por parte de los estudiantes en un distrito escolar del sur de Texas)

    ERIC Educational Resources Information Center

    Nava Gómez, Guadalupe Nancy; García, Hilda

    2012-01-01

    This study focused on investigating whether the teachers' geographical distribution influences their attitudes towards their students' use of code switching. The study was guided by the following research question: Are there differences between teachers' opinions of the north elementary schools and teachers' opinions of the south elementary…

  5. Talking, Singing, Rhyming: Activities for Families with Children Ages 3 to 5 [Presented by]"Between the Lions[R]" = Hablar, cantar, recitar: Actividades para familias con ninos de 3 a 5 anos [presentado por]"Between the Lions[R]."

    ERIC Educational Resources Information Center

    WGBH-TV, Boston, MA.

    "Between the Lions" is a Public Broadcasting System program promoting literacy for children ages 4 through 7 years combining state-of-the-art puppetry, animation, live action, and music to achieve its mission of helping young children learn to read. This guide, in English- and Spanish-language versions, provides literacy activities for…

  6. Exploring with Technology: Activities for Families with Children Ages 3 to 5 [Presented by]"Between the Lions[R]" = Exploremos con tecnologia: Actividades para familias con ninos de 3 a 5 anos [presentado por]"Between the Lions[R]."

    ERIC Educational Resources Information Center

    WGBH-TV, Boston, MA.

    "Between the Lions" is a Public Broadcasting System program promoting literacy for children ages 4 through 7 years combining state-of-the-art puppetry, animation, live action, and music to achieve its mission of helping young children learn to read. This guide, in English- and Spanish-language versions, provides computer literacy…

  7. Reading with Children: Activities for Families with Children Ages 3 to 5 [Presented by]"Between the Lions[R]" = La lectura con los ninos: Actividades para familias con ninos de 3 a 5 anos [presentado por]"Between the Lions[R]."

    ERIC Educational Resources Information Center

    WGBH-TV, Boston, MA.

    "Between the Lions" is a Public Broadcasting System program promoting literacy for children ages 4 through 7 years combining state-of-the-art puppetry, animation, live action, and music to achieve its mission of helping young children learn to read. This guide, in English- and Spanish-language versions, provides literacy activities for…

  8. Words All around Us: Activities for Families with Children Ages 3 to 5 [Presented by]"Between the Lions[R]" = Palabras y palabras a nuestro alrededor: Actividades para familias con ninos de 3 a 5 anos [presentado por]"Between the Lions[R]."

    ERIC Educational Resources Information Center

    WGBH-TV, Boston, MA.

    "Between the Lions" is a Public Broadcasting System program promoting literacy for children ages 4 through 7 years combining state-of-the-art puppetry, animation, live action, and music to achieve its mission of helping young children learn to read. This guide, in English- and Spanish-language versions, provides literacy activities for…

  9. Measurement of the branching ratio for the doubly cabibbo suppressed decay D++ K-K+K+; Medida da razao de ramificacao do Decaimento D++ K-K+K+ duplamente suprimido por cabibbo

    SciTech Connect

    Silva Carvalho, Hendly da

    1997-07-01

    In this thesis, we performed a study for the decay modes D++ K-K+K+ and D+s+ K-K+K+, using the data collected by the E791, a hadroproduction of charm experiment at Fermilab. The D++ K-K+K+ decay is doubly Cabibbo suppressed while the D+s+ K-K+K+ decay is singly Cabibbo suppressed. We found 11.6 +- 3.9 events in the D+ mass region and 8.9 +- 3.3 in the D+s mass region. The D++ K-K+K+ branching ratio is measured to be (3.7 +- 1.3 +- 0.6) x 10-4 while the D++ K-K+K+ branching ratio relative to D+s+ K-K+K+ is measured to be (4.2 +- 1.5 +- 0.6) x 10-2.

  10. Modèle numérique de terrain comme outil pour contrôler et mesurer l'érosion de ravinsModelos digitales de elevación como un instrumento para seguir y medir erosión por cárcavas

    NASA Astrophysics Data System (ADS)

    Betts, Harley D.; DeRose, Ronald C.

    This paper describes the use of Digital Elevation Models (DEMs), constructed from sequential aerial photographs, as a tool for measuring gully erosion in a geomorphologically unstable environment. The technique is applied to a case study that examines erosion in 26 gullies in two study areas in the upper Waipaoa catchment, eastern North Island, New Zealand. Changes over two consecutive time periods, ranging in length from 14.0 years to 33.2 years, were studied at each site, drawing on available historical aerial photography. Several key aspects of the method used are described and discussed in detail, and recommendations are made for future application of DEMs for assessment of landscape change. DEM-measured gully degradation rates are directly proportional to the square root of the gully area.From this relationship it should be possible to rapidly estimate gully erosion at a catchment scale on the basis of gully areas alone. DEM-based measurement techniques, together with appropriate consideration for the sensitivity of the method, have significant cost and efficiency advantages over manual approaches to erosion measurements.

  11. A Visit to the Library: Activities for Families with Children Ages 3 to 5 [Presented by]"Between the Lions[R]" = Una visita a la biblioteca: Actividades para familias con ninos de 3 a 5 anos [presentado por]"Between the Lions[R]."

    ERIC Educational Resources Information Center

    WGBH-TV, Boston, MA.

    "Between the Lions" is a Public Broadcasting System program promoting literacy for children ages 4 through 7 years combining state-of-the-art puppetry, animation, live action, and music to achieve its mission of helping young children learn to read. This guide, in English- and Spanish-language versions, provides suggestions for parents…

  12. Los Hispanos: Problemas y Oportunidades. Resumen de la Actual Situacion Demografica, Economica, Social y Politica de los Hispanos en los Estados Unidos y de las Iniciativas Tomadas por la Fundacion Ford Para Hacer Frente a las Necesidades de esta Poblacion en Aumento y Determinar sus Efectos Sobre la Sociedad Estadounidense. Documento de Trabajo de la Fundacion Ford, No. 436.

    ERIC Educational Resources Information Center

    Ford Foundation, New York, NY.

    The Hispanic population's growing impact on American society has caused the Ford Foundation to explore new Foundation initiatives. The 1980 census revealed 14.6 million Hispanics: 60% Mexican American; 14% Puerto Rican; 6% Cuban, and 20% Other. The Hispanic population in the United States is growing and is characterized by diversity; rapid growth…

  13. For a Child, Life is a Creative Adventure: Supporting Development and Learning through Art, Music, Movement, and Dialogue. A Guide for Parents and Professionals. = Para los ninos, la vida es una aventura creativa: Como estimular el desarrollo y el aprendizaje por medio de las artes visuales, la musica, el movimiento y el dialogo. Guia para padres de familia y profesionales.

    ERIC Educational Resources Information Center

    Cohen, Elena

    Recognizing that creativity facilitates children's learning and development, the Head Start Program Performance Standards require Head Start programs to include opportunities for creative self-expression. This guide with accompanying videotape, both in English- and Spanish- language versions, encourages and assists adults to support children's…

  14. Palabras del Secretario de Educacion Publica en la reunion anual de directores de education federal e inspectores generales en los estados que se rigen por el calendario "A". (Address by the Minister of Education at the Annual Meeting of Directors of Federal Education and Inspectors General in Calendar "A" States).

    ERIC Educational Resources Information Center

    Yanez, Agustin

    This document is an English-language abstract (approximately 1,500 words) of a speech by the Mexican Minister of Education at an annual educators meeting. The Minister dealt with the administration and quality of education, the role of the directors and the duties towards them of the inspectors, and the main features of the reform of national…

  15. Mitigation of Disagreement in Peer Review among L2 Learners and Native Speakers in a College Writing Class (Mitigación del Impacto de las Opiniones de Desacuerdo en el Proceso de Revisión por Pares entre Estudiantes de una Segunda Lengua y Hablantes Nativos en una Clase de Escritura a Nivel Universitario)

    ERIC Educational Resources Information Center

    Christoffersen, Katherine O'Donnell

    2015-01-01

    Peer review is now a commonplace practice in process-oriented writing instruction. A crucial aspect of peer review is assessing another classmate's work, which encompasses the act of disagreement. Given its prevalence in the classroom, it is necessary to analyze how L2 learners mitigate disagreement in the context of peer review with other L2…

  16. Art and Writing: Activities for Families with Children Ages 3 to 5 [Presented by]"Between the Lions[R]" = Arte y escritura: Actividades para familias con ninos de 3 a 5 anos [presentado por]"Between the Lions[R]."

    ERIC Educational Resources Information Center

    WGBH-TV, Boston, MA.

    "Between the Lions" is a Public Broadcasting System program promoting literacy for children ages 4 through 7 years combining state-of-the-art puppetry, animation, live action, and music to achieve its mission of helping young children learn to read. This guide, in English- and Spanish-language versions, provides literacy activities for…

  17. Lo que los educadores necesitan saber sobre...El agrupamiento por habilidad [y] La compactacion del curriculum [y] Los alumnos dotados y el aprendizaje cooperativo [y] La actividad tutoral. Guias practica (What Educators Need To Know about...Ability Grouping [and] Curriculum Compacting [and] Gifted Students and Cooperative Learning [and] Mentoring. Practitioners' Guides).

    ERIC Educational Resources Information Center

    Siegle, Del, Ed.

    These four pamphlets in Spanish offer guidelines supported by theory-driven quality research that is problem-based, practice-relevant, and consumer-oriented. Each pamphlet has a section summarizing research from the literature or topic notes as well as implications for the classroom. The first guide offers principles for teachers concerning the…

  18. Evaluation de la qualité de modèles numériques de terrain dérivés par interférométrieEvaluación de la calidad de modelos digitales de elevación derivados por interferometría

    NASA Astrophysics Data System (ADS)

    Gens, Rüdiger

    One of the most important uses of SAR interferometry is in the generation of digital elevation models (DEMs). However, a standard procedure for quality estimation of DEMs does not exist. This paper proposes a method of quality estimation using an adapted Monte Carlo simulation, which has the advantage that it could be used in areas where appropriate reference DEMs are not available. This paper also addresses interferometric processing, with special emphasis on the influence of the input parameters. Practical implementation of the proposed technique is shown on a data set from Lower Saxony in Germany. The error map generated, which is a measure of the quality of the DEM, is also presented. For further analysis of the critical aspects of quality, a reference DEM has also been used.

  19. Análise de Associação por Todo o Genoma para Identificar Locos Relacionados ao Lucro Líquido, à Vida Produtiva e ao Escore de Células Somáticas na raça Jersey1

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A genome scan was conducted in the US Jersey population to identify QTL affecting net merit, productive life, and somatic cell score. Data used at this study were DHI records from the national database of the Animal Improvement Programs Laboratory, USDA (Beltsville, MD). DNA was acquired for 2,380 a...

  20. Análisis clínico y epidemiológico de los accidentes por mordeduras de serpientes del género Bothrops en Venezuela [A clinical and epidemiological analysis of accidental bites by snakes of the genus Bothrops in Venezuela].

    PubMed

    Rodríguez Acosta, A; Uzcategui, W; Azuaje, R; Aguilar, I; Girón, M E

    2000-01-01

    Clinical register of 60 patients bitten by Bothrops snake who assisted at Leopoldo Manrique Hospital and the Institute of Tropical Medicine (HLM-IMT) in Caracas during 1996-1997 were analysed. The accident was more frequent in males (45/75%). In 32 cases (53.3%) the snake was classified and 26 were Bothrops lanceolatus, 4 Bothrops venezuelensis and 2 Bothrops atrox. Anatomic regions more frequent bitten were superior members (40/66.6%): hands (36/60%), forearm (2/3.3%), elbow (1/1.6%) and arm (1/1.6%). On inferior members (20/33.3%): legs (6/10%), feet (10/16.7%), ankle (2/3.3%), and the hip (2:3.3%). The most frequent clinical manifestations in moderate and severe cases (33 patient) were pain (100%), oedema (98%), ecchymosis (76%), blisters (20%), necrosis (12%), abscess (6%) bleeding (19%), heart failure (1/1.6%), renal failure (1/1.6%). The blood clotting was evaluated in 60 (100%) cases and it was altered in 33 (55%) patients. No deaths were recorded.

  1. A protein secretion system linked to bacteroidete gliding motility and pathogenesis

    PubMed Central

    Sato, Keiko; Naito, Mariko; Yukitake, Hideharu; Hirakawa, Hideki; Shoji, Mikio; McBride, Mark J.; Rhodes, Ryan G.; Nakayama, Koji

    2009-01-01

    Porphyromonas gingivalis secretes strong proteases called gingipains that are implicated in periodontal pathogenesis. Protein secretion systems common to other Gram-negative bacteria are lacking in P. gingivalis, but several proteins, including PorT, have been linked to gingipain secretion. Comparative genome analysis and genetic experiments revealed 11 additional proteins involved in gingipain secretion. Six of these (PorK, PorL, PorM, PorN, PorW, and Sov) were similar in sequence to Flavobacterium johnsoniae gliding motility proteins, and two others (PorX and PorY) were putative two-component system regulatory proteins. Real-time RT-PCR analysis revealed that porK, porL, porM, porN, porP, porT, and sov were down-regulated in P. gingivalis porX and porY mutants. Disruption of the F. johnsoniae porT ortholog resulted in defects in motility, chitinase secretion, and translocation of a gliding motility protein, SprB adhesin, to the cell surface, providing a link between a unique protein translocation system and a motility apparatus in members of the Bacteroidetes phylum. PMID:19966289

  2. A protein secretion system linked to bacteroidete gliding motility and pathogenesis.

    PubMed

    Sato, Keiko; Naito, Mariko; Yukitake, Hideharu; Hirakawa, Hideki; Shoji, Mikio; McBride, Mark J; Rhodes, Ryan G; Nakayama, Koji

    2010-01-05

    Porphyromonas gingivalis secretes strong proteases called gingipains that are implicated in periodontal pathogenesis. Protein secretion systems common to other Gram-negative bacteria are lacking in P. gingivalis, but several proteins, including PorT, have been linked to gingipain secretion. Comparative genome analysis and genetic experiments revealed 11 additional proteins involved in gingipain secretion. Six of these (PorK, PorL, PorM, PorN, PorW, and Sov) were similar in sequence to Flavobacterium johnsoniae gliding motility proteins, and two others (PorX and PorY) were putative two-component system regulatory proteins. Real-time RT-PCR analysis revealed that porK, porL, porM, porN, porP, porT, and sov were down-regulated in P. gingivalis porX and porY mutants. Disruption of the F. johnsoniae porT ortholog resulted in defects in motility, chitinase secretion, and translocation of a gliding motility protein, SprB adhesin, to the cell surface, providing a link between a unique protein translocation system and a motility apparatus in members of the Bacteroidetes phylum.

  3. Severe maternal morbidity: a case-control study in Maranhao, Brazil

    PubMed Central

    2013-01-01

    para morbidade materna grave em São Luís, capital de um dos estados mais pobres do Brasil. Método Estudo caso-controle realizado em duas maternidades públicas de alto risco e duas UTIs de referência aos casos obstétricos entre 01/03/2009 e 28/02/2010. Foram incluídas todas as pacientes internadas por complicação do período grávido-puerperal e que preenchiam os critérios de Waterstone e/ou Mantel para morbidade materna grave. Foram selecionados para cada caso, dois controles por sorteio aleatório dentre as pacientes internadas no mesmo período e mesma maternidade que o caso. As informações de domínio sociodemográfico, clínico, obstétrico, comportamental, exposição a eventos estressores na gestação, assistência ao pré-natal, intercorrências obstétricas e atenção ao parto, foram obtidas por meio de entrevista estruturada. As variáveis foram analisadas por modelo de regressão logística múltipla não condicional, baseado em modelo hierarquizado a priori. Resultados Foram identificados como fatores de risco para morbidade materna grave: idade >35 anos (OR=3,11; IC 95%:1,53-6,31), hipertensão prévia à gestação (OR=2,52; IC 95%:1,09-5,80), antecedente de aborto (OR=1,61; IC 95%:0,97-2,68), ter realizado 4–5 consultas pré-natais (OR=1,78; IC 95%:1,05-3,01) ou 1–3 consultas (OR=1,89; IC 95%:1,03-3,49). Conclusão Os resultados do estudo corroboram a importância da assistência à saúde reprodutiva e o pré-natal completo e qualificado na prevenção de eventos mórbidos graves durante o ciclo grávido-puerperal. PMID:23399443

  4. The Practice of Research of a Basic Education Teacher Involving Mental Models of the Phases of the Moon and Eclipses. (Spanish Title: La Práctica de Investigación de un Maestro de Educación BÁsica con El Uso de los Modelos Mentales de Las Fases de la Luna Y Eclipses.) A Prática de Pesquisa de um Professor do Ensino Fundamental Envolvendo Modelos Mentais de Fases da Lua e Eclipses

    NASA Astrophysics Data System (ADS)

    Pessôa Queiroz, Glória; Jubitipan Borges de Sousa, Carlos; Auxiliadora Delgado Machado, Maria

    2009-12-01

    docente. La formación de grupos interinstitucionales para la planificación de la acción y la investigación ha resultado productiva para el trabajo de construcción de conocimiento de apoyo a los procesos educativos en la escuela, mientras que la universidad enriquece su colección de experiencias validadas, considerando los resultados de la educación inicial y continua de maestros. La participación activa del maestro en un grupo de investigación en la universidad lo llevó a reflexiones sobre los posibles caminos didácticos que pueden ser descriptos, analizados y comunicados a los demás docentes. La construcción de una pedagogía propia, que tuvo en cuenta los modelos mentales de los estudiantes sobre los temas básicos de astronomía, y los cambios desarrollados a partir de las lecciones que enseñó, trajeron consecuencias de largo alcance sobre la pedagogía adoptada por el maestro, que ahora incorpora una nueva visión de la ciencia y formas alternativas al diálogo con los estudiantes, los componentes esenciales para un investigador en Educaciónen Ciencias. A inclusão do professor da escola básica no universo da pesquisa é questão controvertida e em pleno debate no meio acadêmico. A oportunidade de trabalho coletivo que incorporou professores de uma escola municipal no Rio de Janeiro a um grupo de ensino de Física da universidade nos possibilitou vislumbrar a ressignificação da função de um professor de Ciências (co-autor deste trabalho) por ele próprio, agora passando a incluir a pesquisa sobre a construção de conhecimento pelos alunos em sua prática como docente. A formação de grupos interinstitucionais para o planejamento de ações e de pesquisas tem-se mostrado produtiva para um trabalho de construção de conhecimentos a fim de subsidiar processos educativos na escola, ao mesmo tempo em que a universidade enriquece seu acervo de experiências validadas criticamente, podendo considerar seus resultados na formação inicial e

  5. Differential Regulation of Duplicate Light-Dependent Protochlorophyllide Oxidoreductases in the Diatom Phaeodactylum tricornutum

    PubMed Central

    Hunsperger, Heather M.; Cattolico, Rose Ann

    2016-01-01

    Background Diatoms (Bacilliariophyceae) encode two light-dependent protochlorophyllide oxidoreductases (POR1 and POR2) that catalyze the penultimate step of chlorophyll biosynthesis in the light. Algae live in dynamic environments whose changing light levels induce photoacclimative metabolic shifts, including altered cellular chlorophyll levels. We hypothesized that the two POR proteins may be differentially adaptive under varying light conditions. Using the diatom Phaeodactylum tricornutum as a test system, differences in POR protein abundance and por gene expression were examined when this organism was grown on an alternating light:dark cycles at different irradiances; exposed to continuous light; and challenged by a significant decrease in light availability. Results For cultures maintained on a 12h light: 12h dark photoperiod at 200μE m−2 s−1 (200L/D), both por genes were up-regulated during the light and down-regulated in the dark, though por1 transcript abundance rose and fell earlier than that of por2. Little concordance occurred between por1 mRNA and POR1 protein abundance. In contrast, por2 mRNA and POR2 protein abundances followed similar diurnal patterns. When 200L/D P. tricornutum cultures were transferred to continuous light (200L/L), the diurnal regulatory pattern of por1 mRNA abundance but not of por2 was disrupted, and POR1 but not POR2 protein abundance dropped steeply. Under 1200μE m−2 s−1 (1200L/D), both por1 mRNA and POR1 protein abundance displayed diurnal oscillations. A compromised diel por2 mRNA response under 1200L/D did not impact the oscillation in POR2 abundance. When cells grown at 1200L/D were then shifted to 50μE m−2 s−1 (50L/D), por1 and por2 mRNA levels decreased swiftly but briefly upon light reduction. Thereafter, POR1 but not POR2 protein levels rose significantly in response to this light stepdown. Conclusion Given the sensitivity of diatom por1/POR1 to real-time light cues and adherence of por2/POR2 regulation to

  6. Farmyard Manure and Fertilizer Effects on Seed Potato (Solanum tuberosum L.) Yield in Green House Production

    NASA Astrophysics Data System (ADS)

    László, M.

    2009-04-01

    ção máximas, principalmente em solos mais ácidos e pobres em matéria orgânico. A adubação fosfatada é muito importante no crescimento inicial da planta e, além de aumentar a produção de tuberculos em peso e números, aumenta também a quantidade e qualidade do amido neles contidos e reduz perdas durante o armazenamento dos mesmos. A quantidade de fósforo a aplicar dependerá da análise do solo considerando- se principalmente o nível de P existente e a textura do solo. Solos de textura média e arenosa necessitam maior conteúdo de fósforo do que os de textura argilosa para serem considerandos solos de baixo, médio ou alto teor de fósfato. Efeito da potássica Embora seja o elemento mais absorbido pela batateira, nem sempre há resposta positiva da aduba potássica sobre o rendimento da cultura. Provavelmente isto esteja relacionado com níveis elevados deste elemento no solo (Kurnik et all. 2001.). Entretanto, em solos com médios e baixos teores de potássio, aumentos significativos são conseguidos. Por isto, as recomendações de adubação com potássio, nas diversas regiões do mundo, variam de 50-300 kg ha-1 de K2O. Resultados de trabalhos em brasiléiros têm demonstrado que a aduba potássica pode ser substituída pela aplicação de 150 m3 ha-1 de vinhaça de cana de açúcar. Ao elevar- se a dose de fertilização potássica deverá haver precaução para que a adubação magnesiana seja suficiente. O K além de aumentar a produção, em solos deficientes, aumenta também o tamanho dos tubérculos produzidos, e a proporção de tubérculos grandes. Deficiência no suprimento de potássio á planta pode acarretar produção de tubérculos com elevada susceptibilidade aos danos mecánicos pós-colheita. Os tubérculos injuriados enegrecem facilmente e este enegrecimento é inversamente proporcional á quantidade de potássio nos tuberculos. Ademais, quando fritos dão origem a um produto escuro, de baixa valor comercial. Manejo de aduba

  7. JPRS Report, West Europe.

    DTIC Science & Technology

    1988-02-09

    finding its market in Jor- dan, Morocco, and Argentina . Outside of theBasque Country, he stresses Instalaza (Zaragoza), specializing in the Latin...30 por 100 J 3por100(Lf) fc 1por100(L$) (20) 4. £Cree qua las mujeres deben ir (2") SI ........... 36 poKlDO V No .......... 67 por 100

  8. Effect of dietary porphyran from the red alga, Porphyra yezoensis, on glucose metabolism in diabetic KK-Ay mice.

    PubMed

    Kitano, Yuki; Murazumi, Koki; Duan, Jingjing; Kurose, Kosuke; Kobayashi, Shunichi; Sugawara, Tatsuya; Hirata, Takashi

    2012-01-01

    Porphyran (POR) from the red alga Porphyra yezoensis is a water soluble dietary fiber. In this study, we investigated the effect of dietary POR on glucose metabolism in KK-Ay mice (a model for type 2 diabetes). Mice were divided into 4 groups and fed a diet containing 5% cellulose (control), POR, POR Arg or POR K. After 3 wk of feeding, plasma insulin levels and the calculated homeostasis model assessment-insulin resistance (HOMA-IR) index were significantly lower in the POR group than in the control group. Compared with the control group, plasma adiponectin levels were significantly increased in the POR, POR Arg and POR K groups. These results suggest that dietary POR should improve glucose metabolism in diabetes via up-regulation of adiponectin levels. In addition, the amount of propionic acid in the cecum of the POR group was significantly higher than in the control group and the profile of bacterial flora was changed by dietary POR. In the cecum of the POR, POR Arg and POR K groups, Bacteroides was significantly increased and Clostridium coccoides was significantly decreased compared with in the control group. The effects of dietary POR on the hindgut environment might contribute to the improvement of glucose metabolism.

  9. Jasmonic acid-isoleucine formation in grapevine (Vitis vinifera L.) by two enzymes with distinct transcription profiles.

    PubMed

    Böttcher, Christine; Burbidge, Crista A; di Rienzo, Valentina; Boss, Paul K; Davies, Christopher

    2015-07-01

    The plant hormone jasmonic acid (JA) is essential for stress responses and the formation of reproductive organs, but its role in fruit development and ripening is unclear. Conjugation of JA to isoleucine is a crucial step in the JA signaling pathway since only JA-Ile is recognized by the jasmonate receptor. The conjugation reaction is catalyzed by JA-amido synthetases, belonging to the family of Gretchen Hagen3 (GH3) proteins. Here, in vitro studies of two grapevine (Vitis vinifera L. cv Shiraz) GH3 enzymes, VvGH3-7 and VvGH3-9, demonstrated JA-conjugating activities with an overlapping range of amino acid substrates, including isoleucine. Expression studies of the corresponding genes in grape berries combined with JA and JA-Ile measurements suggested a primary role for JA signaling in fruit set and cell division and did not support an involvement of JA in the ripening process. In response to methyl JA (MeJA) treatment, and in wounded and unwounded (distal) leaves, VvGH3-9 transcripts accumulated, indicating a participation in the JA response. In contrast, VvGH3-7 was unresponsive to MeJA and local wounding, demonstrating a differential transcriptional regulation of VvGH3-7 and VvGH3-9. The transient induction of VvGH3-7 in unwounded, distal leaves was suggestive of the involvement of an unknown mobile wound signal.

  10. Synthesis and Properties of Gelators Derived from Tetraphenylethylene and Gallic Acid with Aggregation-Induced Emission

    NASA Astrophysics Data System (ADS)

    Luo, Miao; Zhou, Xie; Chi, Zhenguo; Ma, Chunping; Zhang, Yi; Liu, Siwei; Xu, Jiarui

    2013-09-01

    Two novel organogelators (TEG and TAG) based on tetraphenylethylene and 3,4,5-tris(dodecyloxy) benzoic acid were synthesized through ester bond and amido bond linkages, respectively. Compounds TEG and TAG were able to induce gelation in ethanol. Aggregation-induced enhanced emission was observed in these organogelator molecules, with increased fluorescence intensity from the solutions to the gels. The completely thermoreversible gelation occurred due to the aggregation of the organogelators. In the process, a fibrous network was formed by a combination of intermolecular hydrogen bonding, π-π stacking and van der Waals interactions. These phenomena were observed in the xerogels by field-emission scanning electron microscopy and Fourier-transform infrared spectroscopy. The results of differential scanning calorimetry and polarized optical microscopy indicated that compound TAG exhibited stable liquid crystalline phases over a wide temperature range. The linking groups have severe influence on the properties of the organogelators, which was mainly attributed to the hydrogen bonding interaction in compound TAG.

  11. Crystal structure of a 2:1 piroxicam–gentisic acid co-crystal featuring neutral and zwitterionic piroxicam mol­ecules

    PubMed Central

    Horstman, Elizabeth M.; Bertke, Jeffery A.; Woods, Toby J.; Kenis, Paul J. A.

    2016-01-01

    A new 2:1 co-crystal of piroxicam and gentisic acid [systematic name: 4-hy­droxy-1,1-dioxo-N-(pyridin-2-yl)-2H-1λ6,2-benzo­thia­zine-3-carboxamide–2-(4-oxido-1,1-dioxo-2H-1λ6,2-benzo­thia­zine-3-amido)­pyridin-1-ium–2,5-di­hydroxy­benzoic acid, 2C15H13N3O4S·C7H6O4] has been synthesized using a microfluidic platform and initially identified using Raman spectroscopy. In the co-crystal, one piroxicam mol­ecule is in its neutral form and an intra­molecular O—H⋯O hydrogen bond is observed. The other piroxicam mol­ecule is zwitterionic (proton transfer from the OH group to the pyridine N atom) and two intra­molecular N—H⋯O hydrogen bonds occur. The gentisic acid mol­ecule shows whole-mol­ecule disorder over two sets of sites in a 0.809 (2):0.191 (2) ratio. In the crystal, extensive hydrogen bonding between the components forms layers propagating in the ab plane. PMID:27980814

  12. Cationic PAMAM Dendrimers as Pore-Blocking Binary Toxin Inhibitors

    PubMed Central

    2015-01-01

    Dendrimers are unique highly branched macromolecules with numerous groundbreaking biomedical applications under development. Here we identified poly(amido amine) (PAMAM) dendrimers as novel blockers for the pore-forming B components of the binary anthrax toxin (PA63) and Clostridium botulinum C2 toxin (C2IIa). These pores are essential for delivery of the enzymatic A components of the internalized toxins from endosomes into the cytosol of target cells. We demonstrate that at low μM concentrations cationic PAMAM dendrimers block PA63 and C2IIa to inhibit channel-mediated transport of the A components, thereby protecting HeLa and Vero cells from intoxication. By channel reconstitution and high-resolution current recording, we show that the PAMAM dendrimers obstruct transmembrane PA63 and C2IIa pores in planar lipid bilayers at nM concentrations. These findings suggest a new potential role for the PAMAM dendrimers as effective polyvalent channel-blocking inhibitors, which can protect human target cells from intoxication with binary toxins from pathogenic bacteria. PMID:24954629

  13. Expanding sapphyrin: towards selective phosphate binding.

    PubMed

    Katayev, Evgeny A; Boev, Nikolay V; Myshkovskaya, Ekaterina; Khrustalev, Victor N; Ustynyuk, Yu A

    2008-01-01

    The anion-templated syntheses and binding properties of novel macrocyclic oligopyrrole receptors in which pyrrole rings are linked through amide or imine bonds are described. The efficient synthesis was accomplished by anion-templated [1+1] Schiff-base condensation and acylation macrocyclization reactions. Free receptors and their host-guest complexes with hydrochloric acid, acetic acid, tetrabutylammonium chloride, and hydrogen sulfate were analyzed by single-crystal X-ray diffraction analysis. Stability constants with different tetrabutylammonium salts of inorganic acids were determined by standard 1H NMR and UV/Vis titration techniques in [D6]DMSO/0.5% water solution. According to the titration data, receptors containing three pyrrole rings (10 and 12) exhibit high affinity (log Ka=5-7) for bifluoride, acetate, and dihydrogen phosphate, and interact weakly with chloride and hydrogen sulfate. The amido-bipyrrole receptors 11 and 13 with four pyrrole rings exhibit 10(4)- and 10(2)-fold selectivity for dihydrogen phosphate, respectively, as inferred from competitive titrations in the presence of tetrabutylammonium acetate.

  14. Detecting the Formation and Transformation of Oligomers during Insulin Fibrillation by a Dendrimer Conjugated with Aggregation-Induced Emission Molecule.

    PubMed

    Huang, Qin; Xie, Jing; Liu, Yanpeng; Zhou, Anna; Li, Jianshu

    2017-02-08

    The fibrillation of protein is harmful and impedes the use of protein drugs. It also relates to various debilitating diseases such as Alzheimer's diseases. Thus, investigating the protein fibrillation process is necessary. In this study, poly(amido amine) dendrimers (PAMAM) of generation 3 (G3) and generation 4 (G4) were synthesized and conjugated with 4-aminobiphenyl, an aggregation-induced emission (AIE) moiety, at varied grafting ratios. Among them, one fluorescence probe named G3-biph-3 that was grafted average 3.25 4-aminobiphenyl to the G3, can detect the transformations both from native insulin to oligomers and from oligomers to fibrils. The size difference of native insulin, oligomers, and fibrils was proposed to be the main factor leading to the detection of the above transformations. Different molecular weights of sodium polyacrylate (PAAS) were also applied as a model to interact with G3-biph-3 to further reveal the mechanism. The results indicated that PAMAM with a certain generation and grafted with appropriate AIE groups can detect the oligomer formation and transformation during the insulin fibrillation process.

  15. Growth of Er-doped silicon using metalorganics by plasma-enhanced chemical vapor deposition

    NASA Astrophysics Data System (ADS)

    Andry, P. S.; Varhue, W. J.; Ladipo, F.; Ahmed, K.; Adams, E.; Lavoie, M.; Klein, P. B.; Hengehold, R.; Hunter, J.

    1996-07-01

    Epitaxial growth of Er-doped silicon films has been performed by plasma-enhanced chemical vapor deposition at low temperature (430 °C) using an electron cyclotron resonance source. The goal was to incorporate an optically active center, erbium surrounded by nitrogen, through the use of the metalorganic compound tris (bis trimethyl silyl amido) erbium. Films were analyzed by Rutherford backscattering spectrometry, secondary ion mass spectroscopy, and high resolution x-ray diffraction. The characteristic 1.54 μm emission was observed by photoluminescence spectroscopy. Previous attempts to incorporate the complex (ErO6) using tris (2,2,6,6-tetramethyl- 3,5-heptanedionato) erbium (III) indicated that excessive carbon contamination lowered epitaxial quality and reduced photoluminescent intensity. In this study, chemical analysis of the films also revealed a large carbon concentration, however, the effect on epitaxial quality was much less destructive. A factorial design experiment was performed whose analysis identified the key processing parameters leading to high quality luminescent films. Hydrogen was found to be a major cause of crystal quality degradation in our metalorganic plasma-enhanced process.

  16. The Formulation of Aptamer-Coated Paclitaxel-Polylactide Nanoconjugates and Their Targeting to Cancer Cells

    PubMed Central

    Tong, Rong; Yala, Linda; Fan, Timothy M.; Cheng, Jianjun

    2011-01-01

    Paclitaxel-polylactide (Ptxl-PLA) conjugate nanoparticles, termed as nanoconjugates (NCs), were prepared through Ptxl/(BDI)ZnN(TMS)2 (BDI = 2-((2,6-diisopropylphenyl)-amido)-4-((2,6-diisopropylphenyl)-imino)-2-pentene)-mediated controlled polymerization of lactide (LA) followed by nanoprecipitation. Nanoprecipitation of Ptxl-PLA resulted in sub-100 nm NCs with monomodal particle distributions and low polydispersities. The sizes of Ptxl-PLA NCs could be precisely controlled by using appropriate water-miscible solvents and by controlling the concentration of Ptxl-PLA during nanoprecipitation. Co-precipitation of a mixture of PLA-PEG-PLA (PLA = 14 kDa; PEG = 5kDa) and Ptxl-PLA in PBS resulted in NCs that could stay non-aggregated in PBS for an extended period of time. To develop solid formulations of NCs, we evaluated a series of lyoprotectants, aiming to identify candidates that could effectively reduce or eliminate NC aggregation during lyophilization. Albumin was found to be an excellent lyoprotectant for the preparation of NCs in solid form, allowing lyophilized NCs to be readily dispersed in PBS without noticeable aggregates. Aptamer-NCs bioconjugates were prepared and found to be able to effectively target prostate-specific membrane antigen in a cell-specific manner. PMID:20122727

  17. Probing the Electronic Structures of [Cmu(Mu-XR(2)]**N+ Diamond Cores As a Function of the Bridging X Atom (X = N Or P) And Charge (N=0, 1, 2)

    SciTech Connect

    Harkins, S.B.; Mankad, N.P.; Miller, A.J.M.; Szilagyi, R.K.; Peters, J.C.

    2009-05-18

    A series of dicopper diamond core complexes that can be isolated in three different oxidation states ([Cu{sub 2}({mu}-XR{sub 2})]{sup n+}, where n = 0, 1, 2 and X = N or P) is described. Of particular interest is the relative degree of oxidation of the respective copper centers and the bridging XR{sub 2} units, upon successive oxidations. These dicopper complexes feature terminal phosphine and either bridging amido or phosphido donors, and as such their metal-ligand bonds are highly covalent. Cu K-edge, Cu L-edge, and P K-edge spectroscopies, in combination with solid-state X-ray structures and DFT calculations, provides a complementary electronic structure picture for the entire set of complexes that tracks the involvement of a majority of ligand-based redox chemistry. The electronic structure picture that emerges for these inorganic dicopper diamond cores shares similarities with the Cu{sub 2}({mu}-SR){sub 2} Cu{sub A} sites of cytochrome c oxidases and nitrous oxide reductases.

  18. Design considerations for PAMAM dendrimer therapeutics.

    PubMed

    Goonewardena, Sascha N; Kratz, Jeremy D; Zong, Hong; Desai, Ankur M; Tang, Shengzhuang; Emery, Sarah; Baker, James R; Huang, Baohua

    2013-05-15

    We have previously shown that methotrexate (MTX) conjugated to a cancer-specific poly amido amine (PAMAM) dendrimer has a higher therapeutic index than MTX alone. Unfortunately, these therapeutics have been difficult to advance because of the complicated syntheses and an incomplete understanding of the dendrimer properties. We wished to address these obstacles by using copper-free click chemistry to functionalize the dendrimer scaffolds and to exploring the effects of two dendrimer properties (the targeting ligand and drug linkage) on cytotoxicity. We conjugated either ester or amide-linker modified MTX to dendrimer scaffolds with or without folic acid (FA). Because of multivalency, the FA and MTX functionalized dendrimers had similar capacities to target the folate receptor on cancer cells. Additionally, we found that the ester- and amide-linker modified MTX compounds had similar cytotoxicity but the dendrimer-ester MTX conjugates were much more cytotoxic than the dendrimer-amide MTX conjugates. These results clarify the impact of these properties on therapeutic efficacy and will allow us to design more effective polymer therapeutics.

  19. Biodegradation of polyacrylamide by bacteria isolated from activated sludge and oil-contaminated soil.

    PubMed

    Wen, Qinxue; Chen, Zhiqiang; Zhao, Ye; Zhang, Huichao; Feng, Yujie

    2010-03-15

    Polyacrylamide (PAM), a linear water soluble polymeric compound with high molecular weight, is extensively used for oil production in China. Compared with the physico-chemical degradation of PAM, there is no acrylamide monomer, which causes peripheral neuropathy, released in the process of biodegradation. Unfortunately, few microorganisms have been isolated which can degrade PAM. In this study, two PAM-degrading bacterial strains, named HWBI and HWBII, were isolated from the activated sludge and soil in an oil field that had been contaminated by PAM for an extended period. These were subsequently identified as Bacillus cereus and Bacillus flexu, respectively. Both strains grew on a medium composed of 60 mg L(-1) PAM as the sole source of carbon. Although both strains degraded PAM in different rates, after 72 h cultivation more than 70% of the PAM was consumed. This degradation efficiency was much higher than previous studies. Both strains degraded a determinate proportion of PAM when 50-1000 mg L(-1) of the initial PAM was supplied. Glucose with a concentration lower than 200 mg L(-1) can be used as co-metabolism substrate with PAM. The Fourier Transform Infrared (FT-IR) spectrograms of the cultures before and after PAM degradation were also recorded. The result showed that amido groups of the PAM were picked off by the microorganisms from the main chain of the PAM, and metabolism products other than acrylamide were formed in the degradation.

  20. Cr(VI) uptake mechanism of Bacillus cereus.

    PubMed

    Chen, Zhi; Huang, Zhipeng; Cheng, Yangjian; Pan, Danmei; Pan, Xiaohong; Yu, Meijuan; Pan, Zhiyun; Lin, Zhang; Guan, Xiong; Wu, Ziyu

    2012-04-01

    In this study, we investigated the Cr(VI) uptake mechanism in an indigenous Cr(VI)-tolerant bacterial strain -Bacillus cereus through batch and microscopic experiments. We found that both the cells and the supernatant collected from B. cereus cultivation could reduce Cr(VI). The valence state analysis revealed the complete transformation from Cr(VI) into Cr(III) by living B. cereus. Further X-ray absorption fine structure and Fourier transform infrared analyses showed that the reduced Cr(III) was coordinated with carboxyl and amido functional groups from either the cells or supernatant. Scanning electron microscopy and atomic force microscopy observation showed that noticeable Cr(III) precipitates were accumulated on bacterial surfaces. However, Cr(III) could also be detected in bacterial inner portions by using transmission electron microscopy thin section analysis coupled with energy dispersive X-ray spectroscopy. Through quantitative analysis of chromium distribution, we determined the binding ratio of Cr(III) in supernatant, cell debris and cytoplasm as 22%, 54% and 24%, respectively. Finally, we further discussed the role of bacterium-origin soluble organic molecules to the remediation of Cr(VI) pollutants.

  1. Hydroxyapatite-anchored dendrimer for in situ remineralization of human tooth enamel.

    PubMed

    Wu, Duo; Yang, Jiaojiao; Li, Jiyao; Chen, Liang; Tang, Bei; Chen, Xingyu; Wu, Wei; Li, Jianshu

    2013-07-01

    In situ remineralization of hydroxyapatite (HA) on human tooth enamel surface induced by organic matrices is of great interest in the fields of material science and stomatology. In order to mimic the organic matrices induced biomineralization process in developing enamel and enhance the binding strength at the remineralization interface, carboxyl-terminated poly(amido amine) (PAMAM-COOH)-alendronate (ALN) conjugate (ALN-PAMAM-COOH) was synthesized and characterized. PAMAM-COOH has a highly ordered architecture and is capable of promoting the HA crystallization process. ALN is conjugated on PAMAM-COOH due to its specific adsorption on HA (the main component of tooth enamel), resulting in increased binding strength which is tight enough to resist phosphate buffered saline (PBS) rinsing as compared with that of PAMAM-COOH alone. While incubated in artificial saliva, ALN-PAMAM-COOH could induce in situ remineralization of HA on acid-etched enamel, and the regenerated HA has the nanorod-like crystal structure similar to that of human tooth enamel. The hardness of acid-etched enamel samples treated by ALN-PAMAM-COOH can recover up to 95.5% of the original value with strong adhesion force. In vivo experiment also demonstrates that ALN-PAMAM-COOH is effective in repairing acid-etched enamel in the oral cavity. Overall, these results suggest that ALN-PAMAM-COOH is highly promising as a restorative biomaterial for in situ remineralization of human tooth enamel.

  2. Structural modifications of 4-aryl-4-oxo-2-aminylbutanamides and their acetyl- and butyrylcholinesterase inhibitory activity. Investigation of AChE-ligand interactions by docking calculations and molecular dynamics simulations.

    PubMed

    Vitorović-Todorović, Maja D; Koukoulitsa, Catherine; Juranić, Ivan O; Mandić, Ljuba M; Drakulić, Branko J

    2014-06-23

    Congeneric set of thirty-eight 4-aryl-4-oxo-2-(N-aryl/cycloalkyl)butanamides has been designed, synthesized and evaluated for acetyl- and butyrylcholinesterase inhibitory activity. Structural variations included cycloalkylamino group attached to C2 position of butanoyl moiety, and variation of amido moiety of molecules. Twelve compounds, mostly piperidino and imidazolo derivatives, inhibited AChE in low micromolar range, and were inactive toward BChE. Several N-methylpiperazino derivatives showed inhibition of BChE in low micromolar or submicromolar concentrations, and were inactive toward AChE. Therefore, the nature of the cycloalkylamino moiety governs the AChE/BChE selectivity profile of compounds. The most active AChE inhibitor showed mixed-type inhibition modality, indicating its binding to free enzyme and to enzyme-substrate complex. Thorough docking calculations of the seven most potent AChE inhibitors from the set, showed that the hydrogen bond can be formed between amide -NH- moiety of compounds and -OH group of Tyr 124. The 10 ns unconstrained molecular dynamic simulation of the AChE-compound 18 complex shows that this interaction is the most persistent. This is, probably, the major anchoring point for the binding.

  3. Synthesis and spectral properties of polymethine-cyanine dye-nitroxide radical hybrid compounds for use as fluorescence probes to monitor reducing species and radicals

    NASA Astrophysics Data System (ADS)

    Sato, Shingo; Tsunoda, Minoru; Suzuki, Minoru; Kutsuna, Masahiro; Takido-uchi, Kiyomi; Shindo, Mitsuru; Mizuguchi, Hitoshi; Obara, Heitaro; Ohya, Hiroaki

    2009-01-01

    Various hybrid compounds comprised of two types of nitroxide radicals and either a pentamethine (Cy5) or trimethine cyanine (Cy3) were synthesized. The nitroxide radicals were linked either via an ester-bond to one or two N-alkyl carboxyl-terminated groups of Cy5, or via two amido-bonds (aminocarbonyl or carbonylamino group) to the 5-position of the indolenine moieties of Cy5 and Cy3. Changes in fluorescence and ESR intensities of the hybrid compounds were measured before and after addition of Na ascorbate in PBS (pH 7.0) to reduce the radicals. Among the hybrid compounds synthesized, those that linked the nitroxide radicals via an aminocarbonyl residue at the 5-position of the indolenine moieties on Cy5 and Cy3 exhibited a 1.8- and 5.1-fold increase in fluorescence intensity with the reduction of the nitroxide segment by the addition of Na ascorbate, respectively. In contrast, fluorescence intensity was not enhanced in the other hybrid compounds. Thus, the hybrid compounds which exhibited an increase in fluorescent intensity with radical reduction can be used in the quantitative measurement of reducing species such as Fe 2+ and ascorbic acid, and hydroxyl radicals. Because these hybrid compounds have the advantage of fluorescing at longer wavelengths—661 (Cy5) or 568 (Cy3) nm, respectively, they can be used to measure radical-reducing species or radicals either in solution or in vivo.

  4. Fabrication of dendrimer porogen-capsulated mesoporous silica via sol-gel process of silatrane precursor.

    PubMed

    Tanglumlert, Walairat; Wongkasemjit, Sujitra; Imae, Toyoko

    2009-03-01

    Mesoporous silica materials with ordered structures were prepared from a silatrane precursor and a poly(amido amine) dendrimer porogen under the dilute acidic condition via the sol-gel process. With decreasing the concentration of the dendrimer and adding much water, the production of undesirable amorphous silica was diminished and spherical particles with smooth surface became in majority. Two kinds of crystal arrays were found to be produced in the silica particles. Although pore diameters were within sizes of shrank and extended dendrimers, center-to-center distance of template pores was different each other for two arrays, and the difference was close to a molecular length of silatrane. These results indicate that one molecule of silatrane constructed polysiloxane wall in the first array and origomeric silatranes formed wall in the second array. It was referred that the intrinsic (hydrogen bonding) character of hydroxyl groups in the hydrolyzed silatrane resulted in hydrogen bonded oligomers and reinforced the hydrogen bonding interaction with dendrimer porogen as well as electrostatic interaction, giving rise to two types of template arrays.

  5. Cationic PAMAM dendrimers as pore-blocking binary toxin inhibitors.

    PubMed

    Förstner, Philip; Bayer, Fabienne; Kalu, Nnanya; Felsen, Susanne; Förtsch, Christina; Aloufi, Abrar; Ng, David Y W; Weil, Tanja; Nestorovich, Ekaterina M; Barth, Holger

    2014-07-14

    Dendrimers are unique highly branched macromolecules with numerous groundbreaking biomedical applications under development. Here we identified poly(amido amine) (PAMAM) dendrimers as novel blockers for the pore-forming B components of the binary anthrax toxin (PA63) and Clostridium botulinum C2 toxin (C2IIa). These pores are essential for delivery of the enzymatic A components of the internalized toxins from endosomes into the cytosol of target cells. We demonstrate that at low μM concentrations cationic PAMAM dendrimers block PA63 and C2IIa to inhibit channel-mediated transport of the A components, thereby protecting HeLa and Vero cells from intoxication. By channel reconstitution and high-resolution current recording, we show that the PAMAM dendrimers obstruct transmembrane PA63 and C2IIa pores in planar lipid bilayers at nM concentrations. These findings suggest a new potential role for the PAMAM dendrimers as effective polyvalent channel-blocking inhibitors, which can protect human target cells from intoxication with binary toxins from pathogenic bacteria.

  6. ADVANCED OXIDATION PROCESS

    SciTech Connect

    Dr. Colin P. Horwitz; Dr. Terrence J. Collins

    2003-11-04

    The removal of recalcitrant sulfur species, dibenzothiophene and its derivatives, from automotive fuels is an integral component in the development of cleaner burning and more efficient automobile engines. Oxidative desulfurization (ODS) wherein the dibenzothiophene derivative is converted to its corresponding sulfoxide and sulfone is an attractive approach to sulfur removal because the oxidized species are easily extracted or precipitated and filtered from the hydrocarbon phase. Fe-TAML{reg_sign} activators of hydrogen peroxide (TAML is Tetra-Amido-Macrocyclic-Ligand) catalytically convert dibenzothiophene and its derivatives rapidly and effectively at moderate temperatures (50-60 C) and ambient pressure to the corresponding sulfoxides and sulfones. The oxidation process can be performed in both aqueous systems containing alcohols such as methanol, ethanol, or t-butanol, and in a two-phase hydrocarbon/aqueous system containing tert-butanol or acetonitrile. In the biphasic system, essentially complete conversion of the DBT to its oxidized products can be achieved using slightly longer reaction times than in homogeneous solution. Among the key features of the technology are the mild reaction conditions, the very high selectivity where no over oxidation of the sulfur compounds occurs, the near stoichiometric use of hydrogen peroxide, the apparent lack of degradation of sensitive fuel components, and the ease of separation of oxidized products.

  7. Stable Isotope Resolved Metabolomics Analysis of Ribonucleotide and RNA Metabolism in Human Lung Cancer Cells.

    PubMed

    Fan, Teresa W-M; Tan, Jinlian; McKinney, Martin M; Lane, Andrew N

    2012-06-01

    We have developed a simple NMR-based method to determine the turnover of nucleotides and incorporation into RNA by stable isotope resolved metabolomics (SIRM) in A549 lung cancer cells. This method requires no chemical degradation of the nucleotides or chromatography. During cell growth, the free ribonucleotide pool is rapidly replaced by de novo synthesized nucleotides. Using [U-(13)C]-glucose and [U-(13)C,(15)N]-glutamine as tracers, we showed that virtually all of the carbons in the nucleotide riboses were derived from glucose, whereas glutamine was preferentially utilized over glucose for pyrimidine ring biosynthesis, via the synthesis of Asp through the Krebs cycle. Incorporation of the glutamine amido nitrogen into the N3 and N9 positions of the purine rings was also demonstrated by proton-detected (15)N NMR. The incorporation of (13)C from glucose into total RNA was measured and shown to be a major sink for the nucleotides during cell proliferation. This method was applied to determine the metabolic action of an anti-cancer selenium agent (methylseleninic acid or MSA) on A549 cells. We found that MSA inhibited nucleotide turnover and incorporation into RNA, implicating an important role of nucleotide metabolism in the toxic action of MSA on cancer cells.

  8. Cationic Group-IV pincer-type complexes for polymerization and hydroamination catalysis.

    PubMed

    Luconi, Lapo; Klosin, Jerzy; Smith, Austin J; Germain, Stéphane; Schulz, Emmanuelle; Hannedouche, Jérôme; Giambastiani, Giuliano

    2013-12-07

    Neutral Zr(IV) and Hf(IV) dimethyl complexes stabilized by unsymmetrical dianionic {N,C,N'} pincer ligands have been prepared from their corresponding bis-amido complexes upon treatment with AlMe3. Their structure consists of a central σ-bonded aryl donor group (C) capable of forming robust M-C bonds with the metal center, enforced by the synergic effect of both the coordination of peripheral donor groups (N) and the chelating rigid structure of the {N,C,N} ligand framework. Such a combination translates into systems having a unique balance between stability and reactivity. These Zr(IV) and Hf(IV) dimethyl complexes were converted in situ into cationic species [M(IV){N(-),C(-),N}Me][B(C6F5)4] which are active catalysts for the room temperature (r.t.) intramolecular hydroamination/cyclization of primary and secondary aminoalkenes as well as for the high temperature ethylene-1-octene copolymerizations.

  9. Turn-on fluorescent chemosensor for determination of lutetium ion.

    PubMed

    Faridbod, F; Sedaghat, M; Hosseini, M; Ganjali, M R; Khoobi, M; Shafiee, A; Norouzi, P

    2015-02-25

    A turn-on fluorescent chemosensor is introduced for the detection of Lu(3+) ion using N-[3-methyl]-2-[pyridine-2-amido] phenyl] pyridine-2-carboxamide (L) molecule. Fluorescent emission intensity of L enhances after binding to Lu(3+) ions in ethanol-water solution (1:9, v/v). The observed enhancement is the result of a strong covalent binding between Lu(3+) ion and L (the binding constant value is 2.0×10(6) mol(-1) L). The proposed optical chemosensor can be applied for the analysis of Lu(3+) ion in a linear range of 3.3×10(-7) to 1.0×10(-5) mol L(-1). The limit of detection was obtained 8.6×10(-7) mol L(-1). The probe exhibits high selectivity toward Lu(3+) ion in comparison with common metal ions. The proposed fluorescent chemosensor was successfully used in the determination of Lu(3+) ion in some water samples.

  10. Novel polymer gel electrolyte with organic solvents for quasi-solid-state dye-sensitized solar cells.

    PubMed

    Shen, Sheng-Yen; Dong, Rui-Xuan; Shih, Po-Ta; Ramamurthy, Vittal; Lin, Jiang-Jen; Ho, Kuo-Chuan

    2014-11-12

    A cross-linked copolymer was previously synthesized from poly(oxyethylene) diamine (POE-amine) and an aromatic anhydride and cured to generate an amide-imide cross-linking structure. The copolymer containing several chemical groups such as POE, amido acids, and imide, enabled to absorb liquid electrolytes in methoxypropionitrile (MPN) for suitable uses in dye-sensitized solar cells. To establish the advantages of polymer gel electrolytes (PGE), the same copolymer was studied by using different electrolyte solvents including propylene carbonate (PC), dimethylformamide, and N-methyl-2-pyrrolidone, and shown their long-term stability. The morphology of the copolymer after absorbing liquid electrolytes in these solvents was proven the same as a 3D interconnected nanochannels, evidenced field emission-scanning electron microscopy. Among these solvents, PC was selected as the optimized PGE, which demostrated a higher power conversion efficiency (8.31%) than that of the liquid electrolyte (7.89%). In particular, the long-term stability of only a 5% decrease in the cell efficiency after 1000 h of testing was achieved. It was proven the developed copolymer as PGE was versatile for different solvents showing high efficiency and long-term durability.

  11. Utilizing reversible copper(II) peptide coordination in a sequence-selective luminescent receptor.

    PubMed

    Stadlbauer, Stefan; Riechers, Alexander; Späth, Andreas; König, Burkhard

    2008-01-01

    Although vast information about the coordination ability of amino acids and peptides to metal ions is available, little use of this has been made in the rational design of selective peptide receptors. We have combined a copper(II) nitrilotriacetato (NTA) complex with an ammonium-ion-sensitive and luminescent benzocrown ether. This compound revealed micromolar affinities and selectivities for glycine- and histidine-containing sequences, which closely resembles those of copper(II) ion peptide binding: the two free coordination sites of the copper(II) NTA complex bind to imidazole and amido nitrogen atoms, replicating the initial coordination steps of non-complexed copper(II) ions. The benzocrown ether recognizes the N-terminal amino moiety intramolecularly, and the significantly increased emission intensity signals the binding event, because only if prior coordination of the peptide has taken place is the intramolecular ammonium ion-benzocrown ether interaction of sufficient strength in water to trigger an emission signal. Intermolecular ammonium ion-benzocrown ether binding is not observed. Isothermal titration calorimetry confirmed the binding constants derived from emission titrations. Thus, as deduced from peptide coordination studies, the combination of a truncated copper(II) coordination sphere and a luminescent benzocrown ether allows for the more rational design of sequence-selective peptide receptors.

  12. Transepithelial Transport of PAMAM Dendrimers Across Isolated Human Intestinal Tissue.

    PubMed

    Hubbard, Dallin; Enda, Michael; Bond, Tanner; Moghaddam, Seyyed Pouya Hadipour; Conarton, Josh; Scaife, Courtney; Volckmann, Eric; Ghandehari, Hamidreza

    2015-11-02

    Poly(amido amine) (PAMAM) dendrimers have shown transepithelial transport across intestinal epithelial barrier in rats and across Caco-2 cell monolayers. Caco-2 models innately lack mucous barriers, and rat isolated intestinal tissue has been shown to overestimate human permeability. This study is the first report of transport of PAMAM dendrimers across isolated human intestinal epithelium. It was observed that FITC labeled G4-NH2 and G3.5-COOH PAMAM dendrimers at 1 mM concentration do not have a statistically higher permeability compared to free FITC controls in isolated human jejunum and colonic tissues. Mannitol permeability was increased at 10 mM concentrations of G3.5-COOH and G4-NH2 dendrimers. Significant histological changes in human colonic and jejunal tissues were observed at G3.5-COOH and G4-NH2 concentrations of 10 mM implying that dose limiting toxicity may occur at similar concentrations in vivo. The permeability through human isolated intestinal tissue in this study was compared to previous rat and Caco-2 permeability data. This study implicates that PAMAM dendrimer oral drug delivery may be feasible, but it may be limited to highly potent drugs.

  13. Bis(phosphinimino)methanide rare earth amides: synthesis, structure, and catalysis of hydroamination/cyclization, hydrosilylation, and sequential hydroamination/hydrosilylation.

    PubMed

    Rastätter, Marcus; Zulys, Agustino; Roesky, Peter W

    2007-01-01

    A series of yttrium and lanthanide amido complexes [Ln{N(SiHMe(2))2}2{CH(PPh(2)NSiMe(3))2}] (Ln=Y, La, Sm, Ho, Lu) were synthesized by three different pathways. The title compounds can be obtained either from [Ln{N(SiHMe(2))2}3(thf)2] and [CH(2)(PPh(2)NSiMe(3))2] or from KN(SiHMe(2))2 and [Ln{CH(PPh(2)NSiMe(3))2}Cl(2)]2, while in a third approach the lanthanum compound was synthesized in a one-pot reaction starting from K{CH(PPh(2)NSiMe(3))2}, LaCl3, and KN(SiHMe(2))2. All the complexes have been characterized by single-crystal X-ray diffraction. The new complexes, [Ln{N(SiHMe(2))2}2{CH(PPh(2)NSiMe(3))2}], were used as catalysts for hydroamination/cyclization and hydrosilylation reactions. A clear dependence of the reaction rate on the ionic radius of the center metal was observed, showing the lanthanum compound to be the most active one in both reactions. Furthermore, a combination of both reactions--a sequential hydroamination/hydrosilylation reaction--was also investigated.

  14. Ability of a Au(III)-N unit to bond two aurophilically interacting gold(I) centers.

    PubMed

    Fernández, E J; Gil, M; Olmos, M E; Crespo, O; Laguna, A; Jones, P G

    2001-06-18

    The monohapto neutral 2-(diphenylphosphino)aniline (PNH(2)) complexes [Au(C(6)F(5))(2)X(PNH(2))] (X = C(6)F(5) (1), Cl (2)) have been obtained from [Au(C(6)F(5))(3)(tht)] or [Au(C(6)F(5))(2)(micro-Cl)](2) and PNH(2), and the cationic [Au(C(6)F(5))(2)(PNH(2))]ClO(4) (3) has been similarly prepared from [Au(C(6)F(5))(2)(OEt(2))(2)]ClO(4) and PNH(2) or from 2 and AgClO(4). The neutral amido complex [Au(C(6)F(5))(2)(PNH)] (4) can be obtained by deprotonation of 3 with PPN(acac) (acac = acetylacetonate) or by treatment of the chloro complex 2 with Tl(acac). It reacts with [Ag(OClO(3))(PPh(3))] or [Au(OClO(3))(PPh(3))] to give the dinuclear species [Au(C(6)F(5))(2)[PNH(MPPh(3))

  15. Synthesis of curdlan derivatives regioselectively modified at C-6: O-(N)-Acylated 6-amino-6-deoxycurdlan.

    PubMed

    Zhang, Ruoran; Edgar, Kevin J

    2014-05-25

    There has been growing interest in aminopolysaccharide synthesis over the last two decades due to the critical natural functions of aminopolysaccharides, and their potential in biomedical applications. Regioselective introduction of amino groups into polysaccharide backbones is a challenge. Natural curdlan is a linear β-(1→3)-glucan that is of interest both for its physical properties and its biomedical applications. Aminated curdlan derivatives were synthesized in three steps. First, curdlan was regioselectively brominated at the C-6 position in lithium bromide-N,N-dimethylacetamide (DMAc/LiBr). Second, the bromide of the product 6-bromo-6-deoxycurdlan was displaced by nucleophilic substitution with sodium azide (NaN3) in dimethyl sulfoxide (DMSO). Third, O-acylated 6-amido-6-deoxycurdlan was produced by a one-pot method. 6-Azido-6-deoxycurdlan was subjected to Staudinger reduction, followed by reaction in situ with excess carboxylic anhydride, without isolation of the 6-amino-6-deoxycurdlan intermediate. Regioselectivity and degree of substitution (DS) of these derivatives were confirmed by (1)H and (13)C NMR spectroscopy, FTIR spectroscopy, and elemental analysis.

  16. Characterizing the interactions of organic nanoparticles with renal epithelial cells in vivo.

    PubMed

    Nair, Anil V; Keliher, Edmund J; Core, Amanda B; Brown, Dennis; Weissleder, Ralph

    2015-01-01

    Nanotechnology approaches are actively being pursued for drug delivery, novel diagnostics, implantable devices, and consumer products. While considerable research has been performed on the effects of these materials on targeted tumor or phagocytic cells, relatively little is known about their effects on renal cells. This becomes critical for supersmall nanoparticles (<10 nm), designed to be renally excreted. The active endocytic machinery of kidney proximal tubules avidly internalizes filtered proteins, which may also be the case for filtered nanoparticles. To test whether such interactions affect kidney function, we injected mice with either 5 nm dextran-based nanoparticles (DNP) that are similar in composition to FDA-approved materials or poly(amido amine) dendrimer nanoparticles (PNP) of comparable size. These fluorescently tagged nanoparticles were both filtered and internalized by renal tubular epithelial cells in a dose- and time-dependent fashion. The biological effects were quantitated by immunocytochemistry, measuring kidney injury markers and performing functional tests. DNP administration resulted in a dose-dependent increase in urinary output, while cellular albumin endocytosis was increased. The expression of megalin, a receptor involved in albumin uptake, was also increased, but AQP1 expression was unaffected. The effects after PNP administration were similar but additionally resulted in increased clathrin expression and increased endocytosis of dextran. We conclude that there are no major detrimental renal effects of DNP on overall kidney function, but changes in endocytosis-mediating protein expression do occur. These studies provide a framework for the testing of additional nanoparticle preparations as they become available.

  17. pH-responsive mechanism of a deoxycholic acid and folate comodified chitosan micelle under cancerous environment.

    PubMed

    Chen, Daiqin; Song, Peng; Jiang, Feng; Meng, Xiangyue; Sui, Weiping; Shu, Chunying; Wan, Li-Jun

    2013-02-07

    Smart pH-responsive polymeric micelles have attracted much attention as one of the most promising drug delivery candidates. In this paper, a different substitution of deoxycholic acid (DCA) and folic acid (FA) comodified hydroxypropyl chitosans (HPCHS) were synthesized for doxorubicin (DOX) targeted delivery and controllable release. The results indicate that the DOX-release behavior is pH-responsive and closely related with the grafting proportions of the two hydrophobic ingredients. The pH-responsive mechanism for the optimized (6%DCA)-HPCHS-(0.1%FA) was suggested, resulting from a synergistic effect of gradual hydrolysis of the amido bond and electrostatic repulsion between the subsequently protonated DOX and the amino residue of the chitosan backbone under a cancerous microenvironment. Moreover, the DOX/(6%DCA)-HPCHS-(0.1%FA) micelle as a promising targeted drug delivery system in cancer therapy was evaluated by cell growth inhibition assays and confocal laser microscopy in vitro. The results clearly demonstrate a controlled release of its cargo and promoted curative efficacy of DOX.

  18. Chiral benzamidinate ligands in rare-earth-metal coordination chemistry.

    PubMed

    Benndorf, Paul; Kratsch, Jochen; Hartenstein, Larissa; Preuss, Corinna M; Roesky, Peter W

    2012-11-05

    The treatment of the recently reported potassium salt (S)-N,N'-bis-(1-phenylethyl)benzamidinate ((S)-KPEBA) and its racemic isomer (rac-KPEBA) with anhydrous lanthanide trichlorides (Ln = Sm, Er, Yb, Lu) afforded mostly chiral complexes. The tris(amidinate) complex [{(S)-PEBA}(3)Sm], bis(amidinate) complexes [{Ln(PEBA)(2)(μ-Cl)}(2)] (Ln = Sm, Er, Yb, Lu), and mono(amidinate) compounds [Ln(PEBA)(Cl)(2)(thf)(n)] (Ln = Sm, Yb, Lu) were isolated and structurally characterized. As a result of steric effects, the homoleptic 3:1 complexes of the smaller lanthanide atoms Yb and Lu were not accessible. Furthermore, chiral bis(amidinate)-amido complexes [{(S)-PEBA}(2)Ln{N(SiMe(3))(2)}] (Ln = Y, Lu) were synthesized by an amine-elimination reaction and salt metathesis. All of these chiral bis- and tris(amidinate) complexes had additional axial chirality and they all crystallized as diastereomerically pure compounds. By using rac-PEBA as a ligand, an achiral meso arrangement of the ligands was observed. The catalytic activities and enantioselectivities of [{(S)-PEBA}(2)Ln{N(SiMe(3))(2)}] (Ln = Y, Lu) were investigated in hydroamination/cyclization reactions. A clear dependence of the rate of reaction and enantioselectivity on the ionic radius was observed, which showed higher reaction rates but poorer enantioselectivities for the yttrium compound.

  19. Hydrogel Nanocomposites with Independently Tunable Rheology and Mechanics.

    PubMed

    Unterman, Shimon; Charles, Lyndon F; Strecker, Sara E; Kramarenko, Denis; Pivovarchik, Dmitry; Edelman, Elazer R; Artzi, Natalie

    2017-03-28

    Hydrogels are an attractive class of biomaterials for minimally invasive local drug delivery given their injectability, tunability, high water content, and biocompatibility. Broad applicability though is challenged: relatively modest mechanical properties restrict use to soft tissues, while flow properties necessary for injectability limit implantation to dried, enclosed tissues to minimize material migration during gelation. To address these dual concerns, we designed an injectable nanocomposite hydrogel based on dextran aldehyde and a poly(amido amine) dendrimer doped with phyllosilicate nanoplatelet fillers. Balance of components allows for exfoliation of nanoplatelets, significantly changing macromer solution flow, facilitating injection and manipulation in a wide variety of implantation contexts while enhancing compressive modulus of hydrogels at low loading. Importantly, rheological and mechanical effects were dependent on aspect ratio, with high aspect ratio nanoplatelets having much stronger effects on mechanics and low aspect ratio nanoplatelets having stronger effects on rheology, enabling nearly independent control of rheological and mechanical properties. Nanoplatelets enhanced hydrogel properties at a filler loading substantially lower than that of comparably sized nanoparticles. We present a model to explain the role that aspect ratio plays in control of rheology and mechanics in nanoplatelet-containing hydrogels, with lessons for further nanocomposite hydrogel development. This low-cost biocompatible material may be useful as a drug delivery platform in challenging implantation environments.

  20. Absorbent alginate fibres modified with hydrolysed chitosan for wound care dressings--II. Pilot scale development.

    PubMed

    Sweeney, I R; Miraftab, M; Collyer, G

    2014-02-15

    Fibres have been used extensively in wound dressing applications as they provide a high surface area for absorption, ease of fabrication and softness. It is common practice for commercial wound dressings to be produced from natural materials, such a marine polysaccharides, as they are predominantly biocompatible, non-toxic, and often display bioactive properties, such as inherent antimicrobial activity. In this study hydrolysed chitosans were utilised as a sole coagulant for the production of alginate-chitosan fibres via a one-step, direct wet-spinning extrusion process. The levels of chitosan incorporated into the fibres were analysed quantitatively via elemental analysis and qualitatively by staining using Amido Black 10B. It was estimated that the fibres contained between 4.50 and 5.10% (wt.%) chitosan. The presence of chitosan improved tensile properties such as elongation and tenacity of the base alginate fibres. The increased incorporation of chitosan into the fibres also improved the absorption of the fibres in both saline and distilled water; reaching maximum of >30 g/g and >50 g/g, respectively. This work suggests that the observed hydrolysed chitosan content within the fibre may be optimal for the preparation of a novel fibre for wound care application.

  1. Reversible removal of SO2 at low temperature by Bacillus licheniformis immobilized on γ-Al2O3.

    PubMed

    Jia, Lishan; Deng, Renpan; Song, Hao

    2011-01-01

    Bacillus licheniformis R08 biomass was immobilized on γ-Al2O3 and the effects of R08 biomass loading, SO2 concentration, water vapor, oxygen and temperature on removal of SO2 were investigated. The experimental results indicated that SO2 saturation capacity increased with increasing R08 biomass loading and SO2 concentration, but decreased with increasing adsorption temperature. Water vapor activated the adsorbent and promoted SO2 removal. An increase in oxygen concentration from 5 to 10% had little effect on SO2 removal. FTIR analysis revealed that the R08 biomass bound to γ-Al2O3 mainly by forming R-CO-O-Al bonds. X-ray photoelectron spectroscopy analysis indicated that γ-Al2O3 reacted with SO2 and formed aluminum sulfate in the presence of oxygen when R08 biomass loading was 13.8%, but that amido groups of the R08 biomass reacted with SO2 and formed sulfite when biomass loading was 32.4%. Ten continuous adsorption-desorption cycles showed that the adsorbent had an excellent regeneration performance.

  2. Synthesis, structure, and reactivity of mononuclear RE(I) oximato complexes.

    PubMed

    Cuesta, Luciano; Huertos, Miguel A; Morales, Dolores; Pérez, Julio; Riera, Lucía; Riera, Víctor; Miguel, Daniel; Menéndez-Velazquez, Amador; García-Granda, Santiago

    2007-04-02

    Complexes [Re(ONCMe2)(CO)3(bipy)] (1) and [Re(ONCMe2)(CO)3(phen)] (2), synthesized by reaction of the respective triflato precursors [Re(OTf)(CO)3(N-N)] (N-N = bipy, phen) with KONCMe2, feature O-bonded monodentate oximato ligands. Compound [Re(CO)3(phen)(HONCMe2)]BAr'4 (3), with a monodentate N-bonded oxime ligand, was prepared by reaction of [Re(OTf)(CO)3(phen)], HONCMe2, and NaBAr'4. Deprotonation of 3 afforded 2. The oximato complexes reacted with p-tolylisocyanate, p-tolylisothiocyanate, maleic anhydride, and tetracyanoethylene, affording the products of the insertion of the electrophile into the Re-O bond, compounds 4-7. One representative of each type of compound was fully characterized, including single-crystal X-ray diffraction. The reactions of 1 and 2 with dimethylacetylenedicarboxylate were found to involve first an insertion as the ones mentioned above but followed by incorporation of water, loss of acetone, and formation of the charge-separated neutral amido complexes 9 and 10. The structure of 9 and 10 was determined by X-ray diffraction, and key features of their electronic distribution were studied using a topological analysis of the electron density as obtained from the Fourier map.

  3. Comparison of five methods for determination of total plasma protein concentration.

    PubMed

    Okutucu, Burcu; Dinçer, Ayşşe; Habib, Omer; Zihnioglu, Figen

    2007-08-01

    Quantitation of exact total protein content is often a key step and is common to many applications in general biochemistry research and routine clinical laboratory practice. Before embarking on any type of protein analysis, particularly comparative techniques, it is important to accurately quantitate the amount of protein in the sample. In order to assess the quality of total protein estimation results, five methods were tested and were applied to the same pooled plasma sample. For this aim, Bradford (Coomassie Brilliant Blue), Lowry (Folin-Ciocalteau), Biüret, Pesce and Strande (Ponceau-S/TCA), and modified method of Schaffner-Weismann (Amido Black 10B) were used. The last two methods employ simultaneous precipitation of proteins with the acid containing dye solutions followed by dissolution of precipitate in a NaOH solution. It is shown that each assay has advantages and disadvantages relative to sensitivity, ease of performance, acceptance in literature, accuracy and reproducibility/coefficient of variation. All of the methods tested show a CV %<6. Besides pooled plasma, a known concentration of human serum albumin was also analyzed and discussed by means of standardization of plasma total protein content.

  4. Synthesis and evaluation of thymidine kinase 1-targeting carboranyl pyrimidine nucleoside analogs for boron neutron capture therapy of cancer.

    PubMed

    Agarwal, Hitesh K; Khalil, Ahmed; Ishita, Keisuke; Yang, Weilian; Nakkula, Robin J; Wu, Lai-Chu; Ali, Tehane; Tiwari, Rohit; Byun, Youngjoo; Barth, Rolf F; Tjarks, Werner

    2015-07-15

    A library of sixteen 2nd generation amino- and amido-substituted carboranyl pyrimidine nucleoside analogs, designed as substrates and inhibitors of thymidine kinase 1 (TK1) for potential use in boron neutron capture therapy (BNCT) of cancer, was synthesized and evaluated in enzyme kinetic-, enzyme inhibition-, metabolomic-, and biodistribution studies. One of these 2nd generation carboranyl pyrimidine nucleoside analogs (YB18A [3]), having an amino group directly attached to a meta-carborane cage tethered via ethylene spacer to the 3-position of thymidine, was approximately 3-4 times superior as a substrate and inhibitor of hTK1 than N5-2OH (2), a 1st generation carboranyl pyrimidine nucleoside analog. Both 2 and 3 appeared to be 5'-monophosphorylated in TK1(+) RG2 cells, both in vitro and in vivo. Biodistribution studies in rats bearing intracerebral RG2 glioma resulted in selective tumor uptake of 3 with an intratumoral concentration that was approximately 4 times higher than that of 2. The obtained results significantly advance the understanding of the binding interactions between TK1 and carboranyl pyrimidine nucleoside analogs and will profoundly impact future design strategies for these agents.

  5. Geometry, Electronic Structure, and Pseudo Jahn-Teller Effect in Tetrasilacyclobutadiene Analogues

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Wang, Ya; Bersuker, Isaac B.

    2016-03-01

    We revealed the origin of the structural features of a series of tetrasilacyclobutadiene analogues based on a detailed study of their electronic structure and the pseudo Jahn-Teller effect (PJTE). Starting with the D4h symmetry of the Si4R4 system with a square four-membered silicon ring as a reference geometry, and employing ab initio calculations of energy profiles along lower-symmetry nuclear displacements in the ground and several excited states, we show that the ground-state boat-like and chair-like equilibrium configurations are produced by the PJT interaction with appropriate excited sates. For Si4F4 a full two-mode b1g‑b2g adiabatic potential energy surface is calculated showing explicitly the way of transformation from the unstable D4h geometry to the two equilibrium C2h configurations via the D2h saddle point. The PJTE origin of these structural features is confirmed also by estimates of the vibronic coupling parameters. For Si4R4 with large substituents the origin of their structure is revealed by analyzing the PJT interaction between the frontier molecular orbitals. The preferred chair-like structures of Si4R4 analogues with amido substituents, and heavier germanium-containing systems Ge4R4 (potential precursors for semiconducting materials) are predicted.

  6. Ruthenium(II) Complexes Containing Lutidine-Derived Pincer CNC Ligands: Synthesis, Structure, and Catalytic Hydrogenation of C-N bonds.

    PubMed

    Hernández-Juárez, Martín; López-Serrano, Joaquín; Lara, Patricia; Morales-Cerón, Judith P; Vaquero, Mónica; Álvarez, Eleuterio; Salazar, Verónica; Suárez, Andrés

    2015-05-11

    A series of Ru complexes containing lutidine-derived pincer CNC ligands have been prepared by transmetalation with the corresponding silver-carbene derivatives. Characterization of these derivatives shows both mer and fac coordination of the CNC ligands depending on the wingtips of the N-heterocyclic carbene fragments. In the presence of tBuOK, the Ru-CNC complexes are active in the hydrogenation of a series of imines. In addition, these complexes catalyze the reversible hydrogenation of phenantridine. Detailed NMR spectroscopic studies have shown the capability of the CNC ligand to be deprotonated and get involved in ligand-assisted activation of dihydrogen. More interestingly, upon deprotonation, the Ru-CNC complex 5 e(BF4 ) is able to add aldimines to the metal-ligand framework to yield an amido complex. Finally, investigation of the mechanism of the hydrogenation of imines has been carried out by means of DFT calculations. The calculated mechanism involves outer-sphere stepwise hydrogen transfer to the C-N bond assisted either by the pincer ligand or a second coordinated H2 molecule.

  7. Altered architecture and enhanced drought tolerance in rice via the down-regulation of indole-3-acetic acid by TLD1/OsGH3.13 activation.

    PubMed

    Zhang, Sheng-Wei; Li, Chen-Hui; Cao, Jia; Zhang, Yong-Cun; Zhang, Su-Qiao; Xia, Yu-Feng; Sun, Da-Ye; Sun, Ying

    2009-12-01

    Plant architecture is determined by genetic and developmental programs as well as by environmental factors. Sessile plants have evolved a subtle adaptive mechanism that allows them to alter their growth and development during periods of stress. Phytohormones play a central role in this process; however, the molecules responsible for integrating growth- and stress-related signals are unknown. Here, we report a gain-of-function rice (Oryza sativa) mutant, tld1-D, characterized by (and named for) an increased number of tillers, enlarged leaf angles, and dwarfism. TLD1 is a rice GH3.13 gene that encodes indole-3-acetic acid (IAA)-amido synthetase, which is suppressed in aboveground tissues under normal conditions but which is dramatically induced by drought stress. The activation of TLD1 reduced the IAA maxima at the lamina joint, shoot base, and nodes, resulting in subsequent alterations in plant architecture and tissue patterning but enhancing drought tolerance. Accordingly, the decreased level of free IAA in tld1-D due to the conjugation of IAA with amino acids greatly facilitated the accumulation of late-embryogenesis abundant mRNA compared with the wild type. The direct regulation of such drought-inducible genes by changes in the concentration of IAA provides a model for changes in plant architecture via the process of drought adaptation, which occurs frequently in nature.

  8. Altered Architecture and Enhanced Drought Tolerance in Rice via the Down-Regulation of Indole-3-Acetic Acid by TLD1/OsGH3.13 Activation1[C][W

    PubMed Central

    Zhang, Sheng-Wei; Li, Chen-Hui; Cao, Jia; Zhang, Yong-Cun; Zhang, Su-Qiao; Xia, Yu-Feng; Sun, Da-Ye; Sun, Ying

    2009-01-01

    Plant architecture is determined by genetic and developmental programs as well as by environmental factors. Sessile plants have evolved a subtle adaptive mechanism that allows them to alter their growth and development during periods of stress. Phytohormones play a central role in this process; however, the molecules responsible for integrating growth- and stress-related signals are unknown. Here, we report a gain-of-function rice (Oryza sativa) mutant, tld1-D, characterized by (and named for) an increased number of tillers, enlarged leaf angles, and dwarfism. TLD1 is a rice GH3.13 gene that encodes indole-3-acetic acid (IAA)-amido synthetase, which is suppressed in aboveground tissues under normal conditions but which is dramatically induced by drought stress. The activation of TLD1 reduced the IAA maxima at the lamina joint, shoot base, and nodes, resulting in subsequent alterations in plant architecture and tissue patterning but enhancing drought tolerance. Accordingly, the decreased level of free IAA in tld1-D due to the conjugation of IAA with amino acids greatly facilitated the accumulation of late-embryogenesis abundant mRNA compared with the wild type. The direct regulation of such drought-inducible genes by changes in the concentration of IAA provides a model for changes in plant architecture via the process of drought adaptation, which occurs frequently in nature. PMID:19776160

  9. Purification, molecular cloning, and biochemical characterization of subtilisin JB1 from a newly isolated Bacillus subtilis JB1.

    PubMed

    Sung, Ji Hea; Ahn, Sang Jung; Kim, Na Young; Jeong, Soo-Kyoung; Kim, Joong Kyun; Chung, Joon Ki; Lee, Hyung Ho

    2010-10-01

    An extracellular gelatinolytic enzyme obtained from the newly isolated Bacillus subtilis JB1, a thermophilic microorganism relevant to the aerobic biodegradation process of fish-meal production, was purified via ammonium sulfate precipitation, Sephadex G-200 Gel filtration chromatography, and one-dimensional gel electrophoresis separation and subsequently identified via peptide mass fingerprinting and chemically assisted fragmentation matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The subtilisin JB1 gene was sequenced and its recombinant protein prosubtilisin JB1 was expressed in Escherichia coli, and the purified prosubtilisin JB1 (62 kDa) protein was digested with gelatin, bovine serum albumin, azocasein, fibrinogen, and the fluorogenic peptide substrate Ala-Ala-Phe-7-amido-4-methylcoumarin hydrochloride, whereas the serine protease inhibitors phenylmethylsulfonyl fluoride and chymostatin completely inhibited its enzyme activity at an optimal pH of 7.5. Thus, our results show that subtilisin JB1 may serve as a potential source material for use in industrial applications of proteolytic enzymes and microorganisms for fishery waste degradation and fish by-product processing.

  10. A novel sandwiched electrochemiluminescence immunosensor for the detection of carcinoembryonic antigen based on carbon quantum dots and signal amplification.

    PubMed

    Li, Nian-Lu; Jia, Li-Ping; Ma, Rong-Na; Jia, Wen-Li; Lu, Yi-Yang; Shi, Sha-Shan; Wang, Huai-Sheng

    2017-03-15

    In this study, a novel sandwiched electrochemiluminescence (ECL) immunosensor for the detection of carcinoembryonic antigen (CEA) was developed. The nanocomposite of polydopamine and Ag nanoparticles (PDA-AgNPs) was prepared by the redox reaction between Ag(+) and dopamine. This nanocomposite not only provided an effective matrix for the immobilization of primary antibody (Ab1) but also enhanced the conductivity of the electrode. Carbon quantum dots (CQDs) were immobilized on the poly(ethylenimine) functionalized graphene oxide (PEI-GO) through amido-bond. Then Au nanoparticles were decorated on the CQDs modified PEI-GO matrix, and the resulted complex AuNPs/CQDs-PEI-GO was introduced to link secondary antibody (Ab2). The CQDs can be connected to the electrode surface through the combination of CEA with Ab1 and Ab2, and then the amplified electrochemiluminescence signal of CQDs was obtained with the synergistic effect of AgNPs, polydopamine, AuNPs and PEI-GO. Under the optimal conditions, the ECL intensity was proportional to the logarithm value of CEA concentration in the linear range from 5pgmL(-1) to 500ngmL(-1) with a detection limit of 1.67pgmL(-1) for CEA detection. The immunosensor was applied for the CEA detection in real samples with satisfactory results. The proposed ECL immunosensor showed good performance with high sensitivity, specificity, reproducibility, stability and will be potential in clinical detection.

  11. Promising in vitro performances of a new nickel-free stainless steel.

    PubMed

    Montanaro, Lucio; Cervellati, Marina; Campoccia, Davide; Arciola, Carla Renata

    2006-03-01

    Stainless steel is a metallic alloy largely employed in orthopaedics. However, the presence in its composition of a high quantity of nickel, an agent known to trigger toxic and allergic responses, is cause for concern. In this study, we have investigated the in vitro biocompatibility of a new nickel-reduced stainless steel, namely Böhler P558, in comparison to the conventional stainless steel AISI 316L. The neutral red (NR) uptake and the amido black (AB) tests were performed on L929 fibroblasts and MG63 osteoblasts to assess the cytotoxicity, while cytogenetic effects were evaluated on CHOK1 cells by studying the frequency of Sister Chromatid Exchanges (SCE) and chromosomal aberrations. Ames test was used to detect the mutagenic activity. The expression of selected markers typical of differentiated osteoblasts, such as alkaline phosphatase activity (ALP), type I collagen (CICP) and osteocalcin (OC) production, were also monitored in MG63 cells cultured on the tested materials. Our results indicate the absence of significant cytotoxicity and genotoxicity for both test alloys. ALP, CICP and OC analyses confirmed that both materials support the expression of these phenotypic markers. Overall, these data show that this Ni-free alloy possesses good in vitro biocompatibility and could have a potential for orthopaedic applications.

  12. Comparative inhibitory effects of niflumic acid and novel synthetic derivatives on the rat isolated stomach fundus.

    PubMed

    Criddle, David N; Meireles, AnaVanescaP; Macêdo, Liana B; Leal-Cardoso, José H; Scarparo, Henrique C; Jaffar, Mohammed

    2002-02-01

    Novel derivatives of 2-[3-(trifluoromethyl)-analino]nicotinic acid (niflumic acid) were synthesized. The compounds were compared for their inhibitory effects on 5-hydroxytryptamine (5-HT)- and KCI-induced contraction of the rat fundus. The aim was to assess structure-activity relationships regarding the selectivity and potency of these compounds. Niflumic acid (1-100 microM) concentration-dependently inhibited 5-HT-induced tonic contractions with an IC50 value (concentration reducing the control contractile response by 50%, calculated from semi-log graphs) of 0.24 x 10(4) M (n = 9). In contrast, it was significantly less potent at inhibiting KCl-induced responses (IC50 = 1.49 x 10(4) M, n = 9). The methyl ester (NFAme) and amido (NFAm) analogues showed no selectivity between 5-HT- and KCl-induced contractions with IC50 values of 1.64 x 10(-4) M (n = 8) and 1.87 x 10(-4) M (n = 9) for 5-HT responses, and 2.61 x 10(-4) M (n = 8) and 2.55 x 10(-4) M (n = 7) for KCl-induced responses, respectively. Our results suggest that alteration of the carboxylic acid moiety of niflumic acid reduces the selectivity and potency of its inhibitory action on 5-HT-induced contractile responses of the rat fundus, possibly via a reduced interaction with calcium-activated chloride channels.

  13. Cu(2+), Zn(2+), and Ni(2+) Complexes of C2-Symmetric Pseudopeptides with an Aromatic Central Spacer.

    PubMed

    Gorla, Lingaraju; Martí-Centelles, Vicente; Freimuth, Lena; Altava, Belén; Burguete, M Isabel; Luis, Santiago V

    2016-08-01

    Two new tetradentate C2-symmetric pseudopeptidic ligands derived from Val and Phe containing two amino and two amido groups and a central o-substituted aromatic spacer have been prepared. Their complexes with Cu(2+), Zn(2+), and Ni(2+) have been studied by potentiometry, UV-vis spectrophotometry, FT-IR, and ESI-MS. The presence of the aromatic spacer provides Cu(2+) complexes with stability constants several orders of magnitude higher than those observed for related ligands containing aliphatic central spacers. Besides, the formation of [MH-2L] complex species is favored. Crystal structures for the corresponding Cu(2+) and Ni(2+) have been obtained, revealing the metal atom in an essentially square-planar geometry, although, in several instances, the oxygen atom of an amide carbonyl of a second complex species can act as a fifth coordination site. In the case of Zn(2+), the only crystal structure obtained displays a square-pyramidal arrangement of the metal center. Finally, preliminary experiments show the catalytic activity of some of these complexes, in particular, Zn(2+) complexes, for epoxide ring-opening with using aniline as the nucleophile in a ligand accelerated process.

  14. Hydrolases of the ILR1-like family of Arabidopsis thaliana modulate auxin response by regulating auxin homeostasis in the endoplasmic reticulum

    PubMed Central

    Sanchez Carranza, Ana Paula; Singh, Aparajita; Steinberger, Karoline; Panigrahi, Kishore; Palme, Klaus; Dovzhenko, Alexander; Dal Bosco, Cristina

    2016-01-01

    Amide-linked conjugates of indole-3-acetic acid (IAA) have been identified in most plant species. They function in storage, inactivation or inhibition of the growth regulator auxin. We investigated how the major known endogenous amide-linked IAA conjugates with auxin-like activity act in auxin signaling and what role ILR1-like proteins play in this process in Arabidopsis. We used a genetically encoded auxin sensor to show that IAA-Leu, IAA-Ala and IAA-Phe act through the TIR1-dependent signaling pathway. Furthermore, by using the sensor as a free IAA reporter, we followed conjugate hydrolysis mediated by ILR1, ILL2 and IAR3 in plant cells and correlated the activity of the hydrolases with a modulation of auxin response. The conjugate preferences that we observed are in agreement with available in vitro data for ILR1. Moreover, we identified IAA-Leu as an additional substrate for IAR3 and showed that ILL2 has a more moderate kinetic performance than observed in vitro. Finally, we proved that IAR3, ILL2 and ILR1 reside in the endoplasmic reticulum, indicating that in this compartment the hydrolases regulate the rates of amido-IAA hydrolysis which results in activation of auxin signaling. PMID:27063913

  15. TRANSEPITHELIAL TRANSPORT AND TOXICITY OF PAMAM DENDRIMERS: IMPLICATIONS FOR ORAL DRUG DELIVERY

    PubMed Central

    Sadekar, S.; Ghandehari, H.

    2011-01-01

    This article summarizes efforts to evaluate poly(amido amine) (PAMAM) dendrimers as carriers for oral drug delivery. Specifically, the effect of PAMAM generation, surface charge and surface modification on toxicity, cellular uptake and transepithelial transport is discussed. Studies on Caco-2 monolayers, as models of intestinal epithelial barrier, show that by engineering surface chemistry of PAMAM dendrimers, it is possible to minimize toxicity while maximizing transepithelial transport. It has been demonstrated that PAMAM dendrimers are transported by a combination of paracellular and transcellular routes. Depending on surface chemistry, PAMAM dendrimers can open the tight junctions of epithelial barriers. This tight junction opening is in part mediated by internalization of the dendrimers. Transcellular transport of PAMAM dendrimers is mediated by a variety of endocytic mechanisms. Attachment or complexation of cytotoxic agents to PAMAM dendrimers enhances the transport of such drugs across epithelial barriers. A remaining challenge is the design and development of linker chemistries that are stable in the gastrointestinal tract (GIT) and the blood stream, but amenable to cleavage at the target site of action. Recent efforts have focused on the use of PAMAM dendrimers as penetration enhancers. Detailed in vivo oral bioavailability of PAMAM dendrimer – drug conjugates, as a function of physicochemical properties will further need to be assessed. PMID:21983078

  16. Superoleophobic polymers with metal ion affinity toward materials with both oleophobic and hydrophilic properties.

    PubMed

    Darmanin, Thierry; Guittard, Frédéric

    2013-10-15

    Bis(trifluoromethane)sulfonimide salts are used as electrolyte for the elaboration of superoleophobic properties by electrodeposition using a monomer containing a short perfluorobutyl (C4F9), separated from the polymer backbone by a long alkyl spacer, to reduce the mobility of these chains, and an amido connector to form complexes with ions. The electrodeposition in some of these electrolytes induces the formation of microstructures composed of nanosheets able to reach superoleophobic properties. When complexant ions (Na(+), Mg(2+), Ca(2+), Ba(2+)) are used as cation of the electrolyte, these ions are incorporated in the polymer leading to a material with higher oleophobicity than hydrophobicity. Indeed, when a water droplet is deposited on the surface, the migration of the ions induces a decrease in the surface hydrophobicity, while the deposition of an oil droplet (diiodomethane or hexadecane) does not induce this migration. If the incorporation of these ions is not sufficiently stable for applications in oil/water separation, this work opens new strategies in the elaboration of both superoleophobic/oleophobic and superhydrophilic/hydrophilic materials. Such materials can also be used for the ion capture and release.

  17. 2-DE using hemi-fluorinated surfactants.

    PubMed

    Starita-Geribaldi, Mireille; Thebault, Pascal; Taffin de Givenchy, Elisabeth; Guittard, Frederic; Geribaldi, Serge

    2007-07-01

    The synthesis of hemi-fluorinated zwitterionic surfactants was realized and assessed for 2-DE, a powerful separation method for proteomic analysis. These new fluorinated amidosulfobetaine (FASB-p,m) were compared to their hydrocarbon counterparts amidosulfobetaine (ASB-n) characterized by a hydrophilic polar head, a hydrophobic and lipophilic tail, and an amido group as connector. The tail of these FASB surfactants was in part fluorinated resulting in the modulation of its lipophilicity (or oleophobicity). Their effect on the red blood cell (RBC) membrane showed a specific solubilization depending on the length of the hydrophobic part. A large number of polypeptide spots appeared in the 2-DE patterns by using FASB-p,m. The oleophobic character of these surfactants was confirmed by the fact that Band 3, a highly hydrophobic transmembrane protein, was not solubilized by these fluorinated structures. The corresponding pellet was very rich in Band 3 and could then be solubilized by using a strong detergent such as amidosulfobetaine with an alkyl tail containing 14 carbon atoms (ASB-14). Thus, these hemi-fluorinated surfactants appeared as powerful tools when used at the first step of a two-step solubilization strategy using a hydrocarbon homologous surfactant in the second step.

  18. Synthesis and Properties of Star HPMA Copolymer Nanocarriers Synthesised by RAFT Polymerisation Designed for Selective Anticancer Drug Delivery and Imaging.

    PubMed

    Chytil, Petr; Koziolová, Eva; Janoušková, Olga; Kostka, Libor; Ulbrich, Karel; Etrych, Tomáš

    2015-06-01

    High-molecular-weight star polymer drug nanocarriers intended for the treatment and/or visualisation of solid tumours were synthesised, and their physico-chemical and preliminary in vitro biological properties were determined. The water-soluble star polymer carriers were prepared by the grafting of poly(amido amine) (PAMAM) dendrimers by hetero-telechelic N-(2-hydroxypropyl)methacrylamide (HPMA) copolymers, synthesised by the controlled radical Reversible Addition Fragmentation chain Transfer (RAFT) polymerisation. The well-defined star copolymers with Mw values ranging from 2 · 10(5) to 6 · 10(5) showing a low dispersity (approximately 1.2) were prepared in a high yield. A model anticancer drug, doxorubicin, was bound to the star polymer through a hydrazone bond, enabling the pH-controlled drug release in the target tumour tissue. The activated polymer arm ends of the star copolymer carrier enable a one-point attachment for the targeting ligands and/or a labelling moiety. In this study, the model TAMRA fluorescent dye was used to prove the feasibility of the polymer carrier visualisation by optical imaging in vitro. The tailor-made structure of the star polymer carriers should facilitate the synthesis of targeted polymer-drug conjugates, even polymer theranostics, for simultaneous tumour drug delivery and imaging.

  19. Transepithelial transport of PAMAM dendrimers across isolated intestinal tissue

    NASA Astrophysics Data System (ADS)

    Hubbard, Dallin A.

    Poly(amido amine) (PAMAM) dendrimers have shown potential to carry poorly absorbed drugs across the intestinal barrier and into systemic circulation, reducing the need for intravenous injections. Much of the in vitro transepithelial transport of PAMAM dendrimers to date has been investigated using Caco-2 monolayers which lack the microvilli morphology and enzymes present in isolated intestinal tissues. In addition, a challenge in predicting oral absorption is establishing a correlation between transport across rodent and human intestinal tissues. This dissertation focused on investigating the transepithelial transport of PAMAM dendrimers across rat and human isolated intestinal tissues. Permeability values in isolated tissues were compared with those across Caco-2 cell monolayers. Results indicate a difference in transport of PAMAM dendrimers, morphological changes and transepithelial electrical resistance between Caco-2 cell monolayers, rat and human intestinal tissue models. A relatively high transport rate across the tissues, given the macromolecular nature of PAMAM dendrimers, shows promise for use of these constructs for oral delivery in human.

  20. In vitro reconstitution of peptidoglycan assembly from the Gram-positive pathogen Streptococcus pneumoniae.

    PubMed

    Zapun, André; Philippe, Jules; Abrahams, Katherine A; Signor, Luca; Roper, David I; Breukink, Eefjan; Vernet, Thierry

    2013-12-20

    Understanding the molecular basis of bacterial cell wall assembly is of paramount importance in addressing the threat of increasing antibiotic resistance worldwide. Streptococcus pneumoniae presents a particularly acute problem in this respect, as it is capable of rapid evolution by homologous recombination with related species. Resistant strains selected by treatment with β-lactams express variants of the target enzymes that do not recognize the drugs but retain their activity in cell wall building, despite the antibiotics being mimics of the natural substrate. Until now, the crucial transpeptidase activity that is inhibited by β-lactams was not amenable to in vitro investigation with enzymes from Gram-positive organisms, including streptococci, staphylococci, or enterococci pathogens. We report here for the first time the in vitro assembly of peptidoglycan using recombinant penicillin-binding proteins from pneumococcus and the precursor lipid II. The two required enzymatic activities, glycosyl transferase for elongating glycan chains and transpeptidase for cross-linking stem-peptides, were observed. Most importantly, the transpeptidase activity was dependent on the chemical nature of the stem-peptide. Amidation of the second residue glutamate into iso-glutamine by the recently discovered amido-transferase MurT/GatD is required for efficient cross-linking of the peptidoglycan.